WO2024204110A1 - Ｃｏ２吸着材担持ハニカム構造体及びその製造方法、並びにｃｏ２の回収方法 - Google Patents

Ｃｏ２吸着材担持ハニカム構造体及びその製造方法、並びにｃｏ２の回収方法 Download PDF

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WO2024204110A1
WO2024204110A1 PCT/JP2024/011776 JP2024011776W WO2024204110A1 WO 2024204110 A1 WO2024204110 A1 WO 2024204110A1 JP 2024011776 W JP2024011776 W JP 2024011776W WO 2024204110 A1 WO2024204110 A1 WO 2024204110A1
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Prior art keywords
adsorbent
honeycomb structure
face
cells
supporting
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PCT/JP2024/011776
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English (en)
French (fr)
Japanese (ja)
Inventor
玄将 大西
義政 小林
祐司 勝田
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to JP2025510881A priority Critical patent/JPWO2024204110A1/ja
Priority to EP24780226.7A priority patent/EP4691622A1/en
Priority to AU2024246022A priority patent/AU2024246022A1/en
Priority to CN202480015426.6A priority patent/CN120882485A/zh
Publication of WO2024204110A1 publication Critical patent/WO2024204110A1/ja
Priority to US19/318,616 priority patent/US20260048383A1/en
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0454—Controlling adsorption
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40086—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a CO2 adsorbent material-supporting honeycomb structure and a manufacturing method thereof, and also to a CO2 recovery method using the CO2 adsorbent material- supporting honeycomb structure.
  • a typical conventional CO2 capture technology is the temperature swing method, which uses an amine-based material to adsorb CO2 and then heats the material to desorb the CO2 .
  • the temperature swing method has problems such as high energy consumption per amount of CO2 captured, high cost, and thermal degradation of the amine.
  • the humidity swing method in which CO2 is released by exposing an adsorbent that has adsorbed CO2 to a high humidity environment.
  • the humidity swing method does not require heating of the CO2 adsorbent, so it consumes less energy and is expected to lead to a significant reduction in costs and energy consumption.
  • Prior art documents related to the humidity swing method include the following:
  • Patent Document 1 Patent Publication No. 6204333 describes a technology in which carbon dioxide is absorbed into an absorbent containing a strongly basic ion exchange resin, and then the humidity of the absorbent is increased to release the carbon dioxide from the absorbent.
  • Non-patent document 1 (Xiaoyang Shi, Hang Xiao, Kohei Kanamori, Akio Yonezu, Klaus S. Lackner, Xi Chen, "Moisture-Driven CO2 Sorbents", Joule 4, 1823-1837, August 19, 2020) describes the adsorption and desorption of CO2 by humidity swing using an adsorbent powder made of porous carbon material (graphite) carrying carbonate.
  • Non-Patent Document 2 (Rafael Rodriguez-Mosqueda, Eddy A. Bramer, Gerrit Brem, “ CO2 capture from ambient air using hydrated Na2CO3 supported on activated carbon honeycombs with application to CO2 enrichment in greenhouses”, Chem. Eng. Sci. 189(2018) 114-122) describes how an activated carbon honeycomb monolith was wash-coated with an aqueous solution of sodium carbonate to produce a honeycomb monolith carrying sodium carbonate, and a CO2 adsorption/desorption test using a humidity swing was performed.
  • Patent Document 1 uses an ion exchange resin, and there is a concern that cracks may occur in the resin material if humidity swings are repeated to absorb and release CO2 .
  • it is a resin material, there is a concern that it has low durability against heat and ultraviolet rays, resulting in a short lifespan.
  • Non-Patent Document 1 reports an adsorbent using more stable graphite.
  • the amount of CO2 desorbed was small. This is thought to be because graphite is hydrophobic and therefore has poor reactivity with H2O , which prevents sufficient desorption of CO2 .
  • the test was conducted using powdered graphite, there is room for improvement in the CO2 adsorption speed.
  • Non-Patent Document 2 an adsorbent material in which sodium carbonate is supported on a honeycomb monolith made of activated carbon is used, but the adsorption and desorption capacity is small, and sufficient desorption capacity is not obtained even at 60°C. This is thought to be due to the fact that activated carbon is hydrophobic, and that the adsorbent material is not utilized inside the partition walls of the honeycomb monolith.
  • an object of the present invention is to provide a honeycomb structure to which a humidity swing type CO2 recovery method can be suitably applied in one embodiment.
  • An object of the present invention is to provide a method for manufacturing such a honeycomb structure in another embodiment.
  • the present inventors have conducted intensive research to solve the above problems and have found that it is advantageous to at least partially cover the surface of the partition walls of a honeycomb structure with a layer of a CO2 adsorbent material containing an alkali metal carbonate supported on a specific porous material.
  • the present invention has been completed based on the above findings and is exemplified below.
  • a honeycomb structure portion including partition walls extending from a first end surface to a second end surface and partitioning a plurality of cells forming a fluid flow path; a CO2 adsorbent layer at least partially covering a surface of the partition wall, the CO2 adsorbent layer containing one or more selected from zeolite, alumina, and silica, and containing an alkali metal carbonate supported on a porous material having a total content of zeolite, alumina, and silica of 50 mass% or more;
  • a CO2 adsorbent-supporting honeycomb structure comprising: [Aspect 2] A CO2 adsorbent-supporting honeycomb structure according to embodiment 1, wherein the average thickness of the CO2 adsorbent layer is 30 ⁇ m to 250 ⁇ m.
  • the partition walls are made of ceramics.
  • a method for recovering CO2, comprising the steps of: causing a first gas having a first humidity to flow into a first end face or a second end face of a honeycomb structure carrying a CO2 adsorbent according to any one of aspects 1 to 7; capturing CO2 in the first gas by the CO2 adsorbent while the first gas passes through the plurality of cells; and causing the first gas with a reduced CO2 concentration to flow out from the end face opposite the inlet side .
  • the method for recovering CO2 comprising the steps of: causing a second gas, water or a mixture thereof having a second humidity higher than the first humidity to flow into the first end face or the second end face of the CO2 adsorbent-supported honeycomb structure; causing CO2 captured in the CO2 adsorbent to be desorbed from the CO2 adsorbent while the second gas, water or a mixture thereof passes through the plurality of cells; and causing the second gas, water or a mixture thereof with an increased CO2 concentration to flow out from the end face opposite the inlet side.
  • a step A1 of preparing a honeycomb structure part including partition walls extending from a first end face to a second end face and partitioning a plurality of cells forming a fluid flow path;
  • a method for manufacturing a honeycomb structure carrying a CO2 adsorbent material comprising the steps of:
  • [Aspect 12] A method for manufacturing a CO2 adsorbent-supporting honeycomb structure according to aspect 11, wherein the step A3 includes a step of flowing a slurry containing the CO2 adsorbent into the cells from a first end face or a second end
  • a step B1 of preparing a honeycomb structure part including partition walls extending from a first end surface to a second end surface and partitioning a plurality of cells forming a fluid flow path;
  • a method for manufacturing a honeycomb structure carrying a CO2 adsorbent material comprising the steps of:
  • step B4 includes a step of flowing the aqueous solution of the alkali metal carbonate into the cells from a first end face or a second end face of the honeycomb structure portion.
  • the CO2 adsorbent-supported honeycomb structure is useful for improving the CO2 adsorption and desorption capacity because a layer of CO2 adsorbent containing an alkali metal carbonate supported on a specific porous material is provided on the surface of the partition wall, and it is possible to obtain a high CO2 adsorption rate.
  • the honeycomb structure can reduce pressure loss compared to ion exchange resins that fill the gas flow paths. Therefore, the CO2 adsorbent-supported honeycomb structure can be suitably applied to a CO2 recovery method using a humidity swing method.
  • FIG. 1 is a schematic perspective view of a CO 2 adsorbent material-supporting honeycomb structure according to one embodiment of the present invention.
  • 1 is a schematic diagram of a cross section parallel to the height direction (cell extension direction) of a CO 2 adsorbent material-supporting honeycomb structure according to one embodiment of the present invention.
  • 3 is a schematic partial enlarged view of a partition wall and a CO 2 adsorbent layer of a CO 2 adsorbent material-supporting honeycomb structure according to one embodiment of the present invention, observed in a cross section perpendicular to the cell extension direction.
  • FIG. 1 is a schematic perspective view of a CO 2 adsorbent material-supporting honeycomb structure according to one embodiment of the present invention.
  • 1 is a schematic diagram of a cross section parallel to the height direction (cell extension direction) of a CO 2 adsorbent material-supporting honeycomb structure according to one embodiment of the present invention.
  • 3 is a schematic partial enlarged view of a partition
  • 1 is a graph showing the relationship between the elapsed time and the amount of CO 2 desorption when a CO 2 adsorbent having zeolite, silica gel, or activated carbon is used as a porous material.
  • 1 is a graph showing the relationship between the elapsed time and the amount of CO 2 adsorption when CO 2 is adsorbed using a honeycomb structure supporting a CO 2 adsorbent material and a powdered CO 2 adsorbent material.
  • 1 is a graph showing the relationship between the average thickness of a CO2 adsorbent layer and the amount of CO2 adsorption.
  • 1 is a graph showing the relationship between the opening ratio of the first end face and the second end face and the amount of CO 2 adsorption.
  • FIG. 1 shows a schematic perspective view of a CO2 adsorbent-supporting honeycomb structure according to one embodiment of the present invention.
  • Fig. 2 shows a schematic view of a cross section parallel to the height direction (cell extension direction) of the CO2 adsorbent-supporting honeycomb structure shown in Fig. 1.
  • the CO 2 adsorbent-supported honeycomb structure 100 includes an outer peripheral side wall 102 and a honeycomb structure portion including partition walls 112 that are disposed inside the outer peripheral side wall 102, extend from a first end face 104 to a second end face 106, and partition multiple cells 108 that form a fluid flow path. The multiple cells 108 are arranged parallel to each other.
  • the CO 2 adsorbent-supported honeycomb structure 100 according to this embodiment also includes a CO 2 adsorbent layer 114 that at least partially covers the surface of the partition wall 112.
  • the CO 2 adsorbent-supported honeycomb structure 100 is a flow-through type in which both ends of each cell 108 are open to the first end face 104 and the second end face 106, and the fluid that flows in from the inlet of the cell can flow through the cell and flow out from the outlet of the cell.
  • the end face shape of the CO2 adsorbent-supporting honeycomb structure is not particularly limited, and may be, for example, a circular shape, an elliptical shape, a racetrack shape, an oval shape, or other round shape, a triangular shape, a rectangular shape, or other polygonal shape, or other irregular shape.
  • the overall outer shape of the CO2 adsorbent-supporting honeycomb structure may typically be a columnar shape.
  • the CO2 adsorbent-supporting honeycomb structure 100 shown in FIG. 1 has a circular end face shape and is cylindrical as a whole.
  • the CO2 adsorbent-supported honeycomb structure is a columnar body
  • its height is not particularly limited and may be appropriately set according to the application and required performance.
  • the length in the cell extension direction (height direction) of the CO2 adsorbent-supported honeycomb structure there is no particular limit to the length in the cell extension direction (height direction) of the CO2 adsorbent-supported honeycomb structure.
  • the length is preferably 50 to 300 mm, more preferably 60 to 270 mm, and even more preferably 70 to 250 mm.
  • the maximum diameter of each end face of the CO2 adsorbent-supported honeycomb structure is not particularly limited. However, while a larger maximum diameter allows a larger amount of CO2 adsorbent to be supported, if the maximum diameter is too large, it becomes difficult to cover with the CO2 adsorbent. Therefore, the maximum diameter is preferably 50 to 250 mm, more preferably 60 to 230 mm, and even more preferably 70 to 200 mm.
  • Ceramics include cordierite, mullite, zircon, zirconium phosphate, aluminum titanate, silicon carbide (SiC), silicon-silicon carbide composites (e.g., Si-bonded SiC), cordierite-silicon carbide composites, zirconia, spinel, indialite, sapphirine, corundum, titania, silicon nitride, alumina, silica-alumina, etc. These ceramics may contain one type alone or two or more types simultaneously.
  • the honeycomb structure portion is formed of ceramics containing 90 mass% or more of cordierite.
  • the total mass ratio of cordierite ( 2MgO.2Al2O3.5SiO2 ) in 100 mass% of the material constituting the honeycomb structure portion is 90 mass% or more.
  • the mass ratio of cordierite in 100 mass% of the material constituting the honeycomb structure portion is more preferably 95 mass% or more, and even more preferably 99 mass% or more. It is also possible that 100 mass% of the material constituting the honeycomb structure portion is cordierite, excluding unavoidable impurities.
  • the specific heat of the partition walls and the outer peripheral side wall of the honeycomb structure is preferably high. This is because, when the CO2 adsorbent-supported honeycomb structure is dried after supplying moisture into the cells in the process of desorbing CO2 , the temperature of the honeycomb structure is lowered by the heat of vaporization, and the drying time is likely to be long.
  • the specific heat of the partition walls and the outer peripheral side wall of the honeycomb structure is preferably 0.6 kJ/(kg ⁇ K) or more, more preferably 0.61 kJ/(kg ⁇ K) or more, and even more preferably 0.62 kJ/(kg ⁇ K) or more.
  • the specific heat of the partition walls and the outer peripheral side wall of the honeycomb structure is usually 1 kJ/(kg ⁇ K) or less, typically 0.95 kJ/(kg ⁇ K) or less, and more typically 0.9 kJ/(kg ⁇ K) or less. Therefore, the specific heat of the partition walls and the outer peripheral side wall of the honeycomb structure part is preferably 0.6 to 1 kJ/(kg ⁇ K), more preferably 0.61 to 0.95 kJ/(kg ⁇ K), and even more preferably 0.62 to 0.9 kJ/(kg ⁇ K).
  • the partition walls and the outer peripheral side wall of the honeycomb structure part made of cordierite can have a specific heat of about 0.7 to 0.8 kJ/(kg ⁇ K).
  • the partition walls and the outer peripheral side wall of the honeycomb structure part made of silicon-silicon carbide composite material can have a specific heat of about 0.63 to 0.73 kJ/(kg ⁇ K).
  • the specific heat of the partition walls and the outer peripheral side wall of the honeycomb structure part refers to the specific heat at 25° C. measured by a differential scanning calorimeter (DSC).
  • the average thickness of the partition walls is preferably 40 ⁇ m or more, more preferably 45 ⁇ m or more, and even more preferably 50 ⁇ m or more.
  • the average thickness of the partition walls is preferably 440 ⁇ m or less, more preferably 390 ⁇ m or less, and even more preferably 310 ⁇ m or less. Therefore, the average thickness of the partition walls is, for example, preferably 40 to 440 ⁇ m, more preferably 45 to 390 ⁇ m, and even more preferably 50 to 310 ⁇ m.
  • the thickness of the partition walls 112 refers to the length D of a line segment L that crosses the partition walls 112 when the line segment L connects the centers of gravity C of adjacent cells 108 in a cross section perpendicular to the extension direction of the cells 108 (height direction when the CO 2 adsorbent supported honeycomb structure is a columnar body).
  • the average thickness of the partition walls 112 refers to the average value of the thicknesses of all the partition walls 112 of the CO 2 adsorbent supported honeycomb structure.
  • the partition walls can be porous.
  • the average pore diameter is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, and even more preferably 1 ⁇ m or more, from the viewpoint of increasing the adhesion with the CO 2 adsorbent layer.
  • the average pore diameter of the partition walls is preferably 60 ⁇ m or less, more preferably 55 ⁇ m or less, and even more preferably 50 ⁇ m or less, from the viewpoint of ensuring strength. Therefore, the average pore diameter of the partition walls is, for example, preferably 0.5 to 60 ⁇ m, more preferably 0.7 to 55 ⁇ m, and even more preferably 1 to 50 ⁇ m.
  • the average pore size is measured by mercury intrusion porosimetry in accordance with JIS R1655:2003 using a mercury porosimeter.
  • Mercury intrusion porosimetry is a method in which a sample is immersed in mercury in a vacuum state, a uniform pressure is applied, mercury is inject into the sample while gradually increasing the pressure, and the pore size distribution is calculated from the pressure and the volume of mercury injecting into the pores.
  • the pressure is gradually increased, mercury is injecting from the pores with the largest diameter, and the cumulative volume of mercury increases, and when all the pores are finally filled with mercury, the cumulative volume reaches an equilibrium amount.
  • the cumulative volume at this time is the total pore volume (cm 3 /g), and the pore size (D50) at the time when mercury of 50% of the total pore volume is injecting is the average pore size.
  • the porosity of the partition walls is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more, from the viewpoint of ensuring the amount of CO2 adsorbent supported and from the viewpoint of suppressing the pressure loss when a fluid is passed through the cell.
  • the porosity of the partition walls is preferably 75% or less, more preferably 70% or less, and even more preferably 65% or less, from the viewpoint of ensuring the strength of the honeycomb structure. Therefore, the porosity of the partition walls is, for example, preferably 5 to 75%, more preferably 10 to 70%, and even more preferably 15 to 65%. In this specification, the porosity is measured by mercury intrusion porosimetry using a mercury porosimeter in accordance with JIS R1655:2003.
  • the cell density (the number of cells per unit cross-sectional area), but from the viewpoint of improving the contact area between the adsorbent on the partition wall and the gas being passed, it is preferably 20 cells/cm 2 or more, more preferably 25 cells/cm 2 or more, and even more preferably 30 cells/cm 2 or more.
  • the cell density is preferably 200 cells/cm 2 or less, more preferably 195 cells/cm 2 or less, and even more preferably 190 cells/cm 2 or less.
  • the cell density is, for example, preferably 20 to 200 cells/cm 2 , more preferably 25 to 195 cells/cm 2 , and even more preferably 30 to 190 cells/cm 2.
  • the cell density is calculated by dividing the number of cells in the honeycomb structure by the area of one end face excluding the outer peripheral side wall of the honeycomb structure.
  • the opening ratio (OFA) of the first end face and the second end face is large. Therefore, the lower limit of the opening ratio at the first end face and the second end face of the CO 2 adsorbent-supported honeycomb structure is preferably 35% or more, more preferably 40% or more, even more preferably 50% or more, and even more preferably 60% or more. In addition, by increasing the opening ratio (OFA), it is possible to suppress the pressure loss when a fluid is flowed through the cell.
  • the upper limit of the opening ratio at the first end face and the second end face is preferably 75% or less, more preferably 70% or less. Therefore, the opening ratio of the first end face and the second end face is, for example, preferably 35 to 75%, more preferably 40 to 75%, even more preferably 50 to 70%, and even more preferably 60 to 70%.
  • the aperture ratio at the first end face and the second end face of the CO 2 adsorbent-supported honeycomb structure is determined by the following method.
  • Optical microscope photographs (size of one field of view: 6.1 mm ⁇ 4.6 mm, magnification 50 times) of the first end face and the second end face of the CO 2 adsorbent-supported honeycomb structure are taken at five locations on each end face without bias.
  • Each optical microscope photograph is binarized by image processing, the area of only the cell opening is calculated, and the aperture ratio for each microscope photograph is obtained by dividing it by the area of one field of view, and the average value of the aperture ratio for all the microscope photographs is taken as the measured value.
  • the aperture ratio is measured taking into account the adsorbent layer, so for example, if the thickness of the adsorbent layer increases, the cell opening becomes smaller and the aperture ratio also becomes smaller.
  • the CO2 adsorbent layer 114 that at least partially covers the surface of the partition wall 112 contains one or more selected from zeolite, alumina, and silica, and contains an alkali metal carbonate supported on a porous material having a total content of zeolite, alumina, and silica of 50 mass% or more.
  • Zeolite, alumina, and silica have a higher affinity with water than carbon, so that the desorption reaction of CO2 is promoted even at low temperatures.
  • the CO2 adsorbent layer 114 contains a porous material having a total content of zeolite, alumina, and silica of 50 mass% or more, which contributes to improving the adsorption and desorption capacity when performing a humidity swing.
  • the porous material may contain only one of zeolite, alumina, and silica, or may contain two or three types in combination.
  • the total content of zeolite, alumina and silica in the porous material is more preferably 70% by mass or more, even more preferably 90% by mass or more, and can be 99% by mass or more (e.g. 100% by mass excluding unavoidable impurities).
  • the composition of the CO2 adsorbent layer may be specified by the material composition when the material composition when the adsorbent layer is formed is known, but when the material composition is unknown, about 0.1 to 0.5 g of a powdered sample of the adsorbent layer is collected and analyzed by an X-ray diffraction device (XRD, X-ray source: CuK ⁇ ray), and identified and quantified using ICDD data.
  • XRD X-ray diffraction device
  • zeolite a standard sample is prepared by mixing 90 mass% of the powdered sample of the adsorbent layer with 10 mass% of Si powder, and XRD analysis is performed, and the quantification is performed by comparing with the result of XRD analysis of a powder sample (90 mass% pure zeolite + 10 mass% Si powder) prepared separately for comparison.
  • XRD analysis is performed by the calibration curve method using ICP atomic emission spectrometry (ICP-AES), and aluminum is quantified as alumina and silicon is quantified as silica (however, the amount of zeolite quantified earlier is deducted).
  • alkali metal carbonate examples include one or more selected from potassium carbonate, sodium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, and francium carbonate.
  • Alkaline metal carbonates can efficiently chemically adsorb CO 2 in the presence of water vapor. For example, when sodium carbonate (Na 2 CO 3 ) is used as the alkali metal carbonate, CO 2 is chemically adsorbed according to the reaction formula Na 2 CO 3 + H 2 O + CO 2 ⁇ 2NaHCO 3.
  • the average thickness of the CO 2 adsorbent layer 114 is not limited, but is preferably 30 ⁇ m or more, more preferably 35 ⁇ m or more, and even more preferably 40 ⁇ m or more, from the viewpoint of increasing the amount of CO 2 adsorbent per volume of the CO 2 adsorbent-supported honeycomb structure.
  • the CO 2 adsorbent layer becomes too thick, it takes time for gas diffusion in the adsorbent layer, so that the CO 2 adsorption rate per unit mass of the CO 2 adsorbent and the CO 2 adsorption rate per unit volume of the honeycomb structure tend to decrease.
  • the average thickness of the CO 2 adsorbent layer 114 is preferably 250 ⁇ m or less, more preferably 230 ⁇ m or less, and even more preferably 200 ⁇ m or less. Therefore, the average thickness of the CO 2 adsorbent layer 114 is preferably, for example, 30 ⁇ m to 250 ⁇ m, more preferably 35 ⁇ m to 230 ⁇ m, and even more preferably 40 ⁇ m to 200 ⁇ m.
  • the average thickness of the CO2 adsorbent layer 114 is measured by the following method. First, a cross section perpendicular to the cell extension direction of the CO2 adsorbent-supported honeycomb structure 100 is cut out at 1/4, 1/2, and 3/4 of the length in the cell extension direction. Two cross sections are obtained by cutting out one section, and either one of the cross sections may be used. Next, the vicinity of the center of gravity of each of the three cross sections cut out at 1/4, 1/2, and 3/4 of the length in the cell extension direction is photographed at three locations using an optical microscope (size of one field of view: 6.1 mm x 4.6 mm, magnification 50 times). The thickness of the CO2 adsorbent layer 114 is measured at five arbitrary locations in each field of view.
  • the thickness T of the CO2 adsorbent layer 114 per location is defined as the length of the CO2 adsorbent layer 114 at either one of two locations intersected by a line segment L when the line segment L connects the centers of gravity C of adjacent cells 108 ( FIG. 3 ).
  • the average value of the thicknesses of all the CO2 adsorbent layer 114 measured at the three cross sections is defined as the measured value.
  • the CO2 adsorbent layer 114 at least partially covers the surface of the partition wall 112.
  • the surface area ratio of the partition wall 112 covered with the CO2 adsorbent is large.
  • the surface area ratio is preferably 40% or more, more preferably 60% or more, even more preferably 80% or more, and most preferably 100%.
  • the surface area ratio of the partition wall 112 covered with the CO 2 adsorbent is measured by the following method. First, a cross section perpendicular to the cell extension direction of the CO 2 adsorbent-supported honeycomb structure 100 is cut out at 1/4, 1/2, and 3/4 of the length in the cell extension direction. Two cross sections are obtained by cutting out one section, and either one of the cross sections may be used. Next, the vicinity of the center of gravity of each of the three cross sections cut out at 1/4, 1/2, and 3/4 of the length in the cell extension direction is photographed at three locations using an optical microscope (size of one field of view: 6.1 mm x 4.6 mm, magnification 50 times).
  • the total length of the sides of the surface of the partition wall 112 that divides any five cells 108 is measured, and the total value (total partition wall side length) is calculated.
  • the lengths of all the sides of the surfaces of the partition walls 112 that are covered with a layer of CO2 adsorbent material are measured, and the total value (total covered partition wall side length) is calculated.
  • the total covered partition wall side length/total partition wall side length ⁇ 100 (%) is calculated, and this is regarded as the area ratio of the partition wall surface covered with the CO2 adsorbent material in each visual field.
  • the average value of the area ratio in all visual fields measured in the three cross sections is regarded as the measured value for the entire honeycomb structure supporting the CO2 adsorbent material.
  • a method for recovering CO2 using the honeycomb structure carrying the CO2 adsorbent according to the above-mentioned embodiment includes a layer of the CO2 adsorbent containing an alkali metal carbonate carried on a porous material as described above.
  • the alkali metal carbonate carried on the porous material has a property of adsorbing CO2 in a low humidity environment and desorbing CO2 in a high humidity environment, so that the honeycomb structure carrying the CO2 adsorbent can be suitably applied to a CO2 recovery method using a humidity swing method.
  • a CO2 recovery method including the steps of: causing a first gas having a first humidity to flow into the first end face 104 or the second end face 106 of the CO2 adsorbent-supported honeycomb structure 100 according to the embodiment described above; capturing CO2 in the first gas by the CO2 adsorbent while the first gas passes through a plurality of cells 108; and causing the first gas with a reduced CO2 concentration to flow out from the end face opposite the inlet side.
  • the first gas is not particularly limited as long as it is a gas containing CO2 , and examples thereof include environmental air (outdoor air, as well as indoor or indoor air), factory exhaust gas, ship exhaust gas, and power plant exhaust gas.
  • the first humidity of the first gas is preferably 0 to 50% in terms of relative humidity (RH), more preferably 3 to 45%, and even more preferably 5 to 40%.
  • the temperature of the first gas is preferably 0 to 90°C, more preferably 5 to 85°C, and even more preferably 10 to 80°C.
  • the method includes a step of allowing a second gas, water or a mixture thereof having a second humidity higher than the first humidity to flow in from the first end face 104 or the second end face 106 of the CO2 adsorbent-supported honeycomb structure 100 according to the embodiment described above, desorbing the CO2 captured in the CO2 adsorbent from the CO2 adsorbent while the second gas, water or a mixture thereof passes through a plurality of cells 108, and allowing the second gas, water or a mixture thereof with an increased CO2 concentration to flow out from the end face opposite the inflow side.
  • the second gas having a second humidity higher than the first humidity is not particularly limited, and examples thereof include inert gases such as nitrogen, argon, and helium containing water vapor.
  • the inert gas containing water vapor can be obtained by passing the inert gas through water. Because the O2 concentration in the second gas is inhibited in the reaction when CO2 is used, it is preferable that the O2 concentration is 2% by volume or less, more preferably 1% by volume or less, and even more preferably 0% by volume.
  • the water may be liquid water, water vapor, or a combination thereof, and for example, low-temperature waste steam from a factory, for example, waste steam at 90°C or less, may be used.
  • the second gas and water may be used in combination.
  • the second humidity of the second gas is preferably 50 to 100% in relative humidity (RH), more preferably 55 to 100%, and even more preferably 60 to 100%.
  • the temperature of the second gas, water or a mixture thereof is preferably 5 ° C or higher, more preferably 10 ° C or higher, and even more preferably 15 ° C or higher.
  • the temperature of the second gas, water or a mixture thereof is preferably 90 ° C or lower, more preferably 85 ° C or lower, and even more preferably 80 ° C or lower. Therefore, the temperature of the second gas, water or a mixture thereof is preferably 5 to 90 ° C, more preferably 10 to 85 ° C, and even more preferably 15 to 85 ° C.
  • the CO2 adsorbent-supported honeycomb structure according to the above-mentioned embodiment is also applicable to a CO2 recovery method using a temperature swing method, and there is no problem in carrying out a CO2 recovery method using the temperature swing method.
  • the method for manufacturing a CO2 adsorbent-supported honeycomb structure according to the present invention includes a step A1 of preparing a honeycomb structure part having partition walls extending from a first end face to a second end face and partitioning a plurality of cells forming a fluid flow path, a step A2 of preparing a CO2 adsorbent containing an alkali metal carbonate supported on a porous material containing at least one selected from zeolite, alumina, and silica, and having a total content of zeolite, alumina, and silica of 50 mass% or more, and a step A3 of at least partially covering the surface of the partition wall with the CO2 adsorbent.
  • a honeycomb structure part is prepared, the honeycomb structure part having partition walls extending from a first end face to a second end face and partitioning a plurality of cells forming a fluid flow path.
  • a honeycomb structure part itself may be manufactured by any known manufacturing method, but a manufacturing method of a ceramic honeycomb structure part will be described below as an example.
  • a method for manufacturing a ceramic honeycomb structure includes the steps of: manufacturing a honeycomb molded body having an outer peripheral side wall and partition walls disposed inside the outer peripheral side wall and defining a plurality of cells extending from a first end face to a second end face; and sequentially drying, degreasing, and firing the honeycomb molded body.
  • Honeycomb molded bodies can be produced by kneading a raw material composition containing ceramic raw materials, a dispersion medium, a pore-forming material, and a binder to form a puddle, and then extruding the puddle. Additives such as dispersants can be mixed into the raw material composition as necessary. When extruding, a die having the desired overall shape, cell shape, partition wall thickness, cell density, etc. can be used.
  • the ceramic raw material is the raw material of the part that remains after firing and forms the skeleton of the honeycomb structure as ceramic.
  • the ceramic raw material can be provided, for example, in the form of a powder.
  • the ceramic raw material include raw materials for obtaining ceramics such as cordierite, mullite, zircon, zirconium phosphate, aluminum titanate, silicon carbide (SiC), silicon-silicon carbide composites (e.g., Si-bonded SiC), cordierite-silicon carbide composites, zirconia, spinel, indialite, sapphirine, corundum, titania, silicon nitride, alumina, and silica-alumina.
  • Ceramic raw material may be used alone or in combination of two or more types.
  • the pore-forming material is not particularly limited as long as it becomes pores after firing, and examples thereof include wheat flour, starch, foamed resin, water-absorbent resin, silica gel, carbon (e.g., graphite), ceramic balloons, polyethylene, polystyrene, polypropylene, nylon, polyester, acrylic, and phenol.
  • the pore-forming material may be used alone or in combination of two or more types. From the viewpoint of increasing the porosity of the honeycomb structure, the content of the pore-forming material is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass, per 100 parts by mass of the ceramic raw material.
  • the content of the pore-forming material is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 4 parts by mass or less, per 100 parts by mass of the ceramic raw material.
  • binders include organic binders such as methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. In particular, it is preferable to use methyl cellulose and hydroxypropoxyl cellulose in combination.
  • the content of the binder is preferably 4 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 6 parts by mass or more, per 100 parts by mass of the ceramic raw material.
  • the content of the binder is preferably 9 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 7 parts by mass or less, per 100 parts by mass of the ceramic raw material.
  • the binder may be used alone or in combination of two or more types.
  • dispersing agent surfactants such as ethylene glycol, dextrin, fatty acid soap, polyalcohol, etc. can be used.
  • the dispersing agent may be used alone or in combination of two or more types.
  • the content of the dispersing agent is preferably 0 to 2 parts by mass per 100 parts by mass of the ceramic raw material.
  • the dispersion medium can be water or a mixture of water and an organic solvent such as alcohol, but water is particularly suitable.
  • the water content of the honeycomb formed body before the drying process is preferably 20 to 90 parts by mass, more preferably 60 to 85 parts by mass, and even more preferably 70 to 80 parts by mass, per 100 parts by mass of the ceramic raw materials.
  • the water content of the honeycomb formed body is 20 parts by mass or more per 100 parts by mass of the ceramic raw materials, the advantage that the quality of the honeycomb formed body is easily stabilized is easily obtained.
  • the water content of the honeycomb formed body is 90 parts by mass or less per 100 parts by mass of the ceramic raw materials, the amount of shrinkage during drying is small, and deformation can be suppressed.
  • the water content of the honeycomb formed body refers to the value measured by the loss on drying method.
  • the conditions for the drying, degreasing and firing processes may be publicly known conditions according to the material composition of the honeycomb molded body, and although no special explanation is required, specific examples of conditions are given below.
  • a conventionally known drying method such as hot air drying, microwave drying, dielectric drying, reduced pressure drying, vacuum drying, freeze drying, etc.
  • a drying method that combines hot air drying with microwave drying or dielectric drying is preferred, since it allows the entire molded body to be dried quickly and uniformly.
  • the combustion temperature of the binder is about 200°C
  • the combustion temperature of the pore-forming material is about 300 to 1000°C. Therefore, the degreasing process can be carried out by heating the honeycomb formed body to a temperature range of about 200 to 1000°C.
  • the heating time is not particularly limited, but is usually about 10 to 100 hours.
  • the honeycomb formed body after the degreasing process is called a calcined body.
  • the firing process depends on the material composition of the honeycomb molded body, but can be carried out, for example, by heating the calcined body to 1350 to 1600°C and holding it there for 3 to 10 hours.
  • a CO2 adsorbent is prepared that contains one or more selected from zeolite, alumina, and silica, and that contains an alkali metal carbonate supported on a porous material having a total content of 50 mass% or more of zeolite, alumina, and silica.
  • the porous material may contain only one of zeolite, alumina, and silica, or may contain two or three of these in combination.
  • the porous zeolite can be provided in the form of, for example, a powder, and preferably has an average pore size of 0.1 to 2 nm, a BET specific surface area of 30 to 1,500 m2 /g, and a median size (D50) of 0.1 to 200 ⁇ m, more preferably has an average pore size of 0.15 to 1.8 nm, a BET specific surface area of 40 to 1,400 m2 /g, and a median size (D50) of 0.5 to 100 ⁇ m, and even more preferably has an average pore size of 0.2 to 1.5 nm, a BET specific surface area of 50 to 1,300 m2 /g, and a median size (D50) of 0.7 to 80 ⁇ m.
  • D50 median size
  • the porous alumina can be provided in the form of, for example, a powder, and is not limited to, one having an average pore diameter of 0.5 to 100 nm, a BET specific surface area of 1 to 1000 m2 /g, and a median diameter (D50) of 0.1 to 200 ⁇ m is preferably used, one having an average pore diameter of 0.7 to 90 nm, a BET specific surface area of 3 to 950 m2 /g, and a median diameter (D50) of 0.5 to 100 ⁇ m is more preferably used, and one having an average pore diameter of 1 to 80 nm, a BET specific surface area of 5 to 900 m2 /g, and a median diameter (D50) of 0.7 to 80 ⁇ m is even more preferably used.
  • the porous silica can be provided in the form of, for example, a powder, and is not limited thereto, and preferably has an average pore size of 0.5 to 100 nm, a BET specific surface area of 30 to 1500 m2 /g, and a median size (D50) of 0.1 to 200 ⁇ m, more preferably has an average pore size of 0.7 to 90 nm, a BET specific surface area of 40 to 1400 m2 /g, and a median size (D50) of 0.5 to 100 ⁇ m, and even more preferably has an average pore size of 1 to 80 nm, a BET specific surface area of 50 to 1300 m2 /g, and a median size (D50) of 0.7 to 80 ⁇ m.
  • Silica gel is preferably used as the porous silica.
  • the BET specific surface area of the porous material is calculated by a multipoint method using the BET equation from the nitrogen gas adsorption isotherm.
  • the median diameter (D50) of the porous material is determined from a volume-based cumulative particle size distribution obtained by a laser diffraction/scattering method.
  • An example of a method for supporting an alkali metal carbonate on a porous material is a method in which a powder of the porous material and an aqueous solution of the alkali metal carbonate are stirred and mixed to form a slurry, and then the resulting slurry is dried.
  • An example of a drying method is a vacuum drying method. The temperature during drying is not particularly limited, but can be 20 to 200°C. After drying, a CO2 adsorbent containing the alkali metal carbonate supported on the porous material is obtained.
  • step A3 the surface of the partition wall of the honeycomb structure part is at least partially coated with a CO 2 adsorbent.
  • a coating method includes a method of preparing a slurry containing the CO 2 adsorbent by dispersing the CO 2 adsorbent in a solvent, contacting the slurry with the surface of the partition wall, and then drying the slurry.
  • the solvent alcohols such as ethanol, isopropanol, butanol, and other organic solvents can be suitably used.
  • a method of contacting the slurry with the surface of the partition wall a method of immersing the honeycomb structure part in the slurry, or the like, and causing the slurry to flow into the cell from the first end face or the second end face of the honeycomb structure part can be mentioned.
  • a drying method for example, a vacuum drying method can be mentioned.
  • the temperature during drying is not particularly limited, but can be 20 to 200 ° C.
  • a manufacturing method for a CO2 adsorbent-supported honeycomb structure includes a step B1 of preparing a honeycomb structure portion having partition walls extending from a first end face to a second end face and partitioning a plurality of cells which form a fluid flow path, a step B2 of preparing a porous material containing one or more selected from zeolite, alumina and silica, the total content of zeolite, alumina and silica being 50 mass% or more, a step B3 of at least partially covering a surface of the partition wall with the porous material, and a step B4 of supporting an alkali metal carbonate on the porous material at least partially covering the surface of the partition wall.
  • Step B1 is the same as step A1 described above, so a description thereof will be omitted.
  • Step B2 a porous material containing at least one selected from zeolite, alumina, and silica, and having a total content of zeolite, alumina, and silica of 50 mass% or more is prepared.
  • the porous material may be the porous material described in step A2.
  • Step B3 the surface of the partition wall of the honeycomb structure part is at least partially coated with a porous material.
  • a method of coating the porous material includes preparing a slurry containing the porous material by stirring and dispersing the porous material in a solvent, contacting the slurry with the surface of the partition wall, and then drying the slurry.
  • the solvent alcohols such as ethanol, isopropanol, butanol, and other organic solvents, or water can be suitably used.
  • a method of contacting the slurry with the surface of the partition wall a method of immersing the honeycomb structure part in the slurry, or the like, and causing the slurry to flow into the cells from the first end face or the second end face of the honeycomb structure part can be used.
  • a drying method for example, a vacuum drying method can be used.
  • the temperature during drying is not particularly limited, but can be 20 to 200°C.
  • Step B4 an alkali metal carbonate is supported on the porous material at least partially covering the surface of the partition wall of the honeycomb structure part.
  • a method for supporting the alkali metal carbonate on the porous material for example, a method of contacting the surface of the partition wall with an aqueous solution of the alkali metal carbonate and then drying the aqueous solution can be mentioned.
  • a method for contacting the surface of the partition wall with the aqueous solution a method of immersing the honeycomb structure part in the aqueous solution, for example, and causing the aqueous solution to flow into the cells from the first end face or the second end face of the honeycomb structure part can be mentioned.
  • a vacuum drying method can be mentioned.
  • the temperature during drying is not particularly limited, but can be 20 to 200 ° C.
  • a CO 2 adsorbent containing an alkali metal carbonate supported on the porous material is obtained.
  • honeycomb structure For laboratory testing, a sufficient number of cordierite rectangular parallelepiped honeycomb structures with dimensions of 20 mm x 20 mm x height (cell extension length) of 10 mm and open at both ends were prepared for each of the following tests.
  • the honeycomb structures had an average partition wall thickness of 10 mil (254 ⁇ m), an average partition wall pore size of 11 ⁇ m, a partition wall porosity of 56%, and a cell density of 300 cells/in 2 (47 cells/cm 2 ).
  • the cross-sectional shape of the cells in the honeycomb structures was square.
  • the specific heat of the honeycomb structures was 0.76 kJ/(kg ⁇ K).
  • the amount of the CO2 adsorbent A carried by the honeycomb structure A was about 0.5 g.
  • the honeycomb structure A had an opening ratio of 58% at the first end face and the second end face.
  • the CO2 adsorbent B prepared above was put into ethanol so that the concentration was 20% by mass, and the mixture was stirred to form a slurry.
  • the honeycomb structure obtained above was immersed in the slurry, and after 1 minute, it was pulled out and vacuum dried at room temperature for 24 hours. The same immersion and drying process was then performed again to prepare a honeycomb structure B carrying the CO2 adsorbent B.
  • the average thickness of the layer of the CO2 adsorbent B was 52 ⁇ m.
  • the surface area ratio of the partition wall covered by the CO2 adsorbent B was 96%.
  • the amount of the CO2 adsorbent B carried by the honeycomb structure B was about 0.5 g.
  • the honeycomb structure B had an opening ratio of 57% at the first end face and the second end face.
  • the same immersion and drying process was then performed again to prepare a honeycomb structure C carrying the CO2 adsorbent C.
  • the average thickness of the layer of the CO2 adsorbent C was 56 ⁇ m.
  • the surface area ratio of the partition wall covered by the CO2 adsorbent C was 95%.
  • the amount of the CO2 adsorbent C carried by the honeycomb structure C was about 0.5 g.
  • the honeycomb structure C had an opening ratio of 56% at the first end face and the second end face.
  • the honeycomb structures A, B, and C obtained above were subjected to CO2 adsorption and desorption tests using the following test equipment.
  • the test equipment has a 12 L chamber equipped with an air inlet, an air outlet, a fan, a CO2 concentration meter, and a thermo-hygrometer.
  • An air circulation system is connected to this chamber, and the air that flows into the chamber from the air inlet passes through the chamber, flows out from the air outlet, and is piping-configured so that it flows back into the chamber by a circulation pump.
  • a humidifier and a dehumidifier are installed in parallel in the circulation system, making it possible to switch the humidity of the air flowing into the chamber.
  • the fan was rotated at 5 W to agitate the air in the chamber, and humidified air with a relative humidity of 90% or more and a temperature of about 27°C was circulated in the chamber at a flow rate of 12 L/min by a circulation pump, and CO2 was desorbed from the honeycomb structure for 30 minutes (second desorption process).
  • second desorption process the relationship between the elapsed time when CO2 was desorbed and the amount of CO2 desorbed was calculated from the change in CO2 concentration in the chamber.
  • honeycomb structure C supporting the CO 2 adsorbent C using activated carbon as a porous material had a significantly slower desorption rate than the honeycomb structure A (porous material is zeolite) and the honeycomb structure B (porous material is silica gel).
  • Test II Verification of the effect of supporting a CO2 adsorbent on a honeycomb structure> (1. Measurement of CO2 adsorption rate by honeycomb structure B supporting CO2 adsorbent B)
  • a honeycomb structure B carrying a CO 2 adsorbent B using silica gel as a porous material was prepared.
  • a CO 2 adsorption test was performed using a test device similar to that used in Test I. The test procedure is as follows. The honeycomb structure B was placed in a chamber.
  • the results are shown in Figure 5.
  • the CO2 adsorption amount (molar number) per unit mass of the adsorbent was standardized with the CO2 adsorption amount of honeycomb structure B after 120 minutes set to 1.
  • the time required to reach 80% of the CO2 adsorption amount 120 minutes after the start of adsorption 80 % adsorption time) is shown in Table 2. From these results, it can be seen that the CO2 adsorption rate of honeycomb structure B supporting CO2 adsorbent B is significantly higher than that of powdered CO2 adsorbent B.
  • the honeycomb structure part X had an average partition wall thickness of 2.5 mil (64 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 900 cells/in 2 (140 cells/cm 2 ).
  • the cross-sectional shape of the cells of the honeycomb structure part X was square.
  • the specific heat of the honeycomb structure part X was 0.76 kJ/(kg ⁇ K).
  • honeycomb structures supporting CO2 adsorbent B having average layer thicknesses of 30 ⁇ m, 40 ⁇ m, and 70 ⁇ m were produced under the same conditions as above except that the number of times the immersion and drying process was repeated was changed.
  • the average thickness of the layer of CO2 adsorbent B average thickness
  • the surface area ratio of the partition wall covered by CO2 adsorbent B coverage rate
  • the amount of CO2 adsorbent B supported adsorbent amount
  • opening rate opening rate
  • honeycomb structure part Y (2. Production of a honeycomb structure supporting a CO2 adsorbent using the honeycomb structure part Y)
  • a sufficient number of honeycomb structure parts Y made of cordierite in the shape of a rectangular parallelepiped of 20 mm x 20 mm x height (cell extension length) 10 mm and open at both ends were prepared for each of the following tests.
  • the honeycomb structure part Y had an average partition wall thickness of 2.5 mil (64 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 300 cells/in 2 (47 cells/cm 2 ).
  • the cross-sectional shape of the cells of the honeycomb structure part was square.
  • the specific heat of the honeycomb structure part was 0.76 kJ/(kg ⁇ K).
  • the honeycomb structure had an opening ratio of 86% at the first end face and the second end face.
  • honeycomb structures supporting CO2 adsorbent B having average layer thicknesses of CO2 adsorbent B of 200 ⁇ m, 250 ⁇ m, 300 ⁇ m, and 350 ⁇ m were produced under the same conditions as above except that the number of times the immersion and drying process was repeated was changed.
  • the average thickness of the layer of CO2 adsorbent B average thickness
  • the surface area ratio of the partition wall covered by CO2 adsorbent B coverage rate
  • the amount of CO2 adsorbent B supported adsorbent amount
  • opening rate opening rate
  • the results are shown in Figure 6.
  • the CO2 adsorption amount (number of moles) per unit volume of the honeycomb structure was standardized by taking the value of a honeycomb structure in which the average thickness of the layer of CO2 adsorbent B was 100 ⁇ m as 1. It can be seen from Figure 6 that the CO2 adsorption amount per unit volume of the honeycomb structure becomes high when the average thickness of the layer of CO2 adsorbent B is in the range of 30 to 250 ⁇ m.
  • honeycomb structure part 1 For laboratory testing, a flow-through honeycomb structure 1 was prepared, made of cordierite in the shape of a rectangular parallelepiped measuring 20 mm x 20 mm x height (cell extension length) 10 mm, with both ends open.
  • the honeycomb structure 1 had an average partition wall thickness of 4.0 mil (102 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 400 cells/in 2 (62 cells/cm 2 ).
  • the cross-sectional shape of the cells in the honeycomb structure 1 was square.
  • the specific heat of the honeycomb structure 1 was 0.76 kJ/(kg ⁇ K).
  • honeycomb structure part 2 For laboratory testing, a flow-through honeycomb structure 2 was prepared, which was made of cordierite in the shape of a rectangular parallelepiped measuring 20 mm x 20 mm x height (cell extension length) 10 mm and had both ends open.
  • the honeycomb structure 2 had an average partition wall thickness of 3.5 mil (89 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 400 cells/in 2 (62 cells/cm 2 ).
  • the cross-sectional shape of the cells of the honeycomb structure 2 was square.
  • the specific heat of the honeycomb structure 2 was 0.76 kJ/(kg ⁇ K).
  • honeycomb structure 3 For laboratory testing, a flow-through honeycomb structure 3 was prepared, which was made of cordierite in the shape of a rectangular parallelepiped measuring 20 mm x 20 mm x height (cell extension length) 10 mm and had both ends open.
  • the honeycomb structure 3 had an average partition wall thickness of 2.5 mil (64 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 200 cells/in 2 (31 cells/cm 2 ).
  • the cross-sectional shape of the cells of the honeycomb structure 3 was square.
  • the specific heat of the honeycomb structure 3 was 0.76 kJ/(kg ⁇ K).
  • honeycomb structure 4 For laboratory testing, a flow-through honeycomb structure 4 was prepared, which was made of cordierite in the shape of a rectangular parallelepiped measuring 20 mm x 20 mm x height (cell extension length) 10 mm and had both ends open.
  • the honeycomb structure 4 had an average partition wall thickness of 2.5 mil (64 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 300 cells/in 2 (47 cells/cm 2 ).
  • the cross-sectional shape of the cells in the honeycomb structure 4 was square.
  • the specific heat of the honeycomb structure 4 was 0.76 kJ/(kg ⁇ K).
  • honeycomb structure 6 For laboratory testing, a flow-through honeycomb structure 6 was prepared, which was made of cordierite in the shape of a rectangular parallelepiped measuring 20 mm x 20 mm x height (cell extension length) 10 mm and had both ends open.
  • the honeycomb structure 6 had an average partition wall thickness of 2.5 mil (64 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 600 cells/in 2 (93 cells/cm 2 ).
  • the cross-sectional shape of the cells of the honeycomb structure 6 was square.
  • the specific heat of the honeycomb structure 6 was 0.76 kJ/(kg ⁇ K).
  • honeycomb structure 7 For laboratory testing, a flow-through honeycomb structure 7 was prepared, which was made of cordierite in the shape of a rectangular parallelepiped measuring 20 mm x 20 mm x height (cell extension length) 10 mm and had both ends open.
  • the honeycomb structure 7 had an average partition wall thickness of 2.5 mil (64 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 900 cells/in 2 (140 cells/cm 2 ).
  • the cross-sectional shape of the cells in the honeycomb structure 7 was square.
  • the specific heat of the honeycomb structure 7 was 0.76 kJ/(kg ⁇ K).
  • honeycomb structure 8 For laboratory testing, a flow-through honeycomb structure 8 was prepared, which was made of cordierite in the shape of a rectangular parallelepiped measuring 20 mm x 20 mm x height (cell extension length) 10 mm and had both ends open.
  • the honeycomb structure 8 had an average partition wall thickness of 2.5 mil (64 ⁇ m), an average partition wall pore size of 5 ⁇ m, a partition wall porosity of 47%, and a cell density of 1200 cells/in 2 (186 cells/cm 2 ).
  • the cross-sectional shape of the cells of the honeycomb structure 8 was square.
  • the specific heat of the honeycomb structure 8 was 0.76 kJ/(kg ⁇ K).
  • honeycomb structure supporting CO2 adsorbent B (2. Preparation of honeycomb structure supporting CO2 adsorbent B)
  • the CO 2 adsorbent B described in Test I was prepared, and was put into ethanol to a concentration of 20% by mass, and mixed and stirred to form a slurry.
  • the honeycomb structure parts 1 to 8 obtained above were immersed in the slurry, and after 1 minute, they were pulled out and vacuum dried at room temperature for 24 hours. The same immersion and drying process was then performed again to produce a honeycomb structure supporting the CO 2 adsorbent B.
  • the average thickness of the layer of the CO 2 adsorbent B of each honeycomb structure was unified to 100 ⁇ m.
  • the mass when the average thickness of the layer of the CO 2 adsorbent B becomes 100 ⁇ m based on the cell structure of the honeycomb structure part was calculated assuming a porosity of 50%, and the average thickness was adjusted to 100 ⁇ m by performing the immersion and drying process until the mass was reached.
  • the surface area ratio of the partition wall covered with the CO 2 adsorbent B was 94%.
  • Table 5 shows the mass of the CO 2 adsorbent B supported on each honeycomb structure and the opening ratio at the first end face and the second end face of each honeycomb structure.
  • the actual CO2 adsorption performance is determined by the amount of CO2 adsorbed per unit volume of the honeycomb structure. From the above results, it can be seen that the range of opening ratio that provides an excellent balance between the utilization rate of the CO2 adsorbent and the CO2 adsorption performance is 60% to 70%, particularly 62% to 68%.
  • CO2 adsorbent-supporting honeycomb structure 102: Outer peripheral side wall 104: First end face 106: Second end face 108: Cell 112: Partition wall 114: CO2 adsorbent layer

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PCT/JP2024/011776 2023-03-30 2024-03-25 Ｃｏ２吸着材担持ハニカム構造体及びその製造方法、並びにｃｏ２の回収方法 Ceased WO2024204110A1 (ja)

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