WO2024163236A2 - Procédé électrothermique, matériaux, système et appareil - Google Patents

Procédé électrothermique, matériaux, système et appareil Download PDF

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WO2024163236A2
WO2024163236A2 PCT/US2024/012763 US2024012763W WO2024163236A2 WO 2024163236 A2 WO2024163236 A2 WO 2024163236A2 US 2024012763 W US2024012763 W US 2024012763W WO 2024163236 A2 WO2024163236 A2 WO 2024163236A2
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fluid
silicon carbide
conductive silicon
permeable matrix
granules
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PCT/US2024/012763
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English (en)
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Yakov E. Kutsovsky
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Washington Mills Management, Inc.
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    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • 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
    • 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
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00398—Controlling the temperature using electric heating or cooling elements inside the reactor bed
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00407—Controlling the temperature using electric heating or cooling elements outside the reactor bed
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/0015—Controlling the temperature by thermal insulation means
    • B01J2219/00155—Controlling the temperature by thermal insulation means using insulating materials or refractories
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0263—Ceramic
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2461—Heat exchange aspects
    • B01J2219/2467—Additional heat exchange means, e.g. electric resistance heaters, coils
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides

Definitions

  • the present disclosure relates to an electrothermal reaction system and electrofluid reactor apparatus, and more particularly, to an electrothermal process, materials and system for chemical manufacturing, and a fluid-permeable matrix comprising conductive silicon carbide materials having selected conductivity properties, chemical compositions, and physical characteristics.
  • Described herein are example embodiments of electrothermal processes and materials, electrothermal reaction systems, an electro-fluid apparatus, and a fluid-permeable matrix comprising selected conductive silicon carbide materials, all suitable for carrying out high temperature processes and reactions, including those carried out in demanding and corrosive environments.
  • the example embodiments described below offer unexpected solutions to significant challenges posed by electrification of conventional combustion elements in high temperature industrial operations and allow for the efficient use of electrical energy produced by renewable wind, solar and water sources, or by nuclear power, and thus offers a viable path to the goal of carbon neutral operation of chemical processes and systems.
  • the example embodiments may be used, for example, to enable in-situ heating, yield more efficient heat transfer, reduce waste heat, enable the design and construction of smaller and less complex reactor components, replace conventional steam boilers and fuel burners, can replace conventional heat exchange units, reduce startup and shutdown times, can reduce fouling of equipment caused by combustion processes, and reduce maintenance relative to conventional combustion equipment and designs presently used to supply chemical reaction enthalpy.
  • These benefits in high temperature chemical manufacturing operations are enabled by unlocking the underutilized high thermal conductivity and unique electrical conductivity and resistivity properties at high temperatures that are characteristic of the conductive silicon carbide as further described below.
  • Figure 1 is a schematic view that illustrates examples of an apparatus for carrying out an electrothermal process for chemical manufacturing in accordance with embodiments of the present disclosure.
  • Figure 2 is a flowchart illustrating an example of an electrothermal reaction system for using electrical energy for heating either thermal process fluids or reaction fluids to supply reaction enthalpy to a thermal reaction and make a product in accordance with an embodiment of the present disclosure.
  • Electrothermal systems suitable for these purposes are desirable, and especially desirable are those capable of delivering reaction enthalpy in acceptable quantities and in acceptable forms for implementation into existing processes, systems and reactions now utilizing combustion elements.
  • An electrothermal reaction system and electro-fluid reactor apparatus and more particularly, an electrothermal process for chemical manufacturing, and materials for a fluid- permeable matrix comprising conductive silicon carbide having selected electrical properties, chemical compositions and physical characteristics, are disclosed.
  • an electrothermal process for chemical manufacturing comprises: a) supplying electrical energy to a fluid-permeable matrix comprising conductive silicon carbide having resistance to oxidation and gasification and thermal stability; b) conducting the electrical energy through the fluid-permeable matrix to convert the electrical energy into thermal energy and heat the fluid-permeable matrix to generate a heated fluid-permeable matrix; c) passing at least one fluid through the heated fluid-permeable matrix to generate a heated fluid; and e) introducing the heated fluid into at least one chemical manufacturing process.
  • an electrothermal reaction system comprises: a) at least one means to input electrical energy; b) at least one means for converting the electrical energy into thermal energy by conducting the electrical energy through a fluid-permeable matrix to heat the fluid- permeable matrix, the means comprising conductive silicon carbide having resistance to oxidation and gasification and thermal stability, thereby generating a heated fluid- permeable matrix; c) at least one means for introducing at least one fluid into the heated, fluid- permeable matrix and passing the fluid through the heated fluid-permeable matrix to generate a heated fluid having a temperature of 200° C to 1500° C; d) at least one means for removing the heated fluid from the fluid permeable matrix; and e) at least one means for transferring thermal energy from the heated fluid to a substrate.
  • a fluid-permeable matrix comprises conductive silicon carbide granules, wherein the conductive silicon carbide granules comprise 80 to 99%, by weight, silicon carbide, and the conductive silicon carbide granules are characterized by a conductivity of at least 1 x 10 2 S/m, at a temperature in the range from 300° to l,300°C, and at least one of a) and b): a) an average particle size of 0.2 mm to 25 mm; or b) a packed bed porosity of 30 to 60%, by volume of the fluid-permeable matrix; and the conductive silicon carbide comprising 1 to 20%, by weight, of at least one other material selected from dopants, secondary phases, and reactants, and combinations thereof; and wherein the fluid-permeable matrix comprising the conductive silicon granules is permeable to fluid flow at a velocity from 10 to 250 m/s.
  • a fluid-permeable matrix comprises conductive silicon carbide granules, wherein the conductive silicon carbide granules comprise 80 to 99%, by weight, silicon carbide, and the conductive silicon carbide granules are characterized by conductivity of at least 1 x 10 2 S/m and a maximum volume resistivity of 1 x 10 2 fl.cm at a temperature in the range from 300° to l,300°C, and at least one of a) and b): a) an average particle size of 0.2 mm to 25 mm; or b) a packed bed porosity of 30 to 60%, by volume, of the fluid-permeable matrix; and the conductive silicon carbide comprising 1 to 20%, by weight, of at least one other material selected from dopants, secondary phases, and reactants, and combinations thereof; and wherein the fluid-permeable matrix comprising the conductive silicon granules is permeable to fluid flow at a velocity from 10 to 250 m
  • conductive silicon carbide granules comprising 80 to 99%, by weight, silicon carbide and 1 to 20%, by weight, of at least one other material selected from dopants, secondary phases, and reactants, and combinations thereof, and characterized by: (a) an electrical conductivity from 1 x 10 2 S/m, at a temperature in the range from 300° to l,300°C, (b) an average particle size of 500 pm to 10 mm; (c) from 0 to 45 %, by volume, internal porosity; and (d) a thermal conductivity of 1 to 1,000 W/mK.
  • an electrothermal apparatus for resistively heating fluids used in chemical manufacturing to a temperature of 300° to 1300°C comprises (a) a fluid- permeable matrix comprising conductive silicon carbide in a physical form selected from a fluid-permeable packed bed of granules, a fluidized bed of granules, and at least one fluid- permeable porous sintered article, and combinations thereof; (b) an electrical circuit; and (c) a fluid circulator.
  • the use of electrical energy produced by renewal wind, solar and water sources, or by nuclear power may progress towards, and may achieve carbon neutral operation of chemical processes and systems.
  • the fluid-permeable matrix utilized in the electrothermal system, process and apparatus comprises conductive silicon carbide materials having electrical conductivity properties across a temperature range from about 300 to 1,300° C that are suitable for carrying out the efficient conversion of electrical energy to thermal energy.
  • conductive silicon carbide and “conductive silicon carbide materials” mean a material characterized by an electrical conductivity of at least 1 x 10 2 S/m at a temperature range from 300° to l,300°C, or a conductivity of 1 x 10 2 to 5 x 10 4 S/m, at a temperature range from 300° to l,300°C, or a conductivity of 1 x 10 2 to 1 x 10 4 S/m at a temperature range from 300° to 700°C, or a conductivity of 5 x 10 2 to 1 x 10 4 S/m at a temperature range from 500° to l,000°C.
  • conductive materials refers to electrically conductive materials.
  • the conductive silicon carbide materials having an electrical conductivity of at least 1 x 10 2 S/m at 300° to 1,300°C may be further characterized by a maximum volume resistivity of 1 x 10 2 ⁇ .cm measured at 25°C, or 4 x 10 ⁇ .cm measured at 25°C, or 1 ⁇ .cm measured at 25°C, consistent with the chemical and material properties of the conductive silicon carbide materials selected and fabricated for use herein.
  • the conductive silicon carbide materials having an electrical conductivity of at least 1 x 10 2 at a temperature range of 300° to l,300°C may be further characterized by a volume resistivity at a temperature range of 300° to 1 ,300°C as low as 1 x 10" 4 ⁇ .cm , or a volume resistivity ranging from 1 x I0 2 ⁇ .cm to 1 x 10" 4 ⁇ .cm.
  • a dense crystalline silicon carbide bulk particulate material (the “source material” or “source materials”) is manufactured.
  • the source materials may be obtained from known processes used to manufacture silicon carbide, such as the Acheson process, pyrolysis processes, fluid bed processes, plasma processes, C VD processes and various other industrial processes used to react silicon with carbon and/or to react their respective precursors, such as sand, silica, silanes and biomass materials. Dopants and dopant precursors may be present in selected raw materials or may be added during the manufacturing process.
  • the silicon carbide reaction products i.e., the source materials, maybe recovered as a fine powder of, e.g., 0.01 to 3 pm, 0.1 pm to 2pm, or 0.1 pm to 1 pm, average particle size, or in larger pieces of various sizes in a range of, e.g., 3pm to 10,000pm, or 30pm to 900pm, or 100pm to 700pm, or 200pm to 500pm, or 0.2mm to 1mm, or 0.2mm to 10mm, or 0.5mm to 10mm, or 1mm to 20mm, average particle size, and in various degrees of purity, as desired for a particular system or process herein.
  • Such source materials recovered from the silicon carbide manufacturing process may be further processed by chemical doping, shaping, blending and sintering, and/or by sizing (e.g., by grinding or milling and screening, sifting, blending, dispersion, or other sizing processes) to yield the conductive silicon carbide materials in an initial form of source materials with a selected chemical composition, type and size.
  • sizing e.g., by grinding or milling and screening, sifting, blending, dispersion, or other sizing processes
  • the term “granule” or “granules” refer to particulate material of an average particle size than can provide fluid flow and packing characteristics to facilitate electrical and thermal conductivity in the fluid-permeable matrix, and for sufficient fluid flow through the fluid-permeable matrix during process operations.
  • the source materials can be dense polycrystalline forms of silicon carbide.
  • the source materials and granules derived from the source materials comprise non-conductive or semi-conductive silicon carbide, and such source materials are then processed further to transform the silicon carbide into the conductive silicon carbide materials by various processes as described below.
  • the raw materials selected to make the source materials, as made, or after a chemical surface doping step render the source materials sufficiently electrically conductive for use as the conductive silicon carbide materials herein.
  • conductive silicon carbide is produced by selecting a dopant in an appropriate form, e.g., an oxide or carbide form, to be further converted to a primary elemental form and further incorporated into silicon carbide during the manufacture of the silicon carbide source materials.
  • a dopant in an appropriate form, e.g., an oxide or carbide form
  • 3-10 weight % weight percent of boron delivered as boric oxide or boron carbide 3-10 weight % weight percent of aluminum delivered as aluminum oxide or aluminum carbide, or 3-10 weight % weight percent of titania delivered as titanium oxide or titanium carbide, may be used in making the source materials.
  • additives may be mixed with carbon sources, e.g., coke or coal, or with silicon sources, e.g., sand, and loaded into an Acheson furnace where the doped conductive silicon carbide source material is produced.
  • the source materials may be transformed merely by a final sizing process to yield the granules of conductive silicon carbide materials suitable for use in the fluid-permeable matrix.
  • the source materials exist as granules of P-type crystals (cubic, C-SiC) of silicon carbide comprising up to 10 weight % aluminum, having an average particle size of 0.2 to 10mm.
  • these source materials are characterized by an electrical conductivity of at least 1 x 10 2 S/m, or ranging from 1 x 10 2 to 5 x 10 4 S/m, at one or more temperatures within the range of 300° to l,300°C.
  • Such P-type crystal conductive silicon carbide may have a maximum volume resistivity of 4 x 10 ⁇ .cm measured at 25°C.
  • the source materials exist as a-type crystals (hexagonal H-SiC) of silicon carbide.
  • Either silicon carbide crystal type of the source materials may comprise other, non-silicon carbide materials (e.g., dopants, secondary phases, or reactants) in amounts sufficient to increase the conductivity of the grains to levels desired herein, i.e., to an electrical conductivity of at least 1 x 10 2 S/m, or within the range of 1 x 10 2 to 5 x 10 4 S/m, at one or more temperatures within the range of 300° to l,300°C.
  • the a-type crystal silicon carbide source materials may be characterized further by a maximum volume resistivity of 1 x 10 2 ⁇ .cm measured at 25°C.
  • the selection and concentration of dopant elements may be designed to control resistivity, e.g., by balancing aluminum or boron acceptors with nitrogen donors.
  • These various crystalline types and chemical compositions of the initially produced conductive source materials may be produced or may be further processed, to have an average particle size of 3pm to 10,000pm, or 30pm to 900pm, or 100pm to 700pm, or 200pm to 500pm, or 0.2mm to 1mm, or 0.2mm to 10mm, or 0.5mm to 10mm, or 1mm to 20mm.
  • the source materials thus obtained typically are characterized by a density of at least 90% of theoretical density, or 93%, or 95%, or 97%, or 98% of theoretical density.
  • These source materials and granules of conductive silicon carbide materials made from the source materials are characterized by a chemical composition comprising 80 to 99%, by weight, silicon carbide, or 80 to 90%, by weight, 85 to 99%, by weight, 90 to 99% by weight, 85 to 95%, by weight, 90 to 95%, by weight, or 93 to 97%, by weight, silicon carbide, with the balance being an amount of from 1 to 20%, by weight, of other materials selected to yield a total of 100%, by weight. Due to the semi-conductive or non-conductive nature of high purity (> 99% by weight) silicon carbide, it is not a suitable material for conversion of electrical energy to thermal energy. In contrast, the conductive silicon carbide materials described herein are not pure SiC compounds.
  • other materials comprise up to 20%, by weight, of other materials, selected from one or more dopants, secondary phases, and reactants, and combinations thereof.
  • other materials means materials other than silicon carbide. Such other materials may include silicon, nitrogen, calcium, aluminum, boron, titanium, gallium, scandium, beryllium, iron, phosphorus, silica, alumina, aluminosilicates, zirconia, mullite, boron oxides and other metal and ceramic oxides, titanium carbide and boron carbide, and up to 10% by weight, of conductive carbonaceous materials (e.g., carbon, carbon black, graphite, graphene, and carbon nanotubes). These other materials are incorporated during the source materials manufacturing process or during posttreatment of source materials, or both.
  • conductive carbonaceous materials e.g., carbon, carbon black, graphite, graphene, and carbon nanotubes.
  • dopants can be combined to achieve desired conductivity.
  • carbon atom doping can be combined with titanium or nitrogen atom doping.
  • Doping with multiple dopants may be carried out in a single manufacturing process to simplify the manufacture of the conductive silicon carbide materials. Introducing such additives to the source materials manufacturing process, for example, introducing metal oxides or metal carbides with the silicon carbide precursors, enables a final uniform distribution of dopant in the source materials.
  • dopants can be brought into the manufacturing process using selected raw materials, comprising, e g., Fe, Al, B, and the like, which are present in the silica raw material and/or in the carbonaceous raw material, to make silicon carbide with appropriate dopant levels.
  • the specific amount of dopant can be determined through calibration measurements of temperature dependent conductivity as a function of dopant amount and is matched to a given design of the electrothermal chemical system.
  • surface doping with Iron (Fe), Aluminum (Al), Titanium ( Ti), Nitrogen (N) and/or Boron (B) atoms can be employed to increase conductivity of source materials by adding from 1 to 15 weight%, or 1 to 7weight %, of one or more corresponding dopant atoms to the source materials.
  • non-stochiometric silicon carbide is created with addition of an excess of silicon or carbon of up to 10 weight % of Si or C atoms, or up to 5 weight % C or Si atoms, under process conditions that preferentially form a solid solution rather than separate phases.
  • This is most readily done in an impregnation process, e.g., with silane addition during post-treatment of the silicon carbide source materials, and after formation of secondary granules or articles (as described below) and before, or after, sintering such fabricated green-stage granules or articles to be later formed or sized into granules.
  • Source material granules having suitable material properties and average particle size for carrying out the processes herein may be deployed directly as the conductive silicon carbide materials in the fluid-permeable matrix, or source materials maybe further processed into granules having such properties before use as the conductive silicon carbide materials in the fluid-permeable matrix.
  • secondary particulate granules are manufactured from the source material.
  • submicron size particles of the source materials are shaped and sintered at temperatures up to and including about 2500°C to form the granules.
  • the source materials are combined with a binder, e.g., a carbonaceous material such as phenolic resin or carbon black, and/or with boron carbide, and/or some combination of yttrium, magnesium or aluminum oxides, and extruded or formed or cut into shapes (e.g., cubes, platelets, rings, discs, grains, spheres, stars, hexagons, cylinders, tubes, honeycombs, etc., of regular or irregular shape and size) prior to sintering.
  • shapes e.g., cubes, platelets, rings, discs, grains, spheres, stars, hexagons, cylinders, tubes, honeycombs, etc., of regular or irregular shape and size
  • shape and size granules of particulate conductive silicon carbide may be formed prior to sintering.
  • Sintering may be carried out by processes such as hot press or pressure-less or iso-pressure processes, extruding, or 3D-printing processes, and combinations of such processes, utilizing, e.g., microwave, laser, recrystallization or reaction sintering elements.
  • the granules may be impregnated with silicon or other metals to enhance conductivity.
  • sintering under pressure is used to make high density, optionally metal impregnated, larger sized articles, or materials of, e.g., about 5-10 cm average particle size.
  • the materials or articles are further processed to reduce the size, yielding granules of desired shapes and dimensions, e.g., to a 0.2 mm to 25 mm average particle size.
  • the average particle size of the conductive silicon carbide granules may range from, e.g., from 500pm to 10 mm, from 700 pm to 5 mm, from 900 pm to 3 mm, from 500 pm to 3mm, from 500 pm to 2 mm, from 0.2 mm to 2 mm, from 0.5 mm to 5 mm, from 0.5 mm to 10 mm, and from 0.2 mm to 25 mm.
  • Granules can be made into different shapes (e.g., cubes, cylinders, spheres, rings, etc.) to optimize uniformity of flow and temperature and to minimize pressure drop.
  • internal porosity of the granules is fabricated in an amount sufficient to enhance fluid flow and avoid pressure drop across the fluid-permeable matrix at a fluid velocity ranging from 10 to 250 m/s, or 25 to 250 m/s, or 50 to 200 m/s, and to enhance thermal conductivity (e.g., to yield a range from 25 to 1,000 W/mK), and, optionally, in an amount sufficient to allow for impregnation with a secondary phase, e.g., aluminum metal.
  • a secondary phase e.g., aluminum metal.
  • granule porosity may range from 0 to 45 %, by volume; from 30 to 40%, by volume; from 35 to 45%, by volume; or from 35 to 40%, by volume, for use in the packed particle bed form of the fluid-permeable matrix.
  • internal porosity of the granules may range from 0 to 40%, by volume, from 5 to 30%, by volume, from 5 to 20%, from 5 to 10%, by volume, from 10 to 30%, by volume, by volume, and from 10 to 20%, by volume.
  • Porosity of the conductive silicon carbide materials is defined as the ratio of its bulk density to its specific density (typically about 3.2 g/cm 3 for silicon carbide), where bulk density is the weight of a sample of the conductive silicon carbide materials divided by the volume of the sample.
  • the silicon carbide granules comprise an internal porosity of up to 30%, by volume, wherein up to 100%, by volume, of the internal porosity is infiltrated with at least 5 weight %, on a silicon carbide granule weight basis, of metal, such as silicon, or aluminum, or a combination thereof.
  • the external porosity i.e., the porosity not internal to the granules, that is present in the fluid-permeable matrix (packed particle bed of granules and sintered article forms) may range from 30 to 60%, by volume, or from 30 to 45%, by volume, of the fluid-permeable matrix comprising the conductive silicon carbide materials.
  • packed bed porosity by volume in the fluid-permeable matrix, average particle size and internal porosity of the granules of conductive silicon carbide materials are selected and adjusted to balance desired fluid velocity, electrical conductivity, material phases, and mechanical and thermal stability of the fluid-permeable matrix, so as to optimize performance for its intended use.
  • Secondary phases e.g., mullite, and dopant oxide or carbide contents, may be tuned to maximize conductivity, and such other materials may be present in the conductive silicon carbide granules at, e.g., 0.1 to 20.0%, by weight, 0.5 to 15%, by weight, 0.8 to 10%, by weight, 1.0 to 10%, by weight, and 1.0 to 5%, by weight, and may comprise compounds present in the source materials, together with additives to the source materials during a further step of their manufacture.
  • Such other materials may be selected from dopants, secondary phase materials and reactant materials, and combinations thereof, and may include, silicon, carbon, graphite, mullite, silica, alumina and aluminosilicates, boron and boron oxides, titanium and titanium carbide, phosphorous, nitrogen, scandium, beryllium, iron and iron oxides, gallium, aluminum and calcium, and various other metal and ceramic oxides as may be naturally occurring in raw materials, and up to 10%, by weight, or, up to 5%, by weight, of conductive carbonaceous materials (e.g., carbon, carbon black, graphite, graphene, and carbon nanotubes).
  • conductive carbonaceous materials e.g., carbon, carbon black, graphite, graphene, and carbon nanotubes.
  • the granules of conductive silicon carbide are impregnated with carbon and boron to enhance conductivity.
  • Conductive silicon carbide source materials are washed with mineral acid to reduce the amount of surface oxygen below about 1%, by weight.
  • Boron carbide particles (used in the process as sintering aids) are washed with mineral acid to reduce surface oxygen below about 1%, by weight.
  • the washed silicon carbide is combined with 5-15%, by weight, of the washed boron carbide, along with a carbon precursor, e.g., phenolic resin in an amount of up to 15%, by weight, preferentially up to 10%, by weight, or a combination of carbon black and carbon precursor, so that the combined amount of added carbon is up to about 15%, preferentially up to about 10%, by weight, based upon the total weight of the conductive silicon carbide mixture.
  • a carbon precursor e.g., phenolic resin in an amount of up to 15%, by weight, preferentially up to 10%, by weight, or a combination of carbon black and carbon precursor, so that the combined amount of added carbon is up to about 15%, preferentially up to about 10%, by weight, based upon the total weight of the conductive silicon carbide mixture.
  • a carbon precursor e.g., phenolic resin in an amount of up to 15%, by weight, preferentially up to 10%, by weight, or a combination of carbon black and carbon precursor, so
  • Extruded material may be cut or further fabricated into desired lengths and sizes, e.g., 0.2 mm to 25 mm, cylinders.
  • conductive doped 0-type crystals of silicon carbide (cubic, C-SiC) are produced by mixing these crystals with carbon or silicon source streams in an electrically heated fluid bed reactor.
  • conductive silicon carbide advantageously provide highly efficient conversion of electrical energy to thermal energy.
  • these conductive silicon carbide materials are characterized by high electrical and thermal conductivity, enabling uniform heating of fluids, and by high mechanical strength and excellent thermal stability, enabling operation in demanding and often corrosive environments at extremely high temperatures, e.g., 500-1500° C, without significant degradation of mechanical strength or functional properties.
  • the conductive silicon carbide has the unique material property of exhibiting a significant reduction in electrical resistivity at high temperatures (as much as a 15X reduction at temperatures of about 450 to 950° C), accompanied by a nonlinear increase in voltage and conductivity, making conductive silicon carbide a uniquely effective material for a resistance heater operated at such high temperatures.
  • resistance to oxidation and gasification means the conductive silicon carbide is chemically stable and does not undergo significant chemical reaction or degradation in the presence of oxygen, steam, or reactive chemicals, such as carbon-based compounds (which gasify to CO 2 and other gases at high temperatures), nor when exposed to pH fluctuations, in high temperature processes.
  • the resistance to oxidation and gasification of the conductive silicon carbide materials offers significant benefits over other electrothermal materials, e.g., those consisting essentially of conductive carbon materials, used in industrial processes and systems (e.g., as in US 2,958,584; US 4,543,240; and Chem. & Eng. News, November 21, 1960, pp 55-56.).
  • Such benefits enabled by this resistance to oxidation and gasification in industrial processes may include the benefit of an operating life of substantially equivalent duration to that of other material and equipment components deployed in combination with the conductive silicon materials.
  • the benefits enabled by this resistance to oxidation and gasification may include the benefit of an operating life at least 10 times longer than the operating life of an electrothermal materials system operated without the conductive silicon carbide.
  • the fluid permeable matrix of conductive silicon carbide materials may undergo oxidation or gasification reactions in temperatures ranging from 300 to 1,300° C at a material loss rate (e.g., a corrosion recession rate) of less than 1,000 ⁇ g/cm 2 -hour, 500 ⁇ g/cm 2 -hour, or less than 300 ⁇ g/cm 2 -hour, or less than 100 ⁇ g/cm 2 -hour.
  • a material loss rate e.g., a corrosion recession rate
  • the fluids heated by direct contact with the conductive silicon carbide in the fluid-permeable matrix may comprise air, oxygen, steam, or hydrocarbon compounds, or combinations thereof, under industrial conditions of chemical manufacturing without significant loss of mechanical, chemical or electrical properties of the conductive silicon carbide over typical periods of operation.
  • thermal stability means, relative to other structural materials (e.g., metal alloys), the fluid permeable matrix, and the conductive silicon carbide contained within it, substantially maintain mechanical strength and dimensional shape and size, without functional degradation across a temperature range from 0° to 1500° C.
  • the granules of conductive silicon carbide materials are characterized by a low coefficient of thermal expansion, e.g., 4.02 x IO" 6 at 0 to 700°C, and a high thermal conductivity of, e.g., 21 W/cm at 1000°C, or 100 W/mK, or 250 W/mK, or greater than 20 W/cm, or from 25 to 500 W/mK, or 50 to 500 W/mK, or 100 to 700 W/mK, or 1 to 1,000 W/mK, or 25 to 1 ,000 W/mK, together with strong resistance to thermal shock across the temperature range of processes disclosed herein
  • thermal conductivity is higher for solid granules relative to porous granules.
  • granules having from 10 to 45%, by volume, internal porosity are characterized by thermal conductivity of 1 to 1,000 W/mK. In an embodiment, granules having from 0 up to 10%, by volume, internal porosity are characterized by thermal conductivity of 25 to 1,000 W/mK.
  • conductive silicon carbide granules may be fabricated with a stochiometric excess of either carbon or silicon, or both, of up to 10 weight % of the silicon carbide, to increase conductivity.
  • the amount of carbon dopant is minimized (e.g., is ⁇ 2% by weight of the silicon carbide) to avoid gasification losses.
  • the porosity may be minimized in systems that benefit from higher mechanical strength, or in conductive silicon carbide materials having lesser amounts of conductive dopants or other materials, so as to yield sufficient conductivity through the granules of conductive silicon carbide materials in the fluid-permeable matrix that otherwise would be characterized by unfavorable percolation properties.
  • Internal porosity may be minimized (e.g., be less than 30%, by volume; or from 0 to 10%, by volume) in granules of silicon carbide materials used in a fluidized bed type of fluid-permeable matrix, wherein fluid velocity is more readily optimized, relative to a packed particle bed of granules, or a sintered porous article form of the fluid-permeable matrix.
  • catalysts are generally not desirable in the conductive silicon carbide materials used in the fluid-permeable matrix, in chemical manufacturing processes wherein the fluid being heated in the fluid-permeable matrix is a reaction fluid, rather than a process fluid, as described below, catalysts may be present at up to about 1 to 3%, by weight, and may comprise catalysts used in the dehydrogenation, isomerization, reformation, or polymerization of hydrocarbons, such as zeolites, iron oxides, platinum and the like. In other embodiments the conductive silicon carbide materials are void of catalysts. Reactants in the form of the reaction fluid may comprise hydrocarbons, the products of hydrocarbon reforming, or other fluid chemical streams.
  • a porous sintered article consists essentially of these selected conductive silicon carbide materials shaped and sintered into the form of a hollow cylinder (e.g., for use with a co-axial electrode), a ring or series of rings, a grid or a series of grids, a rod or series of rods, a plate or a series of plates, a tube or a series of tubes, and so on.
  • the porous sintered article may be sintered in the manner described above for sintered granules, from the same set of starting materials and using the same processes, including, e.g., impregnation processes, to enhance conductivity of the silicon carbide materials.
  • the resulting sintered articles consisting essentially of conductive silicon carbide materials are characterized by resistance to oxidation and gasification, thermal stability, fluid permeability, thermal conductivity and heat capacity essentially equivalent to these characteristics of the conductive silicon carbide granules.
  • the physical arrangement of the conductive silicon carbide materials in the fluid-permeable matrix element of an electrothermal heating unit is selected so as to maintain the silicon carbide granules in electrical contact with one another and, thus, enable a consistent high volume flow of electrons to be conducted upon application of voltage through the fluid- permeable matrix. It has been demonstrated that at the high voltage ranges achievable by means of the fluid-permeable matrix herein, electrons will cross over or tunnel in high electric field, even in the case of poorer electrical contact.
  • electrical energy may be delivered to the fluid-permeable matrix in the form of resistive heat, or in the form of inductive heat, or in a combination of the two.
  • resistive heating is more efficient than other electrical energy options in the operation of the higher (e g., over about 600°) temperature processes herein Tn an embodiment, a combination of resistive and inductive heating is used employing a series of specific electrode designs and placement, prioritizing inductive heating for the lower part of the temperature range, e.g., up to 300 or 400°C, and resistive heating for the higher part of the temperature range, e.g., for temperatures above 300°C.
  • the system and apparatus can be adapted to utilize available electric energy characteristics of a particular operation, e.g., AC or DC voltage, along with a power supply adequate for a selected process, system and apparatus, e.g., with a power supply operating across a range from 5 to 100 MW, 10 to 100 MW, 20 to 100 MW, 20 to 60 MW, 50 to 100 MW, and 20 to 80 MW.
  • the type of voltage and the amount of power supplied may vary across unit operations within a large-scale process or system, and different types and quantities of power may be supplied to different unit operations. Selection of a suitable power source may be guided by geometry and size of the heating vessel containing the fluid-permeable matrix, the voltage and current energy load of a process, and the desired through-put of materials and heated product.
  • DC voltage is supplied to deliver sufficient power (e.g., 20 to 100MW) to cause a current flow of about 200 to 700A across the conductive silicon carbide materials in the fluid-permeable matrix at a temperature in the range of 500 to 1100° C and a fluid velocity of about 50 to 250 m/s, and thereby to yield on the order of about 15 to 30 MT/hour of heated fluid.
  • the fluid- permeable matrix comprises packed granules of, or a sintered porous article of, the conductive silicon carbide materials characterized by resistance to oxidation and gasification and by thermal stability.
  • the fluid-permeable matrix of conductive silicon carbide materials 101 is contained within a vessel 105, having two electrodes 102, with one situated at each of two opposite ends of the fluid matrix, a fluid inlet 103 and a fluid outlet 104. Electrodes 102 are in electrical connection with the fluid-permeable matrix of conductive silicon carbide materials 101, and with an electrical supply circuit (not shown in the Figures).
  • the electrodes and the electrode leads may be constructed with the conductive silicon carbide materials in a sintered article form as described herein.
  • the electrodes 102 are not in electrical connection with the vessel 105 nor with the fluid inlet 103 and fluid outlet 104.
  • the fluid-permeable matrix of conductive silicon carbide materials 101b in the form of packed granules or a sintered porous article, is contained within a vessel 105b, having a fluid inlet 103b and a fluid outlet 104b.
  • the two electrodes 102a and 102b can be coaxially arranged and can, for example, consist of a central electrode 102a situated within the fluid-permeable matrix 101b and an outer electrode 102b situated along the exterior of the fluid-permeable matrix 101b and within the vessel 105b.
  • the Figure IB electrodes 102a and 102b are in electrical connection with the fluid-permeable matrix of conductive silicon carbide materials 101b and with an electrical supply circuit (not shown in the Figures).
  • the electrodes 102a and 102b are not in electrical connection with the vessel 105b nor with the fluid inlet 103b and fluid inlet 104b.
  • the apparatus comprises one or more central electrodes made from sintered articles of conductive silicon carbide with the counter electrode being a sintered cylindrical shell also made from conductive silicon carbide situated within the vessel containing the fluid-permeable matrix.
  • the vessel containing the fluid-permeable matrix may be constructed from various temperature resistant materials having structural stability over a temperature range from 200 to 1500° C. For vessels operated at temperatures over 1000° C, refractory ceramics such as fused alumina and silicon carbide are used in lieu of than metals for structural stability.
  • the apparatus as illustrated in Figure 1A and IB is a direct resistive heat unit suitable for transfer of chemical reaction enthalpy to fluids, including reaction fluids, such as hydrocarbon streams, and process fluids, such as air and steam that function to transfer heat indirectly, supplying the necessary enthalpy to a chemical reaction.
  • reaction fluids such as hydrocarbon streams
  • process fluids such as air and steam that function to transfer heat indirectly, supplying the necessary enthalpy to a chemical reaction.
  • the illustrations shown in Figure 1 A and IB are one example of the electrothermal reaction system as shown in the Figure 2 flowchart.
  • One or more such units may be employed in a an electrothermal chemical process or electrothermal reaction system.
  • the fluid-permeable matrix comprising conductive silicon carbide materials is the sole or primary heat source to fluids delivering enthalpy to the electrothermal reaction process step.
  • the example electrothermal reaction system illustrated in Figure 2 utilizes electrical energy, not combustion energy, together with the fluid-permeable matrix of an electro-fluid reactor to directly heat reaction fluids, or heat process fluids which indirectly supply heat to a thermal reaction, to carry out a thermal reaction and make a product.
  • the electrothermal reaction system may be adapted to a wide variety of thermochemical reactions, both large scale and small scale, and, e.g., incorporated into mobile apparatus systems, environmental emission control systems, and the like.
  • a resistive heat unit comprising the conductive silicon carbide in a fluid-permeable matrix provides an efficient, carbon neutral, effective means of delivering reaction enthalpy over a temperature range from 200 to 1500°C.
  • Such a resistance heat unit comprising the conductive silicon carbide in a fluid- permeable matrix is free of known drawbacks observed in resistive heating elements having conductors principally made of carbon or graphite materials (e.g., pet coke, carbon black, or an intimate mixture of silicon carbide and carbon) when used to heat fluids in high temperature chemical reactions. These drawbacks include consumption of the heating elements, e.g., through oxidation and gasification reactions, and undesirable reactions between the heating element and fluids being heated, often necessitating operations under an inert atmosphere and frequent replacement of spent heating elements.
  • resistive heating elements having conductors principally made of carbon or graphite materials (e.g., pet coke, carbon black, or an intimate mixture of silicon carbide and carbon) when used to heat fluids in high temperature chemical reactions. These drawbacks include consumption of the heating elements, e.g., through oxidation and gasification reactions, and undesirable reactions between the heating element and fluids being heated, often necessitating operations under an iner
  • the physical form of the fluid permeable matrix of conductive silicon carbide materials may be selected from a packed particle bed of granules or a sintered porous article as described above, or as granules contained in a fluidized bed, or as granules contained in some other type of fixed, permeable bed. In other embodiments, combinations of these physical forms may be selected.
  • electrical energy is supplied from renewable energy sources.
  • electrical energy may be derived from a central power supply that generates electrical power by combustion of carbonaceous materials from renewable or non-renewable sources, or from a mix of renewable and nonrenewable generation sources.
  • the electrothermal process for chemical manufacturing beneficially utilizes electrical energy, rather than combustion, to supply enthalpy to a chemical manufacturing process or a thermal reaction process.
  • some combustion may be used to supplement the usage of electrical energy, but to a lesser extent than if the techniques described herein were not used.
  • the chemical manufacturing process described herein may be used to heat gases and other fluids commonly found in chemical manufacturing, including two broad categories of fluids: reactant fluids transformed by the chemical process being carried out, delivering reaction enthalpy directly, and process fluids, or thermal transfer fluids, that deliver reaction enthalpy indirectly by heat transfer to a reactor where the chemical reaction is being carried out, or combinations of these two broad categories.
  • a reactant fluid and a process fluid, or more than one reactant fluid or process fluid may be heated simultaneously to carry out a chemical reaction within the fluid-permeable matrix, or such fluids may be heated separately and combined in downstream processes.
  • Various combinations of such fluids may be used to carry out a chemical reaction (in one process or in multiple processes) or to carry out physical processes.
  • non-conductive fluids are used in the chemical manufacturing process.
  • the process temperature may range from 200 to 1,300° C, from 300 to 1,300° C, from 400 to 1,300° C, from 500 to 1,300° C, from 300 to 1,000° C, from 400 to 1,000° C, from 500 to 1,000° C, from 400 to 900° C, from 500 to 900° C, from 600 to 900° C, or from 500 to 800° C.
  • the heated fluid-permeable matrix utilized in the process may have a heat flux of from 2,000 to 20,000 kJ/m 2 s, from 2,000 to 15,000 kJ/m 2 s, from 2,000 to 10,000 kJ/m 2 s, from 3,000 to 20,000 kJ/m 2 s, from 3,000 to 10,000 kJ/m 2 s, from 5,000 to 10,000 kJ/m 2 s, from 4,000 to 8,000 kJ/m 2 s, from 7,000 to 15,000 kJ/m 2 s, or from 10,000 to 20,000 kJ/m 2 s.
  • the heated fluid-permeable matrix utilized in the process may have a specific heat capacity of from 0.2 to 10 J/gK, from 0.5 to 1 J/gK, from 1 to 10 J/gK, from 0.5 to 10 J/gK, or from 0.5 to 6 J/gK.
  • the heated fluid-permeable matrix utilized in the process may have a thermal conductivity from 1 to 1,000 W/mK, from 25 to 1,000 W/mK, from 50 to 1,000 W/mK, from 50 to 800 W/mK, or from 80 to 500 W/mK.
  • the heated fluid-permeable matrix of the process may be operated at atmospheric pressure, or at a pressure greater or lesser than atmospheric pressure, depending upon the configuration of the apparatus and elements of the system selected for the electrothermal process.
  • velocity and pressure conditions are selected to avoid a buildup of back pressure in the fluid-permeable matrix of conductive silicon carbide granules and enable the free flow of fluid through the fluid-permeable matrix.
  • One or more venturi passages may be designed into the apparatus and/or system. Pressure within the apparatus and system may be applied, and component size and configuration may be selected, to yield fluid velocity through the heated fluid-permeable matrix of about 10 to 250 m/s.
  • velocity and fluid velocity refer to superficial velocity that is spatially independent and defined as the hypothetical flow velocity calculated as if the given fluid phase were the only fluid phase flowing through a given cross-sectional area.
  • Vphase superficial velocity
  • the fluid-permeable matrix may be preheated to a temperature of 300-400° C to optimize thermal and electrical conductivity of the conductive silicon carbide materials prior to the commencement of fluid flow through the heated fluid- permeable matrix.
  • Preheating may be done with an external heating unit, such as an externally heated fluid, an electrical resistance heater, an inductive heating unit, or an electric spark plasma heating unit, placed in thermal contact with the fluid-permeable matrix.
  • a fluid such as the fluid being heated in the electrothermal process, may be circulated through the external heating unit, heated, and conveyed through the fluid-permeable matrix to heat the conductive silicon carbide materials to 300-400° C during the start-up stage of the electrothermal process, and such preheating may be then discontinued as the electrothermal process heating commences in the fluid-permeable matrix.
  • Such “booster” heating to 300- 400° C may be accomplished using electrothermal heating of a fluid-permeable matrix comprising the conductive silicon carbide materials, or, e.g., carbon or graphite granules as oxidation and gasification reactions occur at an acceptably slow rate in the 300-400° C temperature range.
  • the conductive silicon carbide utilized in the reactant fluid system may differ from the conductive silicon carbide utilized in the process fluid system, and it may comprise a catalyst or other material chemically reactive with the reactant fluid. In such a system, the conductive silicon carbide utilized in the process fluid system may be free of catalyst or other reactive species.
  • the electrodes and counter electrodes may be constructed of, e.g., graphite, solid, conductive silicon carbide, including selected shapes of the conductive silicon carbide sintered articles herein, or a metal alloy, or other conductive material having sufficient thermal stability to be utilized in the process, system and apparatus herein.
  • the electrodes are made from sintered silicon carbide infiltrated with silicon or other metals. The electrodes are constructed in a shape and configuration designed to make electrical contact between the electrical energy supply and the conductive silicon carbide and thus complete an electrical circuit through the silicon carbide to power the electrothermal process and system.
  • the electrodes are fabricated by 3D printing into the shape suitable for the given process geometries.
  • One or more electrically insulating element may be connected to the matrix vessel and the fluid inlet and outlet, to direct the flow of electricity from the electrodes through the fluid-permeable matrix comprising conductive silicon carbide and away from structural and other elements of the apparatus.
  • the apparatus as exemplified in Figures 1A and IB, comprises a matrix vessel 105 and 105b that may be constructed of a refractory material, such as a ceramic, or of a thermally stable metal. Materials for construction of the matrix vessel are selected to provide thermal and shape stability at the operating temperatures and pressures of the electrothermal process and the system.
  • the fluid-permeable matrix is contained within a matrix vessel that may be constructed of a refractory material, such as a ceramic, or of a thermally stable metal.
  • the apparatus and the system may further comprise process control elements, such as one or more meters, gauges and controllers, structural elements, conduits, connective elements, computers, data collection and control systems, and the like, such as are typical in electrical systems, chemical processing and thermal operations.
  • process control elements such as one or more meters, gauges and controllers, structural elements, conduits, connective elements, computers, data collection and control systems, and the like, such as are typical in electrical systems, chemical processing and thermal operations.
  • the electrothermal process for chemical manufacturing may replace CO 2 generating combustion processes used for the industrial production of petrochemicals, such as the steam cracking or reforming of naphtha, ethane and other feedstocks to produce ethylene, propylene, butadiene and aromatics; aromatic chemicals processes; methanol processes; and processing olefins and aromatic chemicals processing into plastics and various organic chemicals.
  • petrochemicals such as the steam cracking or reforming of naphtha, ethane and other feedstocks to produce ethylene, propylene, butadiene and aromatics
  • aromatic chemicals processes such as the steam cracking or reforming of naphtha, ethane and other feedstocks to produce ethylene, propylene, butadiene and aromatics
  • aromatic chemicals processes such as the steam cracking or reforming of naphtha, ethane and other feedstocks to produce ethylene, propylene, butadiene and aromatics
  • aromatic chemicals processes such as the steam cracking or reforming of naphtha
  • the electrothermal process and system described herein is deployed into the industrial production of inorganic chemicals such as chlorine, sodiumhydroxide, carbon black, soda ash, and industrial gases; and in the industrial production of fertilizers, such as in the production of ammonia.
  • inorganic chemicals such as chlorine, sodiumhydroxide, carbon black, soda ash, and industrial gases
  • fertilizers such as in the production of ammonia.
  • These processes typically employ steam boilers, heat exchangers and other equipment heated by the direct or indirect combustion of natural gas, oil and coal fuels.
  • Associated industrial processes such as the extraction of oil, gas and coal fuels, the transformation of these fuels in petroleum refineries, liquefied natural gas production and synfuel production (hydrogen, methanol, dimethyl ether, and synthetic gasoline and diesel), likewise can be beneficially modified using the electrothermal systems and processes described herein.
  • Complex and expensive equipment such as steam boilers, heat exchangers and other combustion heated equipment typically used in such processes may be beneficially eliminated or reduced in size, frequency or complexity by replacing them
  • the electrothermal process, materials, system and apparatus are employed in industrial operations for petroleum refining and manufacture of base chemicals in reactions conducted at high temperatures, e.g., about 850° C.
  • base chemicals such as ethylene, propylene, butadiene and aromatic isomers
  • the base chemicals may be produced in “steam crackers” or “steam reformers” from naphtha or gas streams, and the base chemicals, in turn, may be used to produce various plastics and organic chemicals, all without the combustion of fossil fuels or use of other non-renewable energy sources, thereby eliminating up to 90% of the CO 2 emissions from conventional manufacturing operations.
  • the electrothermal process, materials, system and apparatus are employed in industrial operations for synthesis of, e.g., methanol or ammonia, and for distillation, separation, absorption, stripping, solvent extraction, and crystallization processes in the manufacture of chemicals at high temperatures ranging from 200 to 1 ,300° C, all without utilizing combustion sources of reaction enthalpy.
  • the electrothermal process, materials, system and apparatus may be employed to generate materials by pyrolysis reactions and other high temperature gas phase reactions, and in carrying out various energy intensive operations at large-scale for making materials such as metals and cement.
  • a steam cracker for processing hydrocarbons utilizes a fluid comprising steam and hydrocarbon gas (e.g., at a ratio of 0.3 to 0.5 parts steam/one part hydrocarbon gas).
  • the fluid is heated in two stages utilizing the thermoelectric system, apparatus and process herein: a pre-heating stage for heating the fluid from room temperature to at least 300° C, optionally up to about 650° C; and a production stage where the fluid is heated to about 650° C to 850° C to carry out the hydrocarbon cracking within the heated fluid-permeable matrix.
  • the steam is separated from the hydrocarbon product in a downstream process. Hydrocarbon cracking is carried out under the following conditions:

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Abstract

L'invention concerne un système de réaction électrothermique et un appareil de réacteur électro-fluide, et plus particulièrement, un procédé électrothermique pour la fabrication chimique, des matériaux pour une matrice perméable aux fluides comprenant du carbure de silicium conducteur ayant des propriétés électriques, des compositions chimiques et des caractéristiques physiques sélectionnées, et des procédés de fabrication de tels matériaux.
PCT/US2024/012763 2023-02-01 2024-01-24 Procédé électrothermique, matériaux, système et appareil WO2024163236A2 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2958584A (en) 1959-08-21 1960-11-01 Shawinigan Chem Ltd Process for preparation of hydrocyanic acid
US4543240A (en) 1980-02-08 1985-09-24 Superior Graphite Co. Method for the continuous production of carbides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2958584A (en) 1959-08-21 1960-11-01 Shawinigan Chem Ltd Process for preparation of hydrocyanic acid
US4543240A (en) 1980-02-08 1985-09-24 Superior Graphite Co. Method for the continuous production of carbides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEM. & ENG. NEWS, 21 November 1960 (1960-11-21), pages 55 - 56

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