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WO2025206305A1 - Dispositif de production de combustible - Google Patents

Dispositif de production de combustible

Info

Publication number
WO2025206305A1
WO2025206305A1 PCT/JP2025/012752 JP2025012752W WO2025206305A1 WO 2025206305 A1 WO2025206305 A1 WO 2025206305A1 JP 2025012752 W JP2025012752 W JP 2025012752W WO 2025206305 A1 WO2025206305 A1 WO 2025206305A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
catalyst layer
fuel production
gas flow
production device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/012752
Other languages
English (en)
Japanese (ja)
Inventor
啓輔 丸市
玄将 大西
雄樹 藤田
義政 小林
一樹 前田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Publication of WO2025206305A1 publication Critical patent/WO2025206305A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B01J35/57—Honeycombs
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions

Definitions

  • the present invention relates to a fuel production device.
  • a primary object of the present invention is to provide a fuel production apparatus capable of efficiently producing synthetic fuel with excellent selectivity for liquid fuel components having 5 to 20 carbon atoms (hereinafter referred to as C5 to C20 selectivity).
  • a fuel production apparatus includes a ceramic substrate and a catalyst layer.
  • the ceramic substrate defines a gas flow path.
  • a raw material gas containing carbon oxides and hydrogen is supplied to the gas flow path.
  • the catalyst layer is provided on a surface of the ceramic substrate so as to face the gas flow path.
  • the catalyst layer includes a first catalyst and a second catalyst.
  • the first catalyst is capable of promoting a Fischer-Tropsch reaction.
  • the second catalyst is capable of promoting a hydrocracking reaction and/or an isomerization reaction of a hydrocarbon compound gas produced by the Fischer-Tropsch reaction.
  • the ceramic substrate may have a thermal conductivity of 0.4 W/m ⁇ K or more.
  • the partition wall may have a porosity of 65% or less.
  • the partition wall may have a porosity of 10% or less.
  • the partition walls may have a thickness of 0.0635 mm or more and 1.27 mm or less.
  • the honeycomb substrate may have a cell density of 50 cpsi or more and 900 cpsi or less.
  • the raw material gas may contain carbon monoxide as the carbon oxide.
  • the raw material gas may contain carbon dioxide as the carbon oxide.
  • the catalyst layer includes a third catalyst.
  • the third catalyst is capable of promoting a reverse shift reaction that converts carbon dioxide into carbon monoxide.
  • the catalyst layer may further include a filler, and the filler may have a thermal conductivity of 0.1 W/m ⁇ K to 500 W/m ⁇ K.
  • a fuel production apparatus 100 includes a ceramic substrate 3 and a catalyst layer 1.
  • the ceramic substrate 3 defines a gas flow path 4.
  • a source gas containing carbon oxides and hydrogen is supplied to the gas flow path 4. Examples of carbon oxides include carbon monoxide (CO) and carbon dioxide (CO 2 ).
  • the source gas typically contains carbon monoxide.
  • the catalyst layer 1 is provided on the surface of the ceramic substrate 3 so as to face the gas flow path 4.
  • the catalyst layer 1 includes a first catalyst capable of promoting the FT reaction and a second catalyst capable of promoting the hydrocracking reaction and/or the isomerization reaction of hydrocarbon compounds produced by the FT reaction.
  • the present inventors have discovered that the flow of the feed gas passing through the gas flow passage affects the C5 to C20 selectivity in the synthetic fuel.
  • the present inventors have found that the C5 to C20 selectivity in the synthetic fuel to be produced can be improved by arranging the first catalyst and the second catalyst so that the feed gas passes through the gas passage uniformly and smoothly. More specifically, since the catalyst layer containing the first catalyst and the second catalyst is provided on the surface of the ceramic substrate so as to face the gas flow path, the raw material gas passes through the gas flow path uniformly and smoothly and comes into appropriate contact with the first catalyst and the second catalyst, compared to when the gas flow path is filled with catalyst-containing pellets.
  • hydrocarbon compounds including alkanes C n H 2n +2
  • hydrocarbon compounds including alkanes C n H 2n +2
  • n is an integer of 1 or more.
  • the hydrocarbon compounds contain n-paraffins (straight-chain alkanes) having 5 to 100 carbon atoms as their main components. Because the feed gas flows easily in the gas flow passage and the uniformity of the feed gas flow is improved, such n-paraffins are sufficiently converted into liquid fuel components having 5 to 20 carbon atoms by the hydrocracking reaction and/or isomerization reaction promoted by the second catalyst. This makes it possible to improve the C5 to C20 selectivity and efficiently produce synthetic fuel that can be suitably used as an alternative fuel to petroleum.
  • the thermal conductivity of the ceramic base 3 is, for example, 0.4 W/m K or more, preferably 0.8 W/m K or more, more preferably 8.0 W/m K or more, even more preferably 50 W/m K or more, and particularly preferably 140 W/m K or more.
  • the upper limit of the thermal conductivity of the ceramic base 3 is typically 500 W/m K.
  • the above-described FT reaction, hydrocracking reaction, and isomerization reaction are typically exothermic reactions. Therefore, when these reactions proceed while supplying a raw material gas to a gas flow path, the heat of reaction may create a temperature gradient in which the temperature decreases from the upstream side to the downstream side in the raw material gas supply direction.
  • the reaction products may differ depending on the temperature conditions.
  • the selectivity of methane may increase and the selectivity of n-paraffins having 5 or more carbon atoms may decrease in the FT reaction.
  • the decrease in the selectivity of n-paraffins having 5 or more carbon atoms also reduces the amount of liquid fuel components having 5 to 20 carbon atoms produced.
  • the ceramic substrate has a thermal conductivity within the above range, which allows the ceramic substrate to rapidly diffuse reaction heat and improve thermal uniformity in the gas flow path.
  • the temperature can be appropriately controlled throughout the gas flow path, and the selectivity for hydrocarbons having 5 or more carbon atoms can be sufficiently ensured in the FT reaction. This allows for a stable improvement in the C5 to C20 selectivity.
  • the ceramic substrate 3 is made of any appropriate ceramic material.
  • ceramic materials include cordierite, SiC, Si-SiC composite materials, mullite, alumina, spinel, silicon carbide-cordierite composite materials, lithium aluminum silicate, aluminum titanate, silicon nitride, and zirconia.
  • the ceramic materials may be used alone or in combination.
  • the material of the ceramic substrate 3 is preferably a ceramic material, more preferably cordierite, SiC, or a Si—SiC composite material, and even more preferably a Si—SiC composite material.
  • the Si-SiC composite material may be a porous body or a dense body. Porous Si-SiC composite materials are described in detail, for example, in Japanese Patent Application Laid-Open No. 2002-201082. Dense Si-SiC composite materials are described in detail, for example, in Japanese Patent Application Laid-Open No. 11-035376. The entire disclosures of these publications are incorporated herein by reference. Among the Si-SiC composite materials, a dense body is preferred. When the ceramic substrate is composed of a dense body of an Si-SiC composite material, the thermal conductivity of the ceramic substrate can be stably adjusted within the above-mentioned range.
  • the catalyst layer 1 may have a single layer structure or a laminated structure. 1 , when the catalyst layer 1 has a single-layer structure, a first catalyst and a second catalyst are dispersed in the catalyst layer 1. With such a configuration, the C5 to C20 selectivity in the synthetic fuel produced can be stably improved compared to when the catalyst layer has a laminated structure. 2 , when the catalyst layer 1 has a laminated structure, the catalyst layer 1 includes a first catalyst layer 11 containing a first catalyst and a second catalyst layer 12 in which a second catalyst is dispersed. In the illustrated example, the second catalyst layer 12 is laminated on the surface of the ceramic substrate 3. The first catalyst layer 11 is laminated on the surface of the second catalyst layer 12 opposite to the ceramic substrate 3.
  • the first catalyst layer 11 is disposed facing the gas flow path 4. Furthermore, the stacking order of the first catalytic layer 11 and the second catalytic layer 12 may be reversed. As shown in Fig. 3 , the first catalytic layer 11 may be stacked on the surface of the ceramic substrate 3, and the second catalytic layer 12 may be stacked on the surface of the first catalytic layer 11 opposite to the ceramic substrate 3. In this case, the second catalytic layer 12 is disposed facing the gas flow path 4.
  • the catalyst layer is illustrated as having a single-layer structure in Figures 4 to 7. However, in the fuel production device described below, the catalyst layer may have either a single-layer structure or a laminated structure.
  • the fuel production apparatus 100 has a flow-through type configuration.
  • the fuel production device 100 has, as the ceramic substrate 3, a cylindrical substrate 3a having a cylindrical shape extending in a predetermined direction.
  • the cylindrical substrate 3a has any suitable shape in cross section perpendicular to the longitudinal direction.
  • Examples of cross-sectional shapes of the cylindrical substrate 3a include triangles, rectangles, pentagons, polygons with hexagons or more, circles, and ellipses.
  • the cylindrical substrate 3a includes a gas flow path 4.
  • the gas flow path 4 is a space formed inside the cylindrical substrate 3a.
  • the gas flow path 4 is formed in a portion of the cross section of the cylindrical substrate 3a where the catalyst layer 1 is not formed (typically the central portion).
  • the gas flow path 4 extends from the first end face E1 (inlet end face) to the second end face E2 (outlet end face) of the fuel production device.
  • the gas flow path 4 has any appropriate shape in a cross section perpendicular to the longitudinal direction.
  • the cross-sectional shape of the gas flow path 4 can be the same as that of the cylindrical substrate 3a described above.
  • the cylindrical substrate 3a is configured to be substantially impermeable to synthetic fuel gas.
  • the thickness of the cylindrical substrate 3a is, for example, 0.1 mm to 10 mm, for example, 0.2 mm to 8 mm, or for example, 0.5 mm to 5 mm. The thickness is measured, for example, by observing a cross section with an SEM (scanning electron microscope).
  • the average pore diameter of the cylindrical substrate 3a is, for example, 0.05 ⁇ m to 1000 ⁇ m, and is measured by, for example, mercury intrusion porosimetry.
  • the porosity of the cylindrical substrate 3a is, for example, 0% to 50%. The porosity can be measured by, for example, mercury intrusion porosimetry. If the average pore size and/or porosity of the cylindrical substrate is within this range, the synthetic fuel can be prevented from permeating the cylindrical substrate and leaking out of the gas flow passages.
  • the catalyst layer 1 is provided on the inner surface of the cylindrical substrate 3a.
  • the catalyst layer 1 may be provided on the entire inner surface of the cylindrical substrate 3a, or on only a portion of it.
  • the catalyst layer 1 contains the first catalyst and the second catalyst.
  • the first catalyst typically contains any suitable active component, such as a transition metal, a noble metal, a rare earth metal, an alkali metal, or an alkaline earth metal.
  • the active components may be used alone or in combination.
  • transition metals include Co, Fe, Ni, Ru, Os, Mn, Cu, Ta, Mo, Zn, Cr, Re, V, Zr, and Ir, and preferably Fe, Co, Ni, and Ru.
  • noble metals include Pt, Pd, and Ru.
  • rare earth elements include La and Ce.
  • alkali metals include Li, Na, K, and Rb.
  • alkaline earth metals include Ca, Ba, and Sr.
  • the first catalyst may contain these elements in a metallic state (for example, pure metal, alloy) or in a compound state (for example, oxide, carbide).
  • the first catalyst preferably contains a transition metal, such as Co, Fe, Ni, or Ru, either singly or in combination.
  • the hydrocarbon compounds described above can be produced more stably from the feed gas.
  • the first catalyst contains Co and/or Fe.
  • the activity of the first catalyst can be improved.
  • the first catalyst may further contain a support.
  • the support is capable of supporting the active component.
  • the support is composed of any suitable inorganic material depending on the application. Examples of inorganic materials include inorganic oxides such as mesoporous materials; carbon materials such as carbon nanotubes and nanoporous carbon; and zeolites. The inorganic materials may be used alone or in combination.
  • the support is composed of an inorganic oxide.
  • inorganic oxides include aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, cerium oxide, zirconium oxide, and composite oxides thereof.
  • silicon oxide is preferable.
  • the pore volume of the carrier is, for example, 0.1 cc/g to 4 cc/g, preferably 0.2 cc/g to 3.0 cc/g, and more preferably 0.3 cc/g to 2.0 cc/g.
  • the pore volume is measured, for example, by mercury intrusion porosimetry or water titration.
  • the first catalyst is typically particulate.
  • the first catalyst is contained as secondary particles in the catalyst layer 1 or first catalyst layer 11, which has a single-layer structure.
  • the average secondary particle diameter of the first catalyst is, for example, 0.01 ⁇ m to 100 ⁇ m, and preferably 0.1 ⁇ m to 10 ⁇ m.
  • Examples of the second catalyst include zeolite, silica alumina, silica, alumina, titania, vanadium oxide, and molybdenum oxide.
  • the second catalyst may be used alone or in combination.
  • the second catalyst contains a zeolite.
  • hydrocarbon compounds can be stably hydrocracking and/or isomerized.
  • the maximum number of rings in a zeolite is, for example, 6 to 16, preferably 8 to 14, and more preferably 10 to 12.
  • the thermal conductivity of the catalyst layer 1 having a single layer structure is, for example, 0.01 W/m ⁇ K to 40 W/m ⁇ K, and preferably 0.1 W/m ⁇ K to 40 W/m ⁇ K.
  • the weighted average value of the thermal conductivity of the catalyst layer 1 having a single layer structure and the thermal conductivity of the ceramic substrate 3 is, for example, 0.1 W/m K or more, preferably 5 W/m K or more, and more preferably 120 W/m K or more.
  • the upper limit of the weighted average value of the thermal conductivity of the catalyst layer 1 having a single layer structure and the thermal conductivity of the ceramic substrate 3 is typically 500 W/m K.
  • the thickness of the second catalytic layer 12 is, for example, 3 ⁇ m to 200 ⁇ m, and preferably 5 ⁇ m to 100 ⁇ m.
  • the second catalyst layer 12 is configured as a denser thin film than when prepared by a coating method.
  • the thickness of the second catalyst layer 12 is, for example, 1 ⁇ m to 80 ⁇ m, and preferably 2 ⁇ m to 50 ⁇ m.
  • the temperature can be appropriately controlled throughout the second catalytic layer, and as a result, the C5 to C20 selectivity can be further improved.
  • the honeycomb substrate 3b may have any suitable shape (overall shape). Examples of shapes for the honeycomb substrate 3b include a cylindrical shape with a circular bottom, an elliptical cylindrical shape with an elliptical bottom, a rectangular prism with a polygonal bottom, and a cylindrical shape with an irregular bottom. In one embodiment, the honeycomb substrate 3b has a cylindrical shape. The outer diameter and length of the honeycomb substrate 3b can be appropriately set depending on the purpose.
  • the honeycomb-shaped substrate 3b includes an outer wall 33 and partition walls 31.
  • the outer wall 33 and partition walls 31 may be formed integrally or as separate bodies. In the illustrated example, the outer wall 33 and partition walls 31 are formed integrally.
  • the outer wall 33 has a cylindrical shape.
  • the thickness of the outer wall 33 can be set appropriately depending on the application of the fuel production device.
  • the thickness of the outer wall 33 is, for example, 0.1 mm to 10 mm, or, for example, 0.2 mm to 8 mm, or, for example, 1 mm to 5 mm.
  • the partitions 31 are located inside the outer wall 33.
  • the partitions 31 have a first partition 31a and a second partition 31b that are perpendicular to each other, and the first partition 31a and the second partition 31b define a plurality of cells 32.
  • Examples of the cross-sectional shape of the cells 32 include a triangle, a rectangle, a pentagon, a polygon with hexagons or more, a circle, and an ellipse.
  • the cross-sectional shape of each of the plurality of cells 32 is a rectangle except for the portions where the first partition 31a and the second partition 31b contact the outer wall 33.
  • the configuration of the partitions is not limited to the partition 31 described above.
  • the partitions may have a first partition extending in the radial direction and a second partition extending in the circumferential direction, which define a plurality of cells.
  • the cells 32 are explained in the same manner as the cylindrical substrate 3a described above.
  • Each of the plurality of cells 32 typically extends in the length direction (axial direction) of the fuel production device from a first end face E1 (inlet end face) to a second end face E2 (outlet end face) of the fuel production device.
  • the above-described catalyst layer 1 is laminated on the inner surface of the cell 32.
  • a gas flow path 4 is formed in a portion of the cross section of the cell 32 where the catalyst layer 1 is not formed (typically the central portion).
  • the gas flow path 4 extends from a first end face E1 (inlet end face) to a second end face E2 (outlet end face) of the fuel production apparatus.
  • the gas flow path 4 has any appropriate shape in a cross section perpendicular to the longitudinal direction.
  • the cross-sectional shape of the gas flow path 4 may be the same as that of the cell 32 described above.
  • the partition wall 31 may be configured to be substantially permeable to the synthetic fuel gas, or may be configured to be substantially impermeable to the synthetic fuel gas.
  • the thickness of the partition wall 31 is, for example, 0.0508 mm or more, preferably 0.0635 mm or more, and more preferably 0.203 mm or more. On the other hand, the thickness of the partition wall 31 is, for example, 1.52 mm or less, preferably 1.27 mm or less, and more preferably 0.305 mm or less.
  • the porosity of the partition walls 31 is, for example, 80% or less, preferably 65% or less, and more preferably 10% or less. On the other hand, the lower limit of the porosity of the partition walls 31 is typically 0%.
  • the thermal conductivity of the partition walls can be stably adjusted to fall within the above-mentioned range of the thermal conductivity of the ceramic substrate.
  • the average pore size in the partition walls 31 is, for example, 5 ⁇ m to 30 ⁇ m, and preferably 8 ⁇ m to 25 ⁇ m.
  • the fuel production apparatus 102 may have a wall-flow type configuration.
  • the fuel production apparatus 102 further has a second gas flow path 5 in addition to the gas flow path 4 (hereinafter, sometimes referred to as the first gas flow path 4).
  • the second gas flow channel 5 is located on the opposite side of the catalyst layer 1 from the gas flow channel 4.
  • the synthetic fuel produced by the hydrocracking reaction and/or the isomerization reaction of the hydrocarbon compounds typically flows into the second gas flow channel 5 in a gaseous state. Therefore, the synthetic fuel can be smoothly recovered from the second gas flow channel.
  • the fuel production device 102 includes a honeycomb substrate 3b and a catalyst layer 1.
  • the partition walls 31 included in the honeycomb substrate 3b define a plurality of first cells 321 and a plurality of second cells 322.
  • Each of the first cell 321 and the second cell 322 is described in the same manner as the cell 32 described above.
  • At least some of the plurality of first cells 321 include the above-described first gas flow path 4.
  • all of the plurality of first cells 321 include the above-described first gas flow path 4.
  • at least some of the second cells 322 include the second gas flow passage 5.
  • all of the second cells 322 include the second gas flow passage 5.
  • the first cell 321 and the second cell 322 are connected to each other so as to share the partition wall 31.
  • the partition wall 31 is configured to be substantially permeable to synthetic fuel (typically synthetic fuel gas). Therefore, the fluid flowing through the fuel production device 102 flows from the gas flow path 4 through the partition wall 31 into the second gas flow path 5.
  • the average pore diameter of the partition walls 31 is, for example, 5 ⁇ m to 30 ⁇ m, and preferably 8 ⁇ m to 25 ⁇ m.
  • the porosity of the partition walls 31 is, for example, 20% to 75%, and preferably 25% to 70%. If the partition walls have an average pore size and/or porosity within these ranges, synthetic fuel gas can be stably transmitted through them.
  • the fuel production device 102 may further include a first sealing portion 6 and/or a second sealing portion 7 .
  • Each of the first sealing portion 6 and the second sealing portion 7 is configured to be substantially impermeable to the source gas.
  • the dimension of the first sealing portion 6 in the extension direction of the first cell 321 is typically larger than the thickness of the partition wall 31.
  • the dimension of the first sealing portion 6 in the extension direction of the first cell 321 is, for example, two times or more, and preferably three times or more, the thickness of the partition wall 31. When the first sealing portion has such dimensions, permeation of the source gas can be sufficiently suppressed.
  • the dimension of the first sealing portion 6 in the extension direction of the first cell 321 is, for example, 180 times or less, preferably 160 times or less, the thickness of the partition wall 31 .
  • the second sealing portion 7 is made of any appropriate material. Examples of the material for the second sealing portion 7 include the same materials as those for the first sealing portion 6. The materials for the second sealing portion 7 may be used alone or in combination. In the illustrated example, the second sealing portion 7 is fixed to the partition wall 31. The second sealing portion 7 may be formed integrally with the partition wall 31 or may be a separate body from the partition wall 31. In one embodiment, the second sealing portion 7 is formed integrally with the partition wall 31.
  • the dimensions of the second sealing portion 7 in the extension direction of the second cell 322 are typically greater than the thickness of the partition wall 31.
  • the range of dimensions of the second sealing portion 7 in the extension direction of the second cell 322 is, for example, the same as the range of dimensions of the first sealing portion 6 described above. When the second sealing portion has such dimensions, permeation of the source gas can be sufficiently suppressed.
  • the catalyst layer 1 may further include, in addition to the first and second catalysts, a third catalyst capable of promoting a reverse shift reaction that converts carbon dioxide to carbon monoxide.
  • the third catalyst may be dispersed in the catalyst layer 1 having a single-layer structure, or the catalyst layer 1 having a laminated structure may include a third catalyst layer containing the third catalyst.
  • a raw material gas containing carbon dioxide and hydrogen is supplied to the gas flow channel 4. Then, the reverse shift reaction shown in the following formula (2) proceeds smoothly in the presence of the third catalyst, producing carbon monoxide.
  • a raw material gas containing carbon dioxide and hydrogen is supplied to the gas flow path 4 of the fuel production device 101.
  • the carbon dioxide content in the raw material gas is, for example, 20 to 40% by volume, and preferably 22 to 29% by volume.
  • the hydrogen content in the raw material gas is, for example, 60% to 80% by volume, and preferably 71% to 78% by volume.
  • the content of n-paraffins in the hydrocarbon compounds is, for example, 30% to 100% by volume, and the content of isoparaffins in the hydrocarbon compounds is, for example, 0% to 15% by volume, and preferably 0% to 10% by volume.
  • the hydrocarbon compound may further contain an olefin (alkene), the carbon number of which is, for example, 3 to 10.
  • the content of olefins in the hydrocarbon compound is, for example, 0 to 70% by volume, and preferably 0 to 60% by volume.
  • n-paraffins hydrocarbon compounds having 5 to 20 carbon atoms
  • liquid fuel components include n-paraffins having 5 to 20 carbon atoms, isoparaffins (branched alkanes) having 5 to 20 carbon atoms, and olefins having 5 to 20 carbon atoms.
  • the liquid fuel components are in a liquid state at room temperature and normal pressure (23°C, 0.1 MPa). Furthermore, the conversion of hydrocarbon compounds to methane is suppressed in the fuel production equipment. This produces a synthetic fuel that is rich in liquid fuel components having 5 to 20 carbon atoms.
  • the content of the liquid fuel component having 5 to 20 carbon atoms in the synthetic fuel gas is, for example, 45% by volume or more, preferably 50% by volume or more, more preferably 55% by volume or more, even more preferably 60% by volume or more, and particularly preferably 65% by volume or more.
  • the content of the liquid fuel component having 5 to 20 carbon atoms in the synthetic fuel gas is, for example, 100% by volume or less, or, for example, less than 85% by volume, or, for example, 80% by volume or less.
  • the content of hydrocarbons having a carbon number of more than 20 in the synthetic fuel gas is, for example, 25% by volume or less, preferably 20% by volume or less, and more preferably 16% by volume or less.
  • the content of hydrocarbons having a carbon number of more than 20 in the synthetic fuel gas is, for example, 0% by volume or more, and, for example, 5% by volume or more.
  • Such synthetic fuels contain a sufficient amount of liquid fuel components having 5 to 20 carbon atoms, and can therefore be suitably used as alternative fuels to petroleum.
  • the C5 to C20 selectivity that can be achieved by the fuel production apparatus is, for example, 45% or more, preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, and particularly preferably 65% or more.
  • the upper limit of the C5 to C20 selectivity is 100%.
  • Example 1 Preparation of honeycomb substrate>>
  • the clay containing the SiC powder was extruded and then dried to prepare a dried honeycomb body, which had a cylindrical shape with a diameter of 20 mm and a length of 50 mm.
  • the dried honeycomb body had partition walls defining a plurality of cells and outer walls surrounding the partition walls. The cross-sectional shape of the cells was rectangular.
  • the cell density of the dried honeycomb body was 300 cpsi, and the thickness of the partition walls was 0.254 mm.
  • a material powder containing Si powder was press-molded and then dried to obtain a Si supply body. Next, the dried honeycomb body was heated at 1500° C.
  • a honeycomb substrate composed of a dense body of Si-SiC composite material was prepared.
  • the partition walls of this honeycomb substrate had no pores. In other words, the porosity of the partition walls of the honeycomb substrate was 0%.
  • the thermal conductivity of the honeycomb substrate is shown in Table 1. ⁇ Preparation of First Catalyst>> Silicon (IV) dioxide particles were introduced into distilled water and then stirred under reduced pressure at room temperature (23°C) for 12 hours. This resulted in a dispersion of metal oxide particles.
  • FT reaction catalyst particles (hereinafter referred to as catalyst particles) as a first catalyst.
  • the catalyst particles contained tricobalt tetroxide ( Co3O4 ) and silicon dioxide ( IV ) supporting tricobalt tetroxide ( Co3O4 ).
  • the content of Co was 20 parts by mass relative to 100 parts by mass of silicon dioxide.
  • the first catalyst comprising tricobalt tetroxide and silicon dioxide may be referred to as first catalyst (Co/SiO 2 ).
  • ⁇ Preparation of catalyst layer>> The same masses of the obtained first catalyst and second catalyst particles were dispersed in distilled water to prepare a catalyst slurry.
  • the catalyst particle content in the catalyst slurry was 10 mass%.
  • the honeycomb substrate prepared above was immersed in the catalyst slurry for 5 seconds under normal pressure (0.1 MPa) and room temperature (23°C). The honeycomb substrate was then lifted out of the catalyst slurry. This coated the catalyst slurry onto the partition wall surfaces.
  • the catalyst slurry coated onto the partition wall surfaces was then heated and dried at 100°C for 120 minutes. The above immersion and drying were repeated to form a catalyst layer having a single layer structure on the partition wall surfaces.
  • the catalyst layer contained aggregates of catalyst particles.
  • the thickness of the catalyst layer was 230 ⁇ m.
  • the amount of catalyst particles supported per unit area of the partition wall was 0.023 g/ cm2 . In this manner, a fuel production device including a honeycomb substrate and a catalyst layer was manufactured.
  • Example 3 Except for changing the clay containing the SiC raw material powder and the metal Si powder to a clay containing cordierite (Cd), a fuel production device was manufactured in the same manner as in Example 1.
  • the average pore diameter of the partition walls was 11 ⁇ m, and the porosity of the partition walls was 52%.
  • Example 1 The first catalyst and the second catalyst prepared in the same manner as in Example 1 were each pressure-molded and pulverized to form pellet-shaped bodies (catalyst-containing pellets) having an aggregate diameter of 0.5 to 1.5 mm.
  • the pellets of the first catalyst and the second catalyst were granulated and mixed in a mass ratio of 1:1, and quartz wool was laid on the top and bottom of a reaction tube, and the space between them was filled with an amount equal to that of Example 1. In this manner, a fuel production device in which catalyst-containing pellets were filled in the gas flow passage was manufactured.
  • Example 4 A fuel production apparatus was produced in the same manner as in Example 1, except that the first catalyst (Co/SiO 2 ) was changed to a first catalyst (K—Co/SiO 2 ) prepared as follows. Silicon dioxide (IV) particles were added to distilled water and stirred under reduced pressure at room temperature (23°C) for 12 hours to obtain a dispersion of metal oxide particles. Cobalt (II) nitrate hexahydrate and potassium nitrate were also dissolved in distilled water to obtain an aqueous solution of cobalt nitrate and potassium nitrate. Next, the aqueous solution was added to a dispersion of metal oxide particles, and the mixture was stirred at room temperature (23°C) for 2 hours.
  • Silicon dioxide (IV) particles were added to distilled water and stirred under reduced pressure at room temperature (23°C) for 12 hours to obtain a dispersion of metal oxide particles.
  • Cobalt (II) nitrate hexahydrate and potassium nitrate were also
  • the mixture of the dispersion and the aqueous solution was then heated to 80°C while stirring to evaporate the water. The remaining solid was then heated at 500° C for 3 hours.
  • the catalyst particles contained potassium nitrate, tricobalt tetroxide ( Co3O4 ), and silicon dioxide (IV) supporting them.
  • the catalyst particles had a Co content of 15% by mass and a K content of 1% by mass.
  • Example 6 A fuel production device was manufactured in the same manner as in Example 1, except that ⁇ -Al 2 O 3 particles were further added as a filler to the catalyst slurry.
  • the addition rate of the ⁇ -Al 2 O 3 particles in the catalyst slurry was 20 parts by mass relative to 100 parts by mass of the first catalyst.
  • the thermal conductivity of the ⁇ -Al 2 O 3 particles was 30 W/m ⁇ K, the average particle size of the ⁇ -Al 2 O 3 particles was 400 nm, and the aspect ratio of the ⁇ -Al 2 O 3 particles was 10.
  • Example 7 A fuel production apparatus was produced in the same manner as in Example 2, except that the first catalyst (Co/SiO 2 ) was changed to the first catalyst (K—Co/SiO 2 ) prepared in Example 4.
  • Example 8 A fuel production apparatus was produced in the same manner as in Example 3, except that the first catalyst (Co/SiO 2 ) was changed to the first catalyst (K—Co/SiO 2 ) prepared in Example 4.
  • Example 9 A fuel production apparatus was produced in the same manner as in Example 1, except that the first catalyst (Co/SiO 2 ) was changed to a first catalyst (Na—Fe 3 O 4 ) prepared as follows. First, triiron tetroxide (Fe 3 O 4 ) particles were synthesized by any suitable method. The synthesized triiron tetroxide ( Fe3O4 ) particles were then added to distilled water and stirred under reduced pressure at room temperature (23°C) for 12 hours to obtain a dispersion of triiron tetroxide. Sodium nitrate was also dissolved in distilled water to obtain an aqueous sodium nitrate solution.
  • catalyst particles as a first catalyst.
  • the catalyst particles contained sodium nitrate and triiron tetroxide ( Fe3O4 ).
  • the Na content in the catalyst particles was 1 mass%.
  • Example 10 A fuel production apparatus was manufactured in the same manner as in Example 1, except that nickel oxide (NiO) and zinc oxide (ZnO) were further added to the catalyst slurry as a third catalyst.
  • the amount of nickel oxide added was 50 parts by mass relative to 100 parts by mass of the first catalyst, and the amount of zinc oxide added was 50 parts by mass relative to 100 parts by mass of the first catalyst.
  • Second Catalyst Layer ⁇ Preparation of Second Catalyst Layer>>
  • HZSM-5 zeolite, manufactured by Nakamura Choukou Co., Ltd.
  • the obtained second catalyst particles were dispersed in distilled water to prepare a second catalyst slurry.
  • the catalyst particle content in the second catalyst slurry was 10 mass%.
  • the honeycomb substrate prepared above was immersed in the second catalyst slurry for 5 seconds under normal pressure (0.1 MPa) and room temperature (23°C). The honeycomb substrate was then pulled out of the second catalyst slurry. In this way, the second catalyst slurry was applied to the surfaces of the partition walls.
  • the second catalyst slurry applied to the surfaces of the partition walls was then heated and dried at 100°C for 120 minutes. The above immersion and drying were repeated to form a second catalyst layer on the surfaces of the partition walls.
  • the thickness of the second catalyst layer was 150 ⁇ m.
  • the amount of the second catalyst particles supported per unit area of the partition walls was 0.13 g/ cm2 .
  • the first catalyst slurry applied to the surface of the second catalyst layer was then heated and dried at 100°C for 120 minutes. The above-mentioned immersion and drying were repeated to form a first catalyst layer on the surface of the second catalyst layer.
  • the thickness of the first catalyst layer was 150 ⁇ m.
  • the amount of the first catalyst particles supported per unit area of the partition wall was 0.13 g/cm 2 . In this manner, a fuel production device equipped with a catalyst layer having a laminated structure was manufactured.
  • Example 2 The first catalyst (K-Co/SiO 2 ) prepared in the same manner as in Example 4 and the second catalyst (HZSM-5) prepared in the same manner as in Example 1 were each pressure-molded and pulverized to form pellet-shaped bodies (catalyst-containing pellets) with an agglomerate diameter of 0.5 to 1.5 mm.
  • the pellets of the first catalyst and the second catalyst were granulated and mixed in a mass ratio of 1:1, and quartz wool was placed on the top and bottom of a reaction tube, and the same amount as in Example 4 was packed between them. In this manner, a fuel production device in which catalyst-containing pellets were filled in the gas flow passage was manufactured.
  • thermocouples were provided in the gas flow passages of the fuel production devices obtained in Examples 1 to 3 and Comparative Example 1. More specifically, the thermocouples were provided in the gas flow passages at positions 5 mm, 20 mm, 32 mm, and 45 mm from the inlet end face.
  • the fuel production apparatus was inserted into a reaction tube with an inner diameter of 21 mm.
  • the fuel production apparatus was heated to 240°C using an electric furnace installed on the outer periphery of the reaction tube, and hydrogen gas was introduced into the reaction tube to reduce the first catalyst.
  • the raw material gas was supplied to the gas flow passage provided in the fuel production apparatus, and the synthetic fuel gas flowed out from the reaction tube.
  • the internal pressure of the gas flow passage was 1 MPa.
  • the composition of the synthetic fuel gas flowing out from the reaction tube after the heating of the electric furnace was stopped was measured by a gas chromatograph-thermal conductivity detector (GC-TCD).
  • the conversion rate (%) of carbon monoxide to hydrocarbon compounds was calculated by the following formula (A-1).
  • CO conversion rate (%) (amount of hydrocarbon compounds contained in synthetic fuel gas (volume %)/total amount of hydrocarbon compounds and carbon monoxide contained in synthetic fuel gas (volume %)) ⁇ 100 (A-1)
  • the conversion rate (%) of carbon dioxide to hydrocarbon compounds was calculated using the following formula (A-2).
  • CO2 conversion rate (%) (amount of hydrocarbon compounds contained in synthetic fuel gas (volume %) / total amount of hydrocarbon compounds and carbon dioxide contained in synthetic fuel gas (volume %)) ⁇ 100 (A-2)
  • the CH4 selectivity (%) was calculated by the following formula (B).
  • Fuel production apparatus can be used to produce synthetic fuels, and are particularly suitable for producing petroleum alternative fuels that contain a sufficient amount of liquid fuel components with 5 to 20 carbon atoms.

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Abstract

Est prévu un dispositif de production de combustible permettant de produire efficacement un combustible synthétique présentant une excellente sélectivité pour des nombres de carbone allant de 5 à 20. Un dispositif de production de combustible selon un mode de réalisation de la présente invention comprend un matériau de base en céramique et une couche de catalyseur. Le matériau de base en céramique définit un trajet d'écoulement gazeux. Un gaz de matière première contenant de l'oxyde de carbone et de l'hydrogène est fourni au trajet d'écoulement gazeux. La couche de catalyseur est disposée sur une surface du matériau de base en céramique de façon à faire face au trajet d'écoulement gazeux. La couche de catalyseur comprend un premier catalyseur et un second catalyseur. Le premier catalyseur permet de favoriser la réaction de Fischer-Tropsch. Le second catalyseur permet de favoriser la réaction d'hydrocraquage et/ou la réaction d'isomérisation d'un gaz composé hydrocarboné produit par la réaction Fischer-Tropsch.
PCT/JP2025/012752 2024-03-29 2025-03-28 Dispositif de production de combustible Pending WO2025206305A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6211255B1 (en) * 1997-02-28 2001-04-03 Den Norske Stats Oljeselskap A.S. Fischer-tropsch synthesis
JP2001288123A (ja) * 2000-04-04 2001-10-16 Toyota Motor Corp 合成ガスからの低級イソパラフィンの合成方法
JP2017144426A (ja) * 2016-02-15 2017-08-24 新日鐵住金株式会社 合成ガスから炭化水素を製造するための触媒、合成ガスから炭化水素を製造するための触媒の製造方法、及び炭化水素の製造方法
WO2024024142A1 (fr) * 2022-07-29 2024-02-01 株式会社日立製作所 Dispositif et procédé de production d'hydrocarbures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6211255B1 (en) * 1997-02-28 2001-04-03 Den Norske Stats Oljeselskap A.S. Fischer-tropsch synthesis
JP2001288123A (ja) * 2000-04-04 2001-10-16 Toyota Motor Corp 合成ガスからの低級イソパラフィンの合成方法
JP2017144426A (ja) * 2016-02-15 2017-08-24 新日鐵住金株式会社 合成ガスから炭化水素を製造するための触媒、合成ガスから炭化水素を製造するための触媒の製造方法、及び炭化水素の製造方法
WO2024024142A1 (fr) * 2022-07-29 2024-02-01 株式会社日立製作所 Dispositif et procédé de production d'hydrocarbures

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