US20180273379A1 - Cracking of a process gas - Google Patents
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- US20180273379A1 US20180273379A1 US15/849,544 US201715849544A US2018273379A1 US 20180273379 A1 US20180273379 A1 US 20180273379A1 US 201715849544 A US201715849544 A US 201715849544A US 2018273379 A1 US2018273379 A1 US 2018273379A1
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0272—Processes for making hydrogen or synthesis gas containing a decomposition step containing a non-catalytic decomposition step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
Abstract
A process gas (such as a hydrocarbon gas) is flowed through a thermal cracking apparatus to crack the process gas into constituent components (such as hydrogen gas and solid carbon nano-particles, e.g., carbon nano-onions, necked carbon nano-onions, carbon nanospheres, graphene, graphite, highly ordered pyrolytic graphite, single walled nanotubes, and/or multi-walled nanotubes). The thermal cracking apparatus has an elongated heating element disposed within an inner volume along a longitudinal axis thereof. The elongated heating element heats the process gas as it flows within a longitudinal elongated reaction zone to thermally crack molecules of the process gas into the constituent components of the molecules.
Description
- This application is a divisional of U.S. patent application Ser. No. 15/470,450, filed Mar. 27, 2017, and entitled “Cracking of a Process Gas,” which is incorporated fully herein by reference.
- Hydrocarbons (e.g., methane, ethane, propane, etc.) can be pyrolyzed or cracked to synthesize hydrogen and/or to produce solid carbon materials, as well as higher order carbon substances. However, many processes used to produce these higher-order carbon substances require the use of catalysts, such as metal catalysts. Additionally, many processes also result in the presence of impurities or contaminants, such as metallic and/or corrosive contaminants that foul the equipment. Furthermore, many processes require additional complex steps to ensure a desired quality or purity of the resulting products.
- In some embodiments, a thermal cracking apparatus for cracking a feedstock process gas includes a body, a feedstock process gas inlet, and an elongated heating element. The body has an inner volume with a longitudinal axis. The inner volume has a reaction zone concentric with the longitudinal axis. A feedstock process gas is flowed into the inner volume through the feedstock process gas inlet during thermal cracking operations. The elongated heating element is disposed within the inner volume along the longitudinal axis and is surrounded by the reaction zone. During the thermal cracking operations, the elongated heating element is heated by electrical power to a molecular cracking temperature to generate the reaction zone, the feedstock process gas is heated from the elongated heating element, and the heat thermally cracks molecules of the feedstock process gas that are within the reaction zone into constituent components of the molecules.
- In some embodiments, a method for cracking a feedstock process gas includes providing a thermal cracking apparatus having an inner volume that has a longitudinal axis and an elongated heating element disposed within the inner volume along the longitudinal axis; heating the elongated heating element by electrical power to a molecular cracking temperature to generate a longitudinal elongated reaction zone within the inner volume; flowing a feedstock process gas into the inner volume and through the longitudinal elongated reaction zone, wherein the feedstock process gas is heated by heat from the elongated heating element; thermally cracking molecules of the feedstock process gas within the longitudinal elongated reaction zone into constituent components thereof (e.g., hydrogen gas and one or more solid products) as the feedstock process gas flows through the longitudinal elongated reaction zone; and collecting the constituent components.
- In some embodiments, the feedstock process gas includes a hydrocarbon gas, and the constituent components include hydrogen and carbon nano-particles (e.g., in a size range of 5-500 nm). In some embodiments, the carbon nano-particles include necked carbon nano-onions or at least one of: carbon nano-onions, carbon nanospheres, graphene, graphite, highly ordered pyrolytic graphite, single walled nanotubes, and multi-walled nanotubes. In some embodiments, the feedstock process gas is preheated (e.g., to 100-500° C.) by flowing the feedstock process gas through a gas preheating region between a heating chamber and a shell of the thermal cracking apparatus before flowing the feedstock process gas into the inner volume. In some embodiments, a gas having nano-particles therein is flowed into the inner volume and through the longitudinal elongated reaction zone to mix with the feedstock process gas; and a coating of a solid product (e.g., layers of graphene) is formed around the nano-particles.
- Other and further embodiments of the present disclosure are described below.
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FIG. 1 depicts a simplified process flow diagram of a method for cracking a feedstock process gas in accordance with at least some embodiments. -
FIG. 2 depicts a simplified schematic view of a cracking apparatus in accordance with at least some embodiments. -
FIG. 3 depicts a simplified cross-sectional view of a cracking apparatus in accordance with at least some embodiments. -
FIG. 4 depicts a simplified isometric exploded view of a cracking apparatus in accordance with at least some embodiments. -
FIG. 5 depicts a simplified isometric view of the cracking apparatus shown inFIG. 3 , in accordance with at least some embodiments. -
FIG. 6 depicts a simplified isometric view of the cracking apparatus ofFIG. 3 , in accordance with at least some embodiments. -
FIG. 7 depicts a simplified schematic view of a cracking apparatus in accordance with at least some embodiments. -
FIGS. 8-12 depict example micrograph images of carbon nano-particles, in accordance with at least some embodiments. -
FIG. 13 depicts a simplified schematic view of a cracking apparatus in accordance with at least some embodiments. -
FIG. 14 depicts a simplified schematic view of a cracking apparatus in accordance with at least some embodiments. -
FIG. 15 depicts a simplified process flow diagram of a method for cracking a feedstock process gas in accordance with at least some embodiments. - Embodiments of the present disclosure provide thermal cracking apparatuses and methods for refining, pyrolyzing, dissociating or cracking feedstock process gases into constituent components to produce solid products (e.g., carbon nano-particles) and gaseous products (e.g., hydrogen gas and/or lower order hydrocarbon gases). The feedstock process gases generally include, for example, hydrogen gas (H2), carbon dioxide (CO2), C1-10 hydrocarbons, other hydrocarbon gases, natural gas, methane, ethane, propane, butane, isobutane, unsaturated hydrocarbon gases, ethene, propene, C2H2, C2H4, C2H6, H2S, SiH4, etc. and mixtures thereof. The carbon nano-particles generally include, for example, carbon nano-onions (CNOs), necked CNOs, carbon nanospheres, graphene, graphite, highly ordered pyrolytic graphite, single walled nanotubes, multi-walled nanotubes, and/or other solid carbon products.
- Some embodiments comprise thermal cracking methods that use, for example, an elongated longitudinal heating element optionally enclosed within an elongated casing, housing or body of a thermal cracking apparatus. The body generally includes, for example, one or more tubes or other appropriate enclosures made of stainless steel, titanium, graphite, quartz, or the like. In some embodiments, the body of the thermal cracking apparatus is generally cylindrical in shape with a central elongate longitudinal axis arranged vertically and a feedstock process gas inlet at or near a top of the body. The feedstock process gas flows longitudinally down through the body or a portion thereof. In the vertical configuration, for embodiments in which the gas flow direction is downward, both gas flow and gravity assist in the removal of the solid products from the body of the thermal cracking apparatus. In some embodiments, the gas flow direction is upward in the vertical configuration.
- The heating element generally includes, for example, a heating lamp, one or more resistive wires or filaments, twisted wire filaments, metal filaments, flat metallic strips, cylindrical rods, and/or other appropriate thermal radical generators or elements that can be heated to a specified temperature (i.e., a molecular cracking temperature) sufficient to thermally crack molecules of the feedstock process gas. The heating element is generally disposed, located or arranged to extend centrally within the body of the thermal cracking apparatus along the central longitudinal axis thereof. For example, if there is only one heating element, then it is placed at or concentric with the central longitudinal axis, and if there is a plurality of the heating elements, then they are spaced or offset generally symmetrically or concentrically at locations near and around and parallel to the central longitudinal axis.
- Thermal cracking is generally achieved by passing the feedstock process gas over, in contact with, or within the vicinity of, the heating element within a longitudinal elongated reaction zone generated by heat from the heating element and defined by and contained inside the body to heat the feedstock process gas to or at a specified molecular cracking temperature as discussed further below. The reaction zone is considered to be the region surrounding the heating element and close enough to the heating element for the feedstock process gas to receive sufficient heat to thermally crack the molecules thereof. The reaction zone is thus generally axially aligned or concentric with the central longitudinal axis of the body. In some embodiments, the thermal cracking is performed under a specified pressure. In some embodiments, the feedstock process gas is circulated around or across the outside surface of a container of the reaction zone or a heating chamber in order to cool the container or chamber and preheat the feedstock process gas before flowing the feedstock process gas into the reaction zone.
- In some embodiments, the carbon nano-particles and/or hydrogen gas are produced without the use of catalysts. In other words, the process can be catalyst-free.
- Some embodiments provide a standalone system that can advantageously be rapidly scaled up or scaled down for different production levels as desired. For example, some embodiments are scalable to provide a standalone hydrogen and/or carbon nano-particle producing station system, a hydrocarbon source or a fuel cell station. Some embodiments can be scaled up to provide higher capacity systems, e.g., for a refinery or the like.
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FIG. 1 depicts a simplified process flow diagram of amethod 100 for cracking a feedstock process gas according to at least some embodiments. In some embodiments, the method obtains desired hydrogen and/or carbon products by thermally dissociating or cracking the feedstock process gas, e.g., gaseous hydrocarbon feedstocks. The particular steps, combination of steps, and order of steps are shown for illustrative and explanatory purposes only. Other embodiments may include other steps, combinations of steps, and/or orders of steps to achieve generally similar results. - The
method 100, and variations thereof, may be carried out in any suitable thermal cracking apparatus as disclosed herein capable of control in accordance with the teachings provided herein. Illustrative, but non-limiting, examples of embodiments of a suitable apparatus are described below with respect toFIGS. 2-7 and 13 . - The
method 100 can produce one or more desired hydrogen and/or carbon products in accordance with some embodiments. In some embodiments, the desired products generally include gaseous products, hydrocarbon liquids, and/or solid products. The gaseous products generally include hydrogen gas and/or hydrocarbon gases. Such gaseous products can be used, for example, for a hydrogen fuel station, as a raw material source for a process requiring hydrogen gas, and/or other appropriate uses. The solid products generally include the carbon nano-particles mentioned herein. Such solid products can be used in, for example, batteries, fuel cells, digital displays, lubricants, tires, biomedical applications, various industrial products, and other applications, or combinations thereof. - The
method 100 generally starts at 102, wherein an inner volume of a thermal cracking apparatus, such as the apparatus described below with respect toFIGS. 2-7 , is at least partially purged of contaminants, for example, air and moisture, for example, by pulling a vacuum. Alternatively or in combination, a purge gas is flowed into the inner volume of the thermal cracking apparatus and optionally removed therefrom. The purge gas may be any suitable gas or gaseous mixture inert to the process and processing environment or that is a feedstock process gas for the process. Examples of suitable purge gases include one or more inert gases, such as noble gases, among others. In some embodiments, the purge gas is flowed into the inner volume of the thermal cracking apparatus at a flow rate of about 0.5 to about 10 slm (standard liter per minute). In some embodiments, the thermal cracking apparatus can be seasoned prior to processing the feedstock process gas by purging the inner volume of the thermal cracking apparatus with one or more purge gases, for example, at the flow rates disclosed above and with the heating element at a temperature of about 600° C. to about 3000° C., or 1600-2200° C. (e.g., at the molecular cracking temperature), for about 5 to about 80 minutes, e.g., about 35 minutes. In some embodiments, the seasoning temperature may be the same temperature as the subsequent processing temperature used to process the feedstock process gas. In some embodiments, methane, compressed/clean natural gas, or pipeline quality natural gas (or any other suitable feedstock process gas) is flowed into the inner volume of the thermal cracking apparatus for a few seconds, optionally heated, and purged from the thermal cracking apparatus. - At 104, the feedstock process gas is flowed into the inner volume of the thermal cracking apparatus and into contact with (or immediately surrounding or in the vicinity of) the heating element, i.e., a reaction zone. The feedstock process gas generally has little or no oxygen, sulfur, chlorine, or metal attached to the molecules thereof. As used herein, little or no means less than 0.5 molar percent of the total feedstock process gas. In some embodiments, the feedstock process gas comprises less than 0.5 molar % oxygen or CxOy complexes. (Some embodiments, on the other hand, use a significant percentage of oxygen in the feedstock process gas, depending on process parameters and desired products.) The feedstock process gas is generally delivered at a known, predetermined flow rate for continuous processing embodiments. In some embodiments, before delivery to the thermal cracking apparatus or before processing, the feedstock process gas is optionally preheated (e.g., by heating delivery conduits or staging vessels). Alternatively or in combination the gaseous hydrocarbon feedstock may be heated within the thermal cracking apparatus (e.g., by providing a heat jacket or other energy source outside the thermal cracking apparatus, etc.). In some embodiments, the feedstock process gas is provided from a liquid source, and the liquid therefrom is brought to a temperature and pressure suitable to maintain the feedstock process gas in a gaseous state when introduced into the inner volume of the thermal cracking apparatus. In some embodiments, the feedstock process gas is heated to about 100 to about 500° C. before delivering the gaseous hydrocarbon feedstock to the inner volume.
- In some embodiments, the feedstock process gas within the inner volume of the thermal cracking apparatus may be maintained at a relatively low pressure. Various example alternative pressure ranges generally include: about 0.5-10 atmospheres, about 1-10 atmospheres, less than about 5 atmospheres, about 1 to 3 atmospheres, and about 1 to 2 atmospheres. The low pressure advantageously allows the use of less expensive equipment compared with typical refining equipment, which operates at about 10 to about 50 atmospheres.
- At 106, the feedstock process gas is thermally cracked, e.g., by heating with thermal energy provided by the heating element disposed within the inner volume of the thermal cracking apparatus. The thermal cracking apparatus thus provides sufficient thermal energy to the feedstock process gas to break or overcome at least some molecular bonds thereof to break down or fragment the reactants of the feedstock process gas into smaller components, i.e., various solid and gaseous products. To do so, for example, the heating element is heated to a temperature of about 600° C. to about 3000° C., or 1600-2200° C. Without intending to be bound by theory, it is believed that the feedstock process gas becomes radicalized and fragmented into various moieties by the thermal energy provided by the heating element. For example, in the case in which a hydrocarbon is the feedstock process gas, the hydrocarbon molecules are heated by the heating element, which cracks the hydrocarbon molecules into, for example, hydrogen ions and charged carbon atoms (and/or other hydrocarbons). The hydrogen ions can associate to form diatomic hydrogen gas. The charged carbon atoms form the carbon nano-particles. The desired products are thus produced.
- In some embodiments, either or both of the carbon nano-particles or the hydrogen gas (or other desired products) can be produced without the use of catalysts, i.e., catalyst-free, using some or all of the methods and apparatus described herein. The absence of catalysts from the methods described herein avoids the use of expensive catalysts and also avoids introducing impurities or contaminants, such as metallic or other corrosive contaminants, into the carbon nano-particles or other desired products. In addition, metals, as are present in many catalysts, may be highly combustible in hydrogen gas, so the catalyst-free process avoids such situations.
- In some embodiments, the carbon nano-particles may comprise a specified size and/or geometry as described more fully below. Also, partially or fully activated carbon nano-particles and gaseous products may be advantageously produced in the absence of a catalyst.
- Moreover, the size of the carbon nano-particles, for example, the diameter of the particles, may be controlled. Some embodiments comprise the production of carbon nano-particles (such as carbon nano-onions) ranging in diameter from, for example, approximately 5 nanometers (nm) to approximately 300 nm in diameter or larger.
- Carbon nano-particle geometry or size or the amount of hydrogen conversion may be controlled, at least in part, by controlling residence time of the feedstock process gas within the reaction zone, or within the vicinity of the heating element. Residence time in the reaction zone can be controlled, for example, by controlling the length of the reaction zone, the flow rate of the feedstock process gas, or combinations thereof. Examples of suitable residence time include between about 0.1 to about 100 seconds. In some embodiments, the feedstock process gas has a residence time greater than about two seconds. Also, in some embodiments, networks of partially and/or fully activated integrated fullerene allotropes are produced. For example, Carbon-60, i.e., “Buckyballs” further comprise layers, such as substantially concentric layers of single-walled nanotubes (SWNT) and multi-walled nanotubes (MWNT), to form carbon nano-onions. At least one example is a Carbon-60 structure surrounded by a Carbon-320 structure of graphene.
- Without intending to be limited by theory, it is believed that thermal gradients are created within the thermal cracking apparatus. For example, the temperature within the inner volume of the thermal cracking apparatus is hottest at or near the heating element and relatively cooler near a wall of the thermal cracking apparatus, wherein a thermal gradient is formed therebetween. It is further believed that at higher temperatures within the thermal gradient, and/or higher residence times, hollow and/or necked carbon nano-onions are formed, having smaller diameters, e.g., approximately an average of 5 nm to approximately 90 nm. At relatively lower temperature regions of the gradient, i.e., near a wall of the thermal cracking apparatus, and at shorter residence times, larger carbon nano-particles are formed, e.g., an average of 150-500 nm. Additionally, shorter residence times generally result in lower hydrogen conversion. Between these extremes of the gradient, other sized carbon nano-particles are formed, e.g., approximately 100 nm. Thus, typical ranges for the sizes of the carbon nano-onions are 5-500 nm, 5-90 nm, 5-100 nm, 100-150 nm, 100-500 nm, and 150-500 nm, among others, depending on process parameters for preheat temperature, heating element temperature, pressure, flow rate, residence time, etc.
- At 108, one or more solid products, such as the carbon nano-particles, are collected in any suitable manner. For example, the carbon nano-particles may be separated from the gas stream and collected via cyclonic separation, filtering, or other appropriate collection or separation technique. In some embodiments, the carbon nano-particles are collected via a collector, such as any of the collectors discussed further below with respect to
FIGS. 2-7 . The collector may be placed at a location suitable to collect the carbon nano-particles from the inner volume of the thermal cracking apparatus. In some embodiments, a charge may be applied to the collector to electrostatically attract the carbon nano-particles. - At 110, gaseous desired products, such as hydrogen gas or hydrocarbon gas, are optionally collected. Various gaseous products, for example, mixtures of hydrogen gas and other hydrocarbons, having various boiling points, can be independently collected, for example, by collecting and delivering the gaseous product to a distillation apparatus to separate desired products based upon their respective boiling points. In some embodiments, the gaseous output is collected and stored for later use. For example, in some embodiments, the output gas may be hydrogen (H2) and the hydrogen may be stored, in tanks or other suitable canisters, e.g., for later use on site or at a different location. Alternatively, in some embodiments, the thermal cracking apparatus may be a point of use generator of a desired product and the gaseous output is routed to another apparatus for use therein. In some embodiments, some gaseous output may be routed to another apparatus for immediate use, while a remaining portion of the gaseous output may be collected and stored.
- Upon completion of collection of the desired products (e.g., at 108 and/or 110), the
method 100 generally ends. However, themethod 100 may include variations and/or additional processing techniques. For example, themethod 100 may include a plurality of thermal cracking apparatuses, operating at the same or different conditions (e.g., varying temperatures, flow rates, and/or pressures). For example, in such embodiments, themethod 100 may further comprise at least one additional thermal cracking apparatus in fluid communication with the inner volume downstream of the thermal cracking apparatus. Also, a plurality of thermal cracking apparatuses may be in fluid communication in parallel or in series. - Furthermore, some embodiments of the
method 100 comprise the use of micro gas chromatograph analysis, such that the output of hydrogen gas can be measured, as well as providing data regarding the particle size, e.g., length and/or diameter of carbon nano-particles and/or the morphology of the carbon nano-particles. For example, an in-situ feedback loop may be provided by feeding data corresponding to the micro gas chromatograph results to a controller to control process parameters such as one or more of flow rate of the feedstock process gas, power provided to the heating element, power provided to gas preheating elements, flow rates of heat transfer fluids used for heating the feedstock conduits or the housing of the thermal cracking apparatus, or other potential parameters. - The
method 100 may be a continuous process capable of operating continuously and/or automatically. Alternately, themethod 100 may be a batch process to process a pre-determined amount of the feedstock process gas. Also, a controller may be coupled to the thermal cracking apparatus to control operation of the thermal cracking apparatus. In some embodiments, the controller may further be configured to communicate with a remote computer network. In some embodiments, the controller may further be configured to communicate with and control operation of one or more additional thermal cracking apparatuses to control operation of the plurality of thermal cracking apparatuses. - Various example and non-limiting embodiments of the
method 100 are disclosed herein and all features of any embodiment may be incorporated within any other embodiment without limitation. For example, in some embodiments, themethod 100 for cracking a feedstock process gas includes flowing a feedstock process gas to an inner volume of the thermal cracking apparatus and into contact with or in the vicinity of the heating element (i.e., the reaction zone) of the thermal cracking apparatus, thereby thermally cracking the feedstock, producing a carbon product and hydrogen gas, as described above, without the use of catalysts, i.e., catalyst-free. - In some embodiments, the
method 100 for cracking a feedstock includes flowing a purge gas, as described above, into the inner volume of the thermal cracking apparatus to remove contaminants therefrom, flowing the feedstock process gas to the inner volume of the thermal cracking apparatus and into contact with or in the vicinity of the heating element to thermally crack the feedstock process gas, producing a carbon product and hydrogen gas, without the use of catalysts, i.e., catalyst-free, wherein the feedstock process gas contains little to no CxOy complexes, for example, wherein the feedstock process gas comprises approximately less than 0.50 molar % oxygen. - In some embodiments, the
method 100 for cracking a feedstock process gas includes flowing a purge gas, as described above, into the inner volume of the thermal cracking apparatus to remove contaminants therefrom, flowing the feedstock process gas to the inner volume of the thermal cracking apparatus and into contact with or in the vicinity of the heating element to thermally crack the feedstock process gas, to produce carbon nano-particles (e.g., solid carbon nano-onions, hollow carbon nano-onions and/or necked carbon nano-onions) that further may comprise additional layers of single-walled nanotubes, multi-walled nanotubes, and/or combinations thereof and/or graphene and/or highly ordered pyrolytic graphite, or the like, wherein varying process conditions, such as feedstock process gas flow rate, thermal cracking apparatus geometry, preheat temperatures, heating element operating temperatures and pressures, and/or feedstock process gas concentration, permits controlled modulation of the diameter of the carbon nano-particles, without the use of catalysts, i.e., catalyst-free. Also, the methods comprise the manufacture of hydrogen gas as a product gas. - In some embodiments, the
method 100 utilizes a first thermal cracking apparatus, as described above, and a second thermal cracking apparatus, wherein the first thermal cracking apparatus and the second thermal cracking apparatus are fluidly coupled. In some embodiments, themethod 100 utilizes a first thermal cracking apparatus, a second thermal cracking apparatus, and at least one additional thermal cracking apparatus situated between the first and second thermal cracking apparatuses, wherein the first thermal cracking apparatus, the second thermal cracking apparatus and the at least one additional thermal cracking apparatus are fluidly coupled. In some embodiments, the thermal cracking apparatuses may be fluidly coupled in series, in parallel, or combinations thereof. Embodiments further comprising more than one thermal cracking apparatus are capable of mitigating and/or eliminating undesirable by-products as well as controlling the output of products, e.g., hydrogen gas and carbon nano-particles. -
FIG. 2 depicts a simplified schematic view of a thermal crackingapparatus 200 in accordance with at least some embodiments and suitable for performing themethod 100 described above. Thethermal cracking apparatus 200 generally includes abody 202, alid 204, acollector 206, aprocess gas supply 208, agas inlet 210, agas outlet 212, alower channel 211, anupper channel 213, aheat transfer source 215, a firstelectrical terminal 216, a secondelectrical terminal 218, aheating element 222, and asupport rod 223, among other possible components not shown for simplicity. - The
body 202 generally defines aninner volume 224, within a portion of which theheating element 222 is disposed. Thebody 202 is thus the heating chamber or reaction tube of the thermal crackingapparatus 200. In some embodiments, theheating element 222 may be axially symmetrically disposed within theinner volume 224 near or concentrically arranged around a central longitudinal axis of thebody 202 of the thermal crackingapparatus 200. The portion of theinner volume 224 through which theheating element 222 extends is considered to contain areaction zone 226 that is generated by theheating element 222 during thermal cracking operations. Thereaction zone 226 may include the entireinner volume 224 or only that portion of theinner volume 224 that is within a certain distance of theheating element 222, e.g., as indicated by the dashed line. - Although the reaction zone 226 (or the inner volume 224) is depicted in
FIG. 2 as being conical in shape, thereaction zone 226 may have other geometries as well. For example, conical, cylindrical, or Venturi-shaped reaction zones may be used, among other geometries. Any of these configurations can have multiple inlet or outlet ports disposed at different locations along the length of the reaction zone to control the length of travel of the feedstock process gas through the reaction zone. - In some embodiments, the
heating element 222 is one or more resistive or conductive wires or filaments, metal filaments, flat conductive strips, and/or other appropriate thermal radical generators or elements that can be heated to a specified temperature. Theheating element 222 may be fabricated from suitable process-compatible conductive materials such as tungsten, tantalum, or the like. The number, diameter, spacing, geometry, arrangements, material composition, etc., of theheating element 222 may be changed as desired to control the temperature, zones, reaction kinetics, resulting products, etc. - In some embodiments, the
heating element 222 represents a single wire or a twisted wire filament. The twisted wire filament is also known as a bundled wire, which is formed of a bundle of multiple individual wire filaments twisted together. Any appropriate number of individual wire filaments can be used in the twisted wire filament, e.g., 4 individual wire filaments or 2-8 individual wire filaments. In some embodiments, the individual wire filaments of the twisted wire filament generally have any appropriate diameter, e.g., a diameter of 0.5 mm or 0.5-12 mm. - In some embodiments, the
heating element 222 is a flat strip, instead of a round wire. For example, a flat strip having a rectangular cross section with a width of 1-15 mm and a thickness of 1-4 mm have been shown to provide a sufficient surface area to enable appropriate heat transfer to the feedstock process gas to crack the reactants into the desired products. - The
heating element 222 is made of any appropriate electrically resistive material capable of the desired temperature level with an appropriate level of applied electrical power. Relevant factors for selecting an appropriate material generally include a lower thermal expansion coefficient, a higher resistivity, and a higher melting point temperature. In some embodiments, for example, theheating filament 222 is made of tungsten (W), tantalum (Ta), molybdenum (Mo), iridium (Ir), rhenium (Re), ruthenium (Ru), nichrome alloys, or graphite. Tungsten and tantalum have relatively high melting points, which generally render them more suitable as heating element materials herein. Tantalum carbides have an even higher melting point than tantalum alone has; whereas, tungsten carbides have a lower melting point than tungsten alone has. Tantalum has a higher resistivity, but also a higher thermal expansion coefficient, than does tungsten. Under some thermal cracking conditions, tungsten is more likely to crack or form graphitic spheres or nodules on its surface. The preferred heating element material thus generally depends on the particular operating parameters and thermal cracking device configuration for a desired thermal cracking operation. - An advantage of the twisted wire filament over a single wire filament is that the twisted wire filament has a larger surface area for radiating heat to the surrounding feedstock process gas during thermal cracking operations. Overall thermal cracking efficiency or conversion when using the twisted wire filament is thus improved or increased, thereby resulting in greater production of desired gaseous and solid products. In some embodiments, a twisted wire filament demonstrated greater than a 50% improvement over a single wire filament for thermal cracking of methane. Another advantage of the twisted wire filament over a single wire filament is that the twisted wire filament is less prone to breakage, particularly after repeated thermal cycling for multiple thermal cracking operations.
- In the illustrated embodiment, the
heating element 222 is a wire, twisted wire filament or flat strip whose ends are coupled toelectrodes heating element 522 is stretched from thefirst electrode 228, down under thesupport rod 223, and back up to thesecond electrode 230. Thesupport rod 223 is coupled to thelid 204 for mechanical stability and extends longitudinally down into the reaction zone 226 (or the inner volume 224). - In some embodiments, the
heating element 222 is coupled to a power supply to cause the generation of heat by conduction of electrical energy from the power supply through theheating element 222. Electrical power may be provided to theheating element 222 from apower supply 232 via the first and secondelectrical terminals electrical terminals electrodes 228 and 230 (and thus to the ends of the heating element 222) and to thepower supply 232. Theheating element 222 is configured to be heated by the electrical power to a suitable temperature to dissociate the feedstock process gas passing through thereaction zone 226 of the thermal crackingapparatus 200. For example, in some embodiments, theheating element 222 may be heated to a temperature of about 600° C. to about 3000° C., or 1600-2200° C. The electrical power level or the temperature may be selected dependent upon at least one of the type of the feedstock process gas to be dissociated or the type of the desired products to be produced. - In some embodiments, the electrical power provided to the
heating element 222 by thepower supply 232 is adjusted by a feedback loop during thermal cracking operations in order to maintain the desired power level. For some types of heating element materials, the conductivity (or resistivity) of theheating element 222 changes due to carbon buildup on, or carbonization of, the heating element material. Tantalum, for example, reacts with the carbon to form carbon tantalum, which has a different resistivity than tantalum. The feedback loop thus detects changes in the resistance of theheating element 222 and adjusts the voltage and/or amperage output level of thepower supply 232 to maintain a relatively constant power level, thereby maintaining a relatively constant operating temperature for the reaction zone. - The
inlet 210 and theoutlet 212 are fluidly coupled to thebody 202 or thelid 204 to access theinner volume 224 proximate a larger diameter end of the inner volume 224 (e.g., proximate the top of the upwardly expanding cone, assuming a conical shape). Theprocess gas supply 208 is coupled to theinlet 210 to provide the feedstock process gas to theinner volume 224. In some embodiments, thecollector 206 is coupled to the bottom of thebody 202 of the thermal crackingapparatus 200 proximate the smaller diameter end of the inner volume 224 (e.g., proximate the bottom of the upwardly expanding cone, assuming a conical shape). - In use during processing, the feedstock process gas is delivered into the
inner volume 224 via theinlet 210. The feedstock process gas is then heated by the thermal energy provided by theheating element 222 sufficiently to at least partially dissociate the molecules thereof. Resultant gaseous products from the thermal dissociation exit the thermal crackingapparatus 200 through theoutlet 212. In embodiments where solid products of the dissociation are created, such as carbon nano-particles, the carbon nano-particles flow, fall, or are pushed down toward the bottom of theinner volume 224 and move into thecollector 206, where they are retained. - In some embodiments, the thermal cracking
apparatus 200 includes a heat transfer apparatus to facilitate cooling the outer components of the thermal crackingapparatus 200, such as thebody 202. For example, in some embodiments, channels are disposed within thebody 202 to flow a heat transfer medium, such as a coolant, supplied by theheat transfer source 215. As illustrated for example inFIG. 2 , thelower channel 211 and theupper channel 213 are provided as shown for this purpose. However, other numbers of channels or configurations of channels may be used as well. Alternatively or in combination, an external cooling jacket may be coupled to thebody 202 to facilitate removal of excess heat from thebody 202. Alternatively or in combination, the thermal crackingapparatus 200 includes thermal insulation around thebody 202 to maintain the outer surfaces thereof at or below a desired temperature, for example, to facilitate safe handling of the thermal crackingapparatus 200 or to minimize undesired reactions, explosion, or other hazards that may be triggered or accelerated due to thermal energy. - In some embodiments, the
lid 204 is coupled to the top of thebody 202 of the thermal crackingapparatus 200. For example, thelid 204 may be removably coupled to thebody 202 to provide internal access for cleaning, maintenance, or the like. Various components, such as theinlet 210 and theoutlet 212 may be disposed in thelid 204, as discussed in greater detail below. -
FIG. 3 depicts a simplified cross-sectional view of a thermal crackingapparatus 500 in accordance with some embodiments. Thethermal cracking apparatus 500 is substantially similar to the thermal crackingapparatus 200 described above except as indicated to the contrary below. Thethermal cracking apparatus 500 generally includes abody 502 having aninner volume 503, alid 504 coupled to the top of thebody 502, and acollector 506 coupled to the bottom of thebody 502. Theinner volume 503 is generally defined by aninner surface 508 ofwalls 509. In some embodiments, thewalls 509 are reinforced with stiffeningelements 507. In some embodiments, thewalls 509 and stiffeningelements 507 are part of an insert disposed within (i.e., inserted within) an outer shell of thebody 502. In use during processing, alongitudinal reaction zone 510 is formed within theinner volume 503 and includes all or part of theinner volume 503, e.g., similar to the reaction zones mentioned above. Thereaction zone 510 is generated by aheating element 522 during thermal cracking operations. Thebody 502 is thus the heating chamber or reaction tube of the thermal crackingapparatus 500. - In some embodiments, the thermal cracking
apparatus 500 further includes afirst housing 516 encapsulating afirst electrode 517 and asecond housing 518 encapsulating asecond electrode 519. The first andsecond housings lid 504 as shown (or an upper portion of the body 502). The first andsecond electrodes inner volume 503 and are coupled to corresponding wire lugs (first and second wire lugs 520 and 521, respectively) of theheating element 522. Theheating element 522 extends into thereaction zone 503 generally along, and spaced or offset generally symmetrically or concentrically at locations near and around, a central longitudinal axis of the thermal crackingapparatus 500 or thebody 502 thereof. Thethermal cracking apparatus 500 functions similarly to the thermal crackingapparatus 200, as described above. - In some embodiments, the
heating element 522 represents a single wire, a twisted wire filament or a flat strip whose ends are coupled to the wire lugs 520 and 521. Theheating element 522 is stretched from thefirst wire lug 520, down under aquartz rod 523, and back up to thesecond wire lug 521. Thequartz rod 523 is coupled to aceiling 505 of thelid 504 for mechanical stability. In some embodiments, theheating element 522 is similar to theheating element 222, as described above. -
FIG. 4 illustrates some variations on the embodiments shown inFIGS. 2 and 3 with an exploded view of a portion of a thermal cracking apparatus 400 (e.g., similar in some respects to a portion of the thermal crackingapparatus 200 and 500). Thethermal cracking apparatus 400 generally includes abody 402 with anouter shell 404 and aninsert 406. In some embodiments, cooling channels are provided to circulate a heat transfer medium (e.g., a coolant) from a coolant source through the cooling channels. The cooling channels are disposed within thebody 402, for example, between theouter shell 404 and theinsert 406. In some embodiments, theinsert 406 has an outer surface with an outer profile that defines, together with the inner surface of theouter shell 404, one or more channels for the heat transfer medium to flow. In some embodiments, a lowerannular channel 408 and an upperannular channel 410 are provided. In some embodiments, the lowerannular channel 408 and the upperannular channel 410 are fluidly coupled within thebody 402. For example, one or more openings may be provided in each of the lowerannular channel 408 and the upperannular channel 410 to couple each of the lowerannular channel 408 and the upperannular channel 410 to each other via an intermediate volume disposed within thebody 402 between the lowerannular channel 408 and the upperannular channel 410 and between theinsert 406 and theouter shell 404. In some embodiments, theinsert 406 has a plurality ofexternal fins 412, which may be disposed within the intermediate volume between the lower and upperannular channels insert 406 to the heat transfer medium flowing between the lowerannular channel 408 and the upperannular channel 410 and through the intermediate volume. In some embodiments, thefins 412 are an integral part of theinsert 406. - The heat transfer medium can be flowed from the lower
annular channel 408 to the upperannular channel 410 or from the upperannular channel 410 to the lowerannular channel 408 to facilitate heat transfer from theinsert 406 to the heat transfer medium. When present, thefins 412 further facilitate heat transfer from theinsert 406 to the heat transfer medium. A heat transfer supply line (not shown) may be coupled to aheat transfer inlet 414 and a heat transfer return line (not shown) may be coupled to aheat transfer outlet 416 of the body 402 (or the outer shell 404) to facilitate flow of the heat transfer medium to/from the thermal crackingapparatus 400. -
FIG. 5 depicts a simplified isometric view of the thermal cracking apparatus 500 (or 200). As illustrated inFIG. 5 , the thermal crackingapparatus 500 may be supported on a plurality oflegs 720. Although not shown inFIG. 3 , the thermal crackingapparatus 500 includes aheat transfer inlet 702, agas inlet 710, and agas outlet 712, which function similarly to theheat transfer inlet 414, thegas inlet 210, and thegas outlet 212, respectively, of the thermal crackingapparatus apparatus 500 generally includes a heat transfer outlet (not shown), e.g., similar to theheat transfer outlet 416 described above. -
FIG. 6 depicts an alternative simplified isometric view of the thermal cracking apparatus 500 (or 200). As illustrated inFIG. 6 , the thermal cracking apparatus 500 (or 200) may be supported on a plurality oflegs 602. -
FIG. 7 depicts a simplified schematic view of a thermal crackingapparatus 900 in accordance with at least some embodiments and suitable for performing themethod 100 described above. Thethermal cracking apparatus 900 generally includes anupper housing 902, alower housing 904, and acollector 906. The upper andlower housings body 902/904 and thecollector 906 are formed of stainless steel, e.g., SST 316 or SST 304, or other appropriate material. In some embodiments, the upper andlower housings lower housings housing - The
upper housing 902 generally includes an interior into which aninsert 910 is disposed, so that theupper housing 902 and theinsert 910 are considered a dual wall structure. Theinsert 910 includes inner walls that define aninner volume 908, all or part of which includes a longitudinal reaction zone generated by aheating element 948 during thermal cracking operations. Theupper housing 902 or theinsert 910 is thus considered the heating chamber or reaction tube of the thermal crackingapparatus 900. - Although the
insert 910 is shown with theinner volume 908 being cylindrical, theinsert 910 may alternatively have a downwardly and inwardly tapering conically shaped inner surface similar to that described above for theinner volume 224 of thebody 202. Theinsert 910 is formed of a thermally reflective material such as, for example, stainless steel, titanium, graphite, quartz, or the like. - Upper and lower ring supports 912 and 914 support the
insert 910 and facilitate coupling, or fixing, of theinsert 910 to the interior of theupper housing 902. In some embodiments, the upper and lower ring supports 912 and 914 are formed of a thermally insulative material, such as a ceramic. Alternatively, or in combination, the upper and lower ring supports 912 and 914 are configured to limit a physical surface contact between the upper and lower ring supports 912 and 914 and theinsert 910 in order to reduce thermal transfer via conduction of heat from theinsert 910 to the ring supports 912 and 914, theupper housing 902, and/or other surrounding components. - In some embodiments, outer surfaces of the upper and lower ring supports 912 and 914 include threads that mate with corresponding threads on an interior wall of the
upper housing 902. In some embodiments, a fastening element (e.g., a screw) is alternatively used to couple the upper and lower ring supports 912 and 914 to the interior of theupper housing 902. - In some embodiments, a
thermal insulator 916 is disposed between theinsert 910 and the interior wall of theupper housing 902. Thethermal insulator 916 is formed of a thermally insulative material, e.g., ceramic. - In some embodiments, the thermal cracking
apparatus 900 further generally includes alid 920. In some embodiments, thelid 920 is permanently or removably coupled to, or integrally formed with, an upper portion of theupper housing 902. Thelid 920 includes aninlet 918 to which a gas source is coupled to provide the feedstock process gas into aninner volume 928 of thelid 920 to provide a generally laminar flow of the feedstock process gas in the thermal crackingapparatus 900. Although theinlet 918 is shown at the top of thelid 920, in some embodiments, theinlet 918 may alternatively be disposed in a side of thelid 920 to provide a rotational gas flow. - In some embodiments, the feedstock process gas is provided in a generally downwardly directional flow into the
insert 910. To improve this flow, the thermal crackingapparatus 900 optionally includes ashower plate 966 having a plurality of through holes 968 (depicted as lines) to allow the feedstock process gas to pass therethrough. - In some embodiments, the
lid 920 further includes a throughhole 922 through which a first bulkhead fitting 924 is disposed. An electrical feedthrough 926 (e.g., a first electrode) extends through the first bulkhead fitting 924 and into theinner volume 928 of thelid 920. - The
lower housing 904 is disposed beneath theupper housing 902 and may either be removably coupled to theupper housing 902 or formed integrally with theupper housing 902. Thelower housing 904 generally includes aceiling 930 having anopening 932 that is open to theinner volume 908 and the reaction zone of theupper housing 902, thereby fluidly connecting theinner volume 908 of theupper housing 902 to aninner volume 933 of thelower housing 904. - The
lower housing 904 further includes ahole 934 through which a second bulkhead fitting 936 extends. An arm 938 (e.g., a second electrode) extends through the second bulkhead fitting 936 into theinner volume 933 of thelower housing 904. Thearm 938 is formed of an electrically conductive material. In some embodiments, the second bulkhead fitting 936 is formed of an electrically insulative material to electrically insulate thelower housing 904 from thearm 938. In some embodiments, an insulative material may alternatively be disposed in thehole 934 between the bulkhead fitting 936, which may or may not be metallic or electrically conducting, and thelower housing 904 to electrically insulate thelower housing 904 from thearm 938. Thearm 938 generally includes ashaft 940 having a base 942 at afirst end 944. Theceiling 930 generally shields at least a portion of thearm 938 from the accumulation of byproducts of the thermal cracking process. - One or more heating elements 948 (one shown) of any appropriate type described above are coupled at one end (the top) to the electrical feedthrough 926 and at an opposite end (the bottom) to the base 942 at or concentric with a central longitudinal axis of the
body 902/904. To flow electricity through theheating element 948, a power supply (not shown) is coupled to the electrical feedthrough 926 and asecond end 946 of thearm 938 is coupled to ground (or vice versa). In some embodiments, the current flowed through theheating element 948 is controlled to control the temperature of theheating element 948. In addition, the length of theheating element 948 is selected to provide a length of the reaction zone in theinner volume 908 that, in combination with the flow rate of the feedstock process gas, controls or determines the residence time of the feedstock process gas in the reaction zone. Thus, to achieve dissociation of a particular feedstock process gas and produce the desired products, the length of theheating element 948, the power provided to theheating element 948, and the flow rate of the feedstock process gas are controlled, in some embodiments, to provide a predetermined residence time of the feedstock process gas at a predetermined temperature within the reaction zone. - The first bulkhead fitting 924 and the base 942 keep the
heating element 948 taut. However, during operation, theheating element 948 may experience thermal expansion/contraction. Therefore, in some embodiments, a biasingelement 950, such as a spring, is coupled to an end of theheating element 948 that extends through the base 942 to compensate for any thermal expansion/contraction of theheating element 948 and maintain tension on theheating element 948. - In some embodiments, the
lower housing 904 may further include asampling port 952 to facilitate access to theinner volume 933 of thelower housing 904 for sampling of byproducts of the process. For example, a gas chromatograph or mass spectrometer may be coupled to thesampling port 952 to sample the byproducts and provide information for controlling the amount or rate of the feedstock process gas supplied and/or the temperature of theheating element 948. - The
collector 906 includes aninner volume 954, in which amesh filter 960 is disposed. To facilitate placement of thefilter 960 within theinner volume 954, thecollector 906 includes aceiling 958 having anopening 956 through which thefilter 960 extends. Thefilter 960 may include acollar 962 having a diameter greater than theopening 956 so that thecollar 962 rests on theceiling 958. Thefilter 960 includes a plurality ofholes 961 through which the cracked gaseous product flows. Each of the plurality ofholes 961 may have a diameter sized to allow the gaseous product to flow therethrough and to prevent the solid product of the thermal cracking process from passing therethrough. In some embodiments, for example, eachhole 961 has a diameter that is less than 1 micron. Thecollector 906 further includes agas outlet 964 disposed beneath thefilter 960 to flow out the gaseous product of the thermal cracking process. - In operation, the feedstock process gas enters the thermal cracking
apparatus 900 through theinlet 918 and flows through theinsert 910. As the feedstock process gas flows past theheating element 948, the feedstock process gas is dissociated into constituent elements or molecules thereof. The solid products of the dissociation are collected in or on thefilter 960, while the gaseous product flows through the plurality ofholes 961 and through thegas outlet 964. - Although the
gas outlet 964 is illustrated at the bottom of the thermal crackingapparatus 900, thegas outlet 964 may alternatively be disposed in thelid 920 in a plane above a plane of theinlet 918. In such an embodiment, theinner volume 928 of thelid 920 generally includes a partition (not shown) to separate the incoming feedstock process gas from the outgoing gaseous product of the dissociation/cracking process. Also, in such an embodiment, thefilter 960 may be excluded and thecollector 906 electrically biased to attract the solid products of the dissociation process. -
FIGS. 8-12 depict example micrograph images of carbon nano-particles (e.g., carbon nano-onions) having differing sizes. Each of the different types of carbon nano-particles can be produced by the thermal cracking apparatuses described herein by tuning various operating parameters thereof, e.g., temperature of the heating element, temperature of the preheated feedstock process gas, pressure within the inner volume, feedstock process gas flow rate, etc. In some embodiments, groupings of integrated carbon nano-particles are fused to create solid carbon nano-particles, hollow carbon nano-particles, and/or necked carbon nano-particles that comprise one or more of spherical or oblong shapes. Moreover, the carbon nano-particles may form highly ordered pyrolytic graphite, partially or fully activated fullerenes that are single-walled nanotubes, multi-walled nanotubes, and/or combinations thereof, such as solid carbon nano-onions, hollow carbon nano-onions and/or necked carbon nano-onions that further comprise additional layers of single-walled nanotubes, multi-walled nanotubes, and/or combinations thereof, and/or graphene, optionally producing novel carbon allotropes. In some embodiments, multi-wall fullerene nanospheres may be integrated with at least one single-walled nanotube, multi-walled nanotube, or both to form integrated fullerene allotropes. In some embodiments, groupings of integrated fullerene allotropes may be randomly fused, creating networks of activated carbon multi-wall fullerene nanospheres. -
FIG. 8 depicts amicrograph image 1000 of carbon nano-onions formed by the thermal cracking apparatus and methods described herein, according to some embodiments.FIG. 8 was taken by transmission electron microscopy (TEM) techniques. Theimage 1000 shows a first small carbon nano-onion 1002 having a diameter of approximately 13 nm and a second small carbon nano-onion 1004 having a diameter of approximately 5.6 nm, which are comprised of a plurality ofgraphene molecules 1006 disposed in a concentric manner. -
FIG. 9 depicts amicrograph image 1100 of a medium-sized carbon nano-onion 1102 formed by the thermal cracking apparatus and methods described herein, according to some embodiments. The carbon nano-onion 1102 has a diameter of approximately 95 nm and acenter 1104.FIG. 9 was taken by TEM techniques. Theimage 1100 also shows that the medium-sized carbon nano-onion 1102 comprises a plurality ofgraphene molecules 1106 disposed in a concentric manner around thecenter 1104. -
FIG. 10 depicts amicrograph image 1200 of a necked carbon nano-onion 1201 formed by the thermal cracking apparatus and methods described herein, according to some embodiments.FIG. 10 was taken by TEM techniques. The necked carbon nano-onion 1201 comprises afirst carbon region 1202 and asecond carbon region 1204, where thefirst carbon region 1202 and thesecond carbon region 1204 are joined by anecked region 1206 with single-walled nanotubes and/or multi-walled nanotubes, forming a conjoined or necked carbon nano-onion having a barbell shape. -
FIG. 11 depicts amicrograph image 1300 of a large carbon nano-onion 1302 formed by the thermal cracking apparatus and methods described herein, according to some embodiments.FIG. 11 was taken by TEM techniques. The large carbon nano-onion 1302 has a spherical shape and a diameter of approximately 300 nm. Although the graphene molecules cannot be seen because theimage 1300 is taken from a further distance, the large carbon nano-onion 1302 nonetheless comprises a plurality of graphene molecules, as is discussed above with respect to the small carbon nano-onions onion 1102. -
FIG. 12 depicts amicrograph image 1400 of at least one necked carbon nano-onion 1401 formed by the thermal cracking apparatus and methods described herein, according to some embodiments.FIG. 12 was taken by TEM techniques. The necked carbon nano-onion 1401 comprises a number of carbon nano-onions 1402 joined together as if in a string or necklace. The carbon nano-onions 1402 are generally connected together by necked regions (generally too small to distinguish at the scale of the micrograph image 1400), such as single-walled nanotubes and/or multi-walled nanotubes. -
FIG. 13 depicts a simplified schematic view of athermal cracking apparatus 1500, in accordance with at least some embodiments. Thethermal cracking apparatus 1500 generally includes abody 1502, atop cap assembly 1504, abottom cap assembly 1506, aheating element 1508, a feedstock processgas preheat inlet 1512, a secondary feedstockprocess gas inlet 1514, one or more cooling gas inlets andoutlets outlet product outlet 1524, among other components shown (but not labeled) or not shown for simplicity and ease of illustration and description. - The
body 1502 generally includes an outer shell orhousing 1526, asecondary shell 1528, an inner reactor tube (an insert or heating chamber) 1530, and anouter reactor tube 1532. Thebody 1502 is considered a dual wall structure or dual tube reactor because it generally includes both of thereactor tubes shells outer reactor tube 1532 is considered to be another shell surrounding theinner reactor tube 1530.) Theshells reactor tubes inner reactor tube 1530 is generally made of quartz, alumina, or other appropriate material for withstanding the operational temperatures of the reaction zone. Theshells outer reactor tube 1532 are generally made of steel, titanium, or other appropriate materials. - The
top cap assembly 1504 and thebottom cap assembly 1506 are generally made of steel or other appropriate materials. Thetop cap assembly 1504 and thebottom cap assembly 1506 are mounted or attached to the top and bottom, respectively, of theshells shells space 1534 there between. Thespace 1534 between theshells - A top and bottom plug, cap or
insert secondary shell 1528 near the top and bottom, respectively, of thebody 1502. The top andbottom plugs bottom plug 1538 is mounted or set within thesecondary shell 1528 down against an inner surface or flange of thebottom cap assembly 1506 and engages bottom ends of thereactor tubes top plug 1536 is mounted or set within thesecondary shell 1528 near a top end of thesecondary shell 1528 and engages top ends of thereactor tubes compression spring assembly 1540 engages thetop plug 1536 and an inner surface or flange of thetop cap assembly 1504 to press thetop plug 1536 to thereactor tubes reactor tubes bottom plug 1538, and thebottom plug 1538 to the inner surface or flange of thebottom cap assembly 1506, thereby holding thereactor tubes bottom plugs reactor tubes secondary shell 1528, with aspace 1542 between theouter reactor tube 1532 and thesecondary shell 1528, and aspace 1544 between theinner reactor tube 1530 and theouter reactor tube 1532. Thespace 1542 between theouter reactor tube 1532 and thesecondary shell 1528 defines a gas coolant region. Thespace 1544 between theinner reactor tube 1530 and theouter reactor tube 1532 defines a feedstock gas preheating region. - The
heating element 1508 is any appropriate type described above and extends along, generally concentrically with, and parallel to, the central longitudinal axis of thebody 1502 or theinner reactor tube 1530. Theheating element 1508 is mounted or attached at a top end to atop electrode assembly 1546 that is mounted or attached to thebody 1502 and extends through theshells top plug 1536. In the illustrated embodiment, theheating element 1508 is mounted or attached at a bottom end to abottom electrode assembly 1548 and aspring bias assembly 1550. Thebottom electrode assembly 1548 is mounted or attached to alower portion 1552 of thebottom cap assembly 1506 and extends through thelower portion 1552 to contact theheating element 1508 through a hole in thebottom electrode assembly 1548. Thespring bias assembly 1550 includes aspring 1554 within acylindrical housing 1556 that is attached or mounted to the underside of thelower portion 1552 of thebottom cap assembly 1506. Theheating element 1508 extends through a hole in thebottom cap assembly 1506 and the hole in thebottom electrode assembly 1548 down to the bottom of thespring 1554. Theheating element 1508 is attached to the bottom of thespring 1554 and is held in tension by thespring 1554 acting against the underside of thebottom electrode assembly 1548. Thus, when theheating element 1508 heats up during gas processing or thermal cracking operations and cools down afterwards, any thermal expansion or contraction of theheating element 1508 is compensated for by thespring bias assembly 1550, which maintains theheating element 1508 in tension, so that theheating element 1508 remains generally concentric and parallel to the central longitudinal axis of thebody 1502 or theinner reactor tube 1530. - An interior surface of a wall of the
inner reactor tube 1530 defines an inner volume, all or part of which includes a longitudinal elongated reaction zone generated in the vicinity of theheating element 1508 during gas processing or thermal cracking operations. Theinner reactor tube 1530 is thus the heating or reaction chamber of thethermal cracking apparatus 1500, and the central longitudinal axis of thebody 1502 or theinner reactor tube 1530 is also considered to be a central longitudinal axis of the longitudinal elongated reaction zone. - Electrical power is provided to the
heating element 1508 through thetop electrode assembly 1546 and thebottom electrode assembly 1548 during gas processing operations. Thetop electrode assembly 1546 electrically connects to, or near, the top of theheating element 1508. Thebottom electrode assembly 1548 electrically connects to, or near, the bottom of theheating element 1508, either directly to the heating element 1508 (within the hole therein) or through an electrical connection to thespring 1554. - The feedstock process
gas preheat inlet 1512 is fluidly connected to a feedstock process gas source (not shown). The feedstock processgas preheat inlet 1512 is also attached or mounted to theshells shells bottom plug 1538, and theouter reactor tube 1532. During gas processing operations, the feedstock process gas is flowed from the source through the feedstock processgas preheat inlet 1512 and into the feedstock process gas preheating region (space 1544). The feedstock process gas then circulates across the outer surface of theinner reactor tube 1530. Theinner reactor tube 1530 is typically very hot due to the thermal gas processing occurring therein. The circulation of the feedstock process gas around theinner reactor tube 1530, thus, serves the dual purpose of cooling theinner reactor tube 1530 and preheating the feedstock process gas with residual heat transferred through the wall of theinner reactor tube 1530 from the reaction zone. For embodiments in which the gas flow direction is downward, a series of holes orapertures 1558 in the wall of theinner reactor tube 1530 near the top of the feedstock gas preheating region (space 1544) allow the preheated feedstock process gas to flow into the inner volume of theinner reactor tube 1530, i.e., the reaction zone. Within the inner volume or the reaction zone, the preheated feedstock process gas circulates around theheating element 1508, which further heats the feedstock process gas in the vicinity thereof to thermally crack the feedstock process gas into constituent elements and/or lower order molecules, i.e., the gaseous and solid products. For embodiments in which the gas flow direction is upward, on the other hand, the series of holes orapertures 1558 in the wall of theinner reactor tube 1530 are placed near the bottom of the feedstock gas preheating region (space 1544) and the feedstock processgas preheat inlet 1512 is placed near the top of the feedstock gas preheating region. - In some embodiments, the secondary feedstock
process gas inlet 1514 is fluidly connected to a source (not shown) of a gas (e.g., a second feedstock process gas) having additional particles (e.g., nano-particles of Silicon (Si), Silicon Carbide (SiC), or other appropriate materials able to withstand the high temperatures of the process without melting) floating or suspended therein. The secondary feedstockprocess gas inlet 1514 is attached or mounted to theshells inner reactor tube 1530 via apertures through theshells top plug 1536, and theinner reactor tube 1530. During gas processing operations, the feedstock process gas with additional particles is flowed from the source through the secondary feedstockprocess gas inlet 1514, through a series of holes or apertures 1560 (in the wall of theinner reactor tube 1530 near the top thereof), and into the inner volume of theinner reactor tube 1530, i.e., the reaction zone. Within the inner volume or the reaction zone, the feedstock process gas with additional particles mixes with the preheated feedstock process gas. In some embodiments, the additional particles have a melting point at or above about 500-1000° C. The temperature to which the additional particles are heated generally depends on various process parameters, such as the temperature of theheating element 1508, the flow rate of the feedstock process gas, the longitudinal length of the reaction zone, and the time that the additional particles spend within the reaction zone. Therefore, since the process parameters are set so that the additional particles are heated to a temperature lower than their melting point when they pass through the reaction zone, the solid carbon product (e.g., the graphene) produced from the feedstock process gas (e.g., the methane, natural gas, or other hydrocarbons) generally forms a coating around the additional particles. The coating generally includes one or more layers of the solid carbon product, such as one or more concentric layers of graphene, surrounding each additional particle. In this manner, carbon-coated nano-particles are formed within the reaction zone. Additionally, in some embodiments, the additional particles act as a catalyst in the thermal cracking of the feedstock process gas in the reaction zone. - In some embodiments, the feedstock process gas having additional particles, the secondary feedstock
process gas inlet 1514, and the series of holes orapertures 1560 are considered optional or are not included in thethermal cracking apparatus 1500. - In some embodiments, the cooling gas inlet and
outlet shells space 1542 between theouter reactor tube 1532 and thesecondary shell 1528, via apertures or holes through theshells gas inlet 1516, and into the gas coolant region (space 1542). The coolant gas thus circulates within the gas coolant region, absorbs some of the heat from the outer reactor tube 1532 (thereby serving to cool the outer reactor tube 1532), and exits through theoutlet 1518 to be cooled, recycled, discarded or stored. - In some other embodiments, the
space 1542 between theouter reactor tube 1532 and thesecondary shell 1528 is filled with a thermally insulating or conducting material, rather than having a coolant gas flow therein. In various embodiments, the use or selection of the coolant gas or the thermally insulating or conducting material for thespace 1542 generally depends on the thermal requirements for the overall configuration of thethermal cracking apparatus 1500, the type of the feedstock process gas, the type or characteristics of the desired solid and/or gaseous products, and/or the process parameters of the gas processing operations. Different embodiments, in other words, generally have different thermal requirements. - In some embodiments, the cooling fluid inlet and
outlet outer shell 1526 to be in fluid communication with the cooling fluid region, i.e., thespace 1534 between theshells outer shell 1526. During gas processing operations, a coolant fluid (e.g., water, etc.) is flowed from a source thereof, through the coolingfluid inlet 1520, and into the cooling fluid region (space 1534). The coolant fluid thus circulates within the cooling fluid region, absorbs some of the heat from the secondary shell 1528 (thereby cooling the secondary shell 1528), and exits through theoutlet 1522 to be cooled, recycled, discarded or stored. In this manner, the action of the coolant fluid, or the combined action of the coolant fluid and the coolant gas, ensures that the outer surface of the thermal cracking apparatus 1500 (i.e., of thebody 1502 or the outer shell 1526) remains cool, or does not become too hot to pose a danger to nearby equipment or personnel. - In the illustrated embodiment, the
product outlet 1524 is mounted or attached to thelower portion 1552 of thebottom cap assembly 1506 for embodiments in which the gas flow direction is downward. (For embodiments in which the gas flow direction is upward, on the other hand, theproduct outlet 1524 is mounted or attached near the top of the inner volume of theinner reactor tube 1530.) The solid and gaseous products generally flow out thebottom cap assembly 1506, e.g., through a series of passageways through thebottom cap assembly 1506 leading to theproduct outlet 1524, and then to an appropriate storage apparatus, hopper, orother receiving mechanism 1562. In some embodiments, the gaseous and solid products enter thehopper 1562 and are exhausted with a Venturi assist and a flow of nitrogen gas. The solid products are removed by detaching thehopper 1562 from theproduct outlet 1524 and pouring them out. The gaseous products are removed by flowing through agaseous product outlet 1564 from thehopper 1562. Thegaseous product outlet 1564 is mounted or attached to thehopper 1562 to provide a fluid connection to the interior of thehopper 1562. Thegaseous product outlet 1564 is also fluidly connected to a downstream storage apparatus or further gas processing apparatus. The gaseous products are thus flowed out through thegaseous product outlet 1564 to the downstream storage apparatus or further gas processing apparatus. Some embodiments incorporating an alternative exhaust system technique that may be used with thethermal cracking apparatus 1500, with appropriate adjustments or modifications thereto, are described below with respect toFIG. 14 . Additionally, in some embodiments, different hoppers (e.g., having the same or different design or configuration) are used for different applications. For example, one hopper is used when producing the solid carbon products, and a different hopper is used when producing the carbon-coated nano-particles. Thus, thebottom cap assembly 1506 and the connection to theproduct outlet 1524 and/or thehopper 1562 are designed for removal and replacement of thehopper 1562, so that a clean ordifferent hopper 1562 can be attached for each application. - In some situations, some of the solid products can accumulate within the inner volume of the
inner reactor tube 1530, e.g., on the interior surface of the wall of theinner reactor tube 1530 and/or theheating element 1508. Some embodiments may also use any appropriate structures or subassemblies for forcibly removing the solid products or cleaning the reaction zone. -
FIG. 14 depicts a simplified schematic view of athermal cracking apparatus 1600, in accordance with at least some embodiments. Some of the features described for thethermal cracking apparatus 1600 can be applied to the embodiment shown for thethermal cracking apparatus 1500 inFIG. 13 , and some of the features described above for thethermal cracking apparatus 1500 can be applied to the embodiment for thethermal cracking apparatus 1600, as will be described below. - The
thermal cracking apparatus 1600 generally includes abody 1602, atop cap assembly 1604, abottom cap assembly 1606, aheating element 1608, a feedstockprocess gas inlet 1612, a secondary feedstockprocess gas inlet 1614, one or more cooling gas inlets andoutlets outlet gaseous product outlet 1624, and asolid product outlet 1626, among other components shown (but not labeled) or not shown for simplicity and ease of illustration and description. - The
body 1602 generally includes an outer shell orhousing 1628, asecondary shell 1630, and a reactor tube (heating chamber) 1632. Thebody 1602 is considered a single wall structure or single tube reactor because it generally includes only thesingle reactor tube 1632 disposed within theshells FIG. 14 is, thus, an alternative to the dual wall structure or dual tube reactor embodiment ofFIG. 13 . Theshells reactor tube 1632 are generally cylindrical in shape with a central longitudinal axis arranged vertically. Thereactor tube 1632 is generally made of quartz, alumina, or other appropriate material for withstanding the operational temperatures of the reaction zone. Theshells - The
top cap assembly 1604 and thebottom cap assembly 1606 are generally made of steel or other appropriate materials. Thetop cap assembly 1604 and thebottom cap assembly 1606 are mounted or attached to the top and bottom, respectively, of theshells shells space 1634 there between. Thespace 1634 between theshells - A top and bottom plug, cap or
insert secondary shell 1630 near the top and bottom, respectively, of thebody 1602. The top andbottom plugs bottom plug 1638 is mounted or set within thesecondary shell 1630 down against an inner surface or flange of thebottom cap assembly 1606 and engages a bottom end of thereactor tube 1632. Thetop plug 1636 is mounted or set within thesecondary shell 1630 near a top end of thesecondary shell 1630 and engages a top end of thereactor tube 1632. Thereactor tube 1632 and the top andbottom plugs FIG. 13 . The top andbottom plugs reactor tube 1632 in a generally concentric arrangement or relationship to thesecondary shell 1630, with aspace 1640 between thereactor tube 1632 and thesecondary shell 1630. Thespace 1640 between thereactor tube 1632 and thesecondary shell 1630 defines a gas coolant region. - The
heating element 1608 is any appropriate type described above and extends along, generally concentrically with, and parallel to, the central longitudinal axis of thebody 1602 or thereactor tube 1632. The heating element 1608 (at or near the top end thereof) contacts atop electrode assembly 1642 that is mounted or attached to thebody 1602 and extends through theshells top plug 1636. Additionally, theheating element 1608 is mounted or attached at a top end to a tensioning assembly 1644 (e.g., a pneumatic tensioning device, a spring biasing assembly, etc.) through a hole in thetop electrode assembly 1642 and a hole in a lower portion of thetop cap assembly 1604. Theheating element 1608 is also mounted or attached at a bottom end to abottom electrode assembly 1646. Thebottom electrode assembly 1646 is mounted or attached to alower portion 1648 of thebottom cap assembly 1606 and extends through thelower portion 1648 to connect to theheating element 1608 at a point along a longitudinal axis of thelower portion 1648, which is coaxial with the longitudinal axis of thebody 1602 or thereactor tube 1632. Theheating element 1608 extends through a hole in aflange 1650 of thebottom cap assembly 1606 down to thebottom electrode assembly 1646. Theheating element 1608 is held in tension by thetensioning assembly 1644 acting against an upper portion of thetop cap assembly 1604. Thus, when theheating element 1608 heats up during gas processing or thermal cracking operations and cools down afterwards, any thermal expansion or contraction of theheating element 1608 is compensated for by thetensioning assembly 1644, which maintains theheating element 1608 in tension, so that theheating element 1608 remains generally concentric and parallel to the central longitudinal axis of thebody 1602 or thereactor tube 1632. - The technique described for
FIG. 14 for mounting or attaching theheating element 1608 using the top andbottom electrodes tensioning assembly 1644 is an alternative embodiment that can be applied to the overall embodiment shown inFIG. 13 , given appropriate modifications to support this alternative structure. On the other hand, the technique described forFIG. 13 for mounting or attaching theheating element 1508 using the top andbottom electrodes spring bias assembly 1550 is an alternative embodiment that can be applied to the overall embodiment shown inFIG. 14 , given appropriate modifications to support this alternative structure. - An interior surface of a wall of the
reactor tube 1632 defines an inner volume, all or part of which includes a longitudinal elongated reaction zone generated in the vicinity of theheating element 1608 during gas processing or thermal cracking operations. Thereactor tube 1632 is thus the heating or reaction chamber of thethermal cracking apparatus 1600, and the central longitudinal axis of thebody 1602 or thereactor tube 1632 is also considered to be a central longitudinal axis of the longitudinal elongated reaction zone. - Electrical power is provided to the
heating element 1608 through thetop electrode assembly 1642 and thebottom electrode assembly 1646 during gas processing operations. Thetop electrode assembly 1642 electrically connects to, or near, the top of theheating element 1608. Thebottom electrode assembly 1646 electrically connects to, or near, the bottom of theheating element 1608. - The feedstock
process gas inlet 1612 is fluidly connected to a feedstock process gas source (not shown). The feedstockprocess gas inlet 1612 is also attached or mounted to theshells reactor tube 1632 via apertures or holes through theshells top plug 1636, and thereactor tube 1632. During gas processing operations, the feedstock process gas is flowed from the source through the feedstockprocess gas inlet 1612 and into the inner volume (the reaction zone) of thereactor tube 1632 through a series of holes orapertures 1652 in the wall of thereactor tube 1632 near the top of thereactor tube 1632, for embodiments in which the gas flow direction is downward. Within the inner volume or the reaction zone, the feedstock process gas circulates around theheating element 1608, which heats the feedstock process gas in the vicinity thereof to thermally crack the feedstock process gas into constituent elements and/or lower order molecules, i.e., the gaseous and solid products. For embodiments in which the gas flow direction is upward, on the other hand, the feedstockprocess gas inlet 1612 and the series of holes orapertures 1652 in the wall of thereactor tube 1632 are placed near the bottom of thereactor tube 1632. - In some embodiments, the secondary feedstock
process gas inlet 1614 is fluidly connected to a source (not shown) of a second feedstock process gas having additional particles (e.g., nano-particles) floating therein. The secondary feedstockprocess gas inlet 1614 is attached or mounted through theshells top plug 1636 to be in fluid communication with the inner volume of thereactor tube 1632 via apertures or holes through theshells top plug 1636. During gas processing operations, the feedstock process gas with additional particles is flowed from the source through the secondary feedstockprocess gas inlet 1614 into the inner volume of thereactor tube 1632, i.e., the reaction zone. Within the inner volume or the reaction zone, the feedstock process gas with additional particles mixes with the feedstock process gas from the feedstockprocess gas inlet 1612. The additional particles (e.g., nano-particles of Silicon, silicon carbide, etc.) - assist in the heating, and thus the thermal cracking, of the feedstock process gas in the reaction zone. In some embodiments, the feedstock process gas having additional particles and the secondary feedstock
process gas inlet 1614 are considered optional or are not included in thethermal cracking apparatus 1500. - The technique described for
FIG. 14 for providing the feedstock process gas with additional particles through the secondary feedstockprocess gas inlet 1614 is an alternative embodiment that can be applied to the overall embodiment shown inFIG. 13 , given appropriate modifications to support this alternative structure. On the other hand, the technique described forFIG. 13 for providing the feedstock process gas with additional particles through the secondary feedstockprocess gas inlet 1514 is an alternative embodiment that can be applied to the overall embodiment shown inFIG. 14 , given appropriate modifications to support this alternative structure. - In some embodiments, the cooling gas inlet and
outlet shells space 1640 between thereactor tube 1632 and thesecondary shell 1630, via apertures or holes through theshells gas inlet 1616, and into the gas coolant region (space 1640). The coolant gas thus circulates within the gas coolant region, absorbs some of the heat from the reactor tube 1632 (thereby serving to cool the reactor tube 1632), and exits through theoutlet 1618 to be cooled, recycled, discarded or stored. - In some other embodiments, the
space 1640 between thereactor tube 1632 and thesecondary shell 1630 is filled with a thermally insulating or conducting material, rather than having a coolant gas flow therein. In various embodiments, the use or selection of the coolant gas or the thermally insulating or conducting material for thespace 1640 generally depends on the thermal requirements for the overall configuration of thethermal cracking apparatus 1600, the type of the feedstock process gas, the type or characteristics of the desired solid and/or gaseous products, and/or the process parameters of the gas processing operations. Different embodiments, in other words, generally have different thermal requirements. - In some embodiments, the cooling fluid inlet and
outlet outer shell 1628 to be in fluid communication with the cooling fluid region, i.e., thespace 1634 between theshells outer shell 1628. During gas processing operations, a coolant fluid (e.g., water, etc.) is flowed from a source thereof, through the coolingfluid inlet 1620, and into the cooling fluid region (space 1634). The coolant fluid thus circulates within the cooling fluid region, absorbs some of the heat from the secondary shell 1630 (thereby cooling the secondary shell 1630), and exits through theoutlet 1622 to be cooled, recycled, discarded or stored. In this manner, the action of the coolant fluid, or the combined action of the coolant fluid and the coolant gas, ensures that the outer surface of the thermal cracking apparatus 1600 (i.e., of thebody 1602 or the outer shell 1628) remains cool, or does not become too hot to pose a danger to nearby equipment or personnel. - In the illustrated embodiment, the
thermal cracking apparatus 1600 further includes aprimary hopper 1656 and asecondary hopper 1658. (As mentioned above for thehopper 1562, in some embodiments,different hoppers 1656 and/or 1658 are used for different applications, so thethermal cracking apparatus 1600 is designed with an attachment mechanism for removal and replacement of thehopper 1656 and/or 1658, so that a clean ordifferent hopper 1656 and/or 1658 can be attached for each application.) Theprimary hopper 1656 is mounted or attached to thelower portion 1648 of thebottom cap assembly 1606. Theprimary hopper 1656 generally has lower andupper portions upper filters lower portion 1648 of thebottom cap assembly 1606 extends through theupper portion 1662 and theupper filter 1666 down to thelower portion 1660 to provide a fluid connection between the inner volume of thereactor tube 1632 and thelower portion 1660. Theupper filter 1666 generally separates the lower andupper portions lower filter 1664 is disposed at or near the bottom of thelower portion 1660 at thesolid product outlet 1626. Thesolid product outlet 1626 is mounted or attached to thelower portion 1660, at or near a bottom thereof. Thegaseous product outlet 1624 is mounted or attached to the upper portion 1662 (at or near a side thereof) to provide a fluid connection between theupper portion 1662 and thesecondary hopper 1658. - During gas processing operations, the gaseous and solid products fall or flow down from the inner volume of the
reactor tube 1632, through the hole in theflange 1650, through thelower portion 1648 of thebottom cap assembly 1606, and into thelower portion 1660 of theprimary hopper 1656, for embodiments in which the gas flow direction is downward. The solid products generally continue to fall and pass out through thesolid product outlet 1626. The desired solid product is typically the carbon nano-particles described above; however, some larger aggregate particles, debris or flake material can also sometimes form within thereactor tube 1632 and fall down into theprimary hopper 1656. Thelower filter 1664 is generally designed or selected to be capable of catching these larger particles and allowing the desired solid product to pass through to thesolid product outlet 1626. The larger particles are periodically removed from theprimary hopper 1656. For embodiments in which the gas flow direction is upward, on the other hand, the solid products flow out of thereactor tube 1632 near the top thereof, unless the solid products are heavy enough to fall against the gas flow, in which case the solid product outlet can be placed near the bottom of thereactor tube 1632, similar to that described previously. - For embodiments in which the gas flow direction is downward, the gaseous product is generally forced to flow (in the direction of arrows 1668) down from the
reactor tube 1632, into thelower portion 1660 of theprimary hopper 1656, up through theupper filter 1666, into theupper portion 1662, and out through thegaseous product outlet 1624. (For embodiments in which the gas flow direction is upward, on the other hand, the gaseous product is generally forced to flow out of thereactor tube 1632 near the top thereof.) Some of the solid product (such as the smaller particles) can potentially be swept up in the flow of the gaseous product, instead of falling to the bottom of theprimary hopper 1656 as mentioned above. Theupper filter 1666 is generally designed or selected to be capable of catching these particles, which eventually are removed with the other solid products through thesolid product outlet 1626. An ultrasonic port 1670 (mounted or attached to the upper portion 1662) provides an ultrasonic or mechanical vibrational assist for removing these particles by theupper filter 1666. The gaseous product is exhausted with a Venturi assist and a flow of nitrogen gas through thegaseous product outlet 1624 to thesecondary hopper 1658. Most of the solid product has been removed from the gaseous product at this point, but some can still remain. Thus, additional gas/solid separation via cyclone or electrical precipitation is implemented for further separation at thesecondary hopper 1658. The gaseous products are then removed by flowing through agaseous product outlet 1672 from thesecondary hopper 1658. Thegaseous product outlet 1672 is mounted or attached to thesecondary hopper 1658 to provide a fluid connection to the interior of thehopper 1658. Thegaseous product outlet 1672 is also fluidly connected to a downstream storage apparatus or further gas processing apparatus. The gaseous products are thus flowed out through thegaseous product outlet 1564 to the downstream storage apparatus or further gas processing apparatus. - The exhaust system technique described for
FIG. 14 for exhausting and separating the gaseous and solid products through thehoppers FIG. 13 , given appropriate modifications to support this alternative structure. On the other hand, the exhaust system technique described forFIG. 13 for exhausting and separating the gaseous and solid products through thehopper 1562 is an alternative embodiment that can be applied to the overall embodiment shown inFIG. 14 , given appropriate modifications to support this alternative structure. - In some situations, some of the solid products can accumulate within the inner volume of the
reactor tube 1632, e.g., on the interior surface of the wall of thereactor tube 1632 and/or theheating element 1608. Some embodiments may also use any appropriate structures or subassemblies for forcibly removing the solid products or cleaning the reaction zone. -
FIG. 15 depicts a simplified process flow diagram of amethod 1800 for cracking a feedstock process gas in accordance with at least some embodiments, which may be an alternative embodiment to, or a more detailed embodiment of, themethod 100 shown inFIG. 1 , so that the steps of themethod 1800 are performed in addition to or in place of some or all of the steps ofmethod 100. The particular steps, combination of steps, and order of steps are shown for illustrative and explanatory purposes only. Other embodiments may include other steps, combinations of steps, and/or orders of steps to achieve generally similar results. - The
method 1800, and variations thereof, may be carried out in any suitable thermal cracking apparatus as disclosed herein capable of control in accordance with the teachings provided herein. Illustrative, but non-limiting, examples of embodiments of a suitable apparatus are described above with respect toFIGS. 2-7, 13 and 14 . - Upon starting the method 1800 (at 1802), the feedstock process gas source (or sources with and without the additional nano-particles) is turned on and the thermal cracking apparatus is allowed to heat up to an operating temperature (e.g., so that the temperature of the inner wall of the reactor tube, or heating chamber, reaches at least 200° C.). In some embodiments, the product separation and exhaust components or assembly (e.g., from the point at which the desired products exit the heating chamber to the downstream storage or further processing components) is also heated to, and maintained at, a temperature of about 300° C., or other appropriate temperature that prevents volatile organic material or compounds from being absorbed in the collected solid product. In some embodiments, the purge gas is flowed through the inner volume of the thermal cracking apparatus, i.e., of the heating chamber, as described above at this time.
- For embodiments that incorporate the preheating features shown in
FIG. 13 (or other suitable preheating structure), the feedstock process gas (without additional nano-particles) is fed (at 1804) into the thermal cracking apparatus (e.g., at the bottom, as shown inFIG. 13 ) for pre-heating before entering the reaction zone. The feedstock process gas thus circulates around the heating chamber (e.g., reaction tube or insert of the body of the thermal cracking apparatus) to cool the heating chamber and preheat the feedstock process gas. - The preheated feedstock process gas (or the non-preheated feedstock process gas, for embodiments that do not include the preheating features) then enters the reaction zone of the heating chamber and (at 1806) is cracked thermally within the reaction zone surrounding the heating element. In some embodiments, the thermal cracking is performed with the heating element at a molecular cracking temperature greater than 1600° C. and less than 2200° C. the gas flow at a rate greater than 1 slm (standard liter per minute), and a minimum temperature of the wall of the heating chamber (i.e., of the inner volume) of 200° C. Other embodiments may use other values for these operating parameters (e.g., as mentioned herein), depending on the thermal requirements for the overall configuration of the thermal cracking apparatus, the type of the feedstock process gas, the type or characteristics of the desired solid and/or gaseous products, and/or the process parameters of the gas processing operations, among other potential considerations.
- A reaction zone cleaning cycle is implemented (at 1808), e.g., by activating an appropriate solid product removal mechanism. In some embodiments, the cleaning cycle is performed every few seconds or minutes, e.g., at a minimum of 100 seconds to a maximum of 600 seconds or other appropriate time interval (dependent on carbon deposition rate), to ensure that the inner surface of the heating chamber and the heating element are kept relatively clean. Experiments have shown that the overall operating efficiency of the thermal cracking apparatus is substantially higher when the cleaning cycle is performed regularly, thereby resulting in a substantially greater production rate for the gaseous and solid products, even at lower temperatures and higher flow rates, compared to an example process in which no cleaning cycle is performed. In some embodiments, the improvement in the operating efficiency or production rate is on the order of about 25-30%.
- The gaseous products and the solid products flow out of, or are collected from, (at 1810) the thermal cracking apparatus either through separate gaseous and solid product outlets or the same combined product outlet. In some embodiments, the gaseous and solid products enter the hopper, are filtered with an ultrasonic or mechanical vibrational assist, and are exhausted with a Venturi assist and a flow of nitrogen gas. In some embodiments, additional gas/solid separation is performed (at 1812) via cyclone or electrical precipitation downstream of an initial separation hopper. In some embodiments, un-abated gas/solid material is sent (at 1814) to a wet and/or dry scrubber.
- Although a few example embodiments have been described in detail above, those skilled in the art will appreciate that many modifications are possible in embodiments without materially departing from the teachings disclosed herein. Any and all such modifications are intended to be included within the embodiments of the invention, and other embodiments may be devised without departing from the scope thereof.
Claims (19)
1. A thermal cracking apparatus, comprising:
a body having an inner volume with a longitudinal axis, the inner volume having a reaction zone concentric with the longitudinal axis;
a feedstock process gas inlet through which a feedstock process gas is flowed longitudinally into the inner volume during thermal cracking operations; and
an elongated heating element disposed within the inner volume along the longitudinal axis and being surrounded by the reaction zone, wherein the elongated heating element is held in tension by a biasing element;
wherein, during the thermal cracking operations, the elongated heating element is heated by electrical power to a molecular cracking temperature to generate the reaction zone, the feedstock process gas is heated by heat from the elongated heating element, and the heat thermally cracks molecules of the feedstock process gas that are within the reaction zone into constituent components of the molecules.
2. The thermal cracking apparatus of claim 1 , wherein:
the body further comprises a shell and a heating chamber disposed within the shell; and
the heating chamber defines the inner volume and contains the reaction zone along the longitudinal axis.
3. The thermal cracking apparatus of claim 2 , wherein:
the shell and the heating chamber define a preheating region in a space between the shell and the heating chamber;
the feedstock process gas is flowed through the preheating region before it is flowed into the inner volume during the thermal cracking operations; and
the feedstock process gas is preheated by heat transferred through the heating chamber from the reaction zone during the thermal cracking operations.
4. The thermal cracking apparatus of claim 3 , wherein:
the feedstock process gas cools the heating chamber when flowed through the preheating region during the thermal cracking operations.
5. The thermal cracking apparatus of claim 1 , wherein:
the elongated heating element is disposed concentrically with the longitudinal axis.
6. The thermal cracking apparatus of claim 1 , wherein:
the elongated heating element further comprises a plurality of heating filaments arranged symmetrically at locations around and parallel to the longitudinal axis.
7. The thermal cracking apparatus of claim 1 , wherein:
the inner volume has a cylindrical shape with a constant diameter along the longitudinal axis.
8. The thermal cracking apparatus of claim 1 , wherein:
the inner volume has a conical shape with an inwardly tapering diameter in a direction of flow of the feedstock process gas along the longitudinal axis.
9. A thermal cracking apparatus, comprising:
a body having a heating chamber disposed within a shell, the heating chamber defining an inner volume with a longitudinal axis, the inner volume having a reaction zone concentric with the longitudinal axis;
an elongated heating element disposed within the inner volume along the longitudinal axis and being surrounded by the reaction zone;
electrodes electrically connected to the elongated heating element to provide electrical power to the elongated heating element to heat the elongated heating element to a molecular cracking temperature to generate the reaction zone during thermal cracking operations;
a gas inlet through which a hydrocarbon gas is flowed longitudinally into the inner volume, wherein the hydrocarbon gas is heated by heat from the elongated heating element, which thermally cracks molecules of the hydrocarbon gas that are within the reaction zone into hydrogen and carbon nano-particles, during the thermal cracking operations; and
a gas preheating region between the heating chamber and the shell through which the hydrocarbon gas is flowed to preheat the hydrocarbon gas and cool the heating chamber before the hydrocarbon gas is flowed into the inner volume during the thermal cracking operations.
10.-27. (canceled)
28. The thermal cracking apparatus of claim 1 , wherein the biasing element comprises a spring.
29. The thermal cracking apparatus of claim 1 , wherein the biasing element is configured to compensate for thermal expansion or contraction of the elongated heating element, maintaining the elongated heating element in a position that is concentric with and parallel to the longitudinal axis during the thermal cracking operations.
30. The thermal cracking apparatus of claim 1 , wherein the elongated heating element comprises a plurality of wire filaments twisted together.
31. The thermal cracking apparatus of claim 1 , wherein the constituent components include solid products.
32. The thermal cracking apparatus of claim 9 , wherein the elongated heating element is held in tension by a biasing element.
33. The thermal cracking apparatus of claim 32 , wherein the biasing element comprises a spring.
34. The thermal cracking apparatus of claim 32 , wherein the biasing element is configured to compensate for thermal expansion or contraction of the elongated heating element, maintaining the elongated heating element in a position that is concentric with and parallel to the longitudinal axis during the thermal cracking operations.
35. The thermal cracking apparatus of claim 9 , wherein the elongated heating element comprises a plurality of wire filaments twisted together.
36. The thermal cracking apparatus of claim 9 , wherein the constituent components include solid products.
Priority Applications (3)
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TW201902819A (en) | 2019-01-16 |
US9862602B1 (en) | 2018-01-09 |
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WO2018182928A1 (en) | 2018-10-04 |
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