WO2024100945A1 - Matériau adsorbant le dioxyde de carbone, dispositif adsorbant le dioxyde de carbone, leur procédé de fabrication et procédé d'adsorption de dioxyde de carbone - Google Patents

Matériau adsorbant le dioxyde de carbone, dispositif adsorbant le dioxyde de carbone, leur procédé de fabrication et procédé d'adsorption de dioxyde de carbone Download PDF

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WO2024100945A1
WO2024100945A1 PCT/JP2023/028179 JP2023028179W WO2024100945A1 WO 2024100945 A1 WO2024100945 A1 WO 2024100945A1 JP 2023028179 W JP2023028179 W JP 2023028179W WO 2024100945 A1 WO2024100945 A1 WO 2024100945A1
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carbon dioxide
amino group
carbon
adsorption
carbon atoms
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Japanese (ja)
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藤章裕
馬見塚璃奈
吉田和行
井上宏志
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株式会社西部技研
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    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • B01J20/34—Regenerating or reactivating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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 carbon dioxide adsorbent that adsorbs carbon dioxide contained in a gas, and in particular to a carbon dioxide adsorbent that suppresses deterioration over time and improves durability.
  • plants grown in greenhouses, etc. absorb carbon dioxide during the day through photosynthesis, and the carbon dioxide concentration around the leaves becomes lower than the carbon dioxide concentration in the atmosphere (approximately 400 ppm).
  • the photosynthesis of the cultivated plants is suppressed, resulting in a decrease in the yield and sugar content of the cultivated plants, so a process is carried out in which carbon dioxide is forcibly supplied from outside to improve the yield of the cultivated plants.
  • carbon dioxide is supplied by burning kerosene or by using liquefied carbon dioxide cylinders.
  • a conventional carbon dioxide supply device that the applicant has developed thus far is a carbon dioxide absorption removal/concentration device that has a carbon dioxide removal rotor that holds a carbon dioxide adsorbent with carbon dioxide absorption function, and divides the carbon dioxide removal rotor into at least an adsorption zone and a desorption zone.
  • the carbon dioxide contained in the air to be treated is absorbed by the retained absorbent in the carbon dioxide removal rotor, separated and removed, and supplied to the supply destination.
  • regeneration air that has recovered the latent heat and sensible heat of the regeneration exhaust from the desorption zone in a total heat exchanger is passed through, causing the retained absorbent to desorb the carbon dioxide absorbed in the adsorption zone, thereby regenerating the retained absorbent (see Patent Document 1).
  • organic absorbents such as triethanolamine and monoethanolamine, or amine-based weakly basic anion exchange resins, amine-supported solid absorbents such as activated carbon, silica gel, and mesoporous silica (hereinafter referred to as "amine compounds”) are used as carbon dioxide adsorbents, taking advantage of their ability to absorb carbon dioxide.
  • the amine compound is heated to desorb the carbon dioxide absorbed by it.
  • this heating causes the amino groups that make up the amine compound to oxidize or desorb.
  • carbon dioxide adsorbents that use amine compounds can easily deteriorate over time due to oxidation, etc., when used for a long period of time, and their carbon dioxide absorption and desorption properties decrease.
  • Non-Patent Document 1 Methods for suppressing the oxidation of amine compounds have also been studied. For example, it is known that the oxidation of amine compounds can be suppressed by forming a nitrogen atmosphere (see Non-Patent Document 1). It is also known that the oxidation of amine compounds can be suppressed by mixing an antioxidant (see Non-Patent Document 2).
  • amine compounds The properties of amine compounds are generally such that they absorb and desorb carbon dioxide at atmospheric pressure through a chemical reaction involving amino groups.
  • amino groups alone are not able to absorb enough carbon dioxide. Therefore, in order to more efficiently absorb and desorb carbon dioxide from the atmosphere, conventional carbon dioxide adsorbents mainly use amine compounds that contain multiple primary and secondary amino groups.
  • known conventional carbon dioxide adsorbents include those that contain organosilicon compounds that contain cyclic or chain amidine moieties (e.g., 1-[3-(trimethoxysilyl)propyl]-2-imidazoline, 1-[3-(trimethoxysilyl)propyl]-1,4,5,6-tetrahydropyrimidine, 1-[3-(silatranyl)propyl]-2-imidazoline, or 1-[3-(silatranyl)propyl]-1,4,5,6-tetrahydropyrimidine) (see Patent Document 2).
  • organosilicon compounds that contain cyclic or chain amidine moieties e.g., 1-[3-(trimethoxysilyl)propyl]-2-imidazoline, 1-[3-(trimethoxysilyl)propyl]-1,4,5,6-tetrahydropyrimidine, 1-[3-(silatranyl)propyl]-2-imi
  • a conventional carbon dioxide adsorbent that has a chemical structure in which functional groups including at least a primary amino group are bonded, contains a polymer compound that repeatedly adsorbs carbon dioxide and releases it when heated, is formed in a porous shape, and has a ratio d/w of the stress at 10% deformation in a dry state d to the stress at 10% deformation in a wet state w, which is a value in the range of 1 or more and 10 or less (see Patent Document 3).
  • some conventional carbon dioxide adsorbents use a composition containing at least one amine compound selected from the group consisting of amine compounds represented by the following general formula and a carrier (in the following formula, R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; n represents 0 or 1; R9 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aminoalkyl group having 3 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms; and R10 and R11 each independently represent an alkylene group having 1 to 4 carbon atoms) (see Patent Document 4).
  • R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • n represents 0 or 1
  • R9 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aminoalkyl group having 3 to 4 carbon atoms, or a hydroxyalky
  • JP 2020-89891 A Patent No. 5498717 JP 2022-122253 A JP 2022-154003 A
  • the amine compound constituting the conventional carbon dioxide adsorbent has a double bond between amino groups.
  • the ⁇ bond forming this double bond has a relatively high electron density. Therefore, the structure is prone to cleavage by radical reactions.
  • R 21 is a hydrogen atom or an alkyl group having 1 to 27 carbon atoms
  • R 22 and R 23 are each independently an alkyl group having 1 to 4 carbon atoms
  • R 24 , R 25 , and R 26 are each independently an alkyl group having 1 to 30 carbon atoms.
  • the alkylene e.g., methylene
  • the alkylene itself connecting the two amino groups is now in a structure that is easily cleaved by the progression of the following Hoffmann elimination (A).
  • the reaction proceeds further with the acid amide compound that exists in this chemical equilibrium state, and the amide carbonyl group is eliminated from the acid amide compound, and the other amine is separated (Hoffmann elimination).
  • the progress of this Hoffmann elimination (A) causes the conventional carbon dioxide adsorbent to decompose.
  • the amino compound of Patent Document 4 also has a structure in which there is no double bond between the amino groups as described above, but the same phenomenon as that of Patent Document 3 occurs.
  • amine compounds particularly aminosilanes
  • carriers with a high specific surface area such as silica gel or mesoporous silica.
  • this further accelerates the adsorption and desorption of carbon dioxide, and in the above-mentioned amine compounds, the frequency with which the amine compounds are oxidized and desorbed also increases, resulting in an accelerated decline in the carbon dioxide adsorption and desorption performance.
  • the present invention was made to solve the above problems, and aims to provide a carbon dioxide adsorbent that suppresses deterioration over time and exhibits high durability even when used repeatedly in carbon dioxide adsorption processes.
  • the carbon dioxide adsorbent disclosed in this application is composed of an amine compound containing a first amino group consisting of a primary amino group, a second amino group consisting of a primary amino group, a secondary amino group, or a tertiary amino group, and a straight-chain alkylene having 2 to 6 carbon atoms substituted with a straight-chain alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, linking the first amino group and the second amino group.
  • FIG. 1 shows a configuration diagram of a carbon dioxide adsorbing material according to a first embodiment of the present invention.
  • FIG. 2 is an explanatory diagram of a method for producing a carbon dioxide adsorbing material according to a first embodiment of the present invention.
  • FIG. 2 is a flowchart showing a method for using the carbon dioxide adsorbing material according to the first embodiment of the present invention.
  • FIG. 4 shows a configuration diagram of a carbon dioxide adsorbing material according to a second embodiment of the present invention.
  • 5 shows an example of a filter shape of a carbon dioxide adsorption device according to a second embodiment of the present invention.
  • FIG. 11 is an explanatory diagram of a method of using a carbon dioxide adsorption device according to a second embodiment of the present invention.
  • FIG. 13 is a flow chart showing a method for using a carbon dioxide adsorption device according to a third embodiment of the present invention.
  • 13A to 13C are explanatory diagrams of a method of using a carbon dioxide adsorption device according to a third embodiment of the present invention.
  • FIG. 11 is a configuration diagram of a honeycomb rotor of a carbon dioxide adsorption device according to a third embodiment of the present invention.
  • 13A to 13C are explanatory diagrams of a method of using a carbon dioxide adsorption device according to a third embodiment of the present invention.
  • 3 shows the results of a durability test of the carbon dioxide adsorbing material in Example 1 according to the present invention.
  • 4 shows the results of a dynamic performance test of the carbon dioxide adsorbing material according to Example 2 of the present invention.
  • the carbon dioxide adsorbent according to the first embodiment is composed of an amine compound including a first amino group consisting of a primary amino group, a second amino group consisting of a primary amino group, a secondary amino group or a tertiary amino group, and a linear alkylene having 2 to 6 carbon atoms substituted with a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, linking the first amino group and the second amino group.
  • this primary amino group is configured as a primary amino group at the end of this amine compound, the NH bonds involved in the carbon dioxide adsorption reaction become abundant, making it possible to adequately adsorb carbon dioxide even under low-temperature conditions, and demonstrating high adsorption performance for carbon dioxide.
  • This second amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, and is not particularly limited. In terms of exhibiting high adsorption performance for carbon dioxide, a primary amino group or a secondary amino group having an NH bond involved in the adsorption reaction of carbon dioxide is preferable.
  • the first amino group and the second amino group are each connected to the carbon atoms at both ends of the linear alkylene by a C-N bond.
  • This linear alkylene has a main skeleton of a linear structure having 2 to 6 carbon atoms, and at least one atom constituting this linear structure is substituted with a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms. Note that if there are many substituted alkyl groups, the specific heat increases and the energy load increases in the desorption of carbon dioxide, so the upper limit is set to 3 carbon atoms for linear alkyl groups and 4 carbon atoms for branched alkyl groups.
  • the linear alkylene has an alkyl group substituting a part of it, which forms an optimal steric hindrance between the primary amino group and the secondary amino group that makes it difficult for carbon dioxide molecules to approach each other sterically, suppressing the desorption of the primary amino group (e.g., Hoffman elimination) and the reduction of the secondary amino group, as well as suppressing the oxidation of the primary amino group (e.g., radical mechanism). It is therefore considered that if the linear alkylene is long, the specific heat increases and the energy load increases in the desorption of carbon dioxide, so the upper limit is set to 6 carbon atoms.
  • the straight-chain alkylene has one carbon atom (methylene)
  • the Hoffmann elimination tends to proceed as described above, so the number of carbon atoms is not set to 1.
  • the ratio of NH bonds involved in the carbon dioxide adsorption reaction relative to the molecular weight of the amine compound decreases, resulting in a decrease in carbon dioxide adsorption performance, so the above-mentioned carbon numbers are set as the upper limit.
  • the linear structure of the main skeleton of this linear alkylene includes ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene, and any of these can be used.
  • ethylene can be used.
  • the alkyl group that substitutes part of the linear structure of the main skeleton of this linear alkylene includes linear groups such as methyl, ethyl, and propyl, and branched groups such as isopropyl and tert-butyl.
  • the alkyl group that replaces part of the straight-chain structure of the main skeleton of this straight-chain alkylene replaces at least one carbon atom that makes up this straight-chain structure, and may replace only one carbon atom that makes up this straight-chain structure, or may replace two or more carbon atoms that make up this straight-chain structure, or may replace multiple hydrogen atoms on the same carbon atom that makes up this straight-chain structure.
  • An example of an amine compound having such a structure is the one shown in the following general formula (1).
  • R1 and R1 ' are functional groups constituting the second amino group, and each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the second amino group constitutes a primary amino group.
  • the second amino group constitutes a secondary amino group.
  • the second amino group constitutes a tertiary amino group.
  • R 21m and R 22m each independently represent a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, at least one of R 21m and R 22m being a linear or branched alkyl group, and m being a natural number of 2 to 6.
  • this natural number m indicates the carbon chain length of the linear alkylene that connects the first amino group and the second amino group. Therefore, the linear alkylene has a chain length longer than ethylene.
  • At least one of the carbon atoms constituting this carbon chain is substituted with a linear or branched alkyl group represented by R 21m or R 22m .
  • R 211 , R 212 , R 221 and R 222 there are four alkyl groups, R 211 , R 212 , R 221 and R 222 , as R 21m and R 22m , and for example, only one of them, R 211 , may be a linear or branched alkyl group, and the other R 212 , R 221 and R 222 may be hydrogen atoms. Also, for example, two of them, R 211 and R 212 , may be linear or branched alkyl groups, and the other R 221 and R 222 may be hydrogen atoms.
  • R 211 , R 212 and R 221 may be linear or branched alkyl groups, and the other R 222 may be hydrogen atoms. Also, for example, all four of them, R 211 , R 212 , R 221 and R 222 , may be linear or branched alkyl groups.
  • the carbon dioxide adsorbent according to this embodiment is preferably made of an aminosilane, among other amine compounds, for ease of handling, and more preferably contains a silicon atom substituted with an alkoxy group having 1 to 6 carbon atoms, and a linear alkylene having 1 to 6 carbon atoms that links the silicon atom to the nitrogen atom in the second amino group.
  • the silicon atom may be substituted with one alkoxy group, two alkoxy groups, or three alkoxy groups. If the alkoxy group has a large number of carbon atoms, the specific heat increases, increasing the energy load for desorption of carbon dioxide, so the upper limit of the carbon number is set to 6. For the same reason, the linear alkylene linking the silicon atom and the nitrogen atom in the second amino group has an upper limit of 6 carbon atoms.
  • the linear alkylene having 1 to 6 carbon atoms that links the nitrogen atom and silicon atom in this second amino group can be, for example, methylene, ethylene, n-propylene, n-butylene, n-pentylene, or n-hexylene, any of which can be used, such as an ethylene group or an n-propylene group.
  • the carbon dioxide adsorbent according to this embodiment may be an amine compound or a derivative thereof represented by the following general formula (2):
  • R 1 , R 21m , R 22m , and m are the same as defined in the above general formula (1).
  • R 31 , R 32 , and R 33 are each independently a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, at least one of R 31 , R 32 , and R 33 is an alkoxy group, and n is a natural number of 1 to 6. If the alkoxy group or alkyl group has a large number of carbon atoms, the specific heat is improved and the energy load for desorption of carbon dioxide increases, so the upper limit is set to 6 carbon atoms.
  • Examples of the above general formula (2) include amine compounds or derivatives thereof having the following structures (2-1) to (2-3).
  • at least one of R 31 , R 32 , and R 33 is a methoxy group, and the others are methyl groups.
  • unsubstituted alkylene e.g., methylene, ethylene
  • methylene ethylene
  • R 33 is a methoxy group
  • the others are methyl groups.
  • the carbon dioxide adsorbent according to this embodiment may have a structure in which one methyl group is added to the alkylene (propylene) between the first amino group and the second amino group, as in the above chemical formula (2-1) and chemical formula (2-2), or may have a structure in which two methyl groups are added to the alkylene (propylene) between the first amino group and the second amino group, as in the above chemical formula (2-3).
  • the amine compounds required for this embodiment of the carbon dioxide adsorbent can be synthesized, but are also available commercially.
  • the carbon dioxide adsorbent of this embodiment configured in this manner, is capable of adsorbing carbon dioxide at room temperature and desorbing carbon dioxide at temperatures below 200°C. Furthermore, it has been confirmed that the material can suppress deterioration over time and exhibits excellent durability when used repeatedly in carbon dioxide adsorption processes (see examples below).
  • the alkyl group substituting a portion of the linear alkylene forms an optimal steric hindrance between the primary amino group and the secondary amino group that makes it difficult for carbon dioxide molecules to approach each other sterically while maintaining the carbon dioxide adsorption performance, thereby suppressing the elimination of the primary amino group (e.g., Hoffmann elimination) and the reduction of the secondary amino group, as well as the oxidation of the primary amino group (e.g., radical mechanism).
  • the carbon dioxide adsorbent 1 configured in this manner has a wide range of applications and is not particularly limited in its mode of use.
  • it can be used as a carbon dioxide adsorption device 10 that has an adsorption section 2 fixed to a specific substrate 21 and separates carbon dioxide from a carbon dioxide-containing gas by contacting the amine compound with the carbon dioxide-containing gas.
  • the substrate 21 is not particularly limited as long as it can fix the carbon dioxide adsorbent 1, but as shown in FIG. 1(b), a porous body having porous holes 21a is preferred because it has a high specific surface area.
  • a substrate 21 can be selected from the group consisting of silica, vermiculite, activated carbon, alumina, aluminosilicate, diatomaceous earth, porous glass, porous resin, porous fiber, and zeolite.
  • the carbon dioxide adsorbent 1 is supported on a substrate 21 having porous holes 21a as shown in FIG. 2(a) by spraying, immersion, coating, or by using a silane coupling reaction, impregnation, evaporation to dryness, or other adhesion as shown in FIG. 2(b) (supporting process).
  • the carbon dioxide adsorbent 1 can be made into a solution and then sprayed onto the substrate 21 by spraying or immersing the substrate 21, thereby making it supported on the substrate 21.
  • the carbon dioxide adsorbent 1 can be made into a solution and then impregnated into the substrate 21, or it can be supported on the substrate 21 by evaporating to dryness or applying the solution.
  • the carbon dioxide adsorbent 1 when the amine compound constituting the carbon dioxide adsorbent 1 is an aminosilane represented by the above general formula (2), the carbon dioxide adsorbent 1 can be supported on the substrate 21 by a silane coupling reaction, and high adhesion to the substrate 21 can be obtained.
  • the carbon dioxide adsorbent 1 permeates the porous holes 21a.
  • the adsorbent 2 is formed by supporting the carbon dioxide adsorbent 1 on the substrate 21 through a silane coupling reaction, impregnation, evaporation to dryness, or other adhesion methods.
  • This substrate 21 may or may not be a porous body as described above, but if the substrate 21 is particularly porous, it has high permeability, resulting in high impregnation efficiency and strong support.
  • the carbon dioxide adsorption method using this carbon dioxide adsorption device 10 makes it possible to adsorb carbon dioxide by circulating a carbon dioxide-containing gas (S1: adsorption process).
  • the target carbon dioxide-containing gas is not particularly limited as long as it is a gas that contains carbon dioxide, and for example, the atmosphere and exhaust gases emitted from factories and automobiles can also be used since they contain carbon dioxide.
  • a fan that generates forced convection can be used as a method for circulating the carbon dioxide-containing gas.
  • the carbon dioxide adsorption device 10 has a wide range of uses, for example, it can adsorb and remove carbon dioxide from the atmosphere and supply air with a low carbon dioxide concentration to a living space. It can also be used as an air purifying material that adsorbs and concentrates carbon dioxide in combustion exhaust gas.
  • the carbon dioxide adsorption device 10 like the first embodiment, comprises the carbon dioxide adsorbent 1, the base material 21, and the adsorption section 2, and further comprises a filter section 3 consisting of a filter to which the adsorption section 2 is fixed, as shown in FIG. 4.
  • the shape of the filter section 3 is not particularly limited, but can be, for example, a honeycomb structure.
  • this honeycomb structure includes a structure in which hollow regular hexagonal columns like a honeycomb are lined up without gaps as a honeycomb structure in the narrow sense, but is not limited to this shape and includes a honeycomb structure in the broad sense of the word in which any hollow three-dimensional figure is lined up without gaps, not limited to hollow regular hexagonal columns.
  • a honeycomb structure in which non-flammable inorganic fibers are processed into a cardboard shape and stacked to form a rotor shape is also included.
  • This honeycomb structure increases the surface area of the carbon dioxide adsorbent 1, which is the processing part of the carbon dioxide adsorption device 10, as shown in Figure 6.
  • the filter section 3 can easily and efficiently adsorb carbon dioxide, and the carbon dioxide-removed gas Xa is discharged.
  • the carbon dioxide adsorption method using the carbon dioxide adsorption device 10 according to the third embodiment includes the adsorption step (S1) as in the first and second embodiments, and further includes a regeneration step (S2) of heating or depressurizing the carbon dioxide adsorbent 1 that has adsorbed carbon dioxide in the adsorption step (S1) to release carbon dioxide, as shown in FIG. 7 .
  • the heating in this regeneration step (S2) may involve directly heating the carbon dioxide adsorbent 1, or a high-temperature gas may be circulated through the carbon dioxide adsorbent 1.
  • the pressure reduction in this regeneration step (S2) may involve directly depressurizing the carbon dioxide adsorbent 1, or a low-pressure gas may be circulated through the carbon dioxide adsorbent 1.
  • the carbon dioxide adsorption device 10 As shown in FIG. 8(a), the carbon dioxide adsorption device 10 according to the third embodiment is in an initial state L in which the carbon dioxide adsorbent 1 does not contain carbon dioxide, and a carbon dioxide-containing gas X, such as the atmosphere, is fed into the carbon dioxide adsorption device 10.
  • a carbon dioxide-containing gas X such as the atmosphere
  • this carbon dioxide adsorbent 1 suppresses deterioration over time and exhibits excellent durability against repeated use in carbon dioxide adsorption processes, allowing it to be used repeatedly for a long period of time.
  • the carbon dioxide adsorption device 10 according to the third embodiment can also be configured in the shape of a honeycomb rotor.
  • a honeycomb rotor is a rotor having a honeycomb-structured filter section 3 formed into a drum shape with a circular cross section.
  • the cross section of the carbon dioxide adsorption device 10 configured as this honeycomb rotor is divided into two to form an adsorption zone A and a desorption zone B. More preferably, as shown in FIG. 9, the circular cross section of this honeycomb rotor 1 is divided into two equal parts by the diameter of the circle to form two semicircular cross sections, with the adsorption zone A and the desorption zone B being formed.
  • this carbon dioxide adsorption device 10 As a honeycomb rotor, carbon dioxide-containing gas X, such as the atmosphere, is sent into the adsorption zone A of the honeycomb rotor, and as shown in FIG. 10(a), the carbon dioxide in the carbon dioxide-containing gas X is adsorbed by the carbon dioxide adsorbent 1 in the adsorption zone A of the honeycomb rotor, and carbon dioxide-removed gas Xa is discharged.
  • carbon dioxide-containing gas X such as the atmosphere
  • carbon dioxide is adsorbed by the carbon dioxide adsorbent 1 in adsorption zone A of the honeycomb rotor.
  • the side that was originally in adsorption zone A is now located in desorption zone B, and carbon dioxide is adsorbed in desorption zone B.
  • the desorption zone B which is rich in carbon dioxide, is heated or depressurized. This releases carbon dioxide-containing gas Xb containing a high concentration of carbon dioxide, and regenerates the carbon dioxide adsorption performance of the carbon dioxide adsorbent 1 (S2: regeneration process).
  • the resulting carbon dioxide-containing gas Xb has a higher concentration of carbon dioxide than the raw material carbon dioxide-containing gas X, and can therefore be used in a wide variety of applications where carbon dioxide can be utilized.
  • the growth of cultivated plants can be promoted by supplying carbon dioxide-containing gas Xb to a plant greenhouse (vinyl greenhouse).
  • the growth of algae can also be promoted by supplying carbon dioxide-containing gas Xb.
  • Example 1 As the carbon dioxide adsorbent according to Example 1, an amine compound having the above-mentioned structure (2-4) was obtained from the market.
  • R 31 , R 32 and R 33 are a methoxy group, and the others are methyl groups.
  • R 31 , R 32 and R 33 are a methoxy group, and the others are methyl groups.
  • the amine compound according to Example 1 above and the conventional amine compound were each supported on silica, and this silica was supported on the filter section 3 having the above-mentioned honeycomb structure to construct the carbon dioxide adsorption device 10 according to the third embodiment.
  • the amine compound of Example 1 maintained a high carbon dioxide adsorption capacity even after accelerated testing and exhibited more than twice the durability of the conventional amine compound of the comparative example. From this, it can be said that, unlike the conventional product, the amine compound of Example 1 inhibits the elimination of primary amino groups (e.g., Hoffman elimination) and the reduction of secondary amino groups, as well as inhibiting deterioration reactions such as the oxidation of primary amino groups (e.g., radical mechanism).
  • primary amino groups e.g., Hoffman elimination
  • secondary amino groups e.g., as well as inhibiting deterioration reactions such as the oxidation of primary amino groups (e.g., radical mechanism).
  • Example 2 As in Example 1, the amine compound according to Example 1 and the conventional amine compound were each supported on silica, and this silica was supported on the filter unit 3 having the above-mentioned honeycomb structure to construct the carbon dioxide adsorption device 10 of the above-mentioned embodiment 3.
  • a dynamic performance test for confirming the dynamic performance of carbon dioxide adsorption using this carbon dioxide adsorption device having a honeycomb structure was carried out under the following conditions.
  • Adsorption zone inlet temperature TP1 23.5°C
  • adsorption zone inlet absolute humidity XP1 12g/kg'
  • Desorption zone inlet temperature TR1 45°C
  • desorption zone inlet absolute humidity XR1 18.5g/kg'
  • the carbon dioxide concentration of the carbon dioxide-containing gas Xb shown in Fig. 10 in the carbon dioxide adsorption device of the above-mentioned embodiment 3 was measured for each honeycomb rotor rotation speed [rph] in terms of the regeneration outlet CO2 concentration [ppm], and the results are plotted in Fig. 12. From the obtained results, it was confirmed that the amine compound of the above-mentioned example 1 exhibits carbon dioxide adsorption performance equal to or greater than that of the conventional amine compound of the comparative example.
  • Example 3 As the carbon dioxide adsorbent according to Example 3, amine compounds having the following structures were obtained from the market (from top to bottom: ethylenediamine, 2-methyl-1,3-propanediamine, and 1,4-diaminobutane). These amine compounds differ in the length of their carbon chains and in the presence or absence of branching in the carbon chains. Each of these amine compounds was supported on silica in the same manner as in Example 1 to prepare an adsorbent.
  • Carbon dioxide adsorbent 2 Adsorption section 21 Substrate 21a Porous hole 3 Filter section 10 Carbon dioxide adsorption device

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Abstract

Le problème décrit par la présente invention est de fournir un matériau adsorbant le dioxyde de carbone qui peut supprimer l'apparition d'une détérioration due au vieillissement et qui peut présenter une durabilité élevée même lorsqu'il est utilisé de manière répétée pour un procédé d'adsorption de dioxyde de carbone. La solution selon l'invention porte sur un matériau adsorbant le dioxyde de carbone qui comprend un composé amine comprenant : un premier groupe amino formé d'un groupe amino primaire ; un second groupe amino formé d'un groupe amino primaire, d'un groupe amino secondaire ou d'un groupe amino tertiaire ; et un alkylène linéaire qui a de 2 à 6 atomes de carbone, qui relie le premier groupe amino et le second groupe amino, et qui est substitué par un groupe alkyle linéaire ayant de 1 à 3 atomes de carbone ou un groupe alkyle ramifié ayant 3 ou 4 atomes de carbone.
PCT/JP2023/028179 2022-11-10 2023-08-01 Matériau adsorbant le dioxyde de carbone, dispositif adsorbant le dioxyde de carbone, leur procédé de fabrication et procédé d'adsorption de dioxyde de carbone WO2024100945A1 (fr)

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JP2006051486A (ja) * 2003-10-28 2006-02-23 Sk Kaken Co Ltd 吸着剤
JP2015113337A (ja) * 2013-12-16 2015-06-22 株式会社ノリタケカンパニーリミテド アミノ化合物担持多孔質材とその製造方法
US20190169027A1 (en) * 2016-08-22 2019-06-06 Sabic Global Technologies B.V. Rod-shaped mesoporous carbon nitride materials and uses thereof
WO2018074270A1 (fr) * 2016-10-21 2018-04-26 ラサ工業株式会社 Déodorant blanc, produit chimique à fonction désodorisante, procédé d'utilisation et de fabrication d'un déodorant blanc
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CN108993413A (zh) * 2018-07-25 2018-12-14 南京工业大学 一种氨基改性沉淀氧化硅的制备方法
US20210260561A1 (en) * 2020-02-21 2021-08-26 King Fahd University Of Petroleum And Minerals Magnesium oxide-polyamine adsorbent and a method of capturing carbon dioxide
WO2022102683A1 (fr) * 2020-11-16 2022-05-19 Ａｇｃ株式会社 Adsorbant

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