[go: up one dir, main page]

WO2025019808A2 - Procédés et réacteurs de conversion catalytique directe d'hydrocarbures en hydrogène - Google Patents

Procédés et réacteurs de conversion catalytique directe d'hydrocarbures en hydrogène Download PDF

Info

Publication number
WO2025019808A2
WO2025019808A2 PCT/US2024/038818 US2024038818W WO2025019808A2 WO 2025019808 A2 WO2025019808 A2 WO 2025019808A2 US 2024038818 W US2024038818 W US 2024038818W WO 2025019808 A2 WO2025019808 A2 WO 2025019808A2
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
catalyst
bed
inert media
particulates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/038818
Other languages
English (en)
Other versions
WO2025019808A3 (fr
Inventor
Eric W. Mcfarland
Amit MAHULKAR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Czero Inc
Original Assignee
Czero Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Czero Inc filed Critical Czero Inc
Publication of WO2025019808A2 publication Critical patent/WO2025019808A2/fr
Publication of WO2025019808A3 publication Critical patent/WO2025019808A3/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/008—Pyrolysis reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B01J8/1863—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised followed by a downward movement outside the reactor and subsequently re-entering it
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/52—Channel black ; Preparation thereof

Definitions

  • This reaction has the potential for producing a hydrogen product without carbon dioxide which is a major challenge in society today.
  • the reaction requires very high temperatures (T >1000 °C) and there are many technical challenges associated with heat management in such high temperature processes.
  • the carbon product produced is typically associated with polycyclic hydrocarbon contaminants. To date there have been no significant commercial processes using pyrolysis to produce hydrogen as a primary product.
  • a chemical reactor for converting hydrocarbons gases to solid carbon and hydrogen products comprises a reactor vessel and a bed of particulates disposed within the reactor vessel.
  • the reactor vessel comprises a first inlet for hydrocarbon gases, a second inlet for catalyst or catalyst precursors, a third inlet for inert media, one or more first outlets for product gases, and product solids with catalyst, or both, and one or more second outlets for inert media.
  • a diameter of the reactor vessel varies along a height of the reactor vessel, and the diameter of the reactor vessel defines at least three distinct zones each having different diameters.
  • the at least three distinct zones are configured to have different gas-solid interactions based on the different diameters, and the diameter is configured to control a gas velocity within the reactor vessel to control gas-solid interactions within the reactor to allow varying degrees of fluidization of the solids within the reactor vessel.
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media in a stratified arrangement, and the bed of particulates is configured to become partially or wholly segregated under the influence of gases flowing upwards through the reactor vessel.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises: passing a feed gas comprising hydrocarbon gases into a reactor vessel, passing the feed gas through a bed of particulates disposed within the reactor vessel, forming solid carbon and hydrogen as the feed gas passes through the bed of particulates, and stratifying the bed of particulates in response to passing the feed gas through the bed of particulates.
  • the reactor vessel comprises a first inlet for hydrocarbon gases, a second inlet for catalyst or catalyst precursors, a third inlet for inert media, and a first outlet for product gases and product solids with catalyst, and a second outlet for inert media.
  • a diameter of the reactor vessel varies along a height of the reactor vessel, and the diameter of the reactor vessel defines at least three distinct zones each having different diameters.
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media in a stratified arrangement, and the bed of particulates partially or wholly segregates under the influence of the feed gas flow ing upwards through the reactor vessel.
  • an integrated system for converting hydrocarbons gases to solid carbon and hydrogen products comprises: a preheater configured to exchange heat between a feed stream of hydrocarbon gases and reaction product gases, a pyrolysis reactor comprising a bed of particulates disposed in a reactor vessel, a heating section in fluid communication with the pyrolysis reactor, a separator system in fluid communication with the pyrolysis reactor through the product gas outlet, a heat exchanger configured to remove heat from the reaction product gases exiting the pyrolysis reactor.
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media
  • the pyrolysis reactor comprises a feed gas inlet at a lower portion of the bed of particulates, a product gas and solid outlet above the bed of particulates, an inlet for heated inert media particles near a top of the bed of particulates, an outlet for the inert media near a bottom of the bed of particulates.
  • the heating section is configured to heat the inert media in a hot gas stream and lift the heated inert media to the top of the heating section to return the heated inert media through the top inert media inlet.
  • the separator system is configured to separate any particulates in a product gas produced in the pyrolysis reactor.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises heating a feed stream to produce a heated feed stream by exchanging heat between the feed stream and a reaction product gas stream, passing the heated feed stream to a pyrolysis reactor, contacting the heated feed stream with the catalyst particles to form reaction products comprising solid carbon and hydrogen from the hydrocarbon gas, removing a portion of the inert media from the bed of particulates during the contacting, heating the inert media removed from the bed of particulates in a heating section to form heated inert media, passing the heated inert media back to the bed of particulates, separating the reaction products to form a solid carbon product and a gaseous product, and extracting heat from the reaction products downstream of the pyrolysis reactor.
  • the feed stream comprises hydrocarbon gas
  • the pyrolysis reactor comprises a bed of particulates disposed in a reactor vessel.
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media.
  • an integrated system for converting hydrocarbons gases to solid carbon and hydrogen products comprises a pyrolysis reactor comprising a bed of particulates disposed in a reactor vessel, a heating section in fluid communication with the pyrolysis reactor, and a carbon formation reactor in fluid communication with an outlet of the heating section.
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media
  • the pyrolysis reactor comprises a feed gas inlet at a low er portion of the bed of particulates, a product gas and solid outlet above the bed of particulates, an inlet for heated inert media particles near a top of the bed of particulates, an outlet for the inert media near a bottom of the bed of particulates.
  • the heating section is configured to heat the inert media in a hot gas stream and lift the heated inert media to the top of the heating section to return the heated inert media through the top inert media inlet.
  • the carbon formation reactor is configured to receive the hot gas stream from the heating section and convert at least a portion of carbon oxides in the hot gas stream to solid carbon and water.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises passing a feed stream through a bed of particulates in a reactor vessel, forming a product stream within the reactor vessel based on reacting the feed stream with the catalyst particles, passing a portion of the inert media from the reactor vessel to a heating section, combusting a combustion gas in the heating section to produce combustion products, contacting the combustion products with the inert media to produce heated inert media, passing the combustion products to a carbon formation reactor, and converting at least a portion of the carbon oxides in the combustion products to solid carbon within the carbon formation reactor.
  • the feed stream comprises hydrocarbon gas
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media.
  • the product stream comprises solid carbon and hydrogen, and the combustion products comprise carbon oxides.
  • an integrated system for converting hydrocarbons gases to solid carbon and hydrogen products comprises a preheater configured to exchange heat between a feed stream of hydrocarbon gases and a heated particulate stream to produce a cold solids stream, a pyrolysis reactor comprising a bed of particulates disposed in a reactor vessel, a separator system in fluid communication with the pyrolysis reactor through the product gas outlet, and a heat exchanger configured to exchange heat between the cold solids stream and the product gas.
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media
  • the pyrolysis reactor comprises a feed gas inlet at a lower portion of the bed of particulates, a product gas and solid outlet above the bed of particulates, an inlet for inert media particles near a top of the bed of particulates, an outlet for the inert media near a middle of the bed of particulates.
  • the pyrolysis reactor is configured to convert a hydrocarbon gas into solid carbon and hydrogen in the bed or particulates
  • the separator system is configured to separate any particulates in a product gas produced in the pyrolysis reactor.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises: heating a feed stream using heat exchange with a particulate stream to produce a heated feed stream and a cold solids stream, passing the heated feed stream to a pyrolysis reactor, converting the hydrocarbon gas to a product stream comprising solid carbon and hydrogen within the pyrolysis reactor, exchanging heat between the cold solids stream and the product stream to form a heated solids stream, and passing the heated solids stream back to the pyrolysis reactor.
  • the feed stream comprises hydrocarbon gas
  • the pyrolysis reactor comprises a bed of particulates disposed in a reactor vessel.
  • the bed of particulates comprises catalyst particles, solid carbon, and inert media.
  • Figure 1 shows schematically how iron containing catalysts evolve according to some embodiments.
  • Figure 2 is a schematic diagram of the pyrolysis process according to some embodiments.
  • Figures 3 is a schematic diagram of a pyrolysis reactor whereby heat is provided by way of a circulating inert media according to some embodiments.
  • Figure 4 is a schematic of a variable diameter two-phase reactor whereby different gas solid behavior is achieved in each reactor zone according to some embodiments according to some embodiments.
  • Figure 5 is another schematic of a variable diameter two-phase reactor with 4 zones according to some embodiments.
  • Figure 6 is a process flow diagram of a preferred integrated process according to some embodiments.
  • Figure 7 is a schematic diagram of a combustor according to some embodiments.
  • Figure 8 is a process diagram of the pyrolysis process with combustion gases converted to carbon according to some embodiments.
  • Figure 9 is a block flow diagram of an integrated process with carbon dioxide conversion to solid carbon according to some embodiments.
  • Figure 10 shows block flow diagrams of a configuration with carbon dioxide conversion to solid carbon block flow.
  • Figure 11 shows schematic diagram of a pyrolysis reactor with separation according to some embodiments.
  • Figure 12 shows performance data from an integrated process.
  • Figure 13 shows a chart showing stratification criteria.
  • Figure 14 shows a fluidization map
  • Figure 15 shows an approach temperature and flow ratio diagram.
  • Figure 16 shows a schematic representation of a heat integrated pyrolysis reactor system according to some embodiments.
  • the feed gas can comprise any suitable hydrocarbon, including but not limited to, light alkanes such as methane, ethane, natural gas, alkenes, alcohols, as well as other gaseous hydrocarbons, including those that can be gasified such as the gasified or pyrolyzed products of liquid, and solid hydrocarbons (e.g. crude oil, biomass, naphtha, etc.).
  • the conversion can occur according to the following equation:
  • This reaction has the potential for producing a molecular hydrogen product without carbon dioxide which is a major challenge in society today.
  • the reaction requires very high temperatures (T >1000 °C) and there are many technical challenges associated with heat management in such high temperature processes.
  • the carbon product produced is typically associated with polycyclic hydrocarbon contaminants. To date there have been no significant commercial processes using pyrolysis to produce hydrogen as a primary product.
  • metallic catalysts have been shown to be active including transition metals (e.g. Fe, Ni, Co) and their carbides. Catalytic pyrolysis of methane has been observed at temperatures as low' as 600 °C on the most active pyrolysis catalysts.
  • solid catalysts used for pyrolysis in fixed bed reactors rapidly deactivate as the solid carbon is deposited on the catalyst surface, thereby blocking access to the catalytic sites by the hydrocarbon and plugging the reactor.
  • sufficient hydrogen can be produced prior to catalyst deactivation, it is possible to make use of catalysts in a process that either regenerates the catalyst activity or disposes of the catalyst together with the solid carbon.
  • the catalyst can be replaced or regenerated at a very low cost and the hydrogen yield per unit mass of catalyst is sufficiently high such a process can be cost-effective.
  • iron has been found to have sufficiently low-cost and high hydrogen yields to be of potential use in the pyrolysis of hydrocarbons; however, with sufficient recovery the process disclosed herein can make use of other catalytic metals.
  • a number of different solid catalyst precursors can become active catalysts.
  • the systems and processes disclosed herein make use of iron which may be introduced in various forms into the reactor under high carbon concentrations and through a process of segregation, made possible by the reactions of carbon containing molecules with iron, evolves and fragments into nanoparticulate catalysts composed primarily of iron carbide from which a solid carbon product is produced.
  • various catalysts can be used in the system for the pyrolysis of hydrocarbons.
  • exemplary catalysts can include catalytic components such as iron (e.g., iron oxide), nickel, cobalt, or any other suitably catalytic components.
  • the catalysts used herein can be in the solid or liquid phase within the reactor.
  • nanoparticles of iron carbide can melt as low as 360 °C such that they would be in a liquid or liquid like state in a pyrolysis reactor operating at temperatures between about 750 °C to about 1000 °C.
  • a catalyst in a liquid or liquid like state can be referred to as a condensed phase catalyst in this disclosure.
  • the use of a condensed phase catalyst may be useful in providing a segregated fluidized bed as disclosed herein, which can provide a stratified bed within the reactor when operated under the proper conditions.
  • the catalyst can start as a larger particle comprising an ore. an oxide, a carbide, or an elemental form of a catalyst.
  • other components such as silica, alumina, or the like may also be present.
  • a dissociated carbon e.g., a methane dissociated in contact with the catalyst, and/or one or more carbon oxides within the reactor
  • the catalyst comprises iron
  • an iron carbide can be formed upon contact with a carbon under reaction conditions. Additional carbon can then form a filamentous carbon on the carbide.
  • FIG. 2 shows schematically the basic process 10 of hydrocarbon pyrolysis.
  • the hydrocarbon feedstock in stream 12, which can be natural gas or other hydrocarbon, and carbon containing molecules can be pre-heated and introduced into a reactor 14 containing a catalyst where the hydrocarbon is decomposed into solid carbon and hydrogen.
  • at least one region of the reactor can comprise a fluidized bed.
  • the solid carbon can be separated from the hydrogen and other gas phase components in a solid separation unit 16.
  • the separation occurs by entraining the carbon product in the exiting hydrogen gas stream where it is removed by way of one or more cyclones, and after cooling, bag filters.
  • the resulting solids stream comprising carbon can form carbon stream 20.
  • the solid carbon can be removed as a separate stream from the reactor.
  • the hydrogen can be further cooled and the heat of the gas stream can be recovered by way of a number of novel heat transfer systems as described herein.
  • the hydrogen can be separated from other gas phase components in gas separator 118 to form the product stream 22 and any hydrocarbon containing gases can be recycled to the reactor in recycle stream 21.
  • Heat is added to the reactor to provide the reaction energy 7 by way of externally heated circulating inert media.
  • heat addition to catalytic fluidized bed reactors can be facilitated by circulating an inert media.
  • the inert media can comprise any suitable inert, and the inert may have a size that is larger than that of the active catalyst within the reactor 31.
  • Figure 3 illustrates schematically how externally heated coarse, high density 7 , inert media move towards the bottom of the reactor preheating the countercurrent upward flowing gas, and the inert media can be removed from the lower section of the reactor for reheating.
  • novel and specific details of such a process are provided to show optimized means for producing high process energy efficiency and high hydrogen yields.
  • a heating leg or section can be used to remove a portion of the inert media from a lower portion of the reactor.
  • the inert can pass to a heating section where the inert solids are heated by one or more means of heat addition including by not limited to chemical and electrical.
  • combustion gases can be introduced in the riser 46 and used to directly heat the inert media.
  • the heated solids can then pass through a solids separator 48 to allow the combustion gases to leave the system while returning the heated inert particles to the top of the fluidized bed, thereby introducing heat into the reactor.
  • a heated gas can also be used.
  • an electrically heated gas such as nitrogen, carbon dioxide, or hydrogen can be passed through the riser 46 to transport and heat the inert media without the presence of any combustion.
  • the products within the reactor 31 can pass out of an upper section and pass through a separator 42 to produce a gaseous product stream and a solids stream comprising carbon and/or catalyst.
  • a portion of the solid carbon and catalyst can be removed directly from the reactor 31 as a solids stream 44.
  • Makeup catalyst can be introduced into the reactor directly and/or introduced with either the heated recycle stream (e.g., by 7 being introduced upstream of the heating leg 46) and or with the hydrocarbon feed stream 10.
  • the reaction conditions within the reactor 31 can comprise any suitable temperature, pressure, gas flow rate, and catalyst composition to convert at least a portion of the hydrocarbons in the feed stream 10 to solid carbon and hydrogen.
  • the reactor 31 can operate at a temperature of between about 700 °C to about 1100 °C, or between about 750 °C to about 950 °C.
  • the temperature within the reactor 31 may vary such that a temperature in a lower portion of the reactor 31 may be lower due to the incoming hydrocarbon feed stream, while the temperature in an upper portion of the reactor 31 may be higher due to the incoming inert media that has been externally heated.
  • a conversion of the hydrocarbon within the reactor, on a single pass basis, can be between about 25% to about 95%, or between about 30% to about 85%.
  • FIG. 4 Some aspects of the disclosure are illustrated in Figure 4 whereby a novel reactor concept is shown consisting of a stratified two-phase (gas-condensed phase) reactor containing at least two different solid particulate t pes; coarse, high density chemically inert particulates 49 (including but not limited to sand, silica, alumina, zirconia, silicon carbide, carbon, etc.) and smaller, low density, condensed phase catalyst nanoparticles mostly in contact with solid carbon products evolved from the catalyst.
  • Hydrocarbon gases 40 can enter the reactor at the bottom and travel upwards with a gas velocity determined by the reactor diameter, the gas void fraction within the solid bed, and the gas flowrate.
  • the denser and larger inert media returned to the reactor in stream 47 at locations near the top of the solids bed are caused to segregate to the lower zone of the reactor counter-current to the gas flow and transfer heat to the rising hydrocarbon feed stream.
  • the relatively cool inert media are removed from the lower section through a course inert outlet 45, heated, and returned near the top of the bed.
  • a unique feature of the reactor is the specific design of the reactor geometry' to control the gas-solid behavior by selection of the reactor diameter such that there are at least 3 distinct zones where the gas-solid behaviors are different.
  • an internal height of the reactor can be at least about 3, at least about 4, or at least about 5 times the smallest internal reactor diameter.
  • the dense inert particles segregate to the lower region of the reactor where the diameter of the lower zone of the reactor is selected such that the gas velocity is above the minimum fluidization velocity of the inert media which are fluidized into regimes including bubbling, slugging, or turbulent within the lower zone 42, zone 1.
  • the inert media are between 0.1 mm and 10 mm in average diameter.
  • the lower density, smaller carbon products containing nanoparticle catalysts are caused to accumulate near the top 44 of the reactor, zone 3.
  • the pyrolysis reaction occurs as the hydrocarbon reactants contact the catalyst producing solid carbon on the catalyst surface and hydrogen gas.
  • the reactor diameter in zone 3 that is primarily composed of the carbon products containing nanoparticle catalysts is selected to be at or near the minimum fluidization velocity of these smaller, less dense particles.
  • the diameter is selected such that the gas velocity is below the minimum fluidization velocity' allowing a prolonged gas residence time within the zone and providing for the bed to expand as solid carbon is produced on the catalyst causing the carbon/catalyst aggregate to decrease in density and the bed void fraction to increase towards the top.
  • the gas percolates through the expanding bed without significant fluidization.
  • the diameter of zone 3 can be set such that there is fluidization within the top pyrolysis zone, zone 3. In steadystate operation the solid carbon containing the nanoparticulate catalyst exits the reactor either through a specific solid exit stream or by entrainment with the exiting hydrogen gas stream.
  • the transition/segregation zone 43, zone 2, in Figure 4 will have both inert media and more dense solid catalyst that is evolving (as in Figure 1) to the nanoparticulate iron carbon composite product.
  • zone 4 (46 in Fig. 4) where disengagement between the solid and gas is caused to occur.
  • FIG. 5 Another schematic of the reactor is shown in Figure 5.
  • the operation of this reactor can be the same or similar to that shown in Fig. 4.
  • the inert particles existing from the lower zone and returning into the disengagement zone and/or the catalytic pyrolysis zone can be heated in a separate heating section such as that shown in FIG. 3.
  • Other heating sections can also be used.
  • FIG. 6 An integrated process for production of hydrogen and carbon from natural gas is shown as a process flow diagram in Figure 6.
  • the pyrolysis subsystem can include any of those shown in Figures 2-5.
  • the natural gas feed 1 can be combined with a recycle stream 24 to form stream 3, which can be preheated through a cross exchanger 61 using heat from the product gases in stream 10.
  • the resulting heated stream 4 can enter the two-phase reactor 62 where carbon and hydrogen can be produced.
  • the two-phase reactor 62 can be heated by circulating coarse inert material, such as sand, in stream 5 A which is heated by combustion of a small fraction of the hydrogen product or other fuel in combustor 63 as shown in Figure 7.
  • the combustor 63 can heat the inert material to between about 900 °C to about 1,100 °C, or between about 900 °C to about 1,000 °C, or to about 950 °C, using a combustion temperature of approximately 2,000 °C.
  • the heated combustion gases in stream 34 can pass to a steam generator to produce high quality steam in stream 40.
  • the remaining hot combustion cases in stream 36 can be used to pre-heat the oxidant to up to 700 °C to allow the combustor to reach high temperatures.
  • the heated inert material can return to the reactor 62 in stream 5B.
  • the resulting product gases in stream 8 leaving the separator 64 can be used to generate steam in stream 13 while also heating the combined feed stream 3 to a temperature of at least about 250 °C, at least about 300 °C, at least about 350 °C, or at least about 400 °C.
  • the solid carbon in stream 7 in one embodiment, can be removed from the reactor 62 in the product gas stream 6 and removed by a cyclone 64, however, in other embodiments the carbon may leave the reactor through a separate solids outlet.
  • An advantage of the process shown in Figure 6 is the heat integration with high quality steam production from the high temperature reactor exit and the combustion gases which provides for high energy efficiency.
  • combustion gases can be contacted with the coarse inerts to provide heat for the reactor.
  • a combustion system is shown in Figure 7.
  • the combustion system shown in Figure 7 can be used as the combustor 63 of Figure 6 in some embodiments.
  • the combustion system 63 can comprise a vessel/ firebox at similar pressure as the pyrolysis reactor and operating at higher temperature than the pyrolysis reactor.
  • Inert particles in stream 5 A can be heated as they move through the combustor 63.
  • the residence time of particle can be controlled by placing internals, such that particles achieve the required temperature.
  • the flame temperature can be kept as hot as possible to minimize heat loss with flue gas, to achieve high hydrogen yield from the process.
  • Combustor internals are designed to induce natural draft w ithin vessel to make the temperature more uniform.
  • the flame temperature can be as high as 2,000 °C while the circulation can maintain the combustor at a temperature between about 800 °C to about 1,100 °C, or between about 950 °C to about 1,000 °C.
  • the internals are designed such that particles are not exposed to high temperature of the flame, and to avoid short circuiting of hot gases within combustion chamber.
  • the hot solids are collected at the bottom of the combustor from where they are conveyed to the pyrolysis reactor using the same flue gas exiting the combustion chamber.
  • a central combustion section can be used to combust the incoming gases.
  • An internal circulation channel can be used to maintain an even temperature within the combustor 63.
  • the inert material in stream 5 A can fall through a series of plates or channels to allow the combustion gases to contact and heat the inert material within the combustor 63.
  • the flue gases can be used to fluidized and carry the inert material upwards in stream 5B to an upper section f the reactor.
  • a separator can be used at an upper point in the fluidized channel to separate the flue gases entraining the inert material from the solid inert material.
  • FIG. 8 shows a block diagram of a system 80 along with a corresponding process using combustion gases to heat the inert media and then pass the combustion gases to a second reactor where the carbon oxides are converted to solid carbon.
  • a hydrocarbon feed stream 81 can be passed to a pyrolysis reactor 82.
  • the pyrolysis reactor can operate in the absence or substantial absence of oxygen, and can be any of the pyrolysis reactor as described herein.
  • the pyrolysis reactor 82 can be the same or similar to the reactor 14 of Figure 2, or the pyrolysis reactors of Figures 3-5.
  • inert material can circulate with catalytic material, and the two solid phases can stratify within the pyrolysis reactor 82 as described herein.
  • the resulting product can comprise solid carbon along with some amount of the catalyst, hydrogen, and some amount of unreacted hydrocarbons can be present in the outlet stream.
  • the product stream can pass to a solid separator 83 wherein a solid stream 93 comprising the carbon and some amount of catalyst can leave the system 80.
  • the remaining gases can pass to a gas separator 84 to produce a hydrogen product stream 94 and a recycle stream 95 comprising at least a portion of the unreacted hydrocarbons.
  • the inert material can pass from the pyrolysis reactor 82 to a combustor 86.
  • a gas e.g., a fuel gas inlet stream 88
  • the heated inert material can pass back to the pyrolysis reactor 82 to introduce heat into the pyrolysis reactor and allow the pyrolysis reaction to occur.
  • the combustion of the heating gases w ithin the combustor 86 can result in the formation of carbon oxides such as carbon dioxide and carbon monoxide and/or other oxygen containing gases such as water.
  • the combustion gases can then pass as stream 89 into a carbon formation reactor along with a feed stream of hydrogen 90, and optionally, some amount of unreacted hydrocarbons from the combustor 86.
  • the carbon oxides can react with the hydrogen and/or hydrocarbons to form solid carbon and water in the presence of a catalyst.
  • the solid carbon can be separated from the products and pass out of the system as a solid carbon stream 92, which can comprise some amount of catalyst as described herein.
  • a product gas stream comprising water can pass out as stream 91. Some portion of unreacted gases can also pass out with the w ater stream 91 in some aspects.
  • the reactions occurring within the carbon formation reactor 87 can be both exothermic and endothermic.
  • the reaction conditions within the carbon formation reactor 87 may include a pressure of between about 1 bar to about 50 bar. or between about 1 bar to about 20 bar, a temperature of about 400 °C to about 1000 °C, or between about 500 °C to about 750 °C.
  • the temperature within the reactor may be maintained by providing an adiabatic reactor vessel and/or providing the reactants at the desired temperature into the reactor to maintain the temperature within the desired temperature range.
  • the carbon formation reactor 87 can take a variety of forms such as a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, or the like.
  • the carbon formation reactor 87 can use a catalyst to promote the reactions and the formation of solid carbon.
  • the catalyst material can include any material suitable for catalyzing the formation of the solid carbon material from the carbon oxide and the gaseous reducing material.
  • the catalyst material may be an element of Group VI, Group VII, Group VIII, Group IX, or Group X of the Periodic Table of Elements (e.g., iron, nickel, molybdenum, platinum, chromium, cobalt, tungsten, etc.), an actinide, a lanthanide, oxides thereof, alloys thereof, or combinations thereof. Any metal known to be subject to metal coking may also be suitable for use as the catalyst material.
  • the catalyst material may be provided within the carbon formation reactor 87 (e.g., within the reaction chamber) as one or more solid structures (e.g., a particle, a wafer, cylinder, plate, sheet, sphere, pellet, mesh, fiber, etc.), and/or as at least a partial coating on another structure (e.g., particles of the at least one material deposited on a structure, such as a wafer, cylinder, plate, sheet, sphere, mesh, pellet, etc.) within the reactor vessel.
  • the catalyst material may be provided w ithin the reactor as a plurality' of particles or particulates.
  • the catalyst material may be stationary (e.g. , as a catalyst bed) or mobile (e.g., as a fluidized bed) within the reactor. In some embodiments, a portion of the catalyst material may be mobile within the reactor and another portion of the catalyst material may be stationary within the reactor.
  • the catalyst for the carbon formation reaction can include an iron-based catalyst.
  • a dissociated carbon e.g., a methane dissociated in contact with the iron, and/or one or more carbon oxides within the reactor
  • the iron e.g., a ferrite
  • the iron carbide can then dissociate to reform the ferrite along with a layer of carbon (e.g. , graphite, etc.) on the ferrite.
  • the process can continue and result in the buildup of carbon lay ers on the ferrite, where the reaction rate can decrease as the thickness of the carbon layer on the iron builds due to increased diffusion resistance to the reactive iron core.
  • the catalyst may then deactivate upon the buildup of a sufficient carbon layer.
  • the formation of the solid carbon then occurs on or around the catalyst such that the removal of solid carbon from the reactor vessel (e.g., using a separator such as a cyclone, settling chamber, etc.) can also result in the removal of the catalyst from the reactor.
  • a small amount of catalyst may be introduced into the carbon formation reactor 87 along with the reactants while a corresponding amount of catalyst may be removed with the solid carbon.
  • the amount of catalyst added into the reactor may have a mass ratio of catalyst to reactants of between about 0.0001 : 1 to about 1 : 1 , or between about 0.001 : 1 to about 0.1 : 1.
  • the conditions and catalyst of the pyrolysis reaction in the pyrolysis reactor 82, the conditions within the combustor 86, and the catalyst and the catalyst and conditions with the carbon formation reactor 87 can all be the same as or similar to the corresponding conditions described herein.
  • Figure 9 shows another configuration for an integrated pyrolysis process such that air instead of pure oxygen can be utilized.
  • the system and process shown in Figure 9 is similar to the system and process of Figure 8, and the common elements can be the same or similar to those described herein.
  • the hydrocarbon feed stream 81 can comprise any of the hydrocarbons described herein, and the stream can be split into two portions 101A, 101B.
  • the first portion in stream 101 A can pass to the pyrolysis reactor 82 where the hydrocarbon can react to form solid carbon and hydrogen.
  • the solids can be separate, and the product gases can pass to a gas separator 84 to produce a hydrogen product stream 94 and a separated stream 104 comprising at least a portion of the unreacted hydrocarbons.
  • the separated stream 104 can pass to the carbon formation reactor 87.
  • the inert material can pass from the pyrolysis reactor 82 to a combustor 86 in stream 85 A.
  • a gas e.g., the second portion 101B of the hydrocarbon feed stream 81
  • the resulting flue gases can directly contact the inert material as described herein.
  • the heated inert material can pass back to the pyrolysis reactor 82 in stream 85B to introduce heat into the pyrolysis reactor and allow' the pyrolysis reaction to occur.
  • the combustion of the heating gases within the combustor 86 can result in the formation of carbon oxides such as carbon dioxide and carbon monoxide and/or other oxygen containing gases such as water.
  • a separator 109 can be used to separate the carbon oxides such as carbon dioxide or carbon monoxide from the inert gases such as nitrogen.
  • a purge gas stream 106 comprising nitrogen or other inert or non-reacted gases can be separated from the flue gas stream 89 and passed out of the system.
  • the purge gas stream 106 can pass through one or more heat exchanges to extract heat from the purge gas stream 106 prior to passing the purge gas stream 106 out of the system.
  • the remaining stream 105 can comprise primarily the carbon oxides can pass to the carbon formation reactor 87.
  • the carbon oxides in stream 105 can react with the hydrogen and/or hydrocarbons in the separated stream 104 as well as an optional external carbon dioxide stream 107 to form solid carbon and water in the presence of a catalyst, which can pass out of the carbon formation reactor as stream 108.
  • the solid carbon can be separated from the products and pass out of the system, where the solid carbon can comprise some amount of catalyst as described herein.
  • the product stream can be passed through one or more heat exchangers as described herein in order to extract heat and/or generate steam for use in the system.
  • the conditions and catalyst of the pyrolysis reaction in the pyrolysis reactor 82, the conditions within the combustor 86, and the catalyst and the catalyst and conditions with the carbon formation reactor 87 can all be the same as or similar to the corresponding conditions described herein.
  • the hydrocarbon feed stream 81 or any portion thereof e.g., stream 101A and/or stream 101B
  • the oxidant stream 102 can be air or any oxy gen enriched stream.
  • An oxy gen enriched stream refers to any stream having an oxygen concentration greater than the atmospheric concentration of oxygen.
  • the oxygen stream can be obtained at a desired purity from an oxygen storage tank, or via an oxygen enrichment process, for example, the separation of air into nitrogen and oxygen, such as pressure swing adsorption (PSA), vacuum swing adsorption (VSA), or cryogenic separation techniques.
  • the oxygen in the oxygen stream may have at least about 70 vol%, at least 80 vol%, or at least 90 vol % oxygen (e.g.. 90. 91. 92, 93, 94, 95, 96, 97, 98, 99, 99.1, 99.2, 99.3. 99.4. 99.5. 99.6, 99.7, 99.8, 99.9, or 100 vol % oxygen).
  • the oxidant stream 102 can comprise oxygen (e.g., from an oxygen enriched stream) combined with a portion of the flue gas from stream 89 or stream 105, which can allow for the flame temperature to be controlled without introducing additional inert gases such as nitrogen.
  • the oxidant stream 102 can comprise between about 50 vol.% to about 70 vol.% oxygen with the remainder being a recycled portion of the flue gas stream.
  • the resulting oxidant stream 102 can be approximately 20 vol.% oxygen entering the combustor 86.
  • the oxidant stream 102 can be pre-heated to between about 600 °C to about 800 °C, or between about 650 °C to about 750 °C.
  • the resulting flame temperature can be around 2000 °C while keeping the gases contacting the inert media to around 1000 °C.
  • Figure 10 illustrates another configuration for generating hydrogen with the concurrent removal of carbon oxides.
  • the system of Figure 10 is similar to the system of Figure 9, and the similar elements will not be redescribed in the interest of brevity.
  • the main difference between the system of Figure 10 and that in Figure 9 is the use of an oxygen enriched stream as the oxidant stream 103 entering the combustor 86.
  • the use of an oxygen enriched stream can reduce or avoid the presence of inert gases, thereby allow ing the separator 109 of Figure 9 to be avoided.
  • some amount of inert gases can be present in the oxidant stream 103, and the inert gases can pass to the carbon formation reactor 87 and pass out with the product gases. The inert gases can then be separated from the downstream solid carbon and water streams leaving the carbon formation reactor 87.
  • FIG. 11 Another embodiment of a pyrolysis reactor is shown in Figure 11 where the segregation of coarse inert media and fine catalyst is achieved outside the fluidized bed 115 and the reactor 31.
  • One way of achieving this segregation is via series of separators such as cyclones.
  • the solids are withdrawn from the fluidized bed 115 in which pyrolysis occurs and passed through single or multiple cyclones in series.
  • Preheated hydrocarbon feed to the reactor 31 can be used as a motive gas in these cyclones.
  • Coarse inert media can travel to the combustor chamber in a heating section, w hile fine catalyst can be sent back for pyrolysis in the reactor 31.
  • the reactor 31 can operate at any of the conditions disclosed herein for the pyrolysis reactor.
  • a first portion of the hydrocarbon feed stream 10 can pass into the reactor 31, which comprise a fluidized bed comprising inert media, solid carbon, and catalyst as described herein.
  • a portion of the solids can pass out of a lower portion of the reactor 31 using various non-mechanical valve configurations assisted by a gas stream 111, which can comprise a portion of the hydrocarbon feed 10.
  • the non-mechanical valve can enable movement of the solid particulates while providing isolation of the gases.
  • non- mechanical valves can include a loop seal or an L-valve may also be used as a non-mechanical valve.
  • the solid stream can be fluidized and passed to a separator 112 such as a cyclone.
  • the cyclone can comprise a classifier cyclone that can selectively pass particles of a certain size as a solids stream 85 A out of the separator 112, while the remaining solids can pass with the gas stream 114 back to fluidized bed 115 within the reactor 31.
  • This can allow the inert particles to be selectively separated and passed to a heating sect on in the solids stream 85 A while the remaining catalyst particles and carbon entrained in the stream from the reactor 31 back into the reactor 31 without passing to the heating section.
  • the inert media can pass back into the reactor 31 as stream 85B.
  • the inert media can pass back into an upper portion of the reactor 31 above the fluidized bed 115, though in some aspects, the heated inert media in stream 85B can also pass directed back into the fluidized bed 115.
  • the smaller particles in the fluidized bed 115 can pass to an upper portion of the reactor 31 having an increased diameter, and as a result, a lower gas velocity, to allow any entrained inert media to return to the fluidized bed 115.
  • the smaller particles can comprise the solid carbon and some amount of catalyst particles that have degraded into small particles.
  • the smaller particles can be entrained with the gas stream once their size is reduced sufficiently.
  • the outlet stream 113 can pass out of the reactor 31 and pass to a separation system. In some embodiments, one or more separators such as cyclones can be used in parallel or series to separate any solids from the outlet stream 113.
  • a first separator 116 can be used to separate any larger particles of the inert media and/or catalyst for return to the reactor 31.
  • the smaller carbon and catalyst can pass through the separator 116 w ith the gas stream to a second separator 117 such as a cyclone.
  • the second separator 117 can be used to separate all or substantially all of the solids particles from the gas stream to produce a first product stream 119 comprising the solid particles such as the solid carbon and catalyst, and a second product stream 118 comprising solid carbon and catalyst.
  • FIG. 12 An exemplary performance of the process as described herein in terms of hydrogen yield, consumed power, and efficiency of pyrolysis at different extent of feed heat integration is shown in Figure 12.
  • the hydrogen yield increases with increasing hydrocarbon feed temperature due to preheating as well as increased oxidant stream temperature due to pre-heating.
  • Heat integration can be used a way to use the heat of the product gases and flue gases to preheat the hydrocarbon feed and/or air for combustion.
  • High heat integration significantly improves the hydrogen yield.
  • the hydrogen yield is defined as the ratio of hydrogen as product and the amount of hydrogen present in the feed. This process can use both methane and hydrogen as fuel for pyrolysis reaction. For well heat integrated processes hydrogen yield can be near 0.7.
  • results demonstrate that the use of a carbon formation reactor within the system can be used to produce additional heat that can be converted to steam. This process produces excess steam for electricity generation. This can reduce the net power consumption below 1 kWh/kg of hydrogen.
  • the results presented in Figure 12 are based on the use of an oxygen enriched stream. The use of air would reduce the efficiency of the system due to compression costs for the air, which can lead to an additional net power consumption of up to 1.5 kWh/kg of hy drogen.
  • Figure 13 shows criteria affecting the segregation of particles within a fluidized bed.
  • the criterion uses gas velocity, minimum fluidization velocity, and density of dispersed and continuous phase. This criterion informs what fraction of solids will stay segregated.
  • Figure 14 show's a table illustrating a sample calculation for segregating a bed with iron particle of 200 microns with minimum fluidization velocity of 0.02 m/s and inert sand particle of 1000 microns with minimum fluidization velocity of 0.23 m/s. With this configuration if the pyrolysis bed is operated at 0.25m/s, about 57% of the bed will be segregated (as per Figure 13).
  • the fluidization regime map presents the fluidization regime when the pyrolysis bed is operated with 0.25 m/s gas superficial velocity, and iron and sand particle of above-mentioned diameter.
  • the gas velocity can be selected to allow the fluidized bed to operate within a fluidization regime for pyrolysis as a bubbling fluidized bed.
  • Figure 15 presents the ratio of inert media to that of flue gas in the heating section. This can be an important criterion to allow 7 the flue gas to convey the inert media from combustion chamber (e g., the heating section or combustor as described herein, etc.) to the pyrolysis bed in the reactor.
  • a solid to gas mass flow ratio can be less than, or less than or equal to, about 20.
  • the approach temperature represents a temperature differential betw een the operating temperature of the fluidized bed and the inlet temperature of the inert media entering the reactor.
  • Figure 16 shows another configuration of a heat integration scheme applied around the pyrolysis reactor.
  • the configuration of Figure 1 is similar those described herein, and the like components will not be redescribed in the interest of brevity 7 .
  • a small stream 161 of solids can be withdrawn from the pyrolysis zone 44.
  • the solids can be circulated in counter-current contact with cold hydrocarbon feed 10 in a preheating zone 162.
  • the hot solids in stream 161 can exchange heat with cool hydrocarbon feed 10 to cool the solids while heating the hydrocarbons in the hydrocarbon feed stream 10.
  • the flowrate of the solids in stream 161 can be chosen such that temperature of the solids in stream 163 exiting the preheating zone 162 can be approximately equal to the incoming hydrocarbon feed stream 10.
  • a part of cold solids in stream 163 can optionally be removed as a solid product stream 164A.
  • the remaining cold solids in stream 164B can be conveyed up to a heat recover zone 165.
  • the cold solids in stream 164B can first pass through a separator 166 to separate a transport gas used to pneumatically convey the cold solids in stream 164B within the system.
  • the cold solids In the heat recovery zone 165, the cold solids can be contacted in counter current flow with the hot product gases in stream 113 coming from pyrolysis reactor.
  • the solids can be heated by heat transferred from the outgoing gases in stream 113, and the heated solids can be fed to the pyrolysis bed in the reactor as solids stream 166.
  • the raw material used to form the catalyst, or the catalyst itself in stream 168 can optionally be introduced into the heat recovery 7 zone 165 to preheat the catalyst prior to passing the catalyst into the reaction zone.
  • the cooled product gases can then leave the system as stream 167.
  • This configuration can capture heat from the product gases in stream 113 so that the heat is recovered back to preheat the feed using the solids in stream 166 as a heat transport mechanism. It is likely that some pyrolysis can happen in the feed preheating zone and the catalytic solids can gather the resulting carbon.
  • the use of the catalyst solids can help to avoid any buildup of carbon product in the heat recovery zone 165 or the feed preheating zone 162.
  • various systems and methods can allow for heat integration along with a system that can produce hydrogen while reducing or avoiding any discharge of carbon oxides generated within the system.
  • This can provide a number of advantages within the system.
  • the use of a multi -zone reactor configured to provide different gas phase velocities can be useful in providing size/density stratification using a segregated, multiple zone reactor with flow characteristics determined by the gas velocity and reactor dimensions.
  • the multiple zones can allow for the use of an inert material along with a catalytic material to generate solid carbon and hydrogen in a single reactor.
  • the integrated, continuous process can incorporate the stratified reactor, and/or a homogeneous fluidized bed reactor heated with circulating solids can also be used.
  • a condensed phase catalyst which can be all solid but may be all or partially liquid can be used.
  • the catalyst can, in some aspects, include iron carbide nanoparticles. It should be noted that the nanoparticulate catalyst may be liquid or liquid-like. For example, nanoparticles of Fe carbide can melt as low as 360 °C.
  • the various heat integration schemes can also be applied using the pyrolysis reactor and the surrounding systems to provide an efficient system.
  • a chemical reactor for converting hydrocarbons gases to solid carbon and hydrogen products comprises: a reactor vessel comprising a first inlet for hydrocarbon gases, a second inlet for catalyst or catalyst precursors, a third inlet for inert media, one or more first outlets for product gases, and product solids with catalyst, or both, and one or more second outlets for inert media; wherein a diameter of the reactor vessel varies along a height of the reactor vessel, wherein the diameter of the reactor vessel defines at least three distinct zones each having different diameters, where the at least three distinct zones are configured to have different gassolid interactions based on the different diameters, and wherein the diameter is configured to control a gas velocity within the reactor vessel to control gas-solid interactions within the reactor to allow varying degrees of fluidization of the solids within the reactor vessel; and a bed of particulates disposed within the reactor vessel, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media in a stratified arrangement, wherein the bed of particulates
  • a second aspect can include the chemical reactor of the first aspect, further comprising: a heating section in fluid communication with the reactor vessel, wherein the heating section comprises a heating leg configured to receive inert media from the reactor vessel, receive a combustion gas and an oxidant gas, combust the combustion gas with the oxidant gas to heat the inert media and produce heated inert media, and return the heated inert media to the reactor vessel.
  • a heating section in fluid communication with the reactor vessel, wherein the heating section comprises a heating leg configured to receive inert media from the reactor vessel, receive a combustion gas and an oxidant gas, combust the combustion gas with the oxidant gas to heat the inert media and produce heated inert media, and return the heated inert media to the reactor vessel.
  • a third aspect can include the chemical reactor of the first or second aspect, wherein the heating section if configured to receive inert media from a lower zone of the reactor vessel and return the heated inert media to an upper zone of the reactor vessel.
  • a fourth aspect can include the chemical reactor of any one of the first to third aspects, wherein the height of the reactor vessel is at least 5 times the minimum diameter of the reactor vessel.
  • a fifth aspect can include the chemical reactor of any one of the first to fourth aspects, wherein the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a sixth aspect can include the chemical reactor of any one of the first to fifth aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, oxides thereof, carbides thereof, or any combination thereof.
  • a seventh aspect can include the chemical reactor of any one of the first to sixth aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • An eighth aspect can include the chemical reactor of any one of the first to seventh aspects, wherein the inert media has a larger particle size than a particle size of the solid carbon containing the catalyst or catalyst precursors.
  • a ninth aspect can include the chemical reactor of any one of the first to eighth aspects, wherein a first zone of the at least three zones comprises a lower zone, wherein the lower zone has a smaller diameter than any other zone of the at least three zones, and wherein the lower zone is at least 50 wt.% of the inert media in the bed of particulates.
  • a tenth aspect can include the chemical reactor of any one of the first to ninth aspects, wherein a second zone of the at least three zones comprises a pyrolysis zone, wherein the pyrolysis zone has a larger diameter than a zone of the at least three zones having a smallest diameter, and wherein the pyrolysis zone has a smaller diameter than a zone of the at least three zones having a largest diameter, wherein the pyrolysis zone comprises at least 50 vol% catalyst or catalyst precursors in the bed of particulates.
  • An eleventh aspect can include the chemical reactor of any one of the first to tenth aspects, wherein a third zone of the at least three zones comprises a disengagement zone, wherein the disengagement zone has a larger diameter than any other zone of the at least three zones, and wherein the disengagement zone has less than 20 vol.% solids.
  • a twelfth aspect can include the chemical reactor of any one of the first to tenth aspects, wherein a third zone of the at least three zones comprises a disengagement zone, wherein the disengagement zone has a smaller diameter than a zone directly below the third zone.
  • a thirteenth aspect can include the chemical reactor of any one of the first to twelfth aspects, wherein the catalyst or catalyst precursors are in a condensed phase.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises: passing a feed gas comprising hydrocarbon gases into a reactor vessel, wherein the reactor vessel comprises a first inlet for hydrocarbon gases, a second inlet for catalyst or catalyst precursors, a third inlet for inert media, and a first outlet for product gases and product solids with catalyst, and a second outlet for inert media, wherein a diameter of the reactor vessel varies along a height of the reactor vessel, and wherein the diameter of the reactor vessel defines at least three distinct zones each having different diameters, passing the feed gas through a bed of particulates disposed within the reactor vessel, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media in a stratified arrangement, forming solid carbon and hydrogen as the feed gas passes through the bed of particulates; and stratifying the bed of particulates in response to passing the feed gas through the bed of particulates, wherein the bed of particulates partially or wholly segregates
  • a fifteenth aspect can include the process of the fourteenth aspect, further comprising: passing a portion of the inert media from the reactor vessel to a heating section; contacting a heating gas with the inert media to produce heated inert media; and passing the heated inert media back to the reactor vessel.
  • a sixteenth aspect can include the process of the fourteenth aspect, further comprising: combusting a combustion gas in the heating section to produce combustion products, wherein the heating gas comprises the combustion products.
  • a seventeenth aspect can include the process of any one of the fourteenth to sixteenth aspects, wherein the heating section receives inert media from a lower zone of the reactor vessel and returns the heated inert media to an upper zone of the reactor vessel.
  • An eighteenth aspect can include the process of any one of the fourteenth to seventeenth aspects, wherein the height of the reactor vessel is at least 5 times the minimum diameter of the reactor vessel.
  • a nineteenth aspect can include the process of any one of the fourteenth to eighteenth aspects, wherein the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a twentieth aspect can include the process of any one of the fourteenth to nineteenth aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, oxides thereof, carbides thereof, or any combination thereof.
  • a twenty first aspect can include the process of any one of the fourteenth to twentieth aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • a twenty second aspect can include the process of any one of the fourteenth to twenty first aspects, wherein the inert media has a larger particle size than a particle size of the solid carbon containing the catalyst or catalyst precursors, and wherein the catalyst or catalyst precursors segregate from the inert media based on differences in size and density.
  • a twenty third aspect can include the process of any one of the fourteenth to twenty second aspects, wherein a first zone of the at least three zones comprises a lower zone, wherein the lower zone has a smaller diameter than any other zone of the at least three zones, and wherein the lower zone is at least 50 wt.% of the inert media in the bed of particulates.
  • a twenty fourth aspect can include the process of any one of the fourteenth to twenty third aspects, wherein a second zone of the at least three zones comprises a pyrolysis zone, wherein the pyrolysis zone has a larger diameter than a zone of the at least three zones having a smallest diameter, and wherein the pyrolysis zone has a smaller diameter than a zone of the at least three zones having a largest diameter, wherein the pyrolysis zone comprises at least 50 vol% catalyst or catalyst precursors in the bed of particulates.
  • a twenty fifth aspect can include the process of any one of the fourteenth to twenty fourth aspects, wherein a third zone of the at least three zones comprises a disengagement zone, wherein the disengagement zone has a larger diameter than any other zone of the at least three zones, and wherein the disengagement zone has less than 20 vol.% solids.
  • a tw enty sixth aspect can include the process of any one of the fourteenth to twenty fifth aspects, wherein the catalyst or catalyst precursors are in a condensed phase.
  • an integrated system for converting hydrocarbons gases to solid carbon and hydrogen products comprises: a preheater configured to exchange heat between a feed stream of hydrocarbon gases and reaction product gases; a pyrolysis reactor comprising a bed of particulates disposed in a reactor vessel, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media, wherein the pyrolysis reactor comprises a feed gas inlet at a lower portion of the bed of particulates, a product gas and solid outlet above the bed of particulates, an inlet for heated inert media particles near a top of the bed of particulates, an outlet for the inert media near a bottom of the bed of particulates; a heating section in fluid communication with the pyrolysis reactor, wherein the heating section is configured to heat the inert media in a hot gas stream and lift the heated inert media to the top of the heating section to return the heated inert media through the top inert media inlet; a separator
  • a tw enty eighth aspect can include the integrated system of the twenty' seventh aspect, further comprising: a gas absorber-separation system in fluid communication with the pyrolysis reactor, wherein the gas absorber-separation system is configured to separate hydrogen gas from the reaction product gases.
  • a twenty ninth aspect can include the integrated system of the twenty seventh or twenty eighth aspect, wherein the separator system comprises one or more cyclone separators.
  • a thirtieth aspect can include the integrated system of any one of the twenty seventh to twenty ninth aspects, wherein the height of the reactor vessel is at least 5 times the minimum diameter of the reactor vessel.
  • a thirty first aspect can include the integrated system of any one of the twenty seventh to thirtieth aspects, wherein the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a thirty second aspect can include the integrated system of any one of the twenty seventh to thirty first aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, oxides thereof, carbides thereof, or any combination thereof.
  • a thirty third aspect can include the integrated system of any one of the twenty seventh to thirty second aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • a thirty fourth aspect can include the integrated system of any one of the twenty seventh to thirty third aspects, wherein the inert media has a larger particle size than a particle size of the catalyst or catalyst precursors or the solid carbon containing the catalyst or catalyst precursors.
  • a thirty fifth aspect can include the integrated system of any one of the twenty seventh to thirty fourth aspects, wherein a first zone of the at least three zones comprises a lower zone, wherein the lower zone has a smaller diameter than any other zone of the at least three zones, and wherein the lower zone is at least 50 wt.% of the inert media in the bed of particulates.
  • a thirty sixth aspect can include the integrated system of any one of the twenty seventh to thirty fifth aspects, wherein a second zone of the at least three zones comprises a pyrolysis zone, wherein the pyrolysis zone has a larger diameter than a zone of the at least three zones having a smallest diameter, and wherein the pyrolysis zone has a smaller diameter than a zone of the at least three zones having a largest diameter, wherein the pyrolysis zone comprises at least 50 vol% catalyst or catalyst precursors in the bed of particulates.
  • a thirty seventh aspect can include the integrated system of any one of the twenty seventh to thirty 7 sixth aspects, wherein a third zone of the at least three zones comprises a disengagement zone, wherein the disengagement zone has a larger diameter than any other zone of the at least three zones, and wherein the disengagement zone has less than 20 vol.% solids.
  • a thirty eighth aspect can include the integrated system of any one of the twenty seventh to thirty 7 seventh aspects, wherein the catalyst or catalyst precursors are in a condensed phase.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises: heating a feed stream to produce a heated feed stream by exchanging heat between the feed stream and a reaction product gas stream, wherein the feed stream comprises hydrocarbon gas; passing the heated feed stream to a pyrolysis reactor, wherein the pyrolysis reactor comprises a bed of particulates disposed in a reactor vessel, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media; contacting the heated feed stream with the catalyst particles to form reaction products comprising solid carbon and hydrogen from the hydrocarbon gas; removing a portion of the inert media from the bed of particulates during the contacting; heating the inert media removed from the bed of particulates in a heating section to form heated inert media; passing the heated inert media back to the bed of particulates; separating the reaction products to form a solid carbon product and a gaseous product; and extracting heat from the reaction products downstream of the pyrolysis reactor.
  • a fortieth aspect can include the process of the thirty ninth aspect, further comprising: separating a hydrogen gas stream from the reaction products downstream of the pyrolysis reactor.
  • a forty first aspect can include the process of the thirty ninth or fortieth aspect, wherein the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a forty second aspect can include the process of any one of the thirty ninth to forty first aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, oxides thereof, carbides thereof, or any combination thereof.
  • a fort ⁇ 7 third aspect can include the process of any one of the thirty' ninth to forty' second aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • a forty fourth aspect can include the process of any one of the thirty’ ninth to forty third aspects, wherein the inert media has a larger particle size than a particle size of the catalyst or catalyst precursors or the solid carbon containing the catalyst or catalyst precursors.
  • a forty fifth aspect can include the process of any one of the thirty ninth to forty third aspects, wherein the pyrolysis reactor operates at a temperature between about 750 °C to about 1,000 °C.
  • a forty' sixth aspect can include the process of any one of the thirty' ninth to forty' fifth aspects, wherein heated feed stream flows through the bed of particulates at a flow rate sufficient to form a fluidized bed within at least a portion of the reactor vessel.
  • a forty seventh aspect can include the process of any one of the thirty ninth to forty sixth aspects, further comprising: stratifying the bed of particulates in response to passing the heated feed gas through the bed of particulates, wherein the bed of particulates partially or w holly segregates under the influence of the heated feed gas flowing upwards through the reactor vessel.
  • an integrated system for converting hydrocarbons gases to solid carbon and hydrogen products comprises: a pyrolysis reactor comprising a bed of particulates disposed in a reactor vessel, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media, wherein the pyrolysis reactor comprises a feed gas inlet at a lower portion of the bed of particulates, a product gas and solid outlet above the bed of particulates, an inlet for heated inert media particles near a top of the bed of particulates, an outlet for the inert media near a bottom of the bed of particulates; a heating section in fluid communication with the pyrolysis reactor, wherein the heating section is configured to heat the inert media in a hot gas stream and lift the heated inert media to the top of the heating section to return the heated inert media through the top inert media inlet; and a carbon formation reactor in fluid communication with an outlet of the heating section, wherein the carbon formation reactor is configured to receive the
  • a forty ninth aspect can include the integrated system of the forty eighth aspect, further comprising: a feed gas inlet into the carbon formation reactor, wherein the feed gas inlet is configured to receive a hydrogen or hydrocarbon stream for the conversion of at least the portion of carbon oxides in the hot gas stream to the solid carbon and the water.
  • a fiftieth aspect can include the integrated system of the forty eighth or forty ninth aspect, wherein the carbon formation reactor comprises a carbon formation catalyst, and wherein the carbon formation catalyst comprises an element of Group VI, Group VII, Group VIII, Group IX. or Group X of the Periodic Table of Elements, an actinide, a lanthanide, oxides thereof, alloys thereof, or combinations thereof.
  • a fi ty first aspect can include the integrated system of any one of the forty eighth to fiftieth aspects, wherein the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a fifty second aspect can include the integrated system of any one of the forty eighth to fifty first aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, oxides thereof, carbides thereof, or any combination thereof.
  • a fifty third aspect can include the integrated system of any one of the forty eighth to fifty second aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • a fifty fourth aspect can include the integrated system of any one of the forty' eighth to fifty third aspects, wherein the inert media has a larger particle size than a particle size of the catalyst or catalyst precursors or the solid carbon containing the catalyst or catalyst precursors.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises: passing a feed stream through a bed of particulates in a reactor vessel, wherein the feed stream comprises hydrocarbon gas, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media; forming a product stream within the reactor vessel based on reacting the feed stream with the catalyst particles, wherein the product stream comprises solid carbon and hydrogen; passing a portion of the inert media from the reactor vessel to a heating section; combusting a combustion gas in the heating section to produce combustion products, wherein the combustion products comprise carbon oxides; contacting the combustion products with the inert media to produce heated inert media; passing the combustion products to a carbon formation reactor: and converting at least a portion of the carbon oxides in the combustion products to solid carbon within the carbon formation reactor.
  • a fifty sixth aspect can include the process of the fifty fifth aspect, further comprising: passing a hydrogen or hydrocarbon stream into the carbon formation reactor during the converting to form the solid carbon and water.
  • a fifty' seventh aspect can include the process of the fifty fifth or fifty sixth aspect, wherein the carbon formation reactor comprises a carbon formation catalyst, and wherein the carbon formation catalyst comprises an element of Group VI, Group VII, Group VIII, Group IX, or Group X of the Periodic Table of Elements, an actinide, a lanthanide, oxides thereof, alloys thereof, or combinations thereof.
  • a fifty eighth aspect can include the process of any one of the fifty fifth to fifty seventh aspects, wherein the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • the hydrocarbon gases comprise: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a fifty' ninth aspect can include the process of any one of the fifty fifth to fifty' eighth aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, oxides thereof, carbides thereof, or any combination thereof.
  • a sixtieth aspect can include the process of any one of the fifty fifth to fifty ninth aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • a sixty first aspect can include the process of any one of the fifty fifth to sixtieth aspects, wherein the inert media has a larger particle size than a particle size of the catalyst or catalyst precursors or the solid carbon containing the catalyst or catalyst precursors.
  • a sixty' second aspect can include the process of any one of the fifty fifth to sixty' first aspects, wherein the carbon formation reactor operates at a temperature between about 400 °C and about 1000 °C.
  • a sixty third aspect can include the process of any one of the fifty fifth to sixty' second aspects, wherein the carbon formation reactor operates as a fluidized bed reactor.
  • an integrated system for converting hydrocarbons gases to solid carbon and hydrogen products comprises: a preheater configured to exchange heat between a feed stream of hydrocarbon gases and a heated particulate stream to produce a cold solids stream; a pyrolysis reactor comprising a bed of particulates disposed in a reactor vessel, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media, wherein the pyrolysis reactor comprises a feed gas inlet at a lower portion of the bed of particulates, a product gas and solid outlet above the bed of particulates, an inlet for inert media particles near a top of the bed of particulates, an outlet for the inert media near a middle of the bed of particulates, wherein the pyrolysis reactor is configured to convert a hydrocarbon gas into solid carbon and hydrogen in the bed or particulates; a separator system in fluid communication with the pyrolysis reactor through the product gas outlet, where the separator system is configured to separate any
  • a sixty fifth aspect can include the integrated system of the sixty fourth aspect, further comprising a cold solids conveyor, wherein the cold solids conveyor is configured to convey the cold solids from the preheater to the heat exchanger, and wherein the cold solids conveyor comprises a pneumatic conveyor.
  • a sixty sixth aspect can include the integrated system of the sixty fifth aspect, wherein the hydrocarbon gas comprises: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • the hydrocarbon gas comprises: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a sixty seventh aspect can include the integrated system of any one of the sixty fourth to sixty sixth aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, or any combination thereof.
  • a sixty eighth aspect can include the integrated system of any one of the sixty’ fourth to sixty seventh aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • a sixty ninth aspect can include the integrated system of any one of the sixty fourth to sixty eighth aspects, wherein the inert media has a larger particle size than a particle size of the catalyst or catalyst precursors or the solid carbon containing the catalyst or catalyst precursors.
  • a process for converting hydrocarbons gases to solid carbon and hydrogen products comprises: heating a feed stream using heat exchange with a particulate stream to produce a heated feed stream and a cold solids stream, wherein the feed stream comprises hydrocarbon gas; passing the heated feed stream to a pyrolysis reactor, wherein the pyrolysis reactor comprise a bed of particulates disposed in a reactor vessel, wherein the bed of particulates comprises catalyst particles, solid carbon, and inert media; converting the hydrocarbon gas to a product stream comprising solid carbon and hydrogen within the pyrolysis reactor; exchanging heat between the cold solids stream and the product stream to form a heated solids stream; and passing the heated solids stream back to the pyrolysis reactor.
  • a seventy first aspect can include the integrated system of the seventieth aspect, further comprising a cold solids conveyor, wherein the cold solids conveyor is configured to convey the cold solids from the preheater to the heat exchanger, and wherein the cold solids conveyor comprises a pneumatic conveyor.
  • a seventy second aspect can include the integrated system of the seventy first aspect, wherein the hydrocarbon gas comprises: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • the hydrocarbon gas comprises: methane, ethane, natural gas, alkenes, alcohols, liquid hydrocarbons, solid hydrocarbons, or any combination thereof.
  • a seventy third aspect can include the integrated system of any one of the seventy first to seventy second aspects, wherein the catalyst or catalyst precursors comprise iron, nickel, cobalt, or any combination thereof.
  • a seventy fourth aspect can include the integrated system of any one of the seventy first to seventy third aspects, wherein the inert media comprises sand, silica, alumina, zirconia, silicon carbide, carbon, or any combination thereof.
  • a seventy fifth aspect can include the integrated system of any one of the seventy first to seventy fourth aspects, wherein the inert media has a larger particle size than a particle size of the catalyst or catalyst precursors or the solid carbon containing the catalyst or catalyst precursors.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention concerne un système intégré de conversion de gaz d'hydrocarbures en produits solides de carbone et d'hydrogène comprenant un réacteur de pyrolyse comportant un lit de particules disposé dans une cuve de réacteur, une section de chauffage en communication fluidique avec le réacteur de pyrolyse, un système de séparateur en communication fluidique avec le réacteur de pyrolyse à travers la sortie de gaz de produit, et un échangeur de chaleur conçu pour éliminer la chaleur des gaz de produit de réaction sortant du réacteur de pyrolyse. Le lit de particules contient des particules de catalyseur, du carbone solide et des milieux inertes. La section de chauffage est conçue pour chauffer le milieu inerte dans un flux de gaz chaud et soulever le milieu inerte chauffé vers la partie supérieure de la section de chauffage pour renvoyer le milieu inerte chauffé à travers l'entrée de milieu inerte supérieure, et le système de séparateur est conçu pour séparer toute particule dans un produit gazeux produit dans le réacteur de pyrolyse.
PCT/US2024/038818 2023-07-20 2024-07-19 Procédés et réacteurs de conversion catalytique directe d'hydrocarbures en hydrogène Pending WO2025019808A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363514787P 2023-07-20 2023-07-20
US63/514,787 2023-07-20

Publications (2)

Publication Number Publication Date
WO2025019808A2 true WO2025019808A2 (fr) 2025-01-23
WO2025019808A3 WO2025019808A3 (fr) 2025-05-01

Family

ID=94282717

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/038818 Pending WO2025019808A2 (fr) 2023-07-20 2024-07-19 Procédés et réacteurs de conversion catalytique directe d'hydrocarbures en hydrogène

Country Status (1)

Country Link
WO (1) WO2025019808A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025227073A1 (fr) * 2024-04-26 2025-10-30 Czero, Inc. Produits de carbone solide et procédés de production de carbone solide

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284161A (en) * 1963-01-22 1966-11-08 Universal Oil Prod Co Method for hydrogen production by catalytic decomposition of a gaseous hydrocarbon stream
US4344373A (en) * 1979-10-30 1982-08-17 Agency Of Industrial Science And Technology Method for pyrolyzing
WO2014151898A1 (fr) * 2013-03-15 2014-09-25 Seerstone Llc Systèmes de production de carbone solide par réduction d'oxydes de carbone
US11685651B2 (en) * 2019-10-25 2023-06-27 Mark Kevin Robertson Catalytic decomposition of hydrocarbons for the production of hydrogen and carbon
EP3868708A1 (fr) * 2020-02-21 2021-08-25 L 2 Consultancy B.V. Procédé et système de décomposition thermique directe d'un composé d'hydrocarbure en carbone et en hydrogène
EP4139620A4 (fr) * 2020-04-20 2024-05-01 Calix Limited Échangeur de chaleur à poudre/gaz et applications correspondantes
US20230340336A1 (en) * 2020-08-19 2023-10-26 The Regents Of The University Of California Chemical reaction and conversion in thermally heterogeneous and non-steady-state chemical reactors
WO2024206754A2 (fr) * 2023-03-31 2024-10-03 The Regents Of The University Of California Pyrolyse catalytique d'hydrocarbures améliorée par milieux inertes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025227073A1 (fr) * 2024-04-26 2025-10-30 Czero, Inc. Produits de carbone solide et procédés de production de carbone solide

Also Published As

Publication number Publication date
WO2025019808A3 (fr) 2025-05-01

Similar Documents

Publication Publication Date Title
KR102189391B1 (ko) 수소, 일산화탄소 및 탄소-함유 생성물의 병행 제조 방법
US8916128B2 (en) Integrated oxidation, reduction and gasification method for chemical looping syngas and energy production
Rostrup-Nielsen et al. Large-scale hydrogen production
US7914764B2 (en) Hydrogen manufacture using pressure swing reforming
Chen et al. Novel circulating fast fluidized-bed membrane reformer for efficient production of hydrogen from steam reforming of methane
US20040170559A1 (en) Hydrogen manufacture using pressure swing reforming
US20210331918A1 (en) Methane pyrolysis using stacked fluidized beds
BRPI0920029B1 (pt) Processo para a redução direta de minério de ferro
US7951350B1 (en) Fuel-gas reforming systems and methods
Grace et al. Hydrogen production in fluidized beds with in-situ membranes
KR20230068423A (ko) 코크스의 전기 가열과 함께 적층된 유동층을 사용한 메탄 열분해
Agahzamin et al. Investigation and recovery of purge gas streams to enhance synthesis gas production in a mega methanol complex
WO2025019808A2 (fr) Procédés et réacteurs de conversion catalytique directe d'hydrocarbures en hydrogène
Rahimpour et al. Enhancement of hydrogen production via coupling of MCH dehydrogenation reaction and methanol synthesis process by using thermally coupled heat exchanger reactor
WO2024206754A2 (fr) Pyrolyse catalytique d'hydrocarbures améliorée par milieux inertes
EP4655102A1 (fr) Formation en boucle chimique à chaleur intégrée de carbone et d'hydrogène
Booz et al. Production of Synthesis Gas
WO2024263929A2 (fr) Boucle chimique de formation de carbone utilisant de l'oxygène
US11591531B2 (en) Conversion of catalytic coke into synthetic gas from a fluid catalytic cracking (FCC) process using a chemical looping system and methods related thereto
WO2024015306A2 (fr) Boucle chimique de formation de carbone utilisant de l'oxygène
WO2025175109A1 (fr) Réacteurs, catalyseurs et procédés améliorés pour pyrolyse d'hydrocarbures
WO2009136909A1 (fr) Systèmes et procédés de reformage de gaz combustible
EP4638347A2 (fr) Procédés et méthodes de production d'hydrogène et de carbone à partir d'hydrocarbures à l'aide de particules porteuses de chaleur
WO2025227072A1 (fr) Décarbonisation de raffinerie par intégration de procédés et de systèmes d'oxypyrolyse
Boyd et al. A novel autothermal reforming membrane reactor for high purity H2

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24844038

Country of ref document: EP

Kind code of ref document: A2