WO2022181616A1 - 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
WO2022181616A1
WO2022181616A1 PCT/JP2022/007256 JP2022007256W WO2022181616A1 WO 2022181616 A1 WO2022181616 A1 WO 2022181616A1 JP 2022007256 W JP2022007256 W JP 2022007256W WO 2022181616 A1 WO2022181616 A1 WO 2022181616A1
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Prior art keywords
adsorbent
activated carbon
shaped adsorbent
shaped
adsorption
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.)
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PCT/JP2022/007256
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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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Application filed by Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Priority to MX2023009890A priority Critical patent/MX2023009890A/es
Priority to JP2023502441A priority patent/JP7268261B2/ja
Priority to KR1020237032740A priority patent/KR20230148423A/ko
Priority to CA3210734A priority patent/CA3210734A1/en
Priority to EP22759652.5A priority patent/EP4299894B1/en
Priority to CN202280016498.3A priority patent/CN116888356A/zh
Publication of WO2022181616A1 publication Critical patent/WO2022181616A1/ja
Priority to US18/236,597 priority patent/US12576389B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • 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
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    • 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
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • 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
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
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    • 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
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    • 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
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    • 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
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    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • 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
    • 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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    • B01D2253/302—Dimensions
    • B01D2253/306—Surface area, e.g. BET-specific surface
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    • 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
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    • B01D2259/4566—Gas separation or purification devices adapted for specific applications for use in transportation means

Definitions

  • the present invention relates to a shaped adsorbent for canisters, and more particularly to a shaped adsorbent for canisters using activated carbon.
  • transpiration fuel such as gasoline
  • the pressure in the fuel tank fluctuates due to changes in the outside temperature, etc.
  • transpiration fuel fills the fuel tank. Gas 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. Also called.) is provided.
  • 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.
  • JP 2013-173137 A Japanese Patent Application Laid-Open No. 2019-10880 Patent No. 6568328 JP-A-10-5580
  • 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. In addition, research and development have not progressed sufficiently as to what kind of adsorbent should be used when a plurality of storage chambers, such as a main chamber and an auxiliary chamber, are filled with the adsorbent.
  • one of the problems to be solved by the present invention is to provide a new type of adsorbent suitable for high-performance canisters.
  • one of the further problems to be solved by the present invention is a molded article having improved mechanical strength while using activated carbon fibers, and exhibiting excellent effects as an adsorbent for canisters.
  • An object of the present invention is to provide a shaped adsorbent that
  • the present inventors have found that by mixing activated carbon and a fibrous binder having predetermined physical properties to form a shaped adsorbent, it is possible to obtain an adsorbent suitable for the high-performance layer of a canister. and completed the present invention.
  • the present invention can be grasped from various aspects, and means for solving the problems include, for example, the following.
  • X represents the adsorption amount (unit: parts by weight) of n-butane gas per 100 parts by weight of the shaped adsorbent in an atmosphere of 25° C. and a gas pressure of 0.2 kPa
  • Y represents the adsorption amount (unit: parts by weight) of n-butane gas per 100 parts by weight of the shaped adsorbent in an atmosphere of 25° C. and an n-butane gas pressure of 100 kPa.
  • the shaped adsorbent contains activated carbon and a binder, The shaped adsorbent according to any one of [1] to [8] above, wherein the content ratio of the activated carbon and the binder is 0.3 to 20 parts by weight of the binder with respect to 100 parts by weight of the activated carbon.
  • a shaped adsorbent that has excellent adsorption/desorption performance and is suitable for a high performance canister or a high performance layer of a canister. Further, according to one aspect of the present invention, it is possible to provide a shaped adsorbent for a canister that exhibits excellent effects as an adsorbent for a canister, has improved mechanical strength, and is less likely to lose its shape. .
  • 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
  • both “adsorption” and “desorption” may be collectively referred to as “adsorption/desorption”.
  • pore size means the diameter or width of the pore, not the radius of the pore, unless otherwise specified.
  • Shaped Adsorbent The shaped 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.
  • the shape of the shaped adsorbent is not particularly limited, and for example, a shape that can be molded and allows gas to flow is suitable.
  • 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.
  • a laminate may be formed by laminating a plurality of disk-shaped, sheet-shaped, or plate-shaped shaped adsorbents.
  • a preferable embodiment of the present invention is one that satisfies predetermined requirements for the ratio of adsorption amount per pressure represented by Formula 1 or Formula 2 below.
  • the ratio indicating the difference in the adsorption amount under two different gas pressure atmospheres which is expressed, for example, by Equation 1 or 2 is referred to as the adsorption amount ratio per pressure (unit: %).
  • the pressure adsorption rate can be determined between a variety of different pressure combinations.
  • Formula 1 shows the adsorption amount ratio for each pressure using the adsorption amount under the 0.2 kPa atmosphere and the adsorption amount under the 100 kPa atmosphere.
  • Formula 2 shows, as an embodiment, the adsorption amount ratio for each pressure using the adsorption amount under the 100 kPa atmosphere and the adsorption amount under the 50 kPa atmosphere.
  • Equation 1 ⁇ Ratio of adsorption amount per pressure determined by Equation 1: P 0.2/100 >
  • the ratio of adsorption amount per pressure (%) represented by the following formula 1 can be used as the first index.
  • P 0.2/100 X/Y x 100 (Formula 1)
  • X represents the adsorption amount (unit: parts by weight) of n-butane gas per 100 parts by weight of the activated carbon in an atmosphere of 25° C. and a gas pressure of 0.2 kPa.
  • Y represents the adsorption amount (unit: parts by weight) of n-butane gas per 100 parts by weight of the activated carbon in an atmosphere of 25° C. and a gas pressure of 100 kPa.
  • the lower limit of the adsorption amount ratio per pressure (P 0.2/100 ) represented by Formula 1 is preferably 18% or more, more preferably 19% or more, and even more preferably can be 20, 21, 22, 23, 24, or 25% or more.
  • the upper limit of the adsorption amount ratio per pressure (P 0.2/100 ) represented by Formula 1 is preferably 80%, more preferably 75%, and even more preferably 70, 65, or 60%.
  • the adsorption amount ratio (%) per pressure represented by the following formula 2 can be used as the second index.
  • P 100/50 Y/Z x 100 (Formula 2)
  • Z represents the adsorption amount (unit: parts by weight) of n-butane gas per 100 parts by weight of the activated carbon in an atmosphere of 25° C. and a gas pressure of 50 kPa.
  • Y is the same as Y in Formula 1 above. That is, in Formula 2, Y represents the adsorption amount (unit: parts by weight) of n-butane gas per 100 parts by weight of the activated carbon in an atmosphere of 25° C. and a gas pressure of 100 kPa.
  • the adsorption amount ratio per pressure (P 100/50 ) represented by Formula 2 is preferably 120% or less, more preferably 119% or less, still more preferably 118, 117, 116, 115, 114, 112, 110, It can be 108, or 106%.
  • the canister is generally located between the fuel tank, the engine, and the outside air port, and gas flows between them.
  • the fuel vaporized from the fuel tank is captured by the adsorbent inside the canister.
  • the capacity of the adsorbent is exceeded, vaporized gas is released to the outside air through an outside air port leading from the canister.
  • the engine is running, vaporized gas is sent from the adsorbent to the engine due to the negative pressure. That is, the adsorbent in the canister repeatedly adsorbs and desorbs the vaporized gas.
  • adsorbents with different properties for the main chamber (first chamber) and sub chambers (second and subsequent chambers).
  • the main chamber it is required to capture and remove a large amount of highly concentrated evaporative gas flowing in from the fuel tank and the like. That is, the main chamber preferably has a large adsorption capacity.
  • the gas flowing into the sub chamber from the main chamber has a relatively low concentration of vaporized gas, and the adsorbent in the sub chamber is required to have high performance of capturing this low concentration of vaporized gas.
  • the adsorbent in the canister is not only excellent in adsorption ability, but also that the gas is easily replaced when the adsorbent in the canister is purged.
  • the canister adsorbent especially the adsorbent that is required to capture low-concentration evaporative gas, should have not only excellent adsorption capacity, but also sufficient recoverability to desorb to a level at which the adsorption capacity is recovered. preferable. Thus, a higher performance adsorbent is required especially for the sub chamber.
  • an adsorbent having a ratio of adsorption amount per pressure (P 0.2/100 ) represented by Equation 1 that is equal to or greater than a predetermined value can exhibit such high performance as described above.
  • a higher index (P 0.2/100 ) of Equation 1 indicates a higher ability to adsorb vaporized gas even under a low gas pressure atmosphere, that is, a low gas concentration atmosphere.
  • the high adsorption performance in a low-concentration atmosphere makes it suitable as an adsorbent for the high-performance layer of the canister.
  • an adsorbent having a ratio of adsorption amount per pressure (P 100/50 ) represented by Equation 2 below a predetermined value can exhibit such high performance as described above.
  • the adsorption amount ratio for each pressure can be obtained for various gas pressures, but the adsorption amount ratio for each pressure obtained by Equation 2 is obtained under an atmosphere of substantially the maximum gas pressure and under an atmosphere of half the gas pressure (that is, about It is an index showing the difference in the amount of adsorption in a gas concentration atmosphere of 50%) as a ratio.
  • Equation 2 The fact that the ratio of adsorption amount per pressure (P 100/50 ) obtained by Equation 2 is 120% or less indicates that the adsorption amount does not change significantly regardless of whether the evaporated gas concentration is high or low. In other words, it has adsorption performance with low concentration dependence.
  • An adsorbent with such a low concentration dependency is suitable as an adsorbent for a high-performance layer of a canister, which is required to capture vaporized gas even at a low concentration.
  • activated carbon whose pores can be adjusted, from the viewpoint of obtaining an adsorbent with a preferable adsorption amount ratio per pressure as described above.
  • activated carbon fiber is more preferable because it is easy to obtain an adsorbent with low concentration dependence.
  • the shaped adsorbent of the present invention can be a more preferable embodiment by satisfying at least one or arbitrary two or more of the following predetermined items.
  • the lower limit of the specific surface area of the shaped adsorbent that can be used in the present invention is preferably 100 m 2 /g or more, more preferably 200 m 2 /g or more, still more preferably 300, 500, 700, 900, 1000, 1100 or 1200 m 2 . /g or more.
  • the upper limit of the specific surface area of activated carbon that can be used in the present invention may be approximately 2500, 2400, 2300, 2200, 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.
  • a shaped adsorbent having such a specific surface area for example, a form containing activated carbon fibers can be suitably employed.
  • the lower limit of the total pore volume of the shaped adsorbent that can be used in the present invention is preferably 0.50 cm 3 /g or more, more preferably 0.55 cm 3 /g or more, and still more preferably 0.60, 0.65, or 0.65 cm 3 /g or more. 0.70, 0.75, 0.80, 0.85, or 0.90 cm 3 /g or greater.
  • the upper limit of the total pore volume of the shaped adsorbent that can be used in the present invention is preferably 1.20 cm 3 /g or less, more preferably 1.15 cm 3 /g or less, still more preferably 1.10, 1.05, 1 0.03, or 1.00 cm 3 /g or less.
  • a shaped adsorbent having superior adsorption/desorption performance with respect to the transpired fuel gas.
  • a shaped adsorbent having such a total pore volume for example, a form containing activated carbon fibers can be suitably employed.
  • the lower limit of the average pore diameter of the shaped adsorbent that can be used in the present invention is preferably 1.50 nm or more, more preferably 1.60 nm or more, still more preferably 1.70 nm or more.
  • the upper limit of the average pore size of the shaped adsorbent that can be used in the present invention can be arbitrary, it is preferably 2.50 nm or less, more preferably 2.20 nm or less, and still more preferably 2.00 or 1.90 nm or less. .
  • the shaped adsorbent can be made more excellent in adsorption/desorption performance with respect to the transpired fuel gas.
  • the shaped adsorbent having such an average pore diameter for example, one having a form containing activated carbon fibers can be suitably employed.
  • the term "ultramicropores" means pores with a pore size of 0.7 nm or less.
  • the lower limit of the ultramicropore volume of the shaped adsorbent that can be used in the present invention is preferably 0.05 cm 3 /g or more, more preferably 0.10 cm 3 /g or more, and still more preferably 0.12 or 0.14 cm 3 . /g or more.
  • the upper limit of the ultramicropore volume of the shaped adsorbent that can be used in 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, 0.24, 0.29 cm 3 /g or less.
  • the molded adsorbent can be made more excellent in adsorption/desorption performance with respect to the transpired fuel gas.
  • a shaped adsorbent having such an ultra-micropore volume for example, a form containing activated carbon fibers can be suitably employed.
  • micropores means pores with a pore size of 2.0 nm or less.
  • the lower limit of the micropore volume of the shaped adsorbent that can be used in 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. g or greater.
  • the upper limit of the micropore volume of the shaped adsorbents that can be used in the present invention can be 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 or less. .
  • the micropore volume 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.
  • the activated carbon having such an ultra-micropore volume for example, one in a form containing activated carbon fibers can be suitably employed.
  • 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 3 using the ultra-micropore volume value a and the micropore volume value b. can.
  • V 0.7-2.0 b-a (Formula 3)
  • 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 0.30 cm 3 /g or more, more preferably It may be 0.36 cm 3 /g or more, more preferably 0.38, 0.40, 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 1.00 cm 3 /g or less, more preferably It may be 0.90 cm 3 /g or less, more preferably 0.80, 0.75, 0.70, 0.65, or 0.60 cm 3 /g or less.
  • the shaped adsorbent can be made more excellent in adsorption/desorption performance with respect to transpired fuel gas.
  • a shaped adsorbent having such an ultra-micropore volume for example, a form containing activated carbon fibers can be suitably employed.
  • 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 4.
  • R0.7/2.0 a/b x 100 (%) (Formula 4)
  • the lower limit of the abundance ratio R 0.7/2.0 of the volume of ultra-micropores to the volume of micropores is preferably 15.0% or more, more preferably 18% or more, and still more preferably 19%. It can be more than that.
  • the upper limit of the abundance ratio R 0.7/2.0 of the volume of ultra-micropores to the volume of micropores is preferably 60% or less, more preferably 50% or less, still more preferably 40, 30, Or it can be 25% or less.
  • the molded adsorbent can be made more excellent in adsorption/desorption performance with respect to the transpired fuel gas.
  • a shaped adsorbent having such an ultra-micropore volume for example, a form containing activated carbon fibers can be suitably employed.
  • the basis weight of the activated carbon fiber sheet is in the following range.
  • the lower limit of basis weight can be preferably 50.0 g/m 2 or more, more preferably 60.0 g/m 2 or more, and even more preferably 70.0 or 80.0 g/m 2 or more.
  • the upper limit of basis weight can be preferably 200 g/m 2 or less, more preferably 150 g/m 2 or less, and even more preferably 120, 110 or 100 g/m 2 or less.
  • preferred lower and upper dry density limits for the shaped adsorbent can be as follows.
  • the lower limit of the dry density that can be used in the present invention is preferably 0.010 g/cm 3 or more, more preferably 0.015 g/cm 3 or more, still more preferably 0.020 g/cm 3 , 0.030, 0.040, It can be 0.050, or 0.060 g/cm 3 or more.
  • the upper limit of the dry density of activated carbon that can be used in 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 within the range described above, it is possible to obtain a molded adsorbent that is superior in the adsorption and desorption performance per volume required for the canister within the range of the capacity of the adsorbent that can be accommodated in the canister. can. Further, by making the thickness equal to or higher than the above lower limit, it is possible to avoid deterioration of mechanical properties (for example, strength) even in the case of sheet-like or disc-like.
  • the dry density of the shaped adsorbent depends on the fiber diameter of the carbon fiber, the length of the fiber by adjusting the agitation force when defibrating the carbon fiber, and the suction force when suction molding the mixed slurry with a binder such as a fibrous binder. It can be adjusted by adjustment, and the pressure loss of the shaped adsorbent can be suppressed.
  • the shaped adsorbent that can be used in the present invention preferably has a predetermined moisture content.
  • the lower limit of the water content under the conditions of 23° C. and 50% relative humidity is preferably 1% or more, more preferably 2% or more, and even more preferably 3% or more.
  • the upper limit of the water content under conditions of 23° C. and 50% relative humidity is preferably 30% or less, more preferably 25, 20, or 15% or less, and even more preferably 10 or 8% or less.
  • the activated carbon can be made more excellent as a shaped adsorbent for automobile canisters.
  • a shaped adsorbent having such a water content for example, a form containing activated carbon fiber can be suitably employed.
  • 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 4.0 ⁇ m or more, more preferably 6.0 ⁇ m or more, and still more preferably 8.0, 10.0, 12.0, 14 .0, 18.0, 19.0, or 20.0 microns or greater.
  • the upper limit of the fiber diameter of the activated carbon fiber that can be used in the molded adsorbent of the present invention can be arbitrary from the viewpoint of suppressing pressure loss. It is preferably 55.0 ⁇ m or less, more preferably 50.0, 45.0, 40.0, or 35.0 ⁇ m. When the fiber diameter of the activated carbon fiber that can be used for the molded adsorbent is within the above range, the molded adsorbent can be made to further suppress pressure loss.
  • the lower limit of the average 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 still more preferably 950 or more. sell.
  • the upper limit of the average fiber length of the activated carbon fiber 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 even more preferably 1,200 or less.
  • 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 0.100 or more, more preferably 0.200, 0.300, 0.400, 0.500 or more, and further Preferably, it can be 0.600 or more.
  • the upper limit of the fiber length variation coefficient of the activated carbon fiber that can be used in the molded adsorbent of the present invention is preferably 2.500 or less, more preferably 2.000, 1.500, 1.000, 0.900, 0.900, 0.900, 0.900, 0.900, 0.900, 0.900, 0.900, 0.900, 0.900, 1.000, 0.900, 0.900, 0.900, 1.000, 0.900, 0.900, 0.900, 1.000, 0.900, 0.900, 0.900, 1.000, 0.900, 0.900, 0.900, 1.000, 0.900, 0.900, 0.900, 1.000, 1.000, 0.900, 0.900, 0.000 It can be 800 or less, more preferably 0.700 or less.
  • the fiber length variation coefficient of the activated carbon fiber that can be used for the molded adsorbent is within the above range, the molded adsorbent can be made to 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 lower limit of the average particle size of the granular activated carbon that can be used in the shaped adsorbent of the present invention is preferably 100 or more, more preferably 150, 200, 250, 300, 350, 400 or more, and still more preferably 450 or more.
  • the upper limit of the average particle size of the granular activated carbon that can be used in the shaped adsorbent of the present invention is preferably 3000 or less, more preferably 2500, 2000, 1500, 1000 or 800 or less, still more preferably 600 or less.
  • the lower limit of the particle size variation coefficient of the granular activated carbon that can be used in the shaped adsorbent of the present invention is preferably 0.01 or more, more preferably 0.025, 0.050, 0.075, 0.100, 0.125. , 0.150, or more, more preferably 0.175 or more.
  • the upper limit of the particle size variation coefficient of the granular activated carbon that can be used in the shaped adsorbent of the present invention is preferably 2.500 or less, more preferably 2.000, 1.500, 1.000, 0.800, 0.600. , 0.500, 0.400, 0.300 or less, more preferably 0.200 or less.
  • the shaped adsorbent as an adsorbent preferably has a predetermined n-butane adsorption/desorption performance. 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, and further Preferably, it can be 40.0, 50.0, 60.0, 70.0, or 75.0% or more.
  • a form containing activated carbon fibers can be suitably employed.
  • 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 50 minutes, 55 minutes, 60 minutes, 65 minutes, 68 minutes, 69 minutes, or 70 minutes or more.
  • 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.
  • An example of an embodiment of the present invention is a shaped adsorbent containing activated carbon and a binder.
  • the activated carbon that can be used in the present invention is not particularly limited in its form as long as it satisfies the various characteristics detailed below.
  • Examples of activated carbon include powdered activated carbon, granular activated carbon, and activated carbon fiber.
  • the activated carbon mixed with the shaped adsorbent may be used singly or in combination of two or more.
  • the mixing ratio can be changed as appropriate. For example, as the activated carbon, a mixture of 5 to 100 parts by weight of activated carbon fiber and 0 to 95 parts by weight of powdered activated carbon can be used.
  • a binder is used as one component that constitutes 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 activated carbon and binder in the shaped adsorbent can be, for example, 0.3 to 20 parts by weight of binder per 100 parts by weight of activated carbon.
  • 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-mentioned binder as the binder in the above-mentioned content ratio, it is possible to prevent the pores of the activated carbon fiber from being clogged and the properties such as adsorption/desorption performance and pressure loss to be reduced.
  • the excellent properties of the activated carbon fibers can be maintained to provide shaped adsorbents with excellent properties.
  • the shaped adsorbent which is one embodiment of the present invention, may contain constituents other than the activated carbon and the binder as long as the effects of the present invention are not nullified.
  • Shape of Shaped Adsorbent The shape of the shaped adsorbent of the present invention is not particularly limited, and may be, for example, disc-shaped, cylindrical, cylindrical, sheet-shaped, plate-shaped, pellet-shaped, or honeycomb-shaped. Furthermore, the disk-shaped, sheet-shaped or plate-shaped shaped adsorbents may be laminated to form a laminate.
  • 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 shaped adsorbent sheets 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 main surface 10a of the sheet-like shaped adsorbent is 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 the fluid F such as evaporated gas.
  • the side end surfaces 10b of the plurality of sheet-shaped adsorbents face the flow direction of the fluid F. are placed in By arranging in this way, pressure loss can be suppressed.
  • 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 laminated adsorbent as a whole may have a rectangular parallelepiped shape or a cubic shape.
  • 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 adsorption laminate of the present invention can be easily processed or molded into various shapes, and is a material with excellent handleability.
  • 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.
  • activated carbon which has a high n-butane adsorption capacity at a low concentration of about 0.2%, is used in the second compartment or the second housing located later from the engine or fuel tank, or the adsorbent chamber in the later stage. It is suitable as an adsorbent to be stored in.
  • the molded adsorbent of the present invention has a high effective adsorption/desorption amount due to purging. It is also suitable as an adsorbent for use in automobile canisters in that it can reduce the
  • the canister is a canister for an automobile and has a main chamber and a sub chamber for storing the adsorbent,
  • the auxiliary chamber has a smaller volume for containing the adsorbent than the main chamber and is arranged at a position closer to an opening communicating with the outside air,
  • the adsorbent of the present invention is housed in the auxiliary chamber, canister.
  • one main room and one sub-chamber may be provided, or two or more of each may be provided.
  • the shaped adsorbent of the present invention may be accommodated in at least one adsorbent chamber of the sub chamber, preferably in the opening communicating with the outside air. It can be provided in a nearby auxiliary room.
  • the shaped adsorbent of the present invention can be obtained by shaping activated carbon into a predetermined shape.
  • the activated carbon for example, one that satisfies the requirements shown as preferable indicators for the shaped adsorbent (for example, indicators represented by formulas 1 and 2) can be used.
  • An embodiment of the shaped adsorbent of the present invention can be obtained, for example, by mixing activated carbon and a fibrous binder and molding.
  • the activated carbon fibers can be produced, for example, by carbonizing and activating fibers having a predetermined fiber diameter. Carbonization and activation can employ common methods.
  • An embodiment in which an activated carbon fiber sheet is produced using a precursor sheet (raw material sheet) will be exemplified below.
  • activated carbon itself used in the present invention is not limited to a sheet shape.
  • An activated carbon fiber sheet may be produced using a precursor sheet (raw material sheet) as described below, or a predetermined activated carbon powder or the like may be prepared.
  • 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 diameter of single fibers constituting the cellulosic fibers is preferably 5 to 75 ⁇ m and the density is 1.4 to 1.9 m 3 /g.
  • 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. Possible.
  • 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 carried out, for example, by continuously supplying water vapor or carbon dioxide after the heat treatment and maintaining an appropriate activation temperature for a predetermined time to obtain an activated carbon fiber sheet. be able to.
  • 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 containing activated carbon fibers and a fibrous binder there are no particular restrictions on the method of processing a molded body containing activated carbon fibers and a fibrous binder. For example, a mixture of the two may be prepared and molded. As one embodiment, for example, a molded body can be produced as follows.
  • ⁇ Preparation of slurry containing activated carbon fiber and fibrous binder> An activated carbon fiber sheet and a fibrous binder prepared in advance are mixed with water, defibrated and dispersed by a mixer, and the two 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.
  • 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 4 x total pore volume x 10 3 ⁇ specific surface area (Formula 5)
  • ⁇ Sheet basis weight> A sample for measurement (activated carbon fiber sheet, etc.) is allowed to stand in an environment with a temperature of 23 ⁇ 2 ° C and a relative humidity of 50 ⁇ 5% for 12 hours or more, and the sheet basis weight (unit: g / m 2 ) asked for.
  • ⁇ Sheet thickness> A measurement sample (activated carbon fiber sheet, etc.) is left to stand for 12 hours or more in an environment with a temperature of 23 ⁇ 2 ° C and a relative humidity of 50 ⁇ 5%, and a digital small side thicker FS-60DS ) was used to measure the sheet thickness (unit: mm) when a load of 0.3 kPa was applied.
  • Sheet density Sheet basis weight/Sheet thickness/10 3 (Formula 6)
  • ⁇ Measurement of shaped adsorbent> The dimensions of the shaped adsorbent were obtained by measuring with vernier calipers, rulers and the like. The dry weight of the shaped adsorbent was measured with an electronic balance.
  • 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
  • the unit of each numerical value is as follows. 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)
  • ⁇ Adsorption amount per pressure (unit: wt% or g/100g)> Approximately 100 mg of activated carbon fiber sheet, granular activated carbon or shaped adsorbent is taken, dried in vacuum at 200°C for 20 hours, weighed, and measured using a high-precision gas/vapor adsorption measuring device BELSORP-max II (Microtrac Bell). and measured. The amount of n-butane gas adsorbed at 25° C. was measured in the absolute pressure range of 0.1 to 105 kPa to prepare an n-butane adsorption isotherm (unit: g) of the sample.
  • n-butane adsorption isotherm was divided by the sample dry weight (unit: g) to create an n-butane adsorption isotherm (unit: wt %). From this adsorption isotherm, the amounts of n-butane gas adsorbed at 0.2 kPa, 0.5 kPa, 5 kPa, 50 kPa and 100 kPa were read. Of these, the amounts of n-butane gas adsorbed at 0.2 kPa, 100 kPa, and 50 kPa were designated as X, Y, and Z, respectively. An explanation is provided below.
  • X unit: wt% or g/100g
  • Y unit: wt % or g/100 g
  • Z (unit: wt% or g/100g): The amount of n-butane gas adsorbed per 100g of the adsorbent (unit: g) in an atmosphere of 25°C and an n-butane gas pressure of 50kPa.
  • Activated carbon fiber sheet A needle-punched non-woven fabric made of rayon fibers (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. to deposit 8 to 10% by weight.
  • 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.
  • a bottom portion of 18 mm containing a molded body in a wet state is divided from the metal cylinder, and the upper and lower cross sections of the metal cylinder are sandwiched between punching plates, and a weight of 1 kg is placed on the metal cylinder to crush the molded body to a height of 18 mm.
  • 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 sheet.
  • Example 2 Activated carbon fiber sheet The same activated carbon fiber sheet as in Example 1 above.
  • (2.2) Molded adsorbent In the same manner as in Example 1, the activated carbon fiber adsorption slurry and the activated carbon fiber sheet were replaced with granular activated carbon (specific surface area: 1660 m 2 /g, average particle size: 502 ⁇ m, standard deviation: 89 ⁇ m). A granular activated carbon adsorption slurry was obtained.

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