WO2018098495A1 - Procédés et systèmes de formation d'ammoniac et de produits carbonés solides - Google Patents

Procédés et systèmes de formation d'ammoniac et de produits carbonés solides Download PDF

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WO2018098495A1
WO2018098495A1 PCT/US2017/063527 US2017063527W WO2018098495A1 WO 2018098495 A1 WO2018098495 A1 WO 2018098495A1 US 2017063527 W US2017063527 W US 2017063527W WO 2018098495 A1 WO2018098495 A1 WO 2018098495A1
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carbon
catalyst
reacting
hydrogen
natural gas
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Terry A. Ring
Dallas B. Noyes
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Seerstone Llc
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0458—Separation of NH3
    • C01C1/0464—Separation of NH3 by absorption in liquids, e.g. water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Embodiments of the present disclosure relate to methods and systems for concurrently forming ammoma and solid carbon products from a hydrocarbon, such as methane, and other materials, such as water and nitrogen.
  • a hydrocarbon such as methane
  • other materials such as water and nitrogen.
  • Ammoma is an important chemical having many applications, such as in the production of fertilizers, cleaners, explosives, etc. Ammoma is directly or indirectly used in a variety of chemical processes to produce various nitrogen- containing compounds, such as amines, aramid fibers, and pharmaceuticals. The production of ammoma is therefore a major worldwide industry. Ammoma is commonly produced by the Haber-Bosch process.
  • ammoma is synthesized by the reaction of hydrogen and nitrogen in the presence of a catalyst, such as iron, according to Reaction 1 :
  • the rate of reaction of hydrogen and nitrogen in Reaction 1 is a function of the reaction conditions including the temperature, pressure, and presence of catalyst. Increasing the temperature increases the reaction rate, but also shifts the reaction equilibrium.
  • the equilibrium constant K eq defined as the ratio of the product of the partial pressures of the product to the product of the partial pressures of the reactants, as shown in the equation
  • Hydrogen used in Reaction 1 may be from any source, but is conventionally formed from methane, coal, or another hydrocarbon.
  • the preparation of the feed gases is typically a multi-step process including steam reforming, shift conversion, carbon dioxide removal, and methanation, with associated apparatus and operating expenses.
  • a common synthesis route is to form hydrogen from methane. In such a process, the methane is reformed typically in a steam reformer, wherein methane reacts with water in the presence of a nickel catalyst to produce hydrogen and carbon monoxide:
  • Carbon monoxide may be converted to carbon dioxide to form additional hydrogen:
  • the overall result of Reactions 2-6 is that methane and steam are converted to carbon dioxide and hydrogen, with residual methane and steam available for recycle.
  • Conventional preparation of hydrogen from hydrocarbons, such as described for the example of methane, for use in the Haber-Bosch process may be performed in a series of reactors, and may require separation or other treatment of some components of gas streams to form a suitably pure hydrogen stream.
  • Ammonia production as outlined above can result in significant releases of carbon dioxide to the atmosphere.
  • Methods of concurrently forming ammonia and solid carbon products include reacting a first portion of natural gas in the presence of water to form hydrogen and at least one carbon oxide; separating the hydrogen from the at least one carbon oxide; reacting the hydrogen with nitrogen in the presence of a first catalyst to form a first tail gas comprising ammonia; and reacting a second portion of natural gas with the at least one carbon oxide in the presence of a second catalyst to form solid carbon and a second tail gas.
  • the methods may also include removing sulfur from the natural gas.
  • Carbon oxide(s) formed in the production of ammonia may be beneficially used to form solid carbon and water, which may each be valuable products.
  • the formation of ammonia and solid carbon may provide advantages over forming either product alone .
  • a system for concurrently producing ammonia and solid carbon includes a conditioning unit, a methane reformer, a separator, a first reactor, and a second reactor.
  • the conditioning unit is configured to remove sulfur from a natural gas source to form a purified natural gas.
  • the methane reformer is configured to react a first portion of the purified natural gas in the presence of water to form hydrogen and at least one carbon oxide.
  • the separator is configured to separate the hydrogen from the at least one carbon oxide.
  • the first reactor is configured to react the hydrogen with nitrogen in the presence of a first catalyst to form a first tail gas comprising ammonia.
  • the second reactor is configured to react a second portion of the purified natural gas with the at least one carbon oxide in the presence of a second catalyst to form solid carbon and a second tail gas.
  • the system may also include heating systems, refrigeration systems, compressors, etc.
  • FIG. 1 is a block diagram depicting a system for forming ammonia and solid carbon products, and illustrates some embodiments of the method
  • FIGS. 2-7 are charts graphically illustrating some data from Examples 1-22;
  • FIGS. 8-81 are scanning electron microscopy (SEM) images of some samples of carbon formed in Examples 1-22;
  • FIG. 82 is a chart graphically illustrating some data from Examples 23-26.
  • FIGS. 83-90 are SEM images of some samples of carbon formed in Examples 23-26.
  • This disclosure includes methods and systems for forming ammonia and solid carbon products from hydrocarbons in linked (e.g., parallel or series) processes.
  • a hydrocarbon source is treated to remove sulfur-containing products and form a purified hydrocarbon gas.
  • a first portion of the hydrocarbon gas reacts with water in a wet-reforming reaction to form carbon monoxide and hydrogen.
  • the carbon monoxide may further react with water to form carbon dioxide and hydrogen.
  • the hydrogen after removal of the carbon oxides, reacts with nitrogen to form ammonia.
  • the carbon oxides from the ammonia-forming process react with a second portion of the hydrocarbon gas to form solid carbon and water.
  • the solid carbon and the water may be used within the process or may be sold or otherwise used for another process or product.
  • the methods disclosed herein may be used to beneficially use carbon oxides, a material that may be conventionally considered a waste, to form useful products.
  • carbon oxide means and includes carbon monoxide, carbon dioxide, or any combination of carbon monoxide, carbon dioxide, and one or more other materials (e.g., nitrogen, argon, methane, oxygen, etc.).
  • the term "catalyst” means and includes a material formulated to promote one or more reactions described herein.
  • a portion of a catalyst may be removed from a surrounding portion of the catalyst during some reactions and contained in or adhered to a solid product, particularly for carbon products. Thus, some of the catalyst may be physically removed during the reaction, and the catalyst may need to be continually replenished.
  • a portion of the catalyst may not therefore be considered a catalyst in the classical sense, but is nonetheless referred to herein and in the art as a "catalyst,” if the reaction is not believed to alter chemical bonds of the material forming the catalyst.
  • Particularly useful "catalysts” include iron, nickel, cobalt, etc., and alloys and mixtures thereof, as described herein and known to promote Haber-Bosch and carbon synthesis reaction chemistries.
  • solid carbon products means and includes any material that comprises carbon and may include any material comprising at least one of one or more of carbon nanotubes and one or more carbon nanofibers.
  • Solid carbon products may be useful in various applications, such as filters, reactors, electrical components (e.g., electrodes, wires, batteries), structures (e.g., beams, frames, pipes), fasteners, molded parts (e.g., gears, bushings, pistons, turbines, turbine blades, engine blocks), etc.
  • Such solid carbon products may exhibit enhanced properties (e.g. , strength, electrical or thermal conductivity, specific surface area, porosity, etc.) with respect to conventional materials.
  • This disclosure includes a new class of materials that contain a plurality of CNTs, a plurality of carbon nanofibers, or a combination thereof formed into solid shapes under pressure. When such solid shapes are sintered, covalent bonds form between at least some of the CNTs, the carbon nanofibers, or both forming solid shapes. This material has numerous useful properties.
  • FIG. 1 depicts a process flow diagram of one embodiment of a system 100 for forming ammonia and solid carbon products and a method that may be performed using the system 100.
  • the system 100 is divided into several subsystems for illustration purposes.
  • the system 100 includes a conditioning subsystem 104, a reforming subsystem 110, a separation subsystem 120, an ammonia synthesis subsystem 130, a carbon synthesis subsystem 140, and a separation subsystem 150.
  • the subsystems are shown separately, but two or more of the subsystems may be combined into a single apparatus.
  • the system 100 may also include other subsystems, such as for heating, cooling, pressurizing, or controlling the flow of materials.
  • a source gas 102 containing a hydrocarbon enters the conditioning subsystem 104, which is configured to remove various impurities 106 to form a purified source gas 108.
  • the conditioning subsystem 104 may include a filter, an adsorption unit, a compressor and/or any other means to prepare the source gas 102 for reaction in subsequent operations.
  • the conditioning subsystem 104 is configured to remove impurities 106 that poison some catalysts, such as hydrogen sulfide, mercaptans, or chlorine.
  • the conditioning subsystem 104 may include activated carbon, on which the impurities 106 adsorb.
  • the conditioning subsystem 104 may be a packed bed, a fluidized bed, or any other appropriate device.
  • the conditioning subsystem 104 may be configured to process a larger amount of the source gas 102 than a conditioning subsystem of a conventional ammonia-production system having an ammonia-production capacity similar to the system 100, because the conditioning subsystem 104 also provides a portion of the purified source gas 108 to the carbon synthesis subsystem 140.
  • the source gas 102 may optionally include some carbon oxides or other gases. If present, the carbon oxides may be beneficially used in the same manner as carbon oxides formed in the system 100, and described in more detail below.
  • the source gas 102 may be a well gas, a purified natural gas (e.g., as provided by a public utility) or another natural or industrial source of hydrocarbons.
  • the purified source gas 108 may be divided into two or more portions. As shown in FIG. 1, a first portion of the purified source gas 108 enters the reforming subsystem 110 and a second portion of the purified source gas 108 enters the carbon synthesis subsystem 140.
  • the reforming subsystem 110 is also configured to receive water 112, and is operated at conditions that promote the formation of a reformed gas 114 through steam reforming. For example, if the purified source gas 108 includes methane, the reforming subsystem 110 may be operated to promote the reaction of methane with water to form carbon monoxide and hydrogen, as shown in Reaction 2, above. The carbon monoxide may be converted to carbon dioxide to form additional hydrogen in the water-gas shift reaction, as shown in Reaction 5, above.
  • the reforming subsystem 110 may be configured to operate in two or more stages. In some embodiments, a first stage of the reforming subsystem 110 produces a partially reformed gas having a lower concentration of hydrocarbons than the purified source gas 108. A second stage of the reforming subsystem 110 produces the reformed gas 114, having an even lower concentration of hydrocarbons.
  • the reforming subsystem 110 may include any number of stages configured to produce a reformed gas 114 at any selected hydrocarbon concentration.
  • the reforming subsystem 110 may be configured to operate at temperatures from about 700°C to about 1,100°C and at pressures from about 300 kPa to about 25 MPa.
  • the reforming subsystem 110 may include one or more catalyst materials, such as silica-supported nickel.
  • the reforming subsystem 110 may also include one or more heaters, such as a gas-fired heater configured to burn hydrocarbons in the presence of oxygen
  • the purified source gas 108 may receive heat through walls of the heater(s) separating combustion products from the purified source gas 108.
  • the reforming subsystem 110 may include a direct-combustion heat source, in which combustion products are mixed with the purified source gas 108, and are combined to form the reformed gas 114. Direct-combustion heating is described, for example, in U.S. Patent Application Publication 2016/0039677, published February 11, 2016, titled “Direct Combustion Heating,” the entire contents of which are incorporated herein by this reference.
  • heater(s) associated with the reforming subsystem 110 may be sized and configured to provide sufficient heat to meet the needs of subsequent operations, such as in the ammonia synthesis subsystem 130 and/or the carbon synthesis subsystem 140. If the heater(s) of the reforming subsystem 110 are large enough, the need to subsequently or separately heat gases may be reduced or eliminated. Operating conditions of the reforming subsystem 110 may be selected to form CO and/or C0 2 in various ratios. In some embodiments, the reforming subsystem 110 may operate at conditions that yield more CO and less C0 2 than reformers in conventional ammonia-production systems, because the CO can be profitably used in the carbon synthesis subsystem 140.
  • the reformed gas 114 may be separated in the separation subsystem 120 into hydrogen 122 and carbon oxides 124.
  • hydrogen 122 and “carbon oxides” 124
  • these gases may include other materials as impurities, such as water, hydrocarbons, nitrogen, etc.
  • the hydrogen 122 may include some amount of carbon oxides
  • the carbon oxides 124 may include some amount of hydrogen.
  • the separation subsystem 120 may be separate from the reforming subsystem 110, as shown in FIG. 1, or the separation subsystem 120 and the reforming subsystem 110 may be combined into a single subsystem.
  • the separation subsystem 120 may include any appropriate means for separating carbon oxides 124 from hydrogen 122 that are known in the art and not described in detail herein, such as amine absorption or physical absorption in a solvent.
  • the hydrogen 122 enters the ammonia synthesis subsystem 130, which is configured to promote the formation of ammonia 134.
  • Nitrogen 132 also enters the ammonia synthesis subsystem 130, and the nitrogen 132 reacts with the hydrogen 122, such as in the Haber-Bosch process (Reaction 1, above).
  • the ammonia synthesis subsystem 130 may operate at temperatures from about 250°C to about 800°C, such as from about 300°C to about 550°C.
  • the ammonia synthesis subsystem 130 may operate at pressures from about 10 MPa (about 1450 psi) to about 40 MPa (about 5,800 psi), such as at pressures from about 13.8 MPa (about 2000 psi) to about 34.5 MPa (about 5,000 psi). Because the ammonia synthesis subsystem 130 may operate at high pressures, the components of the ammonia synthesis subsystem 130 are typically designed to withstand such conditions. For example, reaction vessels, pipes, and associated equipment may be formed to have steel walls.
  • the ammonia synthesis subsystem 130 may be configured such that the nitrogen 132 and the hydrogen 122 react in the presence of a catalyst. Catalysts may lower the temperature and/or pressure required to form ammonia. Suitable catalysts may include, for example, iron or steel with or without minor amounts of oxides (e.g., K 2 0, CaO, Si0 2 , or Al 2 0 3 ).
  • the ammonia 134 formed in the ammonia synthesis subsystem 130 is generally removed from the ammonia synthesis subsystem 130 in gaseous form (i.e., as anhydrous ammonia, NH 3 ), and may be liquefied for storage and transport.
  • the ammonia 134 may be processed by conventional methods, stored, transported, or sold.
  • the ammonia 134 may be compressed for storage and transport in pressurized tanks.
  • ammonia may be absorbed in water to form aqueous ammonia (NH 4 OH).
  • Anhydrous and aqueous ammonia have industrial uses, and either may be sold as a commodity or processed to form another material.
  • anhydrous ammonia may be mixed with concentrated nitric acid to form ammonium nitrate (NH 4 N0 3 ), which may be used as a fertilizer or as a component of explosives.
  • the carbon oxides 124 and the second portion of the purified source gas 108 enter the carbon synthesis subsystem 140.
  • the carbon oxides 124 and the second portion of the purified source gas 108 may be compressed before entering the carbon synthesis subsystem 140 or within the carbon synthesis subsystem 140. That is, the carbon synthesis subsystem 140 may in some embodiments include one or more compressors.
  • the carbon synthesis subsystem 140 may be structured and configured to promote reactions between the purified source gas 108 and the carbon oxides 124 to form a tail gas 142 containing solid carbon and water:
  • the carbon synthesis subsystem 140 includes one or more catalysts formulated to promote the formation of solid carbon.
  • Some metals from Groups 2-15 of the periodic table such as from groups 5-10, (e.g., nickel, molybdenum, chromium, cobalt, tungsten, iron, manganese, ruthenium, platinum, iridium, etc.) actinides, lanthanides, alloys thereof, and combinations thereof accelerate the reaction rate of Reaction 7 under certain conditions.
  • catalysts include iron, nickel, cobalt, molybdenum, tungsten, chromium, and alloys thereof.
  • the periodic table may have various group numbering systems.
  • group 2 is the group including Be
  • group 3 is the group including Sc
  • group 4 is the group including Ti
  • group 5 is the group including V
  • group 6 is the group including Cr
  • group 7 is the group including Mn
  • group 8 is the group including Fe
  • group 9 is the group including Co
  • group 10 is the group including Ni
  • group 11 is the group including Cu
  • group 12 is the group including Zn
  • group 13 is the group including B
  • group 14 is the group including C
  • group 15 is the group including N.
  • commercially available metals are used without special preparation. Some suitable catalysts are described in U.S. Patent 8,679,444. Other catalysts are described in, for example, U.S.
  • Patent Application Publication 2015/0078981 published March 19, 2015, titled “Methods for Using Metal Catalysts in Carbon Oxide Catalytic Converters," and U.S. Patent Application Publication 2015/0086468, published March 26, 2015, titled “Methods and Structures for Reducing Carbon Oxides with Non-Ferrous Catalysts,” the disclosures of each of which are incorporated herein in their entirety by this reference.
  • Some catalysts facilitate operations at lower temperatures and pressures.
  • steel e.g., mild steel
  • nanoparticles of the catalyst (which may be referred to as "nanocatalyst") are formed and embedded in the solid carbon. These nanoparticles typically form greater than 0.4% by weight of the solid product. These nanoparticles may remain catalytically active in their solid carbon mounts. Without being bound to a particular theory, it is believed that the grain size and composition of the catalyst, as well as reaction conditions, determine the type and morphology of solid carbon formed.
  • 304 stainless steel appears to catalyze the formation of solid carbon (e.g., carbon nanotubes (CNTs), carbon nanofibers (CNFs)), etc.) under a wide range of temperatures, pressures, and gas compositions.
  • solid carbon e.g., carbon nanotubes (CNTs), carbon nanofibers (CNFs)
  • CNFs carbon nanofibers
  • 316L stainless steel appears to catalyze the formation of solid carbon at significantly higher rates than 304 stainless steel, but may also form various morphologies of carbon.
  • 316L stainless steel may be used as a catalyst to achieve high reaction rates, but particular reaction conditions may be maintained to control product morphology.
  • Catalysts may be selected to include Cr, such as in amounts of about 22% or less by weight.
  • 316L stainless steel contains from about 16% to about 18.5% Cr by weight.
  • Catalysts may also be selected to include Ni, such as in amounts of about 8% or more by weight.
  • 316L stainless steel contains from about 10% to about 14% Ni by weight.
  • Catalysts of these types of steel have iron in an austenitic phase, in contrast to alpha-phase iron used as a catalyst in some conventional processes. Given the good results observed with 316L stainless steel, the Ni and/or Cr may have a synergistic effect with Fe.
  • Oxidation and subsequent reduction of the catalyst surface alter the grain structure and grain boundaries of the catalyst. While not intending to be bound by theory, oxidation appears to alter the surface of the metal catalyst in the oxidized areas. Subsequent reduction may result in further alteration of the catalyst surface.
  • the grain size and grain boundary of the catalyst may be controlled by oxidizing and reducing the catalyst surface and by controlling the exposure time of the catalyst surface to the reducing gas and the oxidizing gas.
  • the oxidation and/or reduction temperatures may be in the range from about 500°C to about 1,200°C, from about 600°C to about 1,000°C, or from about 700°C to about 900°C.
  • the resulting grain size may range from about 0.1 ⁇ to about 500 ⁇ , from about 0.2 ⁇ to about 100 ⁇ , from about 0.5 ⁇ to about 10 ⁇ , or from about 1.0 ⁇ to about 2.0 ⁇ .
  • the catalyst may be an oxidized metal (e.g., rusted steel) that is reduced before or during a reaction forming solid carbon. While not intending to be bound by theory, it is believed that removal of oxides leaves voids or irregularities in the surface of the catalyst material, and increases the overall surface area of the catalyst material.
  • Catalysts may be in the form of nanoparticles or in the form of solid materials including, for example, steel or other bulk metals or as domains or grains and grain boundaries within a solid material. Catalysts may be selected to have a grain size related to a characteristic dimension of a desired diameter of the solid carbon product (e.g., a CNT diameter). Examples of suitable catalysts include elements of Groups 5-10 of the periodic table, actinides, lanthanides, alloys thereof, and combinations thereof. Catalysts may be deposited in the carbon synthesis subsystem 140 in the form of solids, beads, granules, powders, or aerosols.
  • the catalyst in the catalytic converter may need to be replenished from time to time, based on the reactor properties (e.g., volume) and reaction conditions (e.g., temperature, pressure, etc.).
  • Catalyst powder may be formed in or near the reaction zone by injecting an aerosol solution such that upon evaporation of a carrier solvent, a selected particle size distribution results.
  • powdered or particulate catalyst may be entrained in the purified source gas 108 or the carbon oxides 124 delivered to the carbon synthesis subsystem 140.
  • the process may be "tuned" to produce selected morphologies of solid carbon product.
  • the catalyst may be formed over a substrate or support, such as an inert oxide that does not participate in the reactions.
  • the substrate is not necessary; in other embodiments, the catalyst material is an unsupported material, such as a bulk metal or particles of metal not connected to another material (e.g., loose particles, shavings, or shot, such as may be used in a fluidized-bed reactor).
  • Carbon activity (A c ) can be used as an indicator of whether solid carbon will form under particular reaction conditions (e.g., temperature, pressure, reactants, concentrations). While not intending to be bound by theory, it is believed that carbon activity is a key metric for determining which allotrope of solid carbon is formed. Higher carbon activity tends to result in the formation of CNTs, lower carbon activity tends to result in the formation of graphitic forms.
  • Carbon activity for a reaction forming solid carbon from gaseous reactants can be defined as the reaction equilibrium constant times the partial pressure of gaseous products, divided by the partial pressure of reactants.
  • the carbon activity A c is defined as K-(P mo 2 Pco 2 'Pc H d-
  • a c is directly proportional to the square of the partial pressure of H 2 0, and inversely proportional to the partial pressures of CH 4 and C0 2 .
  • the carbon activity of this reaction may also be expressed in terms of mole fractions and total pressure: where P T is the total pressure and Y is the mole fraction of a species. Carbon activity generally varies with temperature because reaction equilibrium constants vary generally with temperature. Carbon activity also varies with total pressure for reactions in which a different number of moles of gas are produced than are consumed. Mixtures of solid carbon allotropes and morphologies thereof can be achieved by varying the catalyst(s) and the carbon activity of the reaction gases in the reactor
  • the reaction conditions including the temperature and pressure in the reaction zone, the residence time of the reaction gases, and the grain size, grain boundary, and chemical composition of the catalyst(s) may be controlled to obtain solid carbon products having selected characteristics.
  • the purified source gas 108 and the carbon oxides 124 are recycled through the reaction zone and passed through a condenser with each cycle to remove excess water and to control the partial pressure of the water vapor in the carbon synthesis subsystem 140. Because the partial pressure of water vapor affects the carbon activity, water vapor appears to affect the type and character (e.g., morphology) of solid carbon formed, as well as the kinetics of carbon formation.
  • Reaction conditions of the carbon synthesis subsystem 140 may be optimized to produce a selected type, morphology, purity, homogeneity, etc. of the solid carbon 152.
  • conditions may be selected to promote the formation of CNTs.
  • the solid carbon 152 includes allotropes of carbon or morphologies thereof, including graphite, pyrolytic graphite, graphene, carbon black, fibrous carbon, buckminsterfullerenes, single-wall CNTs, or multi-wall CNTs.
  • the carbon synthesis subsystem 140 may operate at any pressures including pressures of from near vacuum to about 30 MPa (300 bar), such as from about 100 kPa (1.0 bar) to about 1000 kPa (10 bar). In general, higher pressures correspond to faster reaction rates and a shift in equilibrium to the desired products.
  • the carbon synthesis subsystem 140 may operate at temperatures of from about 550°C to about 1200°C, such as from about 650°C to about 800°C.
  • the carbon synthesis subsystem 140 may include two or more reaction vessels.
  • one reaction vessel may operate at conditions favorable to a first step of a reaction, and another reaction vessel may operate at conditions favorable to a second step of a reaction.
  • the carbon synthesis subsystem 140 may include any number of reaction vessels or regions in which materials may react, depending on the particular reactions expected to occur.
  • Each reaction vessel may be configured and operated to optimize a reaction step.
  • reaction vessels may operate at different temperatures or pressures from one another.
  • the tail gas 142 may enter the separation subsystem 150, which is configured to separate solids, liquids, and/or gases.
  • the separation subsystem 150 may be configured to remove solid carbon 152 from water 154 and a recycle gas 156.
  • the separation subsystem 150 may include any device operable to separate particulate matter from gases.
  • the separation subsystem 150 may include a cyclone, a scrubber, an elutriate r, a filter, an electrostatic precipitator, a bag house, a condenser, etc., or any combination thereof.
  • the recycle gas 156 leaving the separation subsystem 150 may be gaseous, and may be substantially free of solids.
  • the recycle gas 156 may include less than about 1%, less than about 0.1%, or even less than about 0.05% solids by mass. Techniques for separation of solids from liquids and gases depend upon the type of equipment of the carbon synthesis subsystem 140 and the expected composition of the tail gas 142.
  • the separation subsystem 150 may include two or more devices operated in series or parallel to provide selected purity (i.e., absence of solids) of the recycle gas 156.
  • the recycle gas 156 may be recycled to another subsystem in the system 100, such as to the conditioning subsystem 104 or the carbon synthesis subsystem 140 (after optionally heating and/or compressing the recycle gas 156). In some embodiments, the recycle gas 156 or a portion thereof may be vented to the atmosphere, for example after appropriate treatment.
  • the solid carbon 152 removed from the separation subsystem 150 may be sold as a commercial product, used in the production of another product, stored for long-term sequestration, etc.
  • a lock hopper system may be used to remove the solid carbon 152 from the carbon synthesis subsystem 140 or from the separation subsystem 150.
  • the lock hopper system may also include a means for cooling the solid carbon 152 to a temperature below the oxidation temperature of the product in air prior to discharging.
  • a lock hopper system or other separation means may control the release of gases to the atmosphere and may purge the solid carbon 152 of reaction gases prior to removal of the solid carbon 152 from the system 100.
  • Other suitable means may used for removing the solid carbon 152 from the system 100 that conserve reaction gases and minimize worker and environmental exposure to the reaction gases.
  • the water 154 leaving the separation subsystem 150 is used within the system 100.
  • the water 154 may be used as the water 112 or to process the ammonia 134 leaving the ammonia synthesis subsystem 130.
  • the water 154 and the ammonia 134 may each enter a scrubber operable to absorb the ammonia 134 in the water 154.
  • the scrubber may include a spray nozzle, a packed tower, an aspirator, etc.. Any remaining gases may be processed as waste or recycled within the system 100.
  • the carbon synthesis subsystem 140 may include two or more reactors configured to operate in series. Each reactor may be configured and operated to optimize formation of solid carbon and water, and water may be removed between the two reactors. Removal of water may promote reactions between the purified source gas 108 and the carbon oxides 124 (e.g., Reaction 7, above) by shifting the equilibrium. Appropriate separation equipment, compressors, heaters, coolers, etc. may be used between reactors, such as the separation subsystem 150 described herein.
  • the carbon synthesis subsystem 140 may be a batch reactor, a continuous-flow reactor, or a semi-continuous- flow reactor (e.g., configured to be operated for a period of time, then shut down for a period of time, such as to regenerate or replace the catalyst).
  • a solid catalyst or catalyst mounted on a solid substrate is moved through a flowing gas stream, the resulting solid carbon is harvested, and the solid surface is renewed and reintroduced to the carbon synthesis subsystem 140.
  • the solid substrate may be the catalyst material (e.g., a solid piece of a chromium-, molybdenum-, cobalt-, iron-, or nickel-containing alloy or superalloy) or a surface on which the catalyst is mounted.
  • the carbon synthesis subsystem 140 includes a fluidized-bed reactor designed to retain the catalyst while allowing the solid carbon to be entrained in the flow of the tail gas 142 and to be lofted out of the reaction zone upon reaching a desired size.
  • the shape of the reactor and the gas flow rates influence the residence time of the elutriates and the corresponding size of the solid carbon (such as the length of CNTs or CNFs).
  • the carbon synthesis subsystem 140 may include one or more batch reactors in which the catalyst is either a fixed solid surface (e.g., the catalyst may be a steel plate) or is mounted on a fixed solid surface (e.g., catalyst nanoparticles deposited on an inert substrate).
  • the catalyst is either a fixed solid surface (e.g., the catalyst may be a steel plate) or is mounted on a fixed solid surface (e.g., catalyst nanoparticles deposited on an inert substrate).
  • solid carbon is grown on the catalyst, and the catalyst and solid carbon 152 are periodically removed from the carbon synthesis subsystem 140 (e.g., instead of or in addition to a distinct separation subsystem 150).
  • the carbon synthesis subsystem 140 may include continuous reactors, wherein the solid carbon 152 is removed from the catalyst as the solid carbon 152 is formed.
  • Some reactant concentrations in the system 100 may be selected to be stoichiometric or near-stoichiometric. That is, the gases may include concentrations and flow rates of reactants (carbon oxide, nitrogen, methane, etc.) that, if fully reacted, would be entirely or almost entirely consumed.
  • the hydrogen 122 may be provided at a molecular flow rate of about three times the molecular flow rate of the nitrogen 132. This mixture, if fully reacted according to Reaction 1, would consume approximately all of the hydrogen 122 and the nitrogen 132 within the ammonia synthesis subsystem 130.
  • Other mixtures may be selected to react according to particular reactions or to obtain a particular product.
  • compositions of gases in some subsystems may be in a ratio other than near stoichiometric.
  • the compositions of gases may be selected based on economics, process controls, environmental regulations, etc.
  • inert gases are present in the system 100, such as argon. In such cases, appropriate venting may control the accumulation of inert gases in the process gas streams if the system recirculates significant portions of the gas.
  • FIGS. 2 and 3 illustrate the relationship between differing gas ratios on the rates of formation of solid carbon.
  • FIGS. 2 and 3 were generated based on data collected in Examples 1-22, described below.
  • FIG. 2 illustrates the highest rate of carbon formation observed at various H 2 :CO ratios in the presence of S-70 carbon-steel shot, as determined in Examples 1-11, with each point on FIG. 2 corresponding to one of these Examples.
  • FIG. 3 illustrates the highest rate of carbon formation observed at various H 2 :(CO+C0 2 ) ratios in the presence of S-70 carbon-steel shot observed in Examples 12-22.
  • FIG. 3 shows that, for the experimental conditions of Examples 12-22, H 2 :(CO+C0 2 ) ratios of about 1.0 or less appear to yield higher rates of carbon formation than higher H 2 :(CO+C0 2 ) ratios.
  • FIGS. 4 and 5 illustrate the relationship between BET surface area of carbon formed and the H 2 :CO or
  • H 2 :(CO+C0 2 ) ratios were, in Examples 1-22.
  • the solid carbon that had the highest growth rate was tested for each gas ratio.
  • Specific surface area may be an indicator of the type of solid carbon formed because some morphologies, such as CNTs, have higher BET surface areas than others, such as amorphous carbon.
  • FIG. 4 shows that, for the experimental conditions of Examples 1-11, H 2 :CO ratios from about 0.7 to about 1.2 appear to yield carbon having higher BET surface areas than other H 2 :CO ratios.
  • FIG. 5 shows that, for the experimental conditions of Examples 12-22, H 2 :(CO+C0 2 ) ratios of about 1.0 and higher appear to yield carbon having higher BET surface areas than lower H 2 :(CO+C0 2 ) ratios.
  • FIG. 6 illustrates the relationship between temperature on the rates of formation of solid carbon for Examples 1-22. As shown in FIG. 6, under the conditions of Examples 1-22, the highest rates of formation may occur from about 500°C to about 750°C.
  • FIG. 7 illustrates the relationship between the BET surface area and the rates of formation of solid carbon.
  • Heat may be recovered from the ammonia 134, the water 154, the recycle gas 156, or any other material within the system 100, such as by passing the water 154 and the source gas 102 through one or more heat exchangers. Such heat recovery may be an effective way to recover a portion of the process heat and help bring the reactants to reaction temperature. Any gas or liquid streams may be processed as known in the art for overall energy optimization.
  • the tail gas 142 may be maintained above the dew point of the water vapor in the tail gas 142 prior to separation of the solid carbon 152 from the water 154 and the recycle gas 156 to limit or prevent the condensation of water in or on the solid carbon 152.
  • the system 100 may include one or more heaters configured to provide the heating needs of the system 100.
  • the system 100 may also include one or more refrigeration systems or condensers configured to provide the cooling needs of the system 100.
  • a single unit may provide refrigeration to condense methane from the reformed gas 114, ammonia 134 formed in the ammonia synthesis subsystem 130, and water 154 formed in the carbon synthesis subsystem 140.
  • a portion of the solid carbon 152 formed in the carbon synthesis subsystem 140 may be used in the conditioning subsystem 104.
  • the solid carbon 152 may be used in the conditioning subsystem 104 to remove impurities 106, such as by adsorption.
  • the solid carbon 152 may be processed to increase its specific surface area or to make it suitable for use in the conditioning subsystem 104 ⁇ e.g., pressed into pellets).
  • the solid carbon 152 may be used as formed in the carbon synthesis subsystem 140.
  • carbon oxides formed in the reforming subsystem 110 may be beneficially used in the carbon synthesis subsystem 140.
  • water formed in the carbon synthesis subsystem 140 may be beneficially used for recovery of ammonia 134 formed in the ammonia synthesis subsystem 130.
  • the combined system 100 may have greater efficiencies than the ammonia synthesis subsystem 130 and the carbon synthesis subsystem 140 operating alone.
  • quartz tube 1.5 cm wide, and the boats were inserted end-to-end into a quartz tube having an inner diameter of about 2.54 cm and a length of about 1.2 m.
  • the quartz tube was then placed in a tube furnace.
  • the quartz tube was purged with hydrogen gas to reduce the surface of the coupons before the tube furnace was heated to operating conditions.
  • reaction gases were introduced into the quartz tube (i.e., flowed continuously through the quartz tube) such that both the upper and lower surfaces of each coupon were exposed to reaction gas.
  • the temperature, pressure, and gas composition were measured at each coupon. After the test, the samples were removed from the quartz tube.
  • the catalyst used for Examples 1-22 was S-70 steel shot, which comprises carbon steel having from about 0.10% to about 0.15% C, from about 0.10% to about 0.25% Si, from about 1.20% to about 1.50% Mn, from about 0.05% to about 0.15% Al, up to about 0.035% P, and up to about 0.035% S, with the remainder Fe.
  • S-70 shot has a particle size distribution such that all the material passes through a #40 sieve, and at least 90% of the material is retained by a #120 sieve.
  • Example 1 H,: CO ratio of 1.0
  • a reaction gas containing about 45% H 2 , 45% CO, and 10% Ar was introduced into the quartz tube at about 310 kPa.
  • the reaction gas had an H 2 :CO ratio of about 1.0.
  • the gases flowed over the shot for about 30 minutes at 1200 seem (standard cubic centimeters per minute). Methane, carbon dioxide, and water were also formed in the quartz tube.
  • FIG. 8 SEM image FIG. 8 FIG. 9 FIG. 10 FIG. 11 FIG. 12
  • Example 2 H,:CO ratio of 0.6
  • Example 3 H,:CO ratio of 0.7
  • Example 4 H,:CO ratio of 0.8
  • FIG. 36 SEM image FIG. 36 FIG. 37 FIG. 38 FIG. 39 FIG. 40
  • Example 5 H,:CO ratio of 0.9
  • Example 6 H,: CO ratio of 1.0
  • Example 7 H?: CO ratio of 1.1
  • FIG. 63 FIG. 64 FIG. 65 FIG. 66 FIG. 67
  • Example 8 H,: CO ratio of 1.2
  • Example 9 H,: CO ratio of 1.3
  • Example 10 H,: CO ratio of 1.4
  • Example 12 H,:(CO+CO?) ratio of 0.6
  • Example 13 H,:(CO+CO,) ratio of 0.7
  • Example 14 H,:(CO+CO,) ratio of 0.8
  • Example 15 H,:(CO+CO?) ratio of 0.9
  • Example 16 H,:(CO+CO?) ratio of 1.0
  • Example 17 H,:(CO+CO,) ratio of 1.1
  • Example 18 H,:(CO+CO,) ratio of 1.2
  • Example 19 H,:(CO+CO?) ratio of 1.3
  • Example 20 H,:(CO+CO,) ratio of 1.4
  • Example 21 H,:(CO+CO,) ratio of 1.5
  • Example 22 H,:(CO+CO?) ratio of 0.6
  • Example 23 H,:CO ratio of 0.8, 310 kPa
  • reaction gases having an H 2 :CO ratio of about 0.8 were provided at about 310 kPa. Methane, carbon dioxide, and water were formed in the quartz tube. After the test, approximately 0.814 g of liquid water was collected.
  • Example 24 H?:CO ratio of 0.8.4.0 lYIPa
  • reaction gases having an H 2 :CO ratio of about 0.8 were provided at about 4.0 MPa. Methane, carbon dioxide, and water were formed in the quartz tube. After the test, approximately 3.351 g of liquid water was collected. Table 24 : Solid Carbon Formation with an H 2 : CO ratio of 0.8
  • Example 25 H,:CO ratio of 0.8, 4.0 MPa
  • reaction gases having an H 2 :CO ratio of about 0.8 were provided at about 4.0 MPa. Methane, carbon dioxide, and water were formed in the quartz tube. After the test, approximately 1.64 g of liquid water was collected.
  • Example 26 H,:CO ratio of 0.8, 4.0 MPa
  • reaction gases having an H 2 :CO ratio of about 0.8 were provided at about 2.1 MPa. Methane, carbon dioxide, and water were formed in the quartz tube. After the test, approximately 1.751 g of liquid water was collected.

Abstract

Des procédés de formation simultanée d'ammoniac et de produits carbonés solides comprennent la mise en réaction d'une première partie de gaz naturel en présence d'eau pour former de l'hydrogène et au moins un oxyde de carbone ; la séparation de l'hydrogène et du ou des oxydes de carbone ; la mise en réaction de l'hydrogène avec de l'azote en présence d'un premier catalyseur pour former un premier gaz résiduaire comprenant de l'ammoniac ; et la mise réaction d'une seconde partie de gaz naturel avec le ou les oxydes de carbone en présence d'un second catalyseur pour former du carbone solide et un second gaz résiduaire. Les procédés peuvent également comprendre l'élimination du soufre de la source de gaz naturel. Un système de production simultanée d'ammoniac et de carbone solide peut comprendre une unité de conditionnement, un reformeur de méthane, un séparateur, un premier réacteur et un second réacteur.
PCT/US2017/063527 2016-11-28 2017-11-28 Procédés et systèmes de formation d'ammoniac et de produits carbonés solides WO2018098495A1 (fr)

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JP2000178467A (ja) * 1998-12-17 2000-06-27 Shimadzu Corp アンモニア製造工程排出ガス利用カーボンブラック製造装置
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