Indirect thermal decomposition with joule heating of powder

Abstract

Systems and methods for heating feedstock, thermal decomposition of feedstock, and chemically activated chemical reaction of feedstock by indirectly heating the feedstock with a volume of joule heated electrically conductive powder that heats the feedstock, wherein the feedstock can be gas, liquid, or solid. The embodiments disclosed herein further relate to systems and methods for joule heating induced pyrolysis or thermal decomposition of feedstock, including methane or other hydrocarbons to produce, for example, hydrogen and / or various carbon materials that are collected.

Description

INDIRECT THERMAL DECOMPOSITION WITH JOULE HEATING OF POWDER This application claims the benefit of U.S. Provisional Patent Application Serial No. 63,629,975, which was filed on October 17, 2023. Field of the Invention

[0001] This invention relates to systems and methods for heating feedstock, thermal decomposition of feedstock, and chemically activated chemical reaction of feedstock by indirectly heating the feedstock with a volume of joule heated electrically conductive powder that heats the feedstock, wherein the feedstock can be gas, liquid, or solid. The embodiments disclosed herein further relate to systems and methods for joule heating induced pyrolysis or thermal decomposition of feedstock, including methane or other hydrocarbons to produce, for example, hydrogen and / or various carbon materials that are collected. Description of the Related Art

[0002] Methane pyrolysis systems include molten salt pyrolysis, where methane gas is bubbled through a molten salt media and undergoes thermal decomposition of methane into hydrogen and carbon. Other methane pyrolysis systems include plasma or microwave induced pyrolysis in which the methane is cracked by plasma energy. Other methane pyrolysis systems include quartz tube ovens where the methane is heated indirectly by radiation from resistive wire filament. In many systems, there is a need for a catalyst to be present in the reactor to improve the efficiency of the methane cracking. In all such systems, methane pyrolysis is not energy efficient due to lack of good thermal energy transfer from the heater to the methane.

[0003] Methane pyrolysis can be done with three common methane paralysis systems and processes. Figure 1A-left shows a hot filament pyrolysis system. With this apparatus, the gas flows in a closed reactor tube and the hot filament can either be outside of the tube or inside the tube. Such an approach is limited as it utilizes a very small hot surface area per unit volume of the reactor and lacks efficient heat transfer from the filament to the gas. Figure 1A-middle shows molten media pyrolysis system. This approach utilizes molten salts and catalyst that have to be kept in liquid state and gas is then bubbled through the molten salt to crack the methaneinto hydrogen and carbon. Such an approach is limited as it experiences catalyst saturation and deactivation that require molten salt replenishment that is not easy to scale. In addition, the resulting carbon has low value because it is contaminated by the catalyst. Figure 1A-right shows a plasma assisted pyrolysis system. This approach utilizes vacuumized reactors in which gas is turned into plasma with the help of electrical power. The methane in the plasma field then decomposes into hydrogen and carbon. Some limitations of this approach are the capital and operating costs, and the limited throughput constrained by the plasma reaction volume that can practically be constructed.

[0004] PCT International Publication No. WO / 2022 / 246325 to Wang et al. discloses a system wherein the heating element is placed inside an oven where the heat transfer between the heating element and the methane gas is improved locally. However, the heating element of this disclosure is a thin heating element made from carbon fibrils. A limitation of this system is that methane pyrolysis is restricted to localized areas near the heated thin element (carbon fibrils). Figure 1B shows an embodiment of this methane pyrolysis apparatus and this system also lacks scalability.

[0005] A flash joule heating synthesis of graphene is disclosed in PCT International Publication No. WO 2020 / 051000 to Tour et al., where electrically conductive solid carbon material is flash joule heated with electrical power to convert the solid carbon into solid graphene. This disclosure does not teach methane pyrolysis, does not teach hydrocarbon pyrolysis, and does not teach gas pyrolysis. Summary Of The Invention

[0006] The current invention comprises heating of feedstock using indirect joule heating. More specifically, the current invention comprises gas pyrolysis using indirect joule heating, in which material powders, including a conductive additive powder, and gases, are rapidly heated using joule heating, causing thermal decomposition of the gas, resulting in desired products, such as for example hydrogen and various carbon materials, that are then collected. The current invention further comprises thermally activated chemical reactions of a single gas, liquid, or solid feedstock or among multiple gas, liquid, or solid feedstocks.

[0007] One exemplary embodiment of the current invention is a method for heating materials, comprising: joule heating a volume of electrically conductive powder inside a powder reactor; moving feedstock through a process reactor; and heating the feedstock inside the process reactor using the powder reactor.

[0008] Another exemplary embodiment of the current invention is a method for thermal gas decomposition, comprising: joule heating a volume of electrically conductive powder inside a powder reactor; flowing feedstock gas through a process reactor; and thermally decomposing the feedstock gas inside the process reactor using heat from the powder reactor.

[0009] Another exemplary embodiment of the current invention is a method for thermally activated chemical reaction of at least one feedstock, comprising: joule heating a volume of electrically conductive powder inside a powder reactor; flowing at least one feedstock through a process reactor; and wherein the feedstock undergoes a thermally activated chemical reaction inside the process reactor using the heat from the powder reactor.

[0010] Another exemplary embodiment of the current invention is a heating system comprising: a powder reactor capable of containing a volume of electrically conductive powder; electrodes for joule heating the volume of electrically conductive powder; a process reactor capable of containing feedstock, wherein said process reactor is arranged inside the powder reactor.

[0011] Another exemplary embodiment of the current invention is a thermal gas decomposition system comprising: a powder reactor capable of containing a volume of electrically conductive powder; electrodes for joule heating the volume of conductive powder; and a process reactor placed inside the powder reactor, wherein the process reactor is capable of containing gas for thermal decomposition.

[0012] Another exemplary embodiment of the current invention is a heating system comprising: a process reactor capable of containing feedstock; a powder reactor capable of containing a volume of electrically conductive powder, wherein said powder reactor is arranged inside the process reactor, wherein the powder reactor comprises of electrodes for joule heating the volume of conductive powder.Brief Description of the Drawings

[0013] The drawings included herewith are for illustrating various examples of articles, methods, and systems relevant to the present specification. In the drawings:

[0014] FIG.1 shows examples of a known methane pyrolysis apparatus.

[0015] FIG.2 shows a methane pyrolysis system and process with indirect joule heating of powder surrounding a pyrolysis process reactor tube.

[0016] FIG.3 shows a methane pyrolysis system and process with indirect joule heating of powder surrounded by a pyrolysis process reactor tube.

[0017] FIG.4A shows side view of a methane pyrolysis in a bucket reactor with indirect joule heating of powder surrounding a pyrolysis process reactor tube.

[0018] FIG.4B shows top view of a methane pyrolysis in a bucket reactor with indirect joule heating of powder surrounding a pyrolysis process reactor tube.

[0019] FIG.4C shows top view of a methane pyrolysis in a bucket reactor and central rod electrode with indirect joule heating of powder surrounding multiple process reactor tubes.

[0020] FIG. 4D shows top view of a methane pyrolysis in a bucket reactor and central rotating oval electrode with indirect joule heating of powder surrounding multiple process reactor tubes.

[0021] FIG.4E shows top view of a methane pyrolysis in a bucket reactor and circularly moving rod electrode with indirect joule heating of powder surrounding multiple process reactor tubes.

[0022] FIG.5A shows side view of a methane pyrolysis in a bucket reactor with indirect joule heating of powder surrounding a pyrolysis process reactor tube assembly with an internal carbon collection reservoir and dispenser.

[0023] FIG.5B shows side view of a methane pyrolysis in a bucket reactor with indirect joule heating of powder surrounding a pyrolysis process reactor tube assembly with an external carbon collection reservoir dispenser.

[0024] FIG.5C shows side view of a methane pyrolysis in a bucket reactor with indirect joule heating of powder surrounding a U-tube shaped process reactor assembly.

[0025] FIG.6A shows side view of a methane pyrolysis in a bucket reactor with removable bottom.

[0026] FIG.6B shows top view of a methane pyrolysis in a bucket reactor with removable bottom. Detailed Description

[0027] Various systems or processes will be described below to provide examples of the claimed embodiments. No embodiment or embodiments described below are intended to limit any claimed embodiment, and any claimed embodiment may cover processes or system in addition to or that differ from those specifically described. The claimed embodiments are not limited to systems or processes having all of the features of any one system or process described, or to features common to some or all of the systems described.

[0028] Embodiments of the present invention comprise innovative methods of gas pyrolysis, more specifically hydrocarbon pyrolysis, and even more specifically methane pyrolysis. Gas pyrolysis refers to the process of thermal decomposition of a gaseous molecule into smaller, simpler gas molecules by heating a gas in the absence of oxygen. Hydrocarbon pyrolysis is a thermal decomposition process where large hydrocarbon molecules are broken down into smaller, simpler hydrocarbon fragments by applying high temperatures in the absence of oxygen. Methane pyrolysis is a chemical process that breaks down methane (CH4) into hydrogen (H2) and solid carbon at high temperatures. This process is also known as methane cracking or methane decomposition. Embodiments of the present invention will be described with a methane pyrolysis as an example but the embodiments equally apply to thermal decomposition of hydrocarbons and other gases, including thermal decomposition of organic compound gas that also contains oxygen or nitrogen in addition to carbon and hydrogen.

[0029] Embodiments of the present invention are directed to the fabrication of all carbon nanostructures, including amorphous carbon, crystalline carbon, nanostructured sp2 carbonforms, such as graphene, fullerene, and carbon nanotubes, stacked graphene such as graphite, and their combinations and variations. Graphene and graphite consists of sp2 carbon hexagonal networks of carbon atoms with covalent bonding between C atoms within a layer, and a weak van der Waals interaction between adjacent layers. Graphite is defined as 3-D layered material formed by stacking more than 10 single-layer graphene layers of 2-D graphene. In this disclosure, the term graphene refers to a layered crystalline carbon structure with up to 10 layers. Layered structures of more than 10 layers are referred to as graphite, as is well known to those experienced in the relevant art. Both graphene and graphite may be ordered (stacked) or disordered (turbostratic), referring to the order of adjacent layers in the structure. While this paragraph discusses the difference between graphene and graphite, and stacked and disordered carbon arrangements, it does not limit any embodiment disclosed herein to a specific arrangement.

[0030] Embodiments of the present invention are directed to systems and methods for thermal decomposition of hydrocarbon gases, including methane, by indirect heating of the hydrocarbon gases with a volume of joule heated electrically conductive powder that heats the hydrocarbon gases without contacting them. The systems and methods for thermal decomposition of this invention also apply to gases than hydrocarbon gases. The systems and methods for thermal decomposition of this invention also applies to gas, liquid, and solid feedstock materials. The disclosed inventions also apply to systems and methods for efficient heating of materials in general. The gas, liquid, and solid materials of embodiment of this present invention that are subjected to a heating or thermal decomposition process are referred to as feedstock or feedstock materials.

[0031] The thermal decomposition of a hydrocarbon gas, including methane, will result in its breakdown into smaller, simpler hydrocarbon fragments. By example, thermal decomposition of methane will break it down into hydrogen and carbon. The process of thermal decomposition of methane is also known as methane pyrolysis or methane cracking, and the process of thermal decomposition of a hydrocarbon is also known as hydrocarbon pyrolysis. In embodiment of the present invention, the term electrical pyrolysis refers to the process of thermal decomposition (pyrolysis, cracking) of a gas by joule heating of electrically conductivepowder. The more general term of gas thermal decomposition in this disclosure is also referred to as gas pyrolysis. The thermal decomposition of embodiments of the present invention also includes thermal decomposition of liquids and solids when liquid and solid precursors are used as feedstock.

[0032] The heating or the thermal decomposition of feedstock in embodiments of the present invention may occur inside a process reactor that is sealed or open. A sealed process reactor refers to a reactor that is isolated from the outside environment, but may allow inlet and outlet, or moving of gas, liquid, or solid feedstocks. An open process reactor refers to a reactor whose feedstock is open to the environment, and wherein gas, liquid, or solid feedstocks may be inserted or removed while being exposed to the surrounding environment, and wherein any process gases, liquids, or solids can freely exit the reactor.

[0033] The heating or the thermal decomposition of feedstock in embodiments of the present invention may occur inside a process reactor while the feedstock is static (does not flow or move) within the reactor, or the feedstock is moving within the reactor. Static feedstock implies that a desired feedstock volume is inserted inside the process reactor, such that the feedstock is being held inside the reactor while the heating or thermal decomposition of the feedstock occurs, after which the heated or decomposed materials are released from the reactor. These steps can be repeated as needed. The movement of feedstock can be continuous, variable, or intermittent. Continuous flow implies that feedstock moves continuously from the inlet side of the process reactor towards the outlet side of the process reactor while the feedstock undergoes heating or thermal decomposition. The feedstock movement can be at a prescribed rate, or it can be variable, where the mass movement rate changes as a function of time or reactor temperature or some other metric, as may be convenient or needed for an efficient process. The feedstock movement can also be intermittent, where the feedstock movement can be stopped and then resumed, as may be convenient or needed for an efficient process.

[0034] Mechanisms for moving the feedstock can depend on the type of feedstock. Various known mechanisms may be used to achieve the desired objective. An exemplary mechanism for moving gas feedstock may comprise a pressurized storage tank to store the gas, valves to open and close the flow of gas, and nozzles to insert (inject) the gas into the processreactor. The gas feedstock is moved by pressurizing the gas to make it flow through the process reactor. An exemplary mechanism for moving liquid feedstock may comprise a liquid storage tank, valves to open and close the flow of liquids, and nozzles to insert (inject) the liquid into the process reactor. In some embodiments, it may be desirable for the liquid feedstock to first be vaporized and then injected into the process reactor as a vapor. An exemplary mechanism for moving solid powder feedstock may comprise a feedstock storage tank to store the solid, a solid powder feeder that may include a screw or functionally similar mechanism that helps with moving the solid powder through solid feed tubes, and a dispenser to feed the solid powder into the process reactor. Optionally, the solid powder feedstock may be moved through the process tube more efficiently if the solids only partially fill the process reactor. Other similar solid feedstock moving mechanisms may include a tilted rotating (or rocking) tube mechanism that moves the powder with the help of gravity and / or tube rotation. Moving the solid feedstock in a vertically oriented process reactor may also be accomplished by gravity feed. It is understood that many different mechanisms can be used in different embodiments of the present invention, and the present invention should not be limited to the above examples.

[0035] The term powder mixing is defined as moving the grains of electrically conductive powder inside the powder reactor to make a more uniform volume of powder, before, during, and / or after the heating or the thermal decomposition process. The term feedstock mixing is defined as moving the feedstock inside the process reactor to make more uniform volume of feedstock, before, during, and / or after the heating or the thermal decomposition process.

[0036] The heating or the thermal decomposition of feedstock in this invention may apply to feedstock that is encapsulated and then inserted into a process reactor and processed (static case) or moved within the reactor (continuous, variable, or intermittent motion). Encapsulating feedstock may be advantageous, for example, when either the feedstock or the decomposed feedstock (materials that result from the thermal decomposition) comprise fine powder that is hard to handle and transport. The feedstock may, for example, be encapsulated into smaller quartz tubes, into cardboard paper, wax paper, and other suitable means. Examples of encapsulated feedstock include iron oxide dust combined with plastics powder encapsulated into a sealed quartz tube, but other encapsulated feedstock examples are also possible.

[0037] Figure 2 illustrates one embodiment of a system according to the present invention for optionally-continuous production of hydrogen and carbon from hydrocarbon gas. In this embodiment methane gas 201 flows through a sealed infrared-transparent tube process reactor 206 that is exposed to intense and instantaneous radiation heat generated from a volume of joule heated electrically conductive powder 207 that is surrounding the process reactor 206.

[0038] A sealed process reactor refers to a reactor that is isolated from the outside environment, but may allow inlet and outlet or moving of gas feedstock. In some embodiments where solid feedstock is used, it may be advantageous to operate an open process reactor. An open process reactor refers to a reactor whose feedstock is exposed to the environment, and the resulting process gas from heating or thermal decomposition may exhaust or be removed from the open reactor freely into the surrounding environment. Infrared-transparent tube and material refers to a material that is substantially transparent (transmissive) to infrared radiation but may also reflect or absorb some of the infrared radiation. For example quartz is substantially infrared-transparent, while glass is generally partially infrared-transparent, and graphite is substantially not transparent to infrared radiation. Under the influence of intense and instantaneous radiation heat, the methane 201 undergoes rapid thermal decomposition and is converted into hydrogen 217 and carbon 216 inside the sealed process reactor 206. The intense and instantaneous radiation heat for the thermal decomposition is provided by joule heating of the electrically conductive powder 207 which is confined within powder reactor 205. Although the main heat transfer from the powder to the feedstock inside the process reactor is via radiation heat transfer, heat transfer via conduction from the hot powder to the process reactor wall and to the feedstock, may be another contributing heat transfer mechanism. Other subsidiary heat transfer mechanisms are not excluded.

[0039] In embodiments of the present invention, the powder reactor 205 may be sealed or open. A sealed powder reactor refers to a reactor that is isolated from the outside environment, but may allow purging with inert gas or by pumping vacuum to remove moisture and / or oxygen. An exemplary mechanism for removing oxygen from a sealed reactor (powder or process) may include a vacuum pump or gas purge assembly that flows gas through the reactor. An open powder reactor refers to a reactor whose powder is exposed to theenvironment. In some embodiments the electrically conductive powder 207 may be carbon powder and the process reactor 206 may be a quartz tube reactor. In some embodiments the powder reactor 205 may be a quartz tube or ceramic tube reactor. In these embodiments reactors 205, 206 may be positioned horizontally, as shown in Figure 2, or substantially horizontally, and in another embodiments reactors 205, 206 may be positioned vertically, substantially vertically, or in tilted position.

[0040] The conversion of methane into hydrogen and carbon can also be described as pyrolysis. The pyrolysis conversion can also be applied to other hydrocarbons or mixture of hydrocarbons. The pyrolysis process according to the present invention can also be applied to other gaseous hydrocarbons besides methane. Hydrocarbons are any of a class of organic chemicals comprising the elements carbon and hydrogen. The carbon atoms join together to form the framework of the compound, and the hydrogen atoms can attach in many different configurations. Other hydrocarbons include, but are not limited to, acetylene (C2H2), ethylene (C2H4), ethane (C2H6), and propane (C3H8). The pyrolysis in embodiments of the present invention can also be applied to natural gas which is known to include gases other than hydrocarbons. The pyrolysis of embodiments of the present invention can also be applied to liquid hydrocarbons like crude oil. The pyrolysis of this invention can also be applied to any organic compound that contains carbon and hydrogen. The pyrolysis of embodiments of the present invention can also be applied to any organic compound that also contains oxygen or nitrogen in addition to carbon and hydrogen. Alcohols are a class of organic compounds that have one or more hydroxyl groups attached to a carbon atom of a hydrocarbon chain. One or more inert gases, such as Nitrogen or Argon before, during, and / or after the pyrolysis process may optionally be used.

[0041] One advantage of having powder as the heating element instead of metal wire filaments or other bulk heating elements is that powders have significantly greater surface area per gram (known as BET - Brunauer-Emmett-Teller) than filaments, where the radiated heat is proportional to the surface area of the object. The typical surface area of filament is from 0.1 to 0.3 m2 / g while carbon powders have surface area from 1 to 100 m2 / g. Another advantage of a powder heater versus classical heating elements is that the sum of the radiation heat from each grain is typically larger than if the heater was a solid body. In addition, the absorption and re-radiation of heat from each grain to its neighbors greatly improves the heat transfer efficiency. Another advantage of a powder heater as for example disclosed in Figure 2, is that hot powder 207 is in physical contact with the outside walls of the quartz process reactor 206 resulting in conductive heating of the process reactor 206 walls, and thus reducing the possibilities for contamination to deposit on the inner walls of the process reactor 206. One of the main sources for process tube wall contamination is the sublimation of impurities from the gas stream to the quartz wall having colder temperatures than the tube core. Another advantage of a powder heater may be that ohmic resistance between powder grains allows for lower bulk resistance which in turn helps improve the practical implementation of the joule heater operation. Other joule heating elements, such as filaments, typically have very low resistance that makes them operate at much higher currents. It is desirable for the powder to be electrically conductive in the order of 1 to 1000 Ohms (bulk resistance) in order to be joule heated using existing industrial utilities having 120 to 480 Volts and current rating of 1 to 1000 Amperes.

[0042] In embodiments of the present invention, the conductive powder 207 may include carbon materials with low impurities (low ash, low sulfur, low volatiles) and may include at least one of the group comprised of but is not limited to: calcinated petroleum coke, metallurgical coke, carbon black, activated carbon, char, graphene, flash graphene, carbon nanotubes, carbon nanofibers, carbon fiber, graphitized carbon fiber. The residue from these conductive powders after they are exposed to joule heating can be minimal. Depending on the powder temperature, the amorphous conductive powders may improve their crystallinity and become more graphitized with each use.

[0043] In other embodiments, the conductive powder 207 may also include carbon materials with higher impurities (ash, sulfur, volatiles) such as: anthracite coal, green petroleum coke, asphaltenes, recycled-tire carbon black, bio char, wood char, plant char, paralyzed cellulose, conductive polymer, conductive plastic, plastic char, plastic ash and their combination thereof. The residue from these conductive powders will be higher than the low impurity carbon powder and may require active exhaust of gases from the powder reactor 205. Depending on the process temperature the higher impurity conductive powders may improve their crystallinity and become more graphitized with each use.

[0044] Depending on the process temperature (controlled by the power of the joule heating), conductive carbon powders may improve their crystallinity and become more graphitized with each use. The applied joule heating power can be selected to be low so that it will not substantially change the carbon powder crystallinity. On the other hand, the applied joule heating power can be selected to induce substantial changes to the powder crystallinity. In other embodiments, the powder crystallinity may be already high so that even a high power joule heating will not substantially change the crystallinity. The amorphous carbon or partially graphitized carbon in the conductive powders may, for example, convert into graphite, turbostratic graphite, graphene, turbostratic graphene, polyhedral graphite, polyhedral graphene, turbostratic polyhedral graphite, turbostratic polyhedral graphene, carbon nanotubes and nanofibers, or graphitized fibers. For example, non-crystalline amorphous carbon may be changed to crystalline graphene or graphite, or polycrystalline (partially crystallized) carbon black may be changed to crystalline (fully crystallized) graphene or graphite. A substantial change of crystallinity (graphitization) means changing from one crystallinity state to another (from one graphitization state to another), such as for example from amorphous to fully crystalline (from partially graphitized to fully graphitized). Not a substantial change of crystallinity (graphitization) means that the crystallinity state (graphitization state) remains largely unchanged.

[0045] The conductive powder 207 of used in the present invention may include all possible morphologies including: powder, grain, pellets, chunks, sphere-like, hollow sphere-like, particles, spheres, nanospheres, microspheres, rods, nanotubes, nanowires, and microwires, microfibers, matrix-forming structures, and their combinations. The conductive powder 207 may include all material structures, including: non-porous, porous, nanoporous, microporous, and having layered structures. The conductive powder 207 may include all powder sizes, from few nanometers to few millimeters. In one embodiment, the conductive powder 207 can comprise Met Coke with grain sizes from 0.5 to 3 mm and surface area of 1-3 m2 / g, in another embodiment the conductive powder 207 can comprise Carbon Black with prime particle size of 30 nm and structure size of about 1 µm, and surface area of 20-40 m2 / g.

[0046] In the embodiment shown, the powder reactor 205 can be filled with an electrically conductive powder 207 that may be confined and compressed into powder reactor205 by two graphite electrode 204, one on each side of the tube. Powder compression can include compacting the powder. When the reactor is partially filled, the electrodes may rest at the open ends of the reactor and the powder may be uncompressed. O-ring 218 may be employed to better seal powder reactor 205 from the atmosphere and vice versa. The graphite electrodes 204 are connected to electrical power sources 203 and 208 to provide power to joule heat the electrically conductive powder 207. It may be desirable to remove residual air and moisture from powder 207, sealed in powder reactor 205, before the powder 207 is joule heated, so as to reduce carbon-oxygen reactions that can consume the powder 207 and decrease its volume, and to prevent unwanted CO2gas formation. Optionally, inert gas may be filled in or can flow through powder 207 to improve convection heating between the powder 207 grains and to the process reactor 206 and keep the process reactor 206 walls heated so as to prevent contamination buildup. In other embodiments, the inert gas flow may be used to cool down the powder 207 for process temperature control. In some embodiments the powder 207 does not have to be replaced or replenished since there may be substantially no pyrolysis reaction in powder reactor 205. In other embodiments powder 207 may be periodically replaced or replenished, for example, if powder 207 accumulates contamination or gets oxidized and thus reduces its electrical and / or thermal conductivity. One mechanism for replenishing the electrically conductive powder may be to disconnect the graphite electrodes 204 that also function as a lid to the powder reactor 205 and to tilt the powder reactor tube 205 to empty the used powder. New powder may be inserted into powder reactor 205, and electrode-lids 204 may be re-inserted.

[0047] In the embodiment of the present invention shown in Figure 2 powder reactor 205 may be a quartz tube. The powder reactor 205 may also be constructed from other materials such as ceramic (Nitride bonded silicon carbide - NB SiC, silicon carbide – SiC, aluminum nitride - AlN), high temperature steels (Hastelloy alloy, Inconel alloy, Nickel based allows), cement, concrete, SiC based refractories and aluminum-based refractories. The size of the powder reactor (diameter and length) from Figure 2 may depend on the desired throughput and power availability. In one embodiment the reactor may be a quartz tube with 6 in. diameter and 3 ft length, having a volume of 22 L. In another embodiment, the reactor has 36 in. diameter and 3ft length, having a volume of 600 L. The reactor shape may be other than tube, such as oval, or rectangular.

[0048] Applying electrical power 203, 208 across the two graphite electrodes 204 will apply joule heating to the powder 207 in the range from 700 to 1300 C to enable pyrolysis of methane. Joule heating of powder 207 can easily achieve temperatures up to 3000 C for alternative process requirements. The preferred power source is AC power, but DC power can also be used. The power for joule heating may be AC, DC, modified AC or DC, or any combination thereof. The temperature can be kept in target range with the help of a power controller that uses pyrometers or thermocouples to read the powder 207 temperature and adjust the power applied to the powder to maintain set temperature. In some embodiments the joule heating power may be automatically adjusted with the help of a controller to achieve a desired heating or decomposition temperature which is set as a target. The electrical power 203, 208 can be adjusted by changing the electrical current, voltage, or both. Electrical power 203, 208 can be actively controlled using a DC Converter Drive or Variable Frequency Drive (VFD). The electrical power 203, 208 can be steady over time or it can be applied in pulses. The electrical power 203, 208 profile can be steady, steer stepped, ramp, or any random profile, that may further be tuned to optimize the pyrolysis process. Due to the fast reaction time of the joule heating process, the powder temperature will also follow the electrical power profile, allowing more flexibility in improving the efficiency of the methane pyrolysis process.

[0049] In other embodiments set points may include consideration of hydrogen purity, yield, or pressure. In one embodiment, the purity of the hydrogen may be measured with a sensor that provides closed loop control feedback to the joule heating controller which can adjust its power output to achieve the desired hydrogen purity set point. The joule heating controller can also adjust the power output applied to the electrically conductive powder inside the reactor based on other sensor inputs, such as hydrogen yield, or reactor pressure due to hydrogen and other gases. The joule heating controller can also be an adaptive controller, or one that uses artificial intelligence that takes input from multiple sensors and / or process models to compute optimal power output. The controller output may include adjusting Power (Watts), Voltage (Volts), Current (Amperes), duty cycle of an AC power (%), pulse width (ms or sec), pulse pattern,or any combination thereof to control the heating intensity of the conductive powder in the reactor.

[0050] In the embodiment of the present invention as shown in Figure 2, sealed process reactor 206 may be a quartz tube that penetrates graphite electrodes 204 and may be concentric with the powder reactor 205 and extends on each side of the powder reactor 205 so as to enable easy installation of gas handling equipment such as flanges, seals, meters, and feeders on both sides of the powder reactor 205. In other embodiments, process reactor 206 and the powder reactor 205 can be positioned perpendicular to each other, or they can be positioned at any angle with respect to each other, with the goal of optimizing heat transfer from the joule heated powder to the process reactor. The process reactor 206 may be sealed to prevent loss of methane to the atmosphere and to prevent oxygen and moisture inside the process reactor volume. Process reactor 206 may have a smaller diameter than powder reactor 205 to fit conductive powder 207 around the process reactor. The process reactor 206 may be electrically insulated from the powder reactor 205. Although Figure 2 shows a single process reactor 206, in other embodiments there may be more than one process reactor, optionally with smaller diameter than a single process reactor. It is preferred that multiple process reactors do not touch each other, but to be surrounded (encased) by conductive powder 207. Multiple process reactors would take better advantage of the radiation heat distribution that has diminishing intensity over longer distances and may be blocked by neighboring opaque powder particles.

[0051] In the exemplary embodiment of Figure 2, a methane gas 201 may be fed (injected) into gas feeder 202 that regulates the methane flow rates and may switch between inlet sources. Inside process reactor 206, during the thermal decomposition process, methane 201 decomposes into hydrogen 217 and solid carbon forms 216. Solid carbon 216 from the process include floating (fine dust or fines) solid carbon 219 that can flow out with the hydrogen gas 217, and carbon form that cannot float in the methane gas flow and settles inside or at the bottom of process reactor 206, that will be called settling solid carbon 220. In some embodiments of the invention, the system reactors 205, 206 are positioned vertically which enables settling solid carbon 220 to also be collected easily with the help of gravity. The solid carbon forms 216, 219, 220 may include amorphous carbon, graphitized carbon, crystallinecarbon, graphite, turbostratic graphite, graphene, turbostratic graphene, polyhedral graphite, polyhedral graphene, carbon nanotubes, nanofibers, and graphitized fibers, as well as any combination thereof.

[0052] During operation, it may also be expected that some methane does not decompose and leaves the reactor as unprocessed methane 215. The gas / fines stream exiting the process reactor 206 may include hydrogen 217, floating solid carbon 219, and unprocessed methane 215, and can be directed into an optional carbon separator 209, where the floating solid carbon 219 is removed (filtered) from the gas / fines stream using tools and techniques known in the art of exhaust treatment, and may be sent to a carbon outlet 213 and collected in a bin. Hydrogen and / or carbon may be removed from the process reactor continuously or intermittently. One such fine carbon removal tool may be a cyclone dust collector. The settling solid carbon 220 in a vertically positioned system can also be collected concurrently with the floating solid carbon 219, and in-line sieving tools can be used to separate the settling solid carbon 220 from the floating solid carbon 219, which are mainly distinguishable by mass and size. After the carbon is removed, the remaining gas stream now only substantially comprises hydrogen and may be small amounts of unprocessed methane, and it can be directed into a hydrogen separator 210 where hydrogen is separated (filtered) from unwanted hydrocarbons or other residual gasses and may be sent to a collection tank via hydrogen outlet 211. The unprocessed methane 215 can optionally be sent back to gas feeder 202 for further reuse or it can be collected separately. Depending on the design of the reactor, the methane 201 flow through the process reactor 206 can be in the range from 1 to 10000 sccm. Preferably, the methane can flow continuously through the process reactor 206, but alternatively, the methane may be static within the process reactor 206 until a pyrolysis reaction happens after which the processed methane volume can be replaced with unprocessed methane.

[0053] In one embodiment of the invention, the feedstock may comprise liquid feedstock. One example of liquid feedstock includes alcohols, such as isopropyl, methyl, and ethyl alcohol types. Another example of liquid feedstock includes oils, such as crude oil, petroleum oil, cooking oil. Liquid feedstock may include a modified feeder that can spray or vaporize the liquid so as to enable it to flow and at least partially pass through process reactor 206. The thermaldecomposition of liquid feedstock can also be described as pyrolysis where the resulting decomposed species may directly or indirectly include hydrogen, carbon, hydrocarbons and gaseous residues or some combination of them.

[0054] In one embodiment of the invention the feedstock may comprise solid feedstock. One example of solid feedstock includes virgin plastics, waste plastics, mixed plastics, polyethylene (high and low density), polypropylene (high and low density), polystyrene, Styrofoam, polyethylene terephthalate (PET), polyacrylonitrile (PAN), paraffines, asphaltenes, sugar, urea, and their combination thereof. Solid feedstock requires modified feeder that can dispense the solid feedstock so as to enable it to flow and at least partially pass through process reactor 206. It is preferred that solid feedstock is a fine powder with 1 to 500 µm average particle size, but other sizes may be used. In one embodiment of the invention, the solid feedstock may include a carbon-based feedstock fraction. One example of a carbon-based feedstock is the same type as the carbon from process 216.

[0055] In one embodiment of the invention, the solid or liquid feedstock may comprise metal-based catalysts that can facilitate the synthesis of additional 2D and 3D carbon formation and morphologies (graphite, graphene, polyhedral graphene, nano-onions, or any combination thereof), and 1D carbon formations with high aspect ratios (for example, nanotubes, nanofibers, nanobelts, or other carbon structure with a high length to diameter ratio, or any combination thereof), or improve the yield of the additional carbon formation morphologies. In another embodiment of the invention the solid or liquid feedstock may comprise metal-based catalysts that may aid the formation of carbides, metal-carbon hybrid structures, or it may coat the metal- based catalysts with the solid carbon layer. Examples of metal-based catalysts include Fe, ferrocene, Co, Ni, Cu, iron acetate, iron chloride, metal chlorides, chlorides, iron acetylacetonate, iron oxide, cobalt oxide, iron hydroxide, nickel hydroxide, or a combination thereof. In one embodiment of the invention, the feedstock may include gas, liquid, solid feedstocks, metal- based catalysts, or any combination thereof.

[0056] Other solid feedstock may include silicon-based feedstock, such as silicon, silicon dioxide, silicon oxide (SiOx), silicon carbide, or any combination thereof. The silicon-based feedstock may be in the form of nanospheres, microspheres, nanotubes, nanowires as well asany combination thereof. Other solid feedstock includes transition metal oxides, transition metal carbides, or metals that alloy with Li, such as aluminum, bismuth, cadmium, magnesium, tin, antimony, and any combination thereof. The silicon-based solid feedstock can facilitate the synthesis of silicon-based composites, including nanostructures that are covered or decorated with graphene, nanotubes, nanofibers, polyhedral graphene, nano-onions or any combination thereof. One example of a silicon-based composite may be a silicon-based particle wrapped in one or more graphene or graphite layers. The particle can be a sphere, hollow sphere, rod, wire, or have any other morphology. Another example of a silicon-based composite is silicon carbide.

[0057] Figure 3 illustrates one embodiment of a system for optionally-continuous production of hydrogen and carbon from hydrocarbon gas where the design of the process and powder reactors are modified from the embodiment of Figure 2. In the embodiment of Figure 3, methane gas 301 flows through a sealed tube process reactor 306 that may be exposed to intense and instantaneous radiation heat generated from a volume of joule heated electrically conductive powder 307 that may be confined within an infrared-transparent tube powder reactor 305, that may be passing through the process reactor 306. Under the influence of intense and instantaneous radiation heat, the methane 301 undergoes rapid thermal decomposition and may be converted into hydrogen 317 and carbon 316 inside the sealed process reactor 306. One example of electrically conductive powder 307 may be carbon powder. One embodiment of powder reactor 305 may be a quartz tube reactor. One embodiment of process reactor 306 may be a ceramic tube, stainless steel tube, or graphite tube reactor. In one embodiment, reactors 305, 306 may be positioned horizontally, as shown in Figure 3, and in another embodiment reactors 305, 306 may be positioned vertically. While embodiments of the present invention are described herein as reactors and systems for gas pyrolysis and in general reactors and systems for joule heating of a powdered material, the reactors and system in this disclosure are described in exemplary orientations, and it is understood that the present invention applies equally to any reactor and system orientation, including horizontal, vertical, and tilted.

[0058] Powder reactor 305 may be filled with an electrically conductive powder 307 that may be confined and compressed into powder reactor 305 by two graphite electrode 304, one on each side of the tube. O-ring 318 may be employed to better seal powder reactor 305 fromthe atmosphere and vice versa. The graphite electrodes 304 are connected to electrical power sources 303 and 308 to provide power to joule heat the electrically conductive powder 307. In normal operation, powder 307 may not have to be replaced or replenished since there is substantially no pyrolysis reaction in powder reactor 305. Optionally, inert gas can flow through powder 307 to improve convection heating between the powder 307 grains and process reactor 306. Alternatively, the inert gas flow may be used to cool down the powder 307 for process temperature control.

[0059] In the embodiment the invention as shown in the Figure 3 sealed process reactor 306, may be a tube reactor that may be concentric with the powder reactor 305 and may include methane gas handling equipment such as flanges, seals, meters, and feeders on both sides of the reactor. In other embodiments, process reactor 306 and powder reactor 305 can be positioned perpendicular to each other or they can be positioned at any angle with respect to each other, with the goal of optimizing heat transfer from the powder to the process reactor. The process reactor 306 may be sealed to prevent loss of methane to the atmosphere and to prevent oxygen and moisture inside the process reactor volume. Process reactor 306 may be have larger diameter than powder reactor 305 to fit at least one powder reactor 305 within the process reactor 306 volume. The process reactor 306 may be electrically insulated from the powder reactor 305. Although Figure 3 shows a single powder reactor 305, in other embodiments, there may be more than one powder reactors, optionally with smaller diameter, that fit within the volume of process reactor 306. It is generally preferred that multiple process reactors do not touch each other, but to each be surrounded by process gas 301. Multiple process reactors would take better advantage of the radiation heat distribution from the heater comprising of powder particles 307.

[0060] In the embodiment of Figure 3, a methane gas 301 may be fed into gas feeder 302 that regulates the methane flow rates and may switch between inlet sources. Inside process reactor 306, during the thermal decomposition process, methane 301 may decompose into hydrogen 317 and solid carbon forms 316, 319, 320. Solid carbon 316 from the process may include floating (fine dust or fines) solid carbon 319 that can flow out with the hydrogen gas 317, and settling solid carbon 320 that cannot float in the methane gas flow and settles inside or atthe bottom of process reactor 306. In some embodiments of the invention, the system reactors 305, 306 may be positioned vertically to enable solid carbon 316 to be collected easily with the help of gravity. The solid carbon forms 316, 319, 320 include amorphous carbon, graphitized carbon, crystalline carbon, graphene, turbostratic graphene, graphite, turbostratic graphite, carbon nanotubes, and nanofibers, as well as any combination thereof.

[0061] The pyrolysis processes of the present invention may also be applied to all gaseous hydrocarbons, including but not limited to acetylene, ethylene, ethane, and propane. In one embodiment of the invention, the feedstock may be liquid feedstock, including but not limited to alcohols and oils. In one embodiment of the invention, the feedstock may be solid feedstock, including but not limited to virgin plastics, waste plastics, mixed plastics, polyethylene, polypropylene, polystyrene, Styrofoam, polyethylene terephthalate, polyacrylonitrile, paraffines, asphaltenes, sugar, and urea. In one embodiment of the invention, the solid feedstock may include carbon-based feedstock fraction. In one embodiment of the invention, the feedstock may comprise metal-based catalysts, including but not limited to Fe, ferrocene, Ni, Co, silicon, silica. In one embodiment of the invention, the feedstock may include gas, liquid, solid feedstocks, metal-based catalysts, or any combination thereof.

[0062] The exemplary embodiments of the present invention shown in Figures 2 and 3 may include compressing the powder within two graphite electrodes to achieve a bulk powder resistance that is needed to apply joule heating to the powder. In these embodiments of Figure 2 and 3, the tube reactor may be sealed with two graphite electrodes, and compression (such as for example compacting) may be applied to the powder. For a higher compression force applied, the powder volume resistance will typically be lower. Thus, the compression may be used to adjust the resistance of the powder. The electrodes are being moved towards each other inside the reactor (or at least one moved and another one being substantially fixed) to compress the powder. As the powder gets compressed / pushed the bulk resistance of the powder may change in a nonlinear manner. After some point, any further force applied to the electrodes will not compress the powder any further and the resistance will not be changed. During joule heating, the powder may expand or contract, so it may be desirable to have spring loaded electrodes to compensate for the powder volume changes. For partially filled reactors, where the powder isnot compressed (compacted), the volume of the powder may determine the bulk resistance of the powder.

[0063] In one embodiment, compression of the powder may not be needed (as with loose, gravity packed, or bulk powder), and the system will still be able to apply joule heating to the powder. Exemplary Figure 4 illustrates a system for the optionally-continuous production of hydrogen and carbon from hydrocarbon gas. Figure 4 may not show some system component details that were shown previously in Figures 2 and 3 for clarity of the illustration.

[0064] Figure 4 illustrates another embodiment of the present invention comprising of (i) an electrically conductive graphite bucket reactor 405, serving as powder container and as one electrode of an electrical system, (ii) electrically conductive bulk powder 407, partially filling graphite bucket reactor 405, serving as volumetrically distributed resistive load, (iii) an infrared- transparent tube process reactor 406 that runs concentrically and through graphite bucket reactor 405 and is surrounded by powder 407, (iv) an electrically conductive electrode assembly 404 positioned to surround process reactor tube 406, without limiting radiant and conduction heat transfer from powder 407 to process reactor 406, serving as second electrode of an electrical system, (v) an electrical insulator bottom 413, fully covering the bottom of bucket reactor 405, directing electrical current from electrode assembly 404 towards inner walls of bucket reactor 405, and with pass through hole for process reactor 406. Electrode assembly 404 can be in the form of four graphite rods that are positioned around the process reactor 406, as shown in Figure 4B, and at the top terminate to a single graphite rod. Alternatively, the number and shape of rods in electrode assembly 404 can be different. Electrode assembly 404 can also be in the form of graphite tube positioned around the process reactor 406, with cutouts to allow radiant and conduction heat transfer from powder 407 to process reactor 406. Alternatively, the number and shape of cutouts in electrode assembly 404 can be different. Conductive powder 407 may substantially fill graphite bucket reactor 405, surrounds process reactor 406, and serves as distributed resistive load. Application of AC or DC electrical power 403, 408 between the electrode assembly 404 and the bucket reactor electrode 405, with powder 407 between, results in joule heating of the powder 407 which produces intense and instantaneous radiation heat that is heating process gas flowing inside sealed process reactor 406. The conduction heat betweenthe powder 407 and the process reactor 406 may also contribute to heating the gas flowing inside sealed process reactor 406. Other heat transfer mechanisms may be possible. Methane gas 401 flowing through sealed infrared-transparent tube process reactor 406 may be exposed to intense and instantaneous radiation heat generated from the volume of joule heated electrically conductive powder 407 that is surrounding the process reactor 406, where methane 401 undergoes rapid thermal decomposition and may be converted into hydrogen 417 and carbon 416 inside the sealed process reactor 406. In the embodiment of Figure 4 the process reactor may be positioned vertically so as to utilize gravity to separate the hydrogen from the carbon. In this configuration methane 401 may be injected from the top of the process reactor and its flow is in downwards direction within the reactor. The resulting hydrogen and carbon decompositions are both collected from the bottom of the reactor 424. In other embodiments, methane 431 may be injected from the bottom of the process reactor and its flow is in an upward direction within the reactor. The resulting hydrogen gas may rise and be collected from the top of reactor 434, and the carbon may fall down with the help of gravity and may be collected from the bottom of reactor 424. One example of electrically conductive powder 407 is carbon powder. One example of process reactor 406 is a quartz tube reactor. The electrically insulating bottom 413 may be a quartz disk.

[0065] Optional electrical insulator disk lid 411 and o-ring 418, may seal powder 407 from the atmosphere to reduce carbon-oxygen reactions that could consume the powder 407 when heated. Optionally, inert gas may be filled in or can flow through powder 407 to improve convection heating between the powder 407 grains and to the process reactor 406 and keep the process reactor 406 walls heated so as to prevent contamination buildup. In normal operation, powder 407 does not have to be replaced or replenished since there is no pyrolysis reaction in bucket reactor 405. However, powder 407 may be periodically replaced or replenished, for example, if powder 407 accumulates contamination or gets oxidized and thus reduces its electrical and / or thermal conductivity. One mechanism for replenishing the electrically conductive powder 407 may be to disconnect the gas tight lid 411 and empty out the powder reactor 405 to remove the used powder. New powder may be inserted into powder reactor 405 and lid 411 may be reinserted. Electrically insulating bucket lid 411 may have a pass-throughhole for process reactor 406 to pass inside bucket reactor 405. The electrically insulating bucket lid 411 may be a quartz or ceramic structure and may be constructed from several components. The lid 411 may be a gas tight lid that isolates the reactor 405 from the outside environment, but may allow inlet and outlet of process gases through inlets outlets. For the embodiment of Figure 4, the gas inlet may be the top of the process reactor 406, and the gas outlet may be the bottom of the process reactor 406, or vice versa. The gas tight lid 411 may optionally include an o-ring 411 that may seal lid 411 with respect to the top of bucket 405 from the atmosphere. Additional seals (not shown) may include a seal between graphite electrode 404 and lid 411 that allows optional rotation of the electrode 404 but does not allow gas from inside bucket 406 to escape into the atmosphere.

[0066] Operation of the embodiment shown in Figure 4 can be similar to operation of the embodiment in Figure 2. Feedstock that can be utilized with the system of Figure 4 process may be the same as the process feedstock disclosed regarding Figures 2 and 3. In the embodiment of Figure 4, a methane gas 401 is fed into process reactor 406, and during the thermal decomposition process, it may decompose into hydrogen 417 and solid carbon forms 416, 419, 420. Solid carbon 416 from the process may include floating solid carbon 419 that can flow out with the hydrogen gas 417, and settling solid carbon 420 that cannot float in the methane gas flow but, because of the vertical process reactor 406 design, may fall down and out of the process reactor 406 via gravity. Floating solid carbon 419 can be removed from the gas / fines stream 424 using know tools, such as for example a cyclone dust collector for separate carbon collection, while settling solid carbon 420 may be collected directly into a collection bin. Hydrogen 417 can be separated from unwanted hydrocarbons or other residual gases and any unprocessed feedstock, with a hydrogen separator system, which can then be collected in a hydrogen collection tank.

[0067] Solid carbon forms 416, 419, 420 may include amorphous carbon, graphitized carbon, crystalline carbon, graphene, turbostratic graphene, graphite, turbostratic graphite, carbon nanotubes, and nanofibers, as well as any combination thereof. The pyrolysis process of this invention can also be applied to all gaseous hydrocarbons, to liquid feedstock, solid feedstock, or any combination thereof.

[0068] Figures 4C and 4D show alternative embodiments of systems according to the present invention for optionally-continuous pyrolysis of hydrocarbons of Figure 4B, and in particular, an alternative arrangement of the graphite electrode assembly 404 and the process reactor tubes 406. Figures 4C and 4D do not show insulator lid and some other system component details shown previously in Figures 4A and 4B for clarity of the illustration. Figure 4C shows a configuration where the cylindrical (rod) graphite electrode assembly 404 may be concentric with graphite bucket reactor 405, and the multiple process reactor tubes 406 may be positioned symmetrically around the cylindrical graphite electrode assembly 404. The size, shape, number, and distribution of process reactor tubes 406 can be different than presented in the figure. In the embodiment of Figure 4C the electrical current path from the rod electrode configuration is radial from the rod electrode to the walls of the graphite bucket, producing radial current density profile where the current density may be higher near the rod electrode than at the walls of the bucket. When the powder resistance is uniform, the temperature profile from the joule heating will follow the current density profile. Positioning at least one process reactor tube 406 within the heated powder volume may allow for more uniform and more efficient heat transfer from the powder 407 to the process reactor tubes 406, wherein methane gas 401 may decompose into hydrogen 417 and solid carbon forms 416 due to the heating from the intense and instantaneous radiation heat and from the conductive heat transfer from the powder 407.

[0069] Referring again to Figure 4, it may be desirable to mix the powder 406 to produce a more uniform temperature profile for the pyrolysis process. Mixing can occur as the thermal decomposition process is ongoing, or the mixing can occur during process pauses, or a combination of each approach. Mixing the powder means that grains comprising the powder are moved with respect to each other to randomize their relative position with respect to each other, or their absolute position within the reactor. One way to achieve the powder mixing may be with a paddle shaped oval electrode, as shown in Figure 4B, that rotates. Preferably, the electrode assembly may be positioned near the center of the lid. Another way of mixing may be to rotate the reactor with respect to the paddle.

[0070] In one embodiment of the invention, shown in Figure 4D, it may be desirable to mix the powder 407 to produce a more uniform temperature profile for the pyrolysis process.One way to achieve the powder mixing may be with a paddle shaped oval electrode, as shown in Figure 4D, that rotates in direction 409. Alternatively, the shape and size of the mixing paddle electrode can be different than shown in Figure 4D or it can be asymmetric. For this configuration it may be preferred that the electrode comprises of a rod top and oval shaped bottom part, so that the top rod can be rotated through an optional bucket lid 411 while the oval shaped bottom part can mix the powder 407. The electrical current path in the oval electrode configuration may be radial from the edges of the rod electrode to the walls of the graphite bucket, producing radial current density profile where the current density may be higher near the rod electrode than at the walls of the bucket. In addition, with oval electrode shape, the electrical current may be more focused in the direction of the long axis of the oval electrode, providing current density that is higher than with a cylindrical rod. In addition, the oval electrode provides rotating current density and therefore rotating heat profile. The above advantages of the oval electrode provide a more uniform and more concentrated heat profile that may improves the efficiency of the methane pyrolysis process. Positioning at least one process reactor tube 406 symmetrically around oval graphite electrode assembly 404 and avoiding the rotating electrode apexes, allows for more uniform and more efficient heat transfer from powder 407 to process reactor tubes 406, wherein methane gas 401 may decompose into hydrogen 417 and solid carbon forms 416 due to the heating from the intense and instantaneous radiation heat and from the conductive heat transfer from the powder 407. The size, shape, number, and distribution of process reactor tubes 406 can be different than presented in the figure.

[0071] In another embodiment, mixing the powder can comprise moving the electrode (for example, rod electrode) in the XY axes with respect to the bucket. Generally, the XY plane is the bottom of the bucket, and the Z axis is in the direction of the bucket height. Lifting and inserting the electrode, in Z axis, in the powder can also achieve mixing. Further, moving the reactor instead of the electrode is also possible. The gas inlet and outlet ports for this embodiment may also be mounted on the bucket. The moving electrode / bucket embodiment can be used for gas pyrolysis and for feedstock heating. During the joule heating of the powder, the reactor may operate using a vacuum or it may be filled with an inert gas. One advantage of joule heating the powder in a vacuum may be the prevention of undesired arcing or plasmageneration (current flow being diverted from flowing through the powder) in or around the powder. Another advantage is to protect the powder from oxidation and degradation.

[0072] In one embodiment of the invention, shown in Figure 4E, it may be desirable to mix the powder 407 to produce a more uniform temperature profile for the pyrolysis process but it may be desirable to use rod (cylindrical) shaped electrodes. One way to achieve the powder mixing may be with a rod-shaped electrode 404, that may be placed off-center and may undergo circular motion around the center of bucket 405 (thus stirring the powder), as shown in Figure 4D. Alternatively, the shape and size of the rod electrode 404 that moves in circle 410 can be different than shown in Figure 4D or it can be asymmetric. Alternatively, the rod electrode motion 410 can be spiral or any other complex motion. Positioning at least one process reactor tubes 406 around the bucket but avoiding the path of moving electrode 404, allows for more uniform and more efficient heat transfer from powder 407 to process reactor tubes 406, wherein methane gas 401 may decompose into hydrogen 417 and solid carbon forms 416. The size, shape, number, and distribution of process reactor tubes 406 can be different than presented in the figure.

[0073] Figure 5 illustrates another embodiment of the present invention that offers variations of the embodiment disclosed in Figure 4. One difference between embodiments from Figure 5 and Figure 4 may be the design of process reactor assembly 506. Figure 5 does not show some system components for clarity of the illustration. The embodiment from Figure 5A has a process reactor assembly 506 that has one section that may be positioned from the outside of bucket reactor 505, from gas inlet, towards a carbon collection reservoir 511, it has a carbon collection reservoir section 511 placed at the bottom of the bucket reactor 505, it has solid carbon dispenser section 514 that is designed to remove settling solid carbon 520 from the carbon collection reservoir 511, and it has another section that is positioned from the carbon collection reservoir 511 towards the outside of the bucket reactor 505 at to a gas outlet 524. In one embodiment process reactor 506 may be made from quartz material. The cross section of the gas inlet and outlet branches of the process reactor 506, may be circular, oval, or any other shape. In another embodiment, process reactor 506 may be made from multiple parts assembled together. One advantage of process reactor assembly 506 from Figure 5A may be that itseparates floating carbon 519 and hydrogen 517 via outlet stream 524 from settling carbon 520 via outlet 525. Since settling carbon 520 does not flow with methane 501 nor hydrogen 517, it is harder to remove from a process reactor. Carbon collection reservoir 511 may offer a place for the heavier settling carbon 520 to settle down and accumulate and be removed from the collection reservoir 511 via solid carbon dispenser 514. Solid carbon dispenser 514 may include a screw or other mechanism that helps with efficient carbon dispensing.

[0074] The embodiment of Figure 5A further may include graphite electrode assembly 504 that can be configured to be static, to rotate 509, or move in circle 510, to mix powder 507 to produce a more uniform temperature profile for the pyrolysis process.

[0075] The system from embodiment of Figure 5A may not need electrical insulator bottom to be fit at the bottom of the bucket reactor 505 because the carbon collection reservoir 511 itself may be electrically insulating and can serve the same function as an optional electrical insulator bottom disk.

[0076] In another embodiment shown in Figure 5B, there may be an electrical insulator bottom and the carbon collection reservoir 511 is located outside and under bucket reactor 505. In this embodiment, the inlet and outlet segments of the process reactor 506 may penetrate the bottom of the reactor bucket 505 and the electrical insulator bottom 513, to connect to the carbon collection reservoir segment 511 of the process reactor assembly 506. External collection reservoir 511 can be made from other materials than quartz or ceramic, for example it can be made from electrically conductive materials such as graphite and stainless steel. When located outside of the hot zone of bucket reactor 505 the carbon collection reservoir 511 can be cooled. In one example, the collection reservoir 511 can be cooled with a cold trap. The externally located collection reservoir 511 can also be used to condense materials for reclaiming, by selecting an appropriate feedstock that can be gas, liquid, or solid, or any combination thereof. In one embodiment, the reclaimed material may be oil. In other embodiments, the reclaimed material may be precious metal, such as Au, Ag, Pt, Pd, Rh, or harmful metals such as Hg, Cd, Pb, Be, Cr, or rare earth materials. In still other embodiment, the reclaimed material may be carbide such as TiC ZrC, HfC, VC, NbC, TaC, Cr2C3, MoC, W2C. In alternative embodiments, the number, size, location, shape, and distribution of the inlet and outlet segments of process reactor 506 canbe different. In one embodiment, the process reactor assembly 506 comprises more than one inlet segment and more than one outlet segment, that may all be connected to an outside- located carbon collection reservoir 511.

[0077] The pyrolysis process embodiments of Figures 5A and 5B may apply to all gaseous hydrocarbons, including but not limited to acetylene, ethylene, ethane, and propane. In one embodiment of the invention, the feedstock may be liquid feedstock, including but not limited to alcohols and oils. In one embodiment of the invention, the feedstock may be solid feedstock, including but not limited to virgin plastics, waste plastics, mixed plastics, polyethylene, polypropylene, polystyrene, Styrofoam, polyethylene terephthalate, polyacrylonitrile, paraffines, asphaltenes, sugar, and urea. In one embodiment of the invention, the solid feedstock may include carbon-based feedstock fraction. In one embodiment of the invention, the feedstock may comprise metal-based catalysts, including but not limited to Fe, ferrocene, Ni, Co, silicon, silica. In one embodiment of the invention, the feedstock may include gas, liquid, solid feedstocks, metal-based catalysts, or their combination thereof. In one embodiment of the invention, multiple inlet segment of the process reactor assembly 506 may be dedicated to different types of feedstocks, such as gas, liquid, solids, metal-based feedstock, silicon-based feedstock, and any combination thereof.

[0078] Figure 5C shows an embodiment of Figure 5A, wherein the bucket reactor 505 may comprise an electrically insulating bottom 513 and wherein the process reactor assembly may be a U-tube shaped reactor 506 that may be inserted into the electrically conductive powder 507 inside the bucket reactor 505. The cross section of the U-tube may be circular, oval, or any other shape. The U-tube shaped reactor 506 may serve the same function as the process reactors of Figure 5A and 5B without the need to penetrate the bucket reactor 505 bottom. The embodiment of Figure 5C may have an electrically insulating bottom 513 to prevent current flow from electrode 504 to the bottom of the bucket 505. The bottom part of the U-tube shaped reactor 506 close to the bottom of reactor 505 may act as carbon collection reservoir where the heavier settling carbon 520 may settle down and accumulate. Removal of the settling carbon 520 may be achieved by vacuuming out carbon 520 from outlet stream port 524 or by removing the U-tube shaped reactor 506 from the bucket 506 and emptying the carbon 520.

[0079] It may be desirable to have a system for continuous thermal decomposition operation where the electrically conductive powder may be replaced (replenished) as needed without completely stopping the thermal decomposition process (for example, in industrial settings pausing the process for 1 to 5 min may be acceptable). In addition, it may be desirable to have a powder reactor without an electrically insulating reactor bottom that may be difficult to clean and maintain as the one positioned at the bottom of a bucket reactor (for example in Figure 4). Furthermore, it may be desirable to have a process reactor whose inner walls can be cleaned from carbon deposition and / or other contamination or obstruction without completely stopping the thermal decomposition process. One source of process wall contamination may be the sublimation of the impurities from the gas stream to the reactor wall having colder temperatures than the tube core. Another source of contamination may be the deposition of unwanted carbon on the inner walls of the process reactor.

[0080] Figure 6 illustrates one embodiment of a system according to the present invention for continuous production of hydrogen and carbon from hydrocarbon gas that may offer certain advantages, including, for example, allowing fast replenishment of conductive powder, an easy to maintain reactor bottom, and various methods of process wall cleaning and maintenance. The embodiment of Figure 6 illustrates a graphite tube powder reactor with removable electrically insulating bottom, with at least one electrode inserted into the graphite tube reactor in electrical contact with the electrically conductive powder. This embodiment shows a single quartz tube process reactor centered within the graphite tube reactor and penetrating the removable bottom. The process reactor of this embodiment may be single process reactor tube or it may comprise one or more stackable quartz tube segments inside the single quartz tube that may be inserted and removed from the single quartz tube. The system may also comprise a cleaning brush that may be inserted into the single quartz tube reactor or into the quartz tube segments to clean them. The system may also include a set of electrically insulating removable bottom disks that may be rotated enable removal of conductive powder from the powder reactor. The system may also include a powder dispenser (not shown in the figures) to fill in new conductive powder. Figure 6 does not show some system component details, such as gas tight lid and movable electrode, for clarity of the illustration.

[0081] The embodiment shown Figure 6 can comprise (i) an electrically conductive graphite tube reactor 605, serving as powder container and as one electrode of an electrical system, (ii) electrically conductive bulk powder 607, partially filling graphite tube reactor 605, serving as volumetrically distributed resistive load, (iii) an infrared-transparent (quartz) tube process reactor 606 that runs concentrically with the graphite tube reactor 605 and is surrounded by powder 607, (iv) at least one electrically conductive electrode 604 inserted into process reactor tube 606 as close to the reactor bottom to have contact with most of the conductive powder volume 607, (v) an electrical insulator removable bottom 613 covering the bottom of tube reactor 605, directing electrical current from electrode 604 towards inner walls of tube reactor 605, and with pass through hole (penetration) for process reactor 606.

[0082] This embodiment of Figure 6A shows an outer quartz tube process reactor 606 centered within graphite tube reactor 605 and penetrating removable bottom 613. The process reactor of this embodiment may comprise an inner process reactor tube 615, comprising of one or more stackable quartz tube segments inside the outer tube 606, where the segments may be inserted and removed from the outer tube 606 to be cleaned externally.

[0083] This embodiment of Figure 6A also shows a cleaning brush assembly 612 that may be inserted into the outer quartz tube reactor 606 to clean the outer tube 606 when inner tubes 615 are not present. The cleaning brush assembly 612 may be inserted into the inner quartz tube reactor 615 to clean the inner tube 615 when inner tubes are present. The cleaning brush assembly 612 may include a mechanism for inserting the brush into process reactor 606, 615, and a mechanism for rotating the brush for more efficient cleaning.

[0084] This embodiment of Figure 6B shows a removable electrically insulating bottom 613 that may comprise a top disk 612 with a wedge opening and a bottom disk 611 with a wedge opening where the top and bottom disks may rotate around the process reactor tube 606. The top 612 and bottom 611 disks may have wedge openings that are same in size, or wherein the bottom wedge opening is smaller than the top wedge opening. The top 612 and bottom 611 disks may be rotated to align their wedge opening to allow replenishment of the powder.

[0085] Electrode 604 can include a single graphite electrode (as shown in Figure 6) or multiple (for example, four) graphite rods positioned around process reactor 606 (not shown). Alternatively, the number and shape of electrode 604 can be different. Conductive powder 607 fills graphite tube reactor 605, surrounds process reactor 606, and serves as distributed resistive load. Application of AC or DC electrical power 603, 608 between the electrode 604 and the tube reactor electrode 605, with powder 607 between, results in joule heating of the powder 607 which produces intense and instantaneous radiation heat that heats the process gas flowing inside process reactor 606. The conduction heat between the powder 607 and the process reactor 606 may also contribute to heating the gas flowing inside process reactor 606. Other heating mechanisms may be possible. Methane gas 601 flowing through the process reactor 606 may be heated by the hot joule heated powder 607 that is surrounding the process reactor 606, where methane 601 undergoes rapid thermal decomposition and may be converted into hydrogen 617 and carbon 616 inside the process reactor 606.

[0086] The embodiments of this innovation describe methods and systems for heating and thermal decomposition of gases, liquids, and solids in general. However, the disclosed methods and systems also apply to a general method for thermally activated chemical reaction of at least one feedstock; or one feedstock with a second feedstock wherein either feedstock may be any combination of gas, liquid, and solid; or a combination of multiple gas-, liquid-, or solid- feedstocks. In one embodiment, the thermally activated chemical reaction may be chlorination of metal oxides and other metal compounds into metal chlorides, wherein one feedstock may comprise chloride salt, for example calcium chloride, that will decompose to produce a chlorine gas, and the second feedstock may comprise metal oxides or compounds that will react with the chlorine from the first feedstock to convert into metal chloride. One example of thermally activated chemical reaction may be one where calcium chloride salt is the first feedstock and lithium ore is the second feedstock to form lithium chloride during a chlorination process as the thermally activated chemical reaction. The chlorination process is commonly used in metallurgy for metal extraction from ores, which may be conducted using not heat efficient reactors at exemplary temperatures ranging from 900 to 1300 C under the influence of chlorine gas.

[0087] In alternative embodiments, the first feedstock may comprises plastic (new or waste) comprising chlorine, for example Polyvinyl Chloride (PVC) plastics which contains up to 67% per weight of chlorine, and the second feedstock may comprise metal oxides or compounds wherein the metal oxides and other metal compounds are converted into metal chloride with the chlorine released from the PVC thermal decomposition under high temperature. In yet other alternative embodiments, the first feedstock may comprise chlorine gas and the second feedstock may comprise metal oxides or compounds wherein the metal oxides and other metal compounds are converted into metal chloride directly with the chlorine gas under high temperature.

[0088] In other alternative embodiments of the invention, the thermally activated chemical reaction may be reduction of oxides with hydrogen, wherein the hydrogen may be introduced as the first gas feedstock, or the hydrogen may be introduced through a plastic feedstock as the first feedstock. In one example, the chemical reaction may be reduction of silicon dioxide into silicon, wherein the reducing agent is hydrogen from the hydrogen gas directly, or indirectly from the thermal decomposition of plastics into hydrogen and carbon.

[0089] In yet another embodiment, the thermally activated chemical reaction may be reduction of iron oxide with hydrogen, wherein the hydrogen may be introduced as the first gas feedstock or the hydrogen may be introduced through a plastic feedstock as the first feedstock. In still another embodiment, the chemical reaction may be reduction of iron oxide into iron, wherein the reducing agent is hydrogen from the hydrogen gas directly, or indirectly from the thermal decomposition of plastics into hydrogen and carbon.

[0090] The gas, liquid, and solid outputs of the processes described in this innovation, including amorphous carbon, graphitized carbon, crystalline carbon, graphite, turbostratic graphite, graphene, turbostratic graphene, polyhedral graphite, polyhedral graphene, carbon nanotubes, nanofibers, and graphitized fibers, as well as any combination thereof, can be used as materials for a wide range of applications. Examples of some applications include, and are not limited to, battery materials, battery anodes and cathodes, rubber and tire, plastic composites, ceramics, coatings, epoxies, paints, polyurethane foam, asphalt, bitumen, cement, concrete, lubricants, and electronic components.

[0091] While the above description provides examples of one or more apparatus, methods, or systems, it will be appreciated that other apparatus, methods, or systems may be within the scope of the claims as interpreted by one of skill in the art.

Claims

AMENDED CLAIMS received by the International Bureau on 7 April 2025 (07.04.2025)1. A method for heating materials, comprising: joule heating a volume of electrically conductive powder inside a powder reactor; feedstock in a process reactor; wherein the electrically conductive powder is not in direct contact with the feedstock; and heating the feedstock inside the process reactor using the powder reactor.

2. The method of Claim 1 wherein the process reactor is arranged inside the powder reactor.

3. The method of Claim 1 wherein the powder reactor is arranged inside the process reactor.

4. The method of Claim 1 wherein the electrically conductive powder is carbon powder.

5. The method of Claim 1, wherein the process reactor is sealed.

6. The method of Claim 1, wherein the applied voltage used for joule heating is AC, DC, modifiedAC or DC, or any combination thereof.

7. The method of Claim 4, wherein the carbon powder is joule heated by applying a voltage between 120 V and 480 V to the powder.

8. The method of Claim 4, wherein the surface area of the carbon powder is between 1 and 75 m2 / g.

9. The method of Claim 4, wherein the bulk electrical resistance of the carbon powder is between1 to 750 Ohms.

10. The method of Claim 4, wherein the carbon powder comprises at least one of: calcinated petroleum coke, metallurgical coke, carbon black, activated carbon, char, graphene, flash graphene, carbon nanotubes, carbon nanofibers, carbon fiber, graphitized carbon fiber.

11. The method of Claim 4, wherein the carbon powder comprises at least one of: anthracite coal, green petroleum coke, asphaltenes, recycled-tire carbon black, bio char, wood char, plant char, paralyzed cellulose, conductive polymer, conductive plastic, plastic char, plastic ash.

12. The method of Claim 4, wherein the carbon powder morphologies comprises at least one of: powder, grain, pellets, chunks, sphere-like, hollow sphere-like, particles, spheres, nanospheres, microspheres, rods, nanotubes, nanowires, and microwires, microfibers, matrix-forming structures, and any combination thereof.

13. The method of Claim 4, wherein the carbon powder material structures comprises at least one of: non-porous, porous, nanoporous, microporous, and layered structures, and any combination thereof.

14. The method of Claim 4, wherein the carbon powder has an average size between 30 nm to 1 micron.

15. The method of Claim 4, wherein the carbon powder has an average size between 1 microns to 5 mm.

16. The method of Claim 4, wherein the carbon powder crystallinity is not substantially changed.

17. The method of Claim 4, wherein the carbon powder crystallinity is substantially changed.

18. The method of Claim 1, comprising thermal decomposition of the feedstock.

19. The method of Claim 18, wherein the feedstock comprises solid materials.

20. The method of Claim 18, wherein the feedstock comprises liquid materials.

21. The method of Claim 18, wherein the feedstock comprises carbon and hydrogen.

22. The method of Claim 21, wherein the feedstock further comprises oxygen or nitrogen or both.

23. The method of Claim 18, wherein the feedstock further comprises hydroxyl groups.

24. The method of Claim 18, wherein the feedstock is thermally decomposed into at least hydrogen and carbon.

25. The method of Claim 24 , wherein the carbon comprises at least graphite, graphene, nanotubes, nanofibers, or any combination thereof.

26. The method of Claim 18, wherein the feedstock comprises at least one non-conductive material such as high density polyethylene, low density polyethylene, polypropylene,polystyrene, Styrofoam, polyethylene terephthalate (PET), polyacrylonitrile (PAN), plastics, waste plastics, cellulose, sugar, paraffins, urea, or any combination thereof.

27. The method of Claim 18, wherein the feedstock comprises at least one metal-based catalyst capable of modifying the feedstock decomposition to include formation of carbon with high aspect ratios.

28. The method of Claim 27, wherein the metal-based catalyst comprises at least one of: Fe, Co,Ni, Cu, iron acetate, iron chloride, metal chlorides, chlorides, iron acetylacetonate, iron oxide, cobalt oxide, iron hydroxide, nickel hydroxide, or a combination thereof.

29. The method of Claim 18, wherein the feedstock comprises at least one silicon-based feedstock capable of synthesis of silicon-based composites.

30. The method of Claim 29, wherein the silicon-based composites are covered with or decorated with carbon from the feedstock decomposition.

31. The method of Claim 29, wherein the silicon-based composite comprises a silicon particle wrapped in one or more graphene layers.

32. The method of Claim 29, wherein the silicon-based composite comprises a silicon carbide.

33. The method of Claim 29, wherein the silicon-based feedstock comprises at least one of silicon, silicon dioxide, silicon oxide (SiOx), silicon carbide, or their combination in the morphological form of at least one of nanospheres, microspheres, nanotubes, nanowires, or any combination thereof.

34. The method of Claim 18, wherein the temperature of the joule heated powder is between700 to 1300 C during the thermal decomposition.

35. The method of Claim 1, wherein the electrical power of the joule heating is automatically adjusted to achieve a desired heating temperature.

36. The method of Claim 1, wherein the feedstock is encapsulated.

37. The method of Claim 36, wherein the encapsulated feedstock is moved through the process reactor.

38. A method for thermal gas decomposition, comprising: joule heating a volume of electrically conductive powder inside a powder reactor; flowing feedstock gas through a process reactor; wherein the electrically conductive powder is not in direct contact with the feedstock gas; and thermally decomposing the feedstock gas inside the process reactor using heat from the powder reactor.

39. The method of Claim 38 wherein the process reactor is arranged inside the powder reactor.

40. The method of Claim 38 wherein the powder reactor is arranged inside the process reactor.

41. The method of Claim 38, further comprising a gas feeder to inject feedstock gas into the process reactor.

42. The method of Claim 38 wherein the electrically conductive powder is carbon powder.

43. The method of Claim 38, wherein the process reactor is sealed from the atmosphere.

44. The method of Claim 38, wherein the gas flow is continuous.

45. The method of Claim 38, wherein the gas flow is intermittent.

46. The method of Claim 38, wherein the thermal feedstock gas decomposition is continuous.

47. The method of Claim 38, wherein the process reactor is substantially infrared transparent.

48. The method of Claim 38, wherein heat transfers from the joule heated powder to the gas via radiation.

49. The method of Claim 38, wherein the heat transfers from the joule heated powder to the gas via radiation, conduction, or a combination thereof.

50. The method of Claim 38, wherein the electrically conductive powder is periodically replaced.

51. The method of Claim 38, wherein the feedstock gas comprises methane.

52. The method of Claim 51, wherein the methane decomposes into at least hydrogen and carbon.

53. The method of Claim 52, wherein the carbon comprises at least one of: settling solid carbon and floating solid carbon.

54. The method of Claim 52, wherein the carbon comprises at least one of amorphous carbon, graphitized carbon, crystalline carbon, graphene, turbostratic graphene, graphite, turbostratic graphite, AB stacked graphite, ABC stacked graphite, carbon nanotubes, and nanofibers.

55. The method of Claim 52, wherein the hydrogen or carbon or both are continuously removed from the process reactor.

56. The method of Claim 55, wherein the removed carbon is filtered from the hydrogen with a carbon separator.

57. The method of Claim 56, wherein the removed carbon comprises at least one of carbon black, graphite, graphene, nanotubes, nanofibers, carbon composites, and any combination thereof.

58. The method of Claim 55, wherein the removed hydrogen is filtered out using a hydrogen separator.

59. The method of Claim 58, wherein residual methane is returned from the hydrogen separator back to the process reactor.

60. The method of Claim 38, wherein electrical power provides the joule heating is where the electrical power is automatically adjusted to achieve a desired heating temperature.

61. The method of Claim 38, wherein the feedstock gas comprises hydrocarbon or a mixture of hydrocarbon gases.

62. The method of Claim 61, wherein the hydrocarbon comprises at least one of methane, acetylene, ethylene, ethane, and propane.

63. The method of Claim 38, wherein the feedstock gas comprises natural gas that includes gases other than hydrocarbons.

64. A method for thermally activated chemical reaction of at least one feedstock, comprising:joule heating a volume of electrically conductive powder inside a powder reactor; flowing at least one feedstock through a process reactor; and wherein the feedstock undergoes a thermally activated chemical reaction inside the process reactor using the heat from the powder reactor.

65. The method of Claim 64, comprising a thermally activated chemical reaction of two or more feedstocks.

66. The method of Claim 65, wherein a first feedstock comprises chloride salt and a second feedstock comprises metal oxide, metal compound, or a combination thereof, and the chemical reaction is chlorination of metal oxide to metal chloride with a chlorine gas from the chloride salt.

67. The method of Claim 65, wherein a first feedstock comprises chloride salt and a second feedstock comprises lithium ore, and the chemical reaction is chlorination of the lithium ore to lithium chloride with a chlorine gas from the chloride salt.

68. The method of Claim 65, wherein a first feedstock comprises plastic and a second feedstock comprises silicon dioxide, and the chemical reaction is reduction of silicon dioxide into silicon with hydrogen from the plastics.

69. The method of Claim 65, wherein a first feedstock comprises plastic and a second feedstock comprises iron oxide, and the chemical reaction is reduction of iron oxide into iron with hydrogen from the plastic.

70. The method of Claim 65, wherein a first feedstock comprises PVC plastic and a second feedstock comprises lithium ore, and the chemical reaction is chlorination of the lithium ore into lithium chloride with the chlorine from the plastics.

71. The method of Claim 65, comprising at least one gas feedstock and at least one solid feedstock.

72. The method of Claim 71, wherein the gas feedstock comprises chlorine, and the solid feedstock comprises metal oxide, metal compound, or a combination thereof, and the chemical reaction is chlorination of the metal oxide to metal chloride with the chlorine gas.

73. The method of Claim 71, wherein the gas feedstock comprises chlorine and the solid feedstock comprises lithium ore, and the chemical reaction is chlorination of the lithium ore to lithium chloride with the chlorine gas.

74. The method of Claim 71, wherein the gas feedstock comprises hydrogen and the solid feedstock comprises iron oxide, and the chemical reaction is reduction of the iron oxide into iron with the hydrogen gas.

75. A heating system comprising: a powder reactor capable of containing a volume of electrically conductive powder; electrodes for joule heating the volume of electrically conductive powder; a process reactor capable of containing feedstock, wherein said process reactor is arranged inside the powder reactor.

76. The system of Claim 75, wherein the powder reactor is capable of heating the feedstock inside the process reactor via joule heating the volume of electrically conductive powder.

77. The system of Claim 75, wherein the process reactor is an open reactor.

78. The system of Claim 77, wherein the process reactor comprises a mechanism for moving the feedstock through the process reactor.

79. The system of Claim 77, wherein the process reactor is an open tube reactor.

80. The system of Claim 77, wherein the process reactor comprises an exhaust.

81. The system of Claim 75, wherein the feedstock comprises gas.

82. The system of Claim 75, wherein the feedstock comprises solid material.

83. The system of Claim 75, wherein the feedstock comprises liquid material.

84. The system of Claim 81, wherein the gas comprises carbon molecules.

85. The system of Claim 84, wherein the gas comprises hydrocarbon gas.

86. The system of Claim 85, wherein the hydrocarbon gas comprises methane.

87. The system of Claim 75, wherein the feedstock is not electrically conductive.

88. The system of Claim 75, further comprising a mechanism for replenishing the electrically conductive powder.

89. The system of Claim 75, wherein the powder reactor is capable of heating a process inside the process reactor.

90. The system of Claim 78, wherein the mechanism moves encapsulated feedstock.

91. The system of Claim 75, wherein the process reactor is sealed from the atmosphere.

92. The system of Claim 75, wherein the powder reactor is sealed from the atmosphere.

93. The system of Claim 75, wherein the process reactor is substantially infrared transparent.

94. The system of Claim 93, wherein the process reactor is a quartz tube.

95. The system of Claim 93, wherein the process reactor is a ceramic tube.

96. The system of Claim 75, wherein the system is capable of continuous operation.

97. The system of Claim 75, further comprising more than one process reactors inside the powder reactor.

98. The system of Claim 75, wherein the process reactor is substantially concentric with the powder reactor.

99. The system of Claim 98, wherein the process reactor and powder reactor are oriented substantially vertically.

100. The system of Claim 75, wherein the process reactor is substantially perpendicular to the powder reactor.

101. The system of Claim 75, wherein the electrodes are graphite electrodes.

102. The system of Claim 75, where the powder reactor is capable of operating with noncompressed conductive powder.

103. The system of Claim 75, where the powder reactor is capable of operating with compressed conductive powder.

104. The system of Claim 75, wherein the powder reactor is a tube.

105. The system of Claim 75, wherein the powder reactor comprises at least one gas tight lid.

106. The system of Claim 75, wherein the powder reactor is a bucket.

107. The system of Claim 106, wherein the powder reactor comprises a gas tight lid.

108. The system of Claim 75, wherein the system includes a controller to control the electrical power of the joule heating.109 The system of Claim 108, wherein the a controller is capable of automatically adjusting the heating temperature.

110. A thermal gas decomposition system comprising: a powder reactor capable of containing a volume of electrically conductive powder; electrodes for joule heating the volume of conductive powder; and a process reactor placed inside the powder reactor, wherein the process reactor is capable of containing gas for thermal decomposition.

111. The system of Claim 110, wherein the powder reactor is capable of heating the gas inside the process reactor via joule heating the volume of electrically conductive powder.

112. The system of Claim 110, wherein the powder reactor is sealed from the atmosphere.

113. The system of Claim 112, further comprising a mechanism for removing oxygen from the sealed powder reactor.

114. The system of Claim 110, wherein the process reactor is sealed from the atmosphere.

115. The system of Claim 114, wherein the process reactor comprises a gas inlet port.

116. The system of Claim 114, wherein the process reactor comprises a gas outlet port.

117. The system of Claim 110, wherein process reactor comprises a mechanism for flowing gases through the process reactor.

118. The system of Claim 110, wherein the gas comprises methane.

119. The system of Claim 118, wherein the methane decomposes into hydrogen and carbon.

120. The system of Claim 119, further comprising at least one of: a gas feeder, a carbon separator, a hydrogen separator, and an unprocessed methane return line.

121. The system of Claim 110, wherein the powder reactor and the process reactors are tube reactors, wherein the electrodes are graphite electrodes positioned at each end of the powder reactor, wherein the process reactor is placed concentrically within the powder reactor, wherein the process reactor penetrates the graphite electrodes, and wherein the process reactor further comprises a gas inlet port and a gas outlet port.

122. The system of Claim 121, further comprising: a gas feeder, a carbon separator, a gas separator, and an unprocessed gas return line.

123. The system of Claim 121, wherein the graphite electrodes can supply electrical power to the powder to joule heat the powder.

124. The system of Claim 110, wherein the powder reactor is a graphite bucket reactor further comprising an electrically insulating lid and an electrically insulating bottom, wherein at least one electrode penetrates the lid and is inserted into the bucket reactor, and is in electrical contact with the electrically conductive powder, wherein at least one process reactor penetrates the bucket reactor lid, the electrically insulating bottom, and the bucket reactor bottom, wherein each process reactor further comprises a gas inlet port and a gas outlet port.

125. The system of Claim 124, further comprising a single process reactor centered within the bucket reactor.

126. The system of Claim 125, further comprising multiple electrodes symmetrically distributed around the process reactor.

127. The system of Claim 124, further comprising a single electrode centered within the bucket reactor.

128. The system of Claim 127, further comprising multiple process reactors symmetrically distributed around the electrode.

129. The system of Claim 127, wherein the electrode has an oval shape that can rotate to mix the electrically conductive powder.

130. The system of Claim 124, further comprising a single electrode that is off-center with respect to the bucket reactor, wherein the electrode can move within the bucket reactor to mix the electrically conductive powder.

131. The system of Claim 130, further comprising multiple process reactors symmetrically distributed around the bucket reactor and away from the electrode movement path.

132. The system of Claim 124, wherein an electrical power can be applied between the electrode and the walls of the graphite bucket reactor to joule heat the powder.

133. The system of Claim 110, wherein the powder reactor is a graphite bucket reactor, wherein a single electrode is centered within the bucket reactor and is in electrical contact with the electrically conductive powder, wherein the process reactor comprises a solid carbon collection reservoir, a solid carbon dispenser, gas inlet and outlet branches connected to the collection reservoir, wherein the gas inlet and outlet branches are inserted into the electrically conductive powder inside the bucket reactor.

134. The system of Claim 133, wherein electrical power can be applied between the electrode and the walls of the graphite bucket reactor to joule heat the powder.

135. The system of Claim 133, wherein the carbon collection reservoir of the process reactor covers the bottom of the bucket reactor and electrically insulates the graphite bucket bottomfrom the electrode and wherein the carbon dispenser of the process reactor penetrates the bucket reactor bottom.

136. The system of Claim 133, wherein the electrode can rotate or move to mix the electrically conductive powder.

137. The system of Claim 133, wherein the carbon collection reservoir of the process reactor is located outside and under the bucket reactor bottom, wherein the bucket reactor has an electrically insulating bottom, and wherein the gas inlet and outlet branches of the process reactor penetrate the insulating bottom and the bucket reactor bottom.

138. The system of Claim 133, wherein the bucket reactor has an electrically insulating bottom and wherein the process reactor is a U-tube shaped reactor that is inserted into the electrically conductive powder inside the bucket reactor.

139. The system of Claim 110, wherein the powder reactor is a graphite tube reactor further comprising a removable electrically insulating bottom, wherein at least one electrode is inserted into the graphite tube reactor, and is in electrical contact with the electrically conductive powder, wherein the process reactor comprises a single quartz tube centered within the graphite tube reactor and penetrates the removable bottom.

140. The system of Claim 139, wherein the process reactor further comprises more than one stacked quartz tube segments capable of being inserted to and removed from the single quartz tube.

141. The system of Claim 140, wherein the quartz tube segments may be removed and replaced during the thermal decomposition process.

142. The system of Claim 139, further comprising a cleaning brush that may be inserted into the single quartz tube reactor to clean the single quartz tube.

143. The system of Claim 140, further comprising a cleaning brush that may be inserted into the quartz tube segments to clean the quartz tube segments.

144. The system of Claim 139, wherein the removable bottom comprises a top disk having a wedge opening and a bottom disk having a wedge opening wherein the top and bottom disks may rotate around the process reactor tube.

145. The system of Claim 144, wherein the top and bottom disks may be rotated to align their wedge openings to allow replenishment of the powder.

146. The system of Claim 139, wherein electrical power can be applied between the electrode and the walls of the graphite tube reactor to joule heat the powder.

147. The system of Claim 110, wherein the powder reactor and the process reactors are tube reactors, wherein the electrodes are graphite electrodes positioned at each end of the powder reactor, wherein the process reactor includes a gas tight lid at each end, wherein the process reactor further comprises a gas inlet port and a gas outlet port connected to the gas tight lid, wherein the powder reactor is placed concentrically within the process reactor, wherein the powder reactor penetrates the gas tight lid.

148. A heating system comprising: a process reactor capable of containing feedstock; a powder reactor capable of containing a volume of electrically conductive powder, wherein said powder reactor is arranged inside the process reactor, wherein the powder reactor comprises of electrodes for joule heating the volume of conductive powder.

149. The system of Claim 148, wherein the powder reactor is capable of heating the feedstock inside the process reactor via joule heating the volume of electrically conductive powder150. The system of Claim 148, further comprising more than one powder reactor151. The system of Claim 148, further comprising at least one of: gas feeder, carbon separator, hydrogen separator, and a unprocessed methane return line.Applicant submits the following Statement Under Article19 ( 1 ) :Regarding claims 1 and 38 , the examiner indicated that" [t] he chamber 112 is thus broadly interpreted as def ining a"powder reactor" for heating the powder 114 , and a "process reactor" for heating and reacting the feedstock 118 due to heat from the heated powder 114 ) . "Claims 1 and 38 have been amended to expl icitly require that "the electrically conductive powder is not in direct contact with the feedstock" to indicate that the powder reactor and the process reactor cannot be met by the same single reactor prior art disclosure .The powder reactor contains a volume of electrically conductive powder for j oule heating . This reactor provides heat for the reaction taking place in the process reactor , but the electrically conductive powder inside the powder reactor is not a reactant , is not in direct contact with the feedstock, and is not processed by the process reactor .The process reactor contains feedstock that is processed using the heat from the powder reactor .Therefore , the electrically conductive powder is not in direct contact with the feedstock, and thus , a single prior art reactor cannot satisfy both, the powder reactor and the process reactor claim limitations .This concept is clearly demonstrated, for example , inFig . 3 ( identifying powder reactor 305 and distinct process reactor 306 , and in specif ication at pars . 57 60 indicating that the process reactor and the powder reactor are distinct , and are not the same reactor . Additional supporting disclosure can be found in pars . 15 , 17 , 18 , 19 , 20 , and 30 .

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