WO2022181571A1 - キャニスタ用成形吸着体 - Google Patents

キャニスタ用成形吸着体 Download PDF

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Publication number
WO2022181571A1
WO2022181571A1 PCT/JP2022/007085 JP2022007085W WO2022181571A1 WO 2022181571 A1 WO2022181571 A1 WO 2022181571A1 JP 2022007085 W JP2022007085 W JP 2022007085W WO 2022181571 A1 WO2022181571 A1 WO 2022181571A1
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WIPO (PCT)
Prior art keywords
activated carbon
adsorbent
carbon fiber
fibers
shaped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2022/007085
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English (en)
French (fr)
Japanese (ja)
Inventor
大介 今井
佳英 渡邉
由生 ▲高▼田
棟▲ヨン▼ 柳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Publication date
Application filed by Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Priority to MX2023009889A priority Critical patent/MX2023009889A/es
Priority to CA3210938A priority patent/CA3210938A1/en
Priority to KR1020237032739A priority patent/KR20230148422A/ko
Priority to EP22759607.9A priority patent/EP4299893A4/en
Priority to JP2023502413A priority patent/JP7268260B2/ja
Priority to CN202280016572.1A priority patent/CN116917612A/zh
Publication of WO2022181571A1 publication Critical patent/WO2022181571A1/ja
Priority to US18/234,466 priority patent/US20230390732A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0415—Beds in cartridges
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J20/28023—Fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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    • B01J20/28042—Shaped bodies; Monolithic structures
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    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/34—Specific shapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4516—Gas separation or purification devices adapted for specific applications for fuel vapour recovery systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4566—Gas separation or purification devices adapted for specific applications for use in transportation means
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir
    • F02M25/0854—Details of the absorption canister

Definitions

  • the present invention relates to a shaped adsorbent suitable for canisters, and more specifically to a shaped adsorbent for canisters using activated carbon fibers.
  • the pressure inside the fuel tank fluctuates due to changes in the outside temperature, etc., and the evaporated fuel gas that fills the fuel tank is released from the fuel tank.
  • the emitted transpiration fuel gas is considered to be one of the causative substances of PM2.5 and photochemical smog, and in order to prevent it from being released into the atmosphere, a canister equipped with an adsorbent such as activated carbon is provided. .
  • the canister mounted on the automobile may be abbreviated as “automobile canister” or simply “canister”.
  • activated carbon fiber In contrast to traditional powdery and granular activated carbon, activated carbon fiber (or fibrous activated carbon) is sometimes called the third activated carbon.
  • activated carbon fibers are said to have a tendency to have fine pores directly opened on the outer surface and to have a high adsorption/desorption rate.
  • activated carbon fibers have not yet been put to practical use in canisters, and research and development have not progressed sufficiently as to what properties of activated carbon fibers are suitable for practical use in canisters.
  • An activated carbon fiber sheet with predetermined properties has been proposed as one of the adsorbents suitable for canisters (Patent Document 2).
  • activated carbon fibers As described above, attempts have been made to use activated carbon fibers as adsorbents for canisters, but activated carbon fibers are still under development as adsorbents for canisters.
  • the inventors of the present invention aimed to put activated carbon fibers into practical use as adsorbents for automobile canisters, and as a result of intensive research, it was found that it was necessary to fix the adsorbents so that they would not wear out due to vibrations during automobile driving. In view of ease of handling, etc., the inventors have found that a sheet formed of activated carbon fibers is a practically preferred embodiment. However, when the activated carbon fiber sheet obtained by carbonization and activation in the same manner as before is filled in the chamber containing the adsorbent without providing a gap, the pressure loss of the canister increases. .
  • one of the problems to be solved by the present invention is to provide an adsorbent using activated carbon fibers, which is suitable for canisters and has suppressed pressure loss. to do.
  • one of the further problems to be solved by the present invention is a molded body that does not easily lose its shape while using activated carbon fibers, and that exhibits excellent effects as an adsorbent for canisters.
  • An object of the present invention is to provide an adsorbent.
  • the present inventors have found that by producing an activated carbon fiber material using fibers with a larger fiber diameter than before, air permeability can be improved, pressure loss can be suppressed, and it is suitable for canisters. It was found that an adsorbent can be obtained. Furthermore, the present inventors have found that by mixing an activated carbon fiber material and a binder to form a molded body, the pressure loss can be suppressed, the mechanical strength is improved, and the shape is less likely to collapse. The present inventors have found that they can do this, and have completed the present invention based on such findings.
  • the present invention can be grasped from various aspects, and means for solving the problems include, for example, the following.
  • a molded adsorbent for a canister comprising an adsorbent containing activated carbon fibers and a binder, The content ratio of the adsorbent containing the activated carbon fiber and the binder is 0.3 to 20 parts by weight of the binder with respect to 100 parts by weight of the adsorbent containing the activated carbon fiber,
  • the activated carbon fiber has a fiber diameter of 13.0 ⁇ m or more.
  • Shaped adsorbent [2] The shaped adsorbent according to [1] above, wherein the fibrous material serving as the precursor of the activated carbon fibers has a fineness of 4.0 to 60.0 dtex.
  • the activated carbon fiber has a pore volume abundance ratio R 0.7/2.0 of 15% or more and less than 50%, and the R 0.7/2.0 is pores having a pore diameter of 2.0 nm or less.
  • a canister comprising the shaped adsorbent according to any one of [1] to [6] above.
  • the canister according to [7] above which is a canister for an automobile.
  • an adsorbent that uses activated carbon fibers is suitable for canisters, and has suppressed pressure loss.
  • a molded adsorbent that is a molded body that does not easily lose its shape even though it uses activated carbon fibers, and that exhibits excellent effects as an adsorbent for a canister. can be done.
  • FIG. 1 is a diagram schematically showing an example of a laminated adsorbent formed by stacking a plurality of sheet-shaped adsorbents, and an example of a flow direction of a fluid passing through the laminated adsorbent. It is a figure which shows an example of the adsorption body shape
  • Shaped Adsorbent for Canister The shaped adsorbent adsorbent of the present invention can be suitably used for a canister.
  • the canister is equipped with an adsorbent, which adsorbs the evaporated fuel to prevent it from being released into the atmosphere. It is a device that plays a role of supplying to the engine.
  • Canisters are generally used in machines or devices with internal combustion engines that use highly volatile hydrocarbon-containing fuels, such as vehicles and watercraft with internal combustion engines. Vehicles include, for example, automobiles that use gasoline as fuel.
  • the vessel includes, for example, a boat using gasoline as fuel.
  • a shaped adsorbent which is one embodiment of the present invention, can be a shaped body containing an adsorbent containing activated carbon fibers and a binder.
  • the "adsorbent containing activated carbon fibers” may be activated carbon fibers alone. Being composed of activated carbon fibers alone corresponds to the case where the entire "adsorbent containing activated carbon fibers" is entirely composed of activated carbon fibers.
  • the "adsorbent containing activated carbon fiber” may contain other adsorbents, such as zeolite, silica gel, activated alumina, metal organic frameworks (MOF), etc. porous materials, preferably activated carbons of types other than activated carbon fibers, such as granular activated carbon. That is, the material constituting the "adsorbent containing activated carbon fibers" may be, as another embodiment, a mixture containing adsorbents such as materials belonging to activated carbons in a broad sense.
  • the molded adsorbent which is one embodiment of the present invention, contains activated carbon fibers as an adsorbent, so it can also be said to be a molded body containing activated carbon fibers and a binder.
  • the adsorbent is obtained by molding activated carbon fibers using a binder.
  • a binder is used as one component of the shaped adsorbent.
  • the binder that can be used is preferably a binder that does not clog the pores of activated carbon fibers and activated carbon.
  • the material include a polyvinyl alcohol-based aqueous solution.
  • a fibrous binder can also be mentioned as a preferable example of a binder.
  • a polyvinyl alcohol-based fibrous binder is exemplified as a wet heat adhesive type.
  • Composite fibers such as core-sheath fibers, parallel fibers, and radially split fibers can also be used.
  • Fibers composed only of polyethylene or polypropylene can also be used as all-melting type.
  • a fibrillated fibrous binder may also be used. There is no particular limitation as long as the fibrillation allows the activated carbon fiber and the granular activated carbon to be entwined and shaped. It can be widely used regardless of whether it is a synthetic product or a natural product.
  • fibrillated fibrous binders include acrylic fibers, polyethylene fibers, polypropylene fibers, polyacrylonitrile fibers, cellulose fibers, nylon fibers, and aramid fibers.
  • the content ratio of the adsorbent containing activated carbon fibers and the binder may be, for example, 0.3 to 20 parts by weight of the binder with respect to 100 parts by weight of the adsorbent containing activated carbon fibers.
  • the lower limit of the binder may preferably be 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 2.0 parts by weight, or 3.0 parts by weight.
  • the upper limit of the binder may be preferably 18 parts by weight, 15 parts by weight, or 10 parts by weight.
  • the above content ratio is also applied. be able to. That is, the content ratio of the activated carbon fiber and the binder in the shaped adsorbent can be, for example, 0.3 to 20 parts by weight of the binder with respect to 100 parts by weight of the activated carbon fiber.
  • the lower limit of the binder may preferably be 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 2.0 parts by weight, or 3.0 parts by weight.
  • the upper limit of the binder may be preferably 18 parts by weight, 15 parts by weight, or 10 parts by weight.
  • the shaped adsorbent can be prepared so as to satisfy both the mechanical strength and the adsorption/desorption performance. If the mechanical strength is desired to be increased, the amount of the binder may be increased, and if the adsorption/desorption performance is more important, the amount of the binder may be set lower.
  • the above content ratio can also be applied when the adsorbent containing activated carbon fibers is a mixture of activated carbon fibers and granular activated carbon. That is, the content ratio of the mixture of activated carbon fiber and granular activated carbon and the binder in the shaped adsorbent is, for example, 0.3 to 20 parts by weight of binder per 100 parts by weight of the mixture of activated carbon fiber and granular activated carbon. Possible.
  • the lower limit of the binder may preferably be 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 2.0 parts by weight, or 3.0 parts by weight.
  • the upper limit of the binder may be preferably 18 parts by weight, 15 parts by weight, or 10 parts by weight.
  • the shaped adsorbent can be prepared so as to satisfy both the mechanical strength and the adsorption/desorption performance. If the mechanical strength is desired to be increased, the amount of the binder may be increased, and if the adsorption/desorption performance is more important, the amount of the binder may be set lower.
  • a binder by blending in the above content ratio, it is possible to prevent the pores of the activated carbon fiber from being clogged and the characteristics such as adsorption / desorption performance and pressure loss to decrease. It is possible to obtain a shaped adsorbent excellent in these properties while maintaining the properties.
  • the molded adsorbent which is one embodiment of the present invention, does not exclude the inclusion of other constituents than the activated carbon fiber and the binder, but the addition of other constituents does not hinder the suppression of pressure loss. should be allowed.
  • granular activated carbon and the like can be added.
  • the lower limit of the fiber diameter of the activated carbon fiber that can be used in the shaped adsorbent of the present invention is preferably 13.0 ⁇ m or more, more preferably 14.0 ⁇ m or more, and still more preferably 15.0, 16.0, 17.0, 18 .0, 19.0, or 20.0 microns or greater.
  • the upper limit of the diameter of the fibers constituting the activated carbon fiber sheet of the present invention may be arbitrary from the viewpoint of suppressing pressure loss, but considering the balance with the adsorption and desorption performance, for example, 60.0 ⁇ m or less, preferably 55 ⁇ m or less 0 ⁇ m or less, more preferably 50.0, 45.0, 40.0, or 35.0 ⁇ m.
  • the activated carbon fiber can be made more capable of suppressing pressure loss.
  • the lower limit of the fiber length of the activated carbon fibers that can be used in the shaped adsorbent of the present invention is preferably 300 or more, more preferably 500, 600, 700, 800, 850, 900 or more, and even more preferably 950 or more.
  • the upper limit of the fiber length constituting the activated carbon fiber sheet of the present invention is preferably 5,000 or less, more preferably 4,000, 3,000, 2,500, 2,000, 1,500 or less, and still more preferably 1,200 or less. When the fiber length of the fibers constituting the activated carbon fiber is within the above range, the activated carbon fiber can further suppress pressure loss.
  • the lower limit of the fiber length variation coefficient of the activated carbon fiber that can be used in the shaped adsorbent of the present invention is preferably 0.1 or more, more preferably 0.2, 0.3, 0.4, 0.5 or more, and further Preferably, it can be 0.6 or more.
  • the upper limit of the fiber length variation coefficient constituting the activated carbon fiber sheet of the present invention is preferably 2.5 or less, more preferably 2.0, 1.5, 1.0, 0.9, 0.8 or less, More preferably, it can be 0.7 or less. When the fiber length of the fibers constituting the activated carbon fiber is within the above range, the activated carbon fiber can further suppress pressure loss.
  • the fiber diameter (in terms of fineness) of the fiber that is the precursor of the activated carbon fiber is preferably within the following range. That is, it can be said that the use of the following fibers as precursors is suitable for obtaining activated carbon fibers capable of suppressing pressure loss.
  • the lower limit of the fiber diameter (in terms of fineness) of the precursor fiber is preferably 4.0 dtex or more, more preferably 5.0 dtex or more, and still more preferably 8.0, 10.0, 12.0, or 15.0 dtex. It can be more than that.
  • the upper limit of the fiber diameter (in terms of fineness) of the precursor fiber is preferably 60.0 dtex or less, more preferably 50.0 dtex or less, and even more preferably 40.0 or 30.0 dtex or less.
  • the activated carbon fiber that can be used in the shaped adsorbent of the present invention can be a more preferable embodiment by satisfying at least one or any two or more of the following predetermined items.
  • the lower limit of the specific surface area of the activated carbon fiber that can be used in the shaped adsorbent of the present invention is preferably 1100 m 2 /g or more, more preferably 1200 m 2 /g or more, still more preferably 1300, 1400, 1500, 1600, 1700, or It can be 1800 m 2 /g or more.
  • the specific surface area of the activated carbon fiber that can be used in the shaped adsorbent of the present invention is generally preferably as wide as possible from the viewpoint of adsorption and desorption performance. , or 2100 m 2 /g or less.
  • the molded adsorbent can have a more excellent adsorption/desorption performance with respect to the transpired fuel gas. Further, in one embodiment of the present invention, it is possible to reduce the pressure loss in the canister while maintaining a wide specific surface area for the adsorption material used in the canister as described above.
  • the lower limit of the total pore volume of the activated carbon fibers that can be used in the shaped adsorbent of the present invention is preferably 0.50 cm 3 /g or more, more preferably 0.60 cm 3 /g or more, and still more preferably 0.70 cm 3 /g or more. 0.80, or 0.90 cm 3 /g or higher.
  • the upper limit of the total pore volume of the activated carbon fibers that can be used in the shaped adsorbent of the present invention is preferably 1.20 cm 3 /g or less, more preferably 1.10 cm 3 /g or less, still more preferably 1.00 cm 3 /g. g or less.
  • pore size refers to the diameter or width of the pore, not the radius of the pore, unless otherwise specified.
  • the lower limit of the average pore diameter of the activated carbon fiber that can be used in the shaped adsorbent of the present invention is preferably 1.69 nm or more, more preferably 1.70 nm or more, and still more preferably 1.72, 1.75, 1.78, or 1.80 nm or more.
  • the upper limit of the average pore diameter of the activated carbon fiber that can be used in the shaped adsorbent of the present invention can be arbitrary, but it is preferably 4.00 nm or less, more preferably 3.50 nm or less, and still more preferably 3.00 nm or less. .
  • the average pore diameter within the above range, the shaped adsorbent can be made more excellent in adsorption/desorption performance with respect to the transpired fuel gas.
  • the term "ultramicropores” means pores with a pore size of 0.7 nm or less.
  • the lower limit of the ultramicropore volume of the activated carbon fibers that can be used in the shaped adsorbent of the present invention is preferably 0.05 cm 3 /g or more, more preferably 0.10 cm 3 /g or more, still more preferably 0.12, or It can be 0.14 cm 3 /g or more.
  • the upper limit of the ultra-micropore volume of the activated carbon fiber that can be used in the shaped adsorbent of the present invention is preferably 0.30 cm 3 /g or less, more preferably 0.29 cm 3 /g or less, and still more preferably 0.26, 0.29 cm 3 /g or less. 0.24, 0.22, or 0.20 cm 3 /g or less.
  • micropores means pores with a pore size of 2.0 nm or less.
  • the lower limit of the micropore volume of the activated carbon fibers that can be used in the shaped adsorbent of the present invention is preferably 0.50 cm 3 /g or more, more preferably 0.60 cm 3 /g or more, still more preferably 0.65 or 0. .70 cm 3 /g or more.
  • the upper limit of the micropore volume of the activated carbon fibers that can be used in the shaped adsorbent of the present invention is preferably 1.00 cm 3 /g or less, more preferably 0.90 cm 3 /g or less, still more preferably 0.80 cm 3 /g. can be: By setting the micropore volume within the range described above, it is possible to obtain a molded adsorbent that is more excellent in terms of adsorption and desorption performance with respect to transpired fuel gas.
  • V 0.7-2.0 ⁇ Pore volume of pores with a pore diameter greater than 0.7 nm and 2.0 nm or less.
  • the pore volume V 0.7-2.0 of pores having a pore diameter greater than 0.7 nm and 2.0 nm or less can be obtained by the following formula 1 using the ultra-micropore volume value a and the micropore volume value b. can.
  • V 0.7-2.0 b-a Formula 1
  • the lower limit of the pore volume V 0.7-2.0 of pores having a pore diameter of more than 0.7 nm and less than or equal to 2.0 nm is preferably 0.20 cm 3 /g or more. , more preferably 0.30 cm 3 /g or more, and still more preferably 0.36, 0.40, 0.45, or 0.50 cm 3 /g or more.
  • the upper limit of the pore volume V 0.7-2.0 of pores having a pore diameter of more than 0.7 nm and 2.0 nm or less is preferably 1.20 cm 3 /g or less.
  • the shaped adsorbent can be made more excellent in adsorption/desorption performance with respect to transpired fuel gas.
  • R 0.7/2.0 ⁇ Ratio of the volume of ultra-micropores to the volume of micropores.
  • the abundance ratio R 0.7/2.0 of the pore volume of ultra-micropores with a pore diameter of 0.7 nm or less in the pore volume of micropores with a pore diameter of 2.0 nm or less is the value of the ultra-micropore volume a and the value b of the micropore volume can be obtained by the following formula 2.
  • R 0.7/2.0 a/b x 100 (%) Formula 2
  • the lower limit of the abundance ratio R 0.7/2.0 of the ultra-micropore volume to the micropore volume is preferably 15.0% or more, more preferably 18% or more, and further Preferably, it can be 19% or more.
  • the upper limit of the abundance ratio R 0.7/2.0 of the ultra-micropore volume to the micropore volume is preferably 60% or less, more preferably 50% or less, and still more preferably It can be 40, 30, or 25% or less.
  • the lower limit of the dry density of the shaped adsorbent of the present invention is preferably 0.010 g/cm 3 or more, more preferably 0.015 g/cm 3 or more, and still more preferably 0.020, 0.030, 0.040, 0. 0.050, or 0.060 g/cm 3 or higher.
  • the upper limit of the dry density of the shaped adsorbent of the present invention is preferably 0.400 g/cm 3 or less, more preferably 0.300 g/cm 3 or less, still more preferably 0.200, 0.150, 0.140, 0. .130, 0.120, 0.110, or 0.100 g/cm 3 or less.
  • the dry density of the molded adsorbent can be adjusted by adjusting the fiber diameter of the carbon fiber, the fiber length by adjusting the stirring force when defibrating the carbon fiber, and the suction force when suction molding the mixed slurry with the binder. Pressure loss of the shaped adsorbent can be suppressed.
  • the shaped adsorbent of the present invention preferably has a predetermined moisture content.
  • the lower limit of water content under conditions of 23° C. and 50% relative humidity is preferably 1.0% or more, more preferably 2.0% or more, and even more preferably 3.0% or more.
  • the upper limit of the water content under the conditions of 23°C and 50% relative humidity is preferably 30.0% or 25.0% or less, more preferably 20.0% or less or 15.0% or less, and even more preferably can be 10.0 or 8.0% or less.
  • the shaped adsorbent of the present invention preferably has a predetermined n-butane adsorption/desorption performance as an adsorbent. Since the adsorption/desorption performance of n-butane is an index of the adsorption/desorption performance of vaporized gas, those having excellent adsorption/desorption performance of n-butane are suitable for automobile canisters.
  • the adsorption and desorption performance of n-butane is determined by measuring the amount of adsorption when repeating adsorption after sufficient absorption and breakthrough of n-butane and desorption from the adsorbent under predetermined desorption conditions. It can be expressed as the effective adsorption amount ratio of n-butane per adsorbent.
  • the effective adsorption/desorption ratio of n-butane determined by the measurement method shown in the following examples is preferably 6.00 wt% or more, more preferably 6.25 wt% or more. , more preferably 6.50, 6.75, or 7.00 wt% or more.
  • the effective adsorption/desorption rate of n-butane obtained according to the measurement method shown in the following examples is preferably 25.0% or more, more preferably 30.0%. % or more, more preferably 40.0, 50.0, 60.0, 70.0, or 75.0% or more.
  • Adsorbents having such adsorption and desorption rates are suitable for canisters, particularly for automobile canisters.
  • the 0 ppm maintenance time obtained according to the measurement method shown in the following examples is preferably 15 minutes or 30 minutes or more, more preferably 40 minutes or more, More preferably, it may be 50 minutes, 55 minutes, 60 minutes, 65 minutes, 68 minutes, 69 minutes, or 70 minutes or longer.
  • a longer 0 ppm maintenance time means a longer time until the adsorbent starts releasing the adsorbed substance. Therefore, the 0 ppm maintenance time is an indicator of the strength of the adsorptive power.
  • the shaped adsorbent for canisters of the present invention is suitable for canisters mounted on automobiles.
  • the upper limit of pressure loss can be preferably 1.50 kPa or less, more preferably 1.20 kPa or less, and even more preferably 1.10, 1.00, 0.90, 0.80, or 0.70 kPa or less. It is not that the lower the pressure loss is, the more preferable it is.
  • the lower limit of the pressure loss is preferably 0.05 kPa or more, more preferably 0.10 kPa or more, further preferably 0.10 kPa or more. It can be 15 kPa or more.
  • the shape of the shaped adsorbent is not particularly limited. Specific shapes include, for example, columnar shapes having end faces such as circular or polygonal shapes, truncated cone shapes such as truncated cones and polygonal truncated pyramids, and shapes such as pellets and honeycombs. A columnar shape, a rectangular parallelepiped shape, and the like can be mentioned. Furthermore, a laminate may be formed by laminating a plurality of disk-shaped, sheet-shaped, or plate-shaped shaped adsorbents. Figures 1-3 illustrate some embodiments. In the drawings, dimensions such as length and thickness are represented schematically for easy understanding of the invention, and are not limited to them.
  • the laminated adsorbent 1 shown in FIG. 1 is a laminate formed by stacking four sheet-shaped molded adsorbents 10 .
  • the sheet-like molded adsorbent 10 is formed by stacking the main surfaces 10a of the sheets on each other.
  • the laminated adsorbent 1 is stored in the canister.
  • the direction in which the tensile strength of the sheet is high is arranged along the gas flow.
  • the main surface 10a of the sheet-like shaped adsorbent may be arranged in a direction not perpendicular to the flow direction of the fluid F such as evaporated gas.
  • the main surface a can be arranged substantially parallel to the flow direction of fluid F such as evaporated gas.
  • the side end surfaces 10b of the plurality of sheet-like molded adsorbents face the flow direction of the fluid F. are arranged as By arranging in this way, the pressure loss can be reduced.
  • the short side end face 10b faces the flow direction of the fluid F, but this is not a limitation, and the long side end face 10c may face the flow direction of the fluid F.
  • the adsorption laminate as a whole may have a rectangular parallelepiped shape or a cubic shape.
  • the shape of the adsorbent chamber in which the adsorbent laminate is accommodated may be matched.
  • FIG. 2 shows another embodiment of the present invention.
  • the shaped adsorbent is shaped like a disc.
  • the disk-shaped molded adsorbents may be stacked to form a cylindrical shape.
  • FIG. 3 shows another embodiment of the present invention.
  • the shaped adsorbent is integrally formed as a cylindrical shaped body.
  • the shaped adsorbent of the present invention can be easily processed or shaped into various shapes and is a material with excellent handling properties.
  • Canister The shaped adsorbent of the present invention is suitable as an adsorbent to be housed in an automobile canister. That is, the present invention can also provide an automobile canister as another embodiment.
  • the automobile canister of the present invention is equipped with a shaped adsorbent as an adsorbent.
  • the structure of the automobile canister is not particularly limited, and a general structure can be adopted.
  • automobile canisters include those having the following structures.
  • a housing for storing an adsorbent in the housing; a first opening for moving gas communication between the sorbent chamber and the engine; a second opening for moving gas communication between the sorbent chamber and the fuel tank; a third opening that opens when a predetermined pressure is applied from the adsorbent chamber or the outside air to allow gas to move between the adsorbent chamber and the outside air;
  • the shaped adsorbent of the present invention can be used as an adsorbent in the canister of the present invention.
  • the molded adsorbent of the present invention can reduce pressure loss, so even if it is filled without any gaps, pressure loss can be suppressed more than when filling a conventional activated carbon fiber sheet. .
  • Each of the first, second and third openings is a delivery inlet through which gas enters and exits.
  • the arrangement of each opening that is a gas delivery inlet is not particularly limited, but the third opening that is an outside air delivery inlet allows gas to move between the first and/or second openings In this case, it is preferable that the gas is arranged at a position that allows the gas to sufficiently pass through the adsorbent.
  • the first and second openings are provided in the first side of the housing, and the third opening is provided in the second side facing the first side. can be taken.
  • the adsorbent chamber may be divided into multiple chambers.
  • the adsorbent chamber may be divided into two or more compartments by partition walls.
  • As the partition wall a perforated plate or the like with air permeability can be used.
  • an external second housing is provided separately from the first housing, and the first housing and the second housing are communicated via a gas passage, and an adsorbent chamber is additionally equipped. You may When a plurality of compartments or housings are provided in this way, as a preferred embodiment, in each compartment or housing unit, from the first or second opening through which the gas flows from the engine or the fuel tank, the third Adsorbents or adsorbent chambers can be arranged such that the adsorption capacities become progressively smaller toward the opening side.
  • a composite canister comprising a main canister (first housing) and a second canister (second housing) attached to the main canister (first housing) on the outside air intake side
  • the compartment or housing into which the evaporated gas first flows from the engine or fuel tank is the main body (first compartment or first housing) with the largest storage volume, and the While conventional inexpensive activated carbon is housed in the main body, the molded adsorbent of the present invention having excellent low-concentration adsorption/desorption performance is housed in the second compartment or after the second housing, which has a relatively small storage volume. Therefore, it is possible to obtain a high-performance canister while suppressing the cost.
  • the air flows in from the front layer.
  • the concentration of transpired fuel gas becomes thinner. Therefore, the shaped adsorbent of the present invention, which has a high n-butane adsorption capacity at a low concentration of about 0.2%, can be used in the second compartment or the second housing, which is positioned later from the engine or the fuel tank, or even further. It is suitable as an adsorbent to be stored in the latter adsorbent chamber.
  • the activated carbon fiber sheet of the present invention has a high effective adsorption and desorption amount due to purging, so transpiration when the automobile is stopped for a long time It is also suitable as an adsorbent for automobile canisters in that it can reduce the amount of fuel gas leakage.
  • An automotive canister having two or more adsorbent chambers For automobiles in which the shaped adsorbent of the present invention is housed in a second or subsequent adsorbent chamber arranged later than the first adsorbent chamber into which gas first flows from the engine or fuel tank. canister.
  • the number of adsorbent chambers may be two or more.
  • the shaped adsorbent of the present invention may be accommodated in at least one adsorbent chamber after the second adsorbent chamber.
  • the activated carbon fibers used in the present invention can be produced by carbonizing and activating fibers having a predetermined fiber diameter.
  • the fibers before carbonization and activation are called precursor fibers, and the sheet formed of the precursor fibers is called precursor fiber sheet.
  • the term “fiber diameter” means the diameter or width of the fiber, not the radius of the fiber, unless otherwise specified.
  • the term “fiber diameter” is mainly used for activated carbon fibers after carbonization and activation.
  • An embodiment of manufacturing an activated carbon fiber sheet will be exemplified below as a method for manufacturing activated carbon fibers.
  • a preferred embodiment of the method for producing an activated carbon fiber sheet includes, for example, the following method.
  • the precursor fiber sheet contains cellulosic fibers, and the fibers have a fiber diameter of 4.0 to 60.0 dtex.
  • the lower limit of the fiber diameter (in terms of fineness) of the precursor fiber is preferably 4.0 dtex or more, more preferably 5.0 dtex or more, and still more preferably 8.0, 10.0, 12.0, or 15.0 dtex. It can be more than that.
  • the upper limit of the fiber diameter (in terms of fineness) of the precursor fiber is preferably 60.0 dtex or less, more preferably 50.0 dtex or less, and even more preferably 40.0 or 30.0 dtex or less.
  • the method for producing sheet-like activated carbon fibers that can be used in the present invention can be carried out, for example, with reference to the following information.
  • raw material sheet preparation of raw material sheet (precursor fiber sheet) ⁇ type of fiber>
  • fibers constituting the raw material sheet include cellulose fibers, pitch fibers, PAN fibers, phenolic resin fibers, and the like, preferably cellulose fibers.
  • Cellulosic fibers are fibers composed mainly of cellulose and/or its derivatives.
  • Cellulose and cellulose derivatives may be of any origin, such as chemically synthesized products, plant-derived cellulose, regenerated cellulose, and cellulose produced by bacteria.
  • Preferred cellulosic fibers include, for example, fibers formed from plant cellulosic substances obtained from trees and the like, and long fibrous fibers obtained by chemically dissolving plant cellulosic substances (cotton, pulp, etc.).
  • a fiber or the like composed of a regenerated cellulosic material can be used.
  • the fibers may contain components such as lignin and hemicellulose.
  • Raw materials for cellulosic fibers include, for example, cotton (short-fiber cotton, medium-fiber cotton, long-fiber cotton, extra-long staple, extra-long staple, etc.), hemp, bamboo, Vegetable cellulose fibers such as mulberry, mitsumata, banana, and tunicate; N-oxide) spun purified cellulose fibers; and acetate fibers such as diacetate and triacetate.
  • cotton short-fiber cotton, medium-fiber cotton, long-fiber cotton, extra-long staple, extra-long staple, etc.
  • hemp such as mulberry, mitsumata, banana, and tunicate
  • N-oxide spun purified cellulose fibers
  • acetate fibers such as diacetate and triacetate.
  • at least one selected from cupra-ammonium rayon, viscose method rayon, and refined cellulose fiber is preferred because of its easy availability.
  • the form of the cellulosic fiber is not particularly limited, and it is possible to use those prepared into raw yarn (unprocessed yarn), false twisted yarn, dyed yarn, single yarn, plied yarn, covering yarn, etc. according to the purpose. can be done.
  • the cellulosic fiber may be a blended yarn, a blended twisted yarn, or the like.
  • the raw materials in various forms described above may be used singly or in combination of two or more. Among these, non-twisted yarn is preferable from the standpoint of compatibility between moldability and mechanical strength of the composite material.
  • a fiber sheet refers to a product obtained by processing a large number of fibers into a thin and wide sheet, and includes woven fabrics, knitted fabrics, non-woven fabrics, and the like.
  • the weave structure of the fabric is also not particularly limited, and the Mihara weave of plain weave, twill weave, and satin weave can be used.
  • the gap between the warp and weft of cellulosic fibers is preferably 0.1 to 0.8 mm, more preferably 0.2 to 0.6 mm, and still more preferably 0.25 to 0.25 mm. It can be 0.5 mm.
  • the fabric made of cellulosic fibers may preferably have a basis weight of 50 to 500 g/m 2 , more preferably 100 to 400 g/m 2 .
  • the carbon fiber fabric obtained by heat-treating this fabric can have excellent strength.
  • the method for producing the nonwoven fabric is not particularly limited, but for example, a method of obtaining a fiber sheet by using the above-mentioned fiber cut to an appropriate length as a raw material by a dry method or a wet method, or by using an electrospinning method or the like. A method of obtaining a fiber sheet directly from a solution, etc. can be mentioned. Furthermore, after the nonwoven fabric is obtained, a treatment such as resin bond, thermal bond, spunlace, or needle punch may be added for the purpose of bonding the fibers together.
  • a catalyst is held on the raw material sheet prepared as described above.
  • a porous activated carbon fiber sheet can be obtained by causing a raw material sheet to retain a catalyst, carrying out a carbonization treatment, and further activating using water vapor, carbon dioxide, air gas, or the like.
  • the catalyst for example, a phosphoric acid-based catalyst, an organic sulfonic acid-based catalyst, or the like can be used.
  • phosphoric acid-based catalysts include phosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, oxyacids of phosphorus such as phosphinic acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, dimethylphosphonopropanamide, ammonium polyphosphate, polyphosphonitrile chloride, and phosphoric acid, tetrakis(hydroxymethyl)phosphonium salts or tris(1-aziridinyl)phosphine oxide and urea, thiourea, melamine, guanine, Examples include cyanamide, hydrazine, dicyandiamide, condensates of these with methylol derivatives, and the like, preferably diammonium hydrogen phosphate.
  • the phosphoric acid-based catalyst may be used alone or in combination of two or more.
  • its concentration is preferably 0.05 to 2.0 mol/L, more preferably 0.1 to 1.0 mol/L.
  • Organic sulfonic acid an organic compound having one or more sulfo groups can be used.
  • compounds having a sulfo group bonded to various carbon skeletons such as aliphatic and aromatic compounds can be used.
  • the organic sulfonic acid catalyst preferably has a low molecular weight.
  • organic sulfonic acid-based catalysts include R—SO 3 H (wherein R is a linear/branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a carbon represents an aryl group having 6 to 20 atoms, and the alkyl group, cycloalkyl group, and aryl group may be substituted with an alkyl group, a hydroxyl group, and a halogen group, respectively.).
  • R is a linear/branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a carbon represents an aryl group having 6 to 20 atoms
  • the alkyl group, cycloalkyl group, and aryl group may be substituted with an alkyl group, a hydroxyl group, and a halogen group, respectively.
  • organic sulfonic acid catalysts examples include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 1-hexanesulfonic acid, vinylsulfonic acid, cyclohexanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, and naphthalenesulfone. acid, benzenesulfonic acid, camphorsulfonic acid, and the like. Among these, methanesulfonic acid can be preferably used. Moreover, the organic sulfonic acid-based catalyst may be used alone or in combination of two or more.
  • the organic sulfonic acid when used as an aqueous solution, its concentration can be preferably 0.05 to 2.0 mol/L, more preferably 0.1 to 1.0 mol/L.
  • the phosphoric acid-based catalyst and the organic sulfonic acid-based catalyst may be mixed and used as a mixed catalyst.
  • the mixing ratio may be adjusted as appropriate.
  • the catalyst is held against the raw material sheet.
  • “holding” means keeping the catalyst in contact with the raw material sheet, and can take various forms such as adhesion, adsorption, and impregnation.
  • the method for holding the catalyst is not particularly limited, but includes, for example, a method of immersing in an aqueous solution containing the catalyst, a method of sprinkling the aqueous solution containing the catalyst on the raw material sheet, a method of contacting with vaporized catalyst vapor, and a method of containing the catalyst.
  • the raw material sheet is immersed in an aqueous solution containing the catalyst, and the interior of the fibers is impregnated with the catalyst.
  • the temperature for immersion in the aqueous solution containing the catalyst is not particularly limited, room temperature is preferred.
  • the immersion time is preferably 10 seconds to 120 minutes, more preferably 20 seconds to 30 minutes.
  • 1 to 150% by mass, preferably 5 to 60% by mass of the catalyst is adsorbed on the fibers constituting the raw material sheet.
  • the raw material sheet is preferably taken out and dried.
  • any method such as leaving at room temperature or introducing into a dryer may be used.
  • drying may be performed until excess moisture evaporates and the sample weight does not change. For example, in room temperature drying, the drying time may be left for 0.5 days or longer. After the change in mass is almost eliminated by drying, the process proceeds to the step of carbonizing the raw material sheet holding the catalyst.
  • the carbonization treatment for obtaining the activated carbon fiber sheet can be carried out according to a general carbonization method for activated carbon, and as a preferred embodiment, it can be carried out as follows.
  • the inert gas atmosphere means an oxygen-free or low-oxygen atmosphere in which carbon hardly undergoes a combustion reaction and is carbonized, and is preferably a gas atmosphere such as argon or nitrogen.
  • the raw material sheet holding the catalyst is heat-treated and carbonized in the predetermined gas atmosphere described above.
  • the lower limit of the heating temperature can be preferably 300° C. or higher, more preferably 350° C. or higher, and still more preferably 400° C. or higher or 750° C. or higher.
  • the upper limit of the heating temperature is preferably 1400° C. or lower, more preferably 1300° C. or lower, and even more preferably 1200° C. or lower or 1000° C. or lower.
  • the lower limit of the heat treatment time is preferably 10 minutes or longer, more preferably 11 minutes or longer, still more preferably 12 minutes, 15 minutes, 20 minutes, 25 minutes or longer, and more preferably 30 minutes or longer. sell.
  • the upper limit of the heat treatment time can be arbitrary, it is preferably 180 minutes or less, more preferably 160 minutes or less, and still more preferably 140 minutes or less.
  • the heat treatment after the above heat treatment (sometimes referred to as primary heat treatment), further heat treatment can be performed in a predetermined gas atmosphere. That is, the carbonization treatment may be performed by dividing the heat treatment with different conditions such as temperature into a plurality of stages.
  • the physical properties can be adjusted, carbonization and subsequent activation can proceed more favorably, and an activated carbon fiber sheet with excellent adsorption and desorption properties can be obtained.
  • the activation treatment in the present invention can be performed, for example, by continuously supplying water vapor, carbon dioxide, or an alkaline chemical after the heat treatment and maintaining the activated carbon fiber at an appropriate activation temperature for a predetermined time. you can get a sheet.
  • the lower limit of the activation temperature can be preferably 300° C. or higher, more preferably 350° C. or higher, and even more preferably 400, 500, 600, 700 or 750° C. or higher.
  • the upper limit of the activation temperature can be preferably 1400° C. or lower, more preferably 1300° C. or lower, and even more preferably 1200 or 1000° C. or lower.
  • the lower limit of the activation time can be preferably 1 minute or longer, more preferably 5 minutes or longer.
  • the upper limit of the activation time can be arbitrary, it is preferably 180 minutes or less, more preferably 160 minutes or less, still more preferably 140 minutes or less, 100 minutes or less, 50 minutes or less, or 30 minutes or less.
  • a molded body can be produced as follows.
  • ⁇ Preparation of slurry containing activated carbon fiber and binder> An activated carbon fiber sheet and a binder prepared in advance are mixed with water, defibrated and dispersed by a mixer, and both are mixed to obtain a slurry containing both. Depending on the scale of the mixer, the activated carbon fiber sheet to be charged into the mixer may be cut into small pieces of an appropriate size before being charged.
  • the fiber length was measured using DIGITAL MICROSCOPE KH-8700 (manufactured by Hylox Co., Ltd.), 20 fibers were randomly extracted from a 50-fold image, and the standard deviation was obtained.
  • ⁇ Specific surface area> Approximately 30 mg of a sample for measurement (activated carbon fiber sheet, etc.) was collected, dried in vacuum at 200° C. for 20 hours, weighed, and measured using a high-precision gas/vapor adsorption measurement device BELSORP-max II (Microtrac Bell). measured by The amount of nitrogen gas adsorbed at the boiling point of liquid nitrogen (77K) was measured in a relative pressure range of 10 -8 order to 0.990 to create an adsorption isotherm for the sample.
  • This adsorption isotherm is analyzed by the BET method in which the analysis relative pressure range is automatically determined under the conditions of adsorption isotherm type I (ISO9277), and the BET specific surface area per weight (unit: m 2 /g) is obtained, This was defined as the specific surface area (unit: m 2 /g).
  • Total pore volume (unit: cm 3 /g) was calculated by the one-point method from the result of the isothermal adsorption line obtained in the section on the specific surface area at a relative pressure of 0.960.
  • Average pore diameter (unit: nm) 4 x total pore volume x 10 3 ⁇ specific surface area Equation 3
  • the volume of the shaped adsorbent was calculated from the measurement results of the shaped adsorbent, or from the size of the mold for the shaped adsorbent.
  • the shaped adsorbent was dried in a dryer at 115 ⁇ 5°C for 3 hours or more, and after cooling, the dry weight was measured. After measuring the mass of an empty adsorption vessel (stainless steel frame vessel having the same nominal shape as the shaped adsorbent and allowing gas to flow), the shaped adsorbent was filled into the adsorption vessel.
  • an empty adsorption vessel stainless steel frame vessel having the same nominal shape as the shaped adsorbent and allowing gas to flow
  • test tube is placed in a circulation device, and 1.0 L/min of n-butane gas diluted with air to a concentration of 0.2% is flowed through the test tube at a test temperature of 25° C. to adsorb n-butane. Remove the test tube from the flow device and measure the mass. This flow of 0.2% concentration n-butane gas was repeated until a constant mass was achieved, that is, until the adsorption amount was saturated. The test tube was reinstalled in the circulation device, and 20.0 L/min of air was flowed through the test tube for 12 minutes at a test temperature of 25°C to desorb n-butane. The test tube was removed from the flow device and weighed.
  • ⁇ Measurement of 0 ppm maintenance time Changes in the concentration of adsorption and desorption when the n-butane was circulated were measured every 6 seconds with a portable gas detector Cosmotector (model number: XP-3160, manufacturer: New Cosmos Electric Co., Ltd.). After repeating the first adsorption and desorption, regarding the concentration change in the second adsorption, the case of less than the lower limit of determination (25 ppm) was set to 0 ppm, and the time to maintain 0 ppm continuously from the beginning was set to 0 ppm maintenance time (minutes). .
  • Effective adsorption/desorption amount (2nd n-butane adsorption amount + 2nd n-butane desorption amount)/2
  • Effective adsorption/desorption amount (2nd n-butane adsorption amount + 2nd n-butane desorption amount)/2
  • Effective adsorption/desorption amount (unit: g) Second n-butane adsorption amount (unit: g) Second n-butane desorption amount (unit: g)
  • Effective adsorption/desorption amount ratio effective adsorption/desorption amount / dry weight of molded adsorbent x 100 The unit of each numerical value is as follows. Effective adsorption/desorption rate (unit: wt%) Effective adsorption/desorption amount (unit: g) Shaped adsorbent dry weight (unit: g)
  • Effective adsorption/desorption rate effective adsorption/desorption amount / first adsorption amount x 100 The unit of each numerical value is as follows. Effective adsorption/desorption rate (unit: %) Effective adsorption/desorption amount (unit: g) First adsorption amount (unit: g)
  • Example 1 (1.1) Activated carbon fiber A web of rayon fiber (56 dtex, fiber length 102 mm) with a basis weight of 400 g/m 2 passed through a carding machine is impregnated with a 6-10% diammonium hydrogen phosphate aqueous solution, squeezed out, and then dried. to deposit 8 to 10% by weight.
  • the obtained pretreated fiber was heated to 900° C. in 45 minutes in a nitrogen atmosphere and held at this temperature for 3 minutes. Subsequently, activation treatment was performed for 17 minutes in a stream of nitrogen containing steam with a dew point of 71° C. at that temperature to obtain activated carbon fibers.
  • a 18 mm bottom part containing the molded body in a wet state was divided from the metal cylinder, and the upper and lower cross sections of the metal cylinder were sandwiched between punching plates, and a weight of 1 kg was placed thereon. After drying for a period of time, the metal cylinder was removed to obtain an adsorbent shaped like a disc having an outer diameter of 62 mm and a height of 18 mm. The obtained shaped adsorbent was more resistant to deformation than the activated carbon fiber.
  • Example 2 (1.1) Activated carbon fiber A needle-punched non-woven fabric made of rayon fiber (17 dtex, fiber length 76 mm) and having a basis weight of 400 g/m 2 was impregnated with a 6-10% aqueous solution of diammonium hydrogen phosphate, squeezed out, and dried. 8 to 10% by weight was deposited. The obtained pretreated nonwoven fabric was heated to 900° C. in 40 minutes in a nitrogen atmosphere and held at this temperature for 3 minutes. Subsequently, activation treatment was performed for 17 minutes in a stream of nitrogen containing water vapor with a dew point of 71° C. at that temperature to obtain an activated carbon fiber sheet.
  • Example 3 (1.1) Activated carbon fiber A needle-punched non-woven fabric made of rayon fiber (7.8 dtex, fiber length 76 mm) and having a basis weight of 400 g/m 2 was impregnated with a 6-10% aqueous solution of diammonium hydrogen phosphate. It was dried to a deposit of 8-10% by weight. The obtained pretreated nonwoven fabric was heated to 900° C. in 45 minutes in a nitrogen atmosphere, and held at this temperature for 3 minutes. Subsequently, activation treatment was performed for 17 minutes in a stream of nitrogen containing water vapor with a dew point of 71° C. at that temperature to obtain an activated carbon fiber sheet.
  • Example 4 (1.1) Activated carbon fiber Activated carbon fiber was prepared in the same manner as in Example 3 except that a needle-punched nonwoven fabric having a basis weight of 400 g/m 2 made of rayon fiber (5.6 dtex, fiber length 76 mm) was used. A fiber sheet was obtained.
  • Example 5 (1.1) Activated carbon fiber Activated carbon fiber was obtained in the same manner as in Example 1 above.
  • the second slurry was suction dehydrated and dried in the same manner as in Example 1 to obtain a disk-shaped adsorbent having an outer diameter of 62 mm and a height of 18 mm.
  • the obtained shaped adsorbent was more resistant to deformation than the activated carbon fiber.
  • Example 7 (1.1) Activated Carbon Fiber An activated carbon fiber sheet was obtained in the same manner as in Example 3 above.
  • Example 8 (1.1) Activated Carbon Fiber An activated carbon fiber sheet was obtained in the same manner as in Example 4 above.
  • Activated carbon fiber A needle-punched non-woven fabric made of rayon fiber (3.3 dtex, fiber length 76 mm) and having a basis weight of 300 g/m 2 was impregnated with a 6-10% aqueous solution of diammonium hydrogen phosphate. It was dried to a deposit of 8-10% by weight. The obtained pretreated nonwoven fabric was heated to 900° C. in 50 minutes in a nitrogen atmosphere, and subsequently activated at that temperature in a stream of nitrogen containing water vapor with a dew point of 60° C. for 13 minutes to obtain an activated carbon fiber sheet. rice field.
  • ⁇ Comparative Example 2 5 parts by weight of the binder used in Example 1 above was placed in a mixer together with 0.5 L of water and fibrillated and dispersed for 30 seconds. The mixture was stirred with a spatula to obtain slurry for adsorbing granular activated carbon. This adsorption slurry was dehydrated and dried by suction in the same manner as in Example 1 to obtain a disk-shaped shaped adsorbent having an outer diameter of 62 mm and a height of 18 mm.
  • a frame which is a columnar container with one side and the opposite side open to allow ventilation was prepared.
  • a frame container having a diameter of 6.2 cm on one side was prepared.
  • the prepared adsorbent was filled inside the frame container so that no gaps were formed, and it was used as a test sample for measuring pressure loss.
  • the pressure loss was measured as follows. 60 L/min of air was passed through the test sample prepared as described above, and the differential pressure at the entrance and exit of the test sample was measured using a testo 510 differential pressure gauge (Testo Co., Ltd.), and the result was defined as pressure loss (kPa).
  • Tables 1-1 to 1-7 show various measurement results for the shaped adsorbent.

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WO2024135516A1 (ja) * 2022-12-22 2024-06-27 日本製紙株式会社 活性炭及びその製造方法、並びにそれらの応用
WO2025032341A1 (en) * 2023-08-10 2025-02-13 Nexeon Limited Composite particles

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TWI750772B (zh) * 2019-08-21 2021-12-21 日商日本製紙股份有限公司 汽車碳罐用活性碳纖維板
TWI742804B (zh) 2019-08-21 2021-10-11 日商日本製紙股份有限公司 汽車碳罐用活性碳纖維板
CA3232778A1 (en) * 2021-09-29 2023-04-06 Nippon Paper Industries Co., Ltd. Formed adsorber for canister

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05103979A (ja) * 1991-10-17 1993-04-27 Osaka Gas Co Ltd 成形吸着材およびその製造方法
JPH105580A (ja) 1996-06-24 1998-01-13 Kuraray Chem Corp 活性炭繊維成形吸着体
JP2013173137A (ja) 2007-09-07 2013-09-05 Kuraray Chemical Co Ltd 吸着材及びその製造方法、並びにキャニスタ及びその使用方法
JP6568328B1 (ja) 2018-06-19 2019-08-28 日本製紙株式会社 自動車キャニスタ用活性炭素繊維シート

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04166225A (ja) * 1990-10-31 1992-06-12 Osaka Gas Co Ltd 吸着体
JP3334294B2 (ja) * 1993-10-28 2002-10-15 株式会社デンソー 吸着体及び多孔吸着材
JPH07251067A (ja) * 1994-03-14 1995-10-03 Nippondenso Co Ltd 複合吸着体及びその製造方法
US7077891B2 (en) * 2002-08-13 2006-07-18 Air Products And Chemicals, Inc. Adsorbent sheet material for parallel passage contactors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05103979A (ja) * 1991-10-17 1993-04-27 Osaka Gas Co Ltd 成形吸着材およびその製造方法
JPH105580A (ja) 1996-06-24 1998-01-13 Kuraray Chem Corp 活性炭繊維成形吸着体
JP2013173137A (ja) 2007-09-07 2013-09-05 Kuraray Chemical Co Ltd 吸着材及びその製造方法、並びにキャニスタ及びその使用方法
JP6568328B1 (ja) 2018-06-19 2019-08-28 日本製紙株式会社 自動車キャニスタ用活性炭素繊維シート
JP2019218943A (ja) * 2018-06-19 2019-12-26 日本製紙株式会社 自動車キャニスタ用活性炭素繊維シート

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4299893A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024135516A1 (ja) * 2022-12-22 2024-06-27 日本製紙株式会社 活性炭及びその製造方法、並びにそれらの応用
WO2025032341A1 (en) * 2023-08-10 2025-02-13 Nexeon Limited Composite particles

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