WO2024048410A1 - Activated carbon fiber non-woven fabric, activated carbon fiber non-woven fabric manufacturing method, element, organic solvent absorpbtion/desorption treatment device, organic solvent recovery system, organic solvent absorption/desorption treatment method, and organic solvent recovery method - Google Patents

Activated carbon fiber non-woven fabric, activated carbon fiber non-woven fabric manufacturing method, element, organic solvent absorpbtion/desorption treatment device, organic solvent recovery system, organic solvent absorption/desorption treatment method, and organic solvent recovery method Download PDF

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WO2024048410A1
WO2024048410A1 PCT/JP2023/030472 JP2023030472W WO2024048410A1 WO 2024048410 A1 WO2024048410 A1 WO 2024048410A1 JP 2023030472 W JP2023030472 W JP 2023030472W WO 2024048410 A1 WO2024048410 A1 WO 2024048410A1
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organic solvent
carbon fiber
activated carbon
nonwoven fabric
fiber nonwoven
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PCT/JP2023/030472
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French (fr)
Japanese (ja)
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武将 岡田
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東洋紡エムシー株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—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
    • 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
    • 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
    • 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
    • C01B32/318—Preparation characterised by the starting materials
    • 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
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres

Definitions

  • the present invention relates to an activated carbon fiber nonwoven fabric, a method for producing the same, and the like.
  • Activated carbon fibers have excellent adsorption and desorption performance, such as a large adsorption capacity for organic solvents and fast adsorption and desorption rates.
  • Activated carbon fiber nonwoven fabrics are obtained by carbonizing and activating nonwoven fabrics mainly composed of cellulose-based, pitch-based, and other precursor fibers such as viscose rayon.
  • Patent Document 1 discloses a cylindrical element formed by wrapping an activated carbon fiber nonwoven fabric having a bulk density of 68 kg/m 3 or more for use in a continuous gas adsorption treatment device.
  • activated carbon fiber nonwoven fabrics have lower load durability in the thickness direction than general organic fiber nonwoven fabrics, and when repeated loads (or pressure) are applied in the thickness direction, the activated carbon fibers gradually break and become nonwoven. The shape of the material collapses, and as a result, the thickness gradually decreases. This is a phenomenon that occurs when a gas to be treated is passed through activated carbon fiber nonwoven fabric, and by repeatedly supplying and stopping the supply of gas to be treated, the pressure in the thickness direction is repeatedly applied and unloaded, and the activated carbon fiber nonwoven fabric is activated. The thickness of the carbon fiber nonwoven fabric gradually becomes thinner.
  • the organic solvent adsorption/desorption treatment apparatus when operated for a long period of time, the winding force of the element in which the activated carbon fiber nonwoven fabric is wrapped in a cylindrical shape decreases, and the activated carbon fiber nonwoven fabric is displaced downward due to gravity. If the shape stability of the element is impaired, the gas to be treated will make a short pass through the activated carbon fiber nonwoven fabric, and the adsorption performance of the organic solvent adsorption/desorption treatment device will deteriorate.
  • the activated carbon fiber nonwoven fabric has not undergone any deterioration such as pore clogging, the shape stability of the element is difficult to maintain in terms of adsorption performance and airflow stability of the gas to be treated.
  • the activated carbon fiber nonwoven fabric may be replaced before it is damaged.
  • the present invention was made to solve the above problems, and its purpose is to provide an activated carbon fiber nonwoven fabric that has high adsorption/desorption performance for organic solvents and improved load durability in the thickness direction.
  • the inventors of the present invention conducted extensive studies and found that an activated carbon fiber nonwoven fabric having a predetermined BET specific surface area, bulk density, and carbon structure not only has high adsorption/desorption performance but also has high load durability in the thickness direction. We have discovered that this can be done, and have completed the present invention.
  • the present invention has a BET specific surface area of 1000 m 2 /g or more and 2000 m 2 /g or less, Bulk density is greater than 100 kg/ m3 , graphite crystallinity Xg in X-ray diffraction is 0.35 or more, R value in Raman spectroscopy is 1.20 or more, and half width of D band in Raman spectroscopy. is 145 cm ⁇ 1 or less.
  • the activated carbon fiber nonwoven fabric of the present invention described above preferably has a pore diameter of 0.7 nm or less and a pore volume V 0.7 of 0.22 cm 3 /g or more.
  • the activated carbon fiber nonwoven fabric of the present invention described above has a ratio (V 0.7 /V a ) of pore volume V 0.7 with a pore diameter of 0.7 nm or less to the total pore volume V a of 0.30. It is preferable that it is above.
  • the present invention includes a step of carbonizing a precursor fiber nonwoven fabric to obtain a carbon fiber nonwoven fabric, and an activation treatment of the carbon fiber nonwoven fabric, wherein the activation treatment is performed by a steam activation method.
  • the present invention is an element constructed using the activated carbon fiber nonwoven fabric of the present invention described above.
  • the present invention includes an adsorption tank filled with an adsorbent, and the adsorbent is brought into contact with a gas to be treated to adsorb an organic solvent and discharge a cleaning gas, and is brought into contact with water vapor or heated gas.
  • This is an organic solvent adsorption/desorption device that desorbs the adsorbed organic solvent and discharges the desorption gas, the organic solvent adsorption/desorption processing device including the above-described activated carbon fiber nonwoven fabric of the present invention as the adsorbent.
  • the present invention provides an organic solvent recovery device that includes the above-described organic solvent adsorption/desorption processing device of the present invention and an organic solvent recovery device that recovers an organic solvent by condensing the desorption gas discharged from the organic solvent adsorption/desorption processing device. It is a system.
  • the present invention allows the organic solvent to be adsorbed by bringing the gas to be treated into contact with an adsorbent and the cleaning gas is discharged, and the adsorbed organic solvent is desorbed by bringing water vapor or heated gas into contact with the adsorbent.
  • the present invention is an organic solvent adsorption/desorption treatment method for discharging gas, wherein the adsorbent comprises the above-described activated carbon fiber nonwoven fabric of the present invention.
  • the present invention allows the organic solvent to be adsorbed by bringing the gas to be treated into contact with an adsorbent and the cleaning gas is discharged, and the adsorbed organic solvent is desorbed by bringing water vapor or heated gas into contact with the adsorbent.
  • An organic solvent recovery method comprising discharging a gas and condensing the discharged desorption gas to recover an organic solvent, the method comprising: the adsorbent comprising the above-described activated carbon fiber nonwoven fabric of the present invention; It is.
  • the activated carbon fiber nonwoven fabric of the present invention has the above-described predetermined BET specific surface area, bulk density, and carbon structure, it not only has high adsorption/desorption performance but also can have high load durability in the thickness direction. Therefore, it is possible to extend the life of the activated carbon fiber nonwoven fabric with excellent adsorption performance, leading to a reduction in industrial waste and reducing environmental burden. Furthermore, the element using the activated carbon fiber nonwoven fabric of the present invention has excellent shape stability. Furthermore, the organic solvent adsorption/desorption treatment device and organic solvent recovery system, as well as the organic solvent adsorption/desorption treatment method and organic solvent recovery method using the activated carbon fiber nonwoven fabric of the present invention, have excellent long-term stability of adsorption performance. .
  • FIG. 1 is a schematic diagram showing an embodiment of an organic solvent recovery system of the present invention.
  • the activated carbon fiber nonwoven fabric of the present invention has a BET specific surface area of 1000 m 2 /g or more and 2000 m 2 /g or less. When the BET specific surface area is within the above range, sufficient adsorption performance can be exhibited even with a small amount of activated carbon fiber. Further, the BET specific surface area is more preferably 1100 m 2 /g or more and 1950 m 2 /g or less, and even more preferably 1200 m 2 /g or more and 1900 m 2 /g or less.
  • the bulk density of the activated carbon fiber nonwoven fabric of the present invention is greater than 100 kg/m 3 . If the bulk density is greater than 100 kg/ m3 , the single fibers are difficult to break even when a load is applied in the thickness direction, making it possible to obtain an element with excellent thickness stability and long-term shape stability. can. Further, the bulk density is more preferably 101 kg/m 3 or more, and even more preferably 105 kg/m 3 or more. Further, although the upper limit of the bulk density is not particularly limited, it is difficult to achieve a bulk density exceeding 400 kg/m 3 .
  • the graphite crystallinity Xg of the activated carbon fiber nonwoven fabric of the present invention in X-ray diffraction is 0.35 or more.
  • Xg Xp ⁇ Xa
  • Xp is the value of the difference between the tangent line and the maximum intensity above the tangent line drawn at both ends of the (002) plane peak of the X-ray diffraction peak profile
  • Xa is the value of the difference between the tangent line and the maximum intensity value above the tangent line.
  • Xp is the peak intensity resulting from the graphite-like crystal structure
  • graphite-like crystallinity Xg is an index of the degree of development of the graphite-like crystal structure. Generally, the larger the value of graphite crystallinity Xg, the greater the graphite crystallinity.
  • the activated carbon fiber nonwoven fabric of the present invention has a graphite crystallinity Xg of 0.35 or more, so it has excellent mechanical strength, and single fibers are difficult to break even when a load is applied in the thickness direction, so it has excellent thickness stability. It is possible to obtain an element with excellent long-term shape stability.
  • the graphite crystallinity Xg is more preferably 0.36 or more, and even more preferably 0.37 or more.
  • the upper limit of the graphite-like crystallinity Xg is not particularly limited, it is difficult to express the BET specific surface area of the present invention with a graphite-like crystallinity Xg exceeding 0.85.
  • the activated carbon fiber nonwoven fabric of the present invention has an R value of 1.20 or more in Raman spectroscopy.
  • the R value is a relative ratio between the peak intensity of the G band (Ig) and the peak intensity of the D band (Id) in the Raman spectrum, and is determined by the following formula.
  • R value Id ⁇ Ig
  • the G band in the Raman spectrum is a peak seen at a wavelength of around 1580 cm ⁇ 1 and is derived from the crystal structure of graphite.
  • the D band is a peak seen at a wavelength of around 1360 cm ⁇ 1 and is derived from the crystal structure of diamond.
  • Diamond is generally known for its high hardness.
  • the activated carbon fiber nonwoven fabric of the present invention has an R value of 1.20 or more in Raman spectroscopy, so it has excellent mechanical strength, and single fibers are difficult to break even when a load is applied in the thickness direction, so it has excellent thickness stability. It is possible to obtain an element with excellent long-term shape stability.
  • the R value is more preferably 1.23 or more, and even more preferably 1.25 or more.
  • the upper limit of the R value is not particularly limited, it is difficult to express the BET specific surface area of the present invention with an R value exceeding 3.0.
  • the half width of the D band in Raman spectroscopy of the activated carbon fiber nonwoven fabric of the present invention is 145 cm -1 or less.
  • the sharpness of the peak in a Raman spectrum is generally related to the crystalline state, and it can be said that the narrower the half-width, the higher the crystallinity. Therefore, the half-width of the D band is an index of the degree of crystallinity of the diamond-like crystal structure.
  • the activated carbon fiber nonwoven fabric of the present invention has a half width of D band measured by Raman spectroscopy of 145 cm -1 or less, so it has excellent mechanical strength, and even when a load is applied in the thickness direction, single fibers are difficult to break, so the thickness is stable. It is possible to obtain an element with excellent properties and long-term shape stability.
  • the half width of the D band is more preferably 140 cm ⁇ 1 or less.
  • the lower limit of the half-value width of the D band is not particularly limited, it is difficult to express the BET specific surface area of the present invention with a half-value width of less than 50 cm ⁇ 1 .
  • the present inventors investigated the bulk density, the graphite-like crystallinity Xg in X -ray diffraction, the R value in Raman spectroscopy, and the D It has been found that when the half width of the band falls within the above range, the load durability in the thickness direction can be significantly improved while maintaining high adsorption performance for organic solvents. More specifically, it has been found that the balance between graphite-like crystallinity, diamond-like crystallinity, and R value is important for load durability in the thickness direction.
  • the activated carbon fiber nonwoven fabric of the present invention preferably has a pore diameter of 0.7 or less and a pore volume V 0.7 of 0.20 cm 3 /g or more.
  • the pore volume V 0.7 is 0.20 cm 3 /g or more, sufficient adsorption performance can be exhibited even with a smaller amount of activated carbon fiber.
  • the pore volume V 0.7 is more preferably 0.21 cm 3 /g or more, and even more preferably 0.22 cm 3 /g or more.
  • the upper limit of the pore volume V 0.7 is not particularly limited, it is difficult to achieve a pore volume V 0.7 exceeding 0.50 cm 3 /g.
  • the ratio (V 0.7 /V a ) of the pore volume V 0.7 with a pore diameter of 0.7 nm or less to the total pore volume V a is 0.28 or more. It is preferable. While pores with a pore diameter of 0.7 nm or less particularly function for adsorption of organic solvents, pores larger than 0.7 nm may not function for adsorption of organic solvents. Furthermore, the presence of mesopores with a pore diameter of 2 to 50 nm and macropores with a pore diameter of more than 50 nm is a factor that reduces the mechanical strength of the activated carbon fiber nonwoven fabric.
  • V 0.7 /V a is 0.28 or more
  • the pores of the activated carbon fiber nonwoven fabric function efficiently for adsorption of organic solvents, and furthermore, the fabric has excellent mechanical strength.
  • the single fibers are difficult to break even when a load is applied in the thickness direction, making it possible to obtain an element with excellent thickness stability and long-term shape stability.
  • V 0.7 /V a is more preferably 0.29 or more, and even more preferably 0.30 or more.
  • the upper limit of the pore volume V 0.7 /V a is not particularly limited, it is difficult to realize an activated carbon fiber nonwoven fabric having a value exceeding 0.95.
  • the precursor fibers of the activated carbon fiber nonwoven fabric of the present invention are not particularly limited, and include, for example, cellulose fibers such as viscose rayon, phenolic resin fibers, polyacrylonitrile fibers, pitch fibers, polyphenylene ether fibers, and polyvinyl alcohol fibers. Examples include fibers. Among these, polyphenylene ether fibers are preferred.
  • the polyphenylene ether constituting the polyphenylene ether fiber includes poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), and polyphenylene ether. (2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dipropyl-1,4-phenylene ether), etc. Among these, poly(2,6- dimethyl-1,4-phenylene ether) is more preferred.
  • poly(2,6-dimethyl-1,4-phenylene ether) commercially available products can also be suitably used.
  • the glass transition temperature of the polyphenylene ether is not particularly limited, but is preferably 170°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher. Further, the upper limit of the glass transition point temperature is not particularly limited, but is preferably 230° C. or lower.
  • the polyphenylene ether used in the present invention may contain two or more types of polyphenylene ethers having different glass transition temperatures, and specifically, in addition to the polyphenylene ether having a glass transition temperature of 170°C or higher, It may contain polyphenylene ether having a glass transition point temperature of less than 170°C.
  • the content of polyphenylene ether having a glass transition point temperature of 170°C or higher is not particularly limited, but is preferably 50% by mass or higher, and 65% by mass or higher based on the total amount of polyphenylene ether used. It is more preferable that the amount is 70% by mass or more.
  • the upper limit is not particularly limited, and is preferably 100% by mass or less.
  • polyphenylene ether having a high glass transition point temperature that is, high molecular weight
  • polyphenylene ether having a high glass transition point temperature that is, high molecular weight
  • the precursor fibers in the order of infusibility treatment, carbonization treatment, and activation treatment after forming them into a nonwoven fabric to obtain an activated carbon fiber nonwoven fabric. Further, the carbonization treatment and the activation treatment may be performed simultaneously.
  • the method for producing the nonwoven fabric of the precursor fibers is not particularly limited, and any method commonly used in this field can be appropriately employed. Examples of the method for producing the nonwoven fabric, which is a preferred example of the molded article of the present invention, include a spunbond method, a melt blow method, a spunlace method, a needle punch method, a thermal bond method, a chemical bond method, and the like. Among these, the needle punch method, which is a method for producing short fiber nonwoven fabrics, is preferred.
  • the infusibility treatment is performed by heating a nonwoven fabric formed from polyphenylene ether fibers at a water vapor concentration of 0.5 to 20 vol. % air atmosphere at 120 to 400° C. for 0.1 to 100 hours to make it infusible.
  • air refers to an environment that is not particularly adjusted.
  • the water vapor concentration is 1 to 15 vol. %, more preferably 2 to 13 vol. % is more preferable.
  • the temperature of the infusibility treatment is more preferably 140 to 370°C, and even more preferably 160 to 350°C.
  • the time for the infusibility treatment is more preferably 1 to 80 hours, and even more preferably 2 to 60 hours.
  • the infusibility treatment may be performed in multiple stages, for example, in two stages of treatment at 120 to 230°C for 0.1 to 50 hours, and then treatment at 230 to 350°C for 0.1 to 10 hours.
  • a processing method can be adopted.
  • the activated carbon fiber nonwoven fabric of the present invention can be produced by activating (activation treatment) a carbon fiber nonwoven fabric obtained by carbonizing (carbonization treatment) a precursor fiber nonwoven fabric.
  • the carbonization (carbonization treatment) can be performed by a known method, and specifically, by heating in the presence of an inert gas.
  • the inert gas include nitrogen and argon.
  • the heating temperature is usually 800 to 2500°C, preferably 950 to 1500°C.
  • the heating time is usually 0.1 to 40 hours, preferably 0.1 to 30 hours, more preferably 0.1 to 10 hours, and even more preferably 0.5 to 5 hours. Note that the carbonization treatment and the activation treatment may be performed simultaneously.
  • the activation treatment can be performed by a known method, and specific examples include a gas activation method and a chemical activation method. However, from the viewpoint of fiber strength and thickness stability of the nonwoven fabric, a steam activation method is preferred. preferable.
  • the temperature for steam activation is usually 600 to 1300°C, preferably 800 to 1000°C, more preferably 880 to 1000°C.
  • the time for steam activation is usually 0.05 to 6 hours, preferably 0.1 to 5 hours, more preferably 0.1 to 3 hours, even more preferably 0.1 to 1 hour. The time is particularly preferably 0.1 to 0.5 hours.
  • the water vapor activation is not particularly limited, but for example, the water vapor concentration is 1 to 40 vol. % nitrogen atmosphere, and the water vapor concentration is 5 to 30 vol. % is more preferable.
  • the carbonization treatment temperature is higher than the activation treatment temperature. More specifically, the carbonization temperature is preferably 50°C or more higher than the activation temperature, more preferably 60°C or more higher, and even more preferably 70°C or more higher.
  • the activated carbon fiber nonwoven fabric of the present invention can, for example, recover organic solvents such as ethyl acetate; remove chlorine compounds such as trihalomethane; remove harmful gases such as malodorous gases, NOx, and SOx; and remove organic solvents such as lead, arsenic, and manganese. Suitable for use in removing heavy metals, etc. However, the applications are not limited to those described here.
  • the element of the present invention can be manufactured by winding the activated carbon fiber nonwoven fabric obtained through the above steps around a cylinder. It is necessary to wrap the activated carbon fiber nonwoven fabric while adjusting the winding tension so as not to crush the activated carbon fiber nonwoven fabric in the thickness direction and break the activated carbon fibers, and the packing density after element processing is A (kg/m 3 ). It is preferable that the relative ratio (B/A ⁇ 100) of the active carbon fiber nonwoven fabric and the bulk density B (kg/m 3 ) of the activated carbon fiber nonwoven fabric is 95% or more. In addition, the packing density A after element processing is calculated
  • Packing density A Weight of rolled activated carbon fiber nonwoven fabric ⁇ (Cylinder height x ((Cylinder outer diameter) 2 - (Cylinder inner diameter) 2 ) x Pi ⁇ 4)
  • the cylinder height here is the height of the activated carbon fiber nonwoven fabric wrapped in a cylindrical shape
  • the cylinder outer diameter is the outer diameter of the activated carbon fiber nonwoven fabric wrapped in a cylindrical shape
  • the cylinder inner diameter is the height of the activated carbon fiber nonwoven fabric wrapped in a cylindrical shape. Indicates inner diameter.
  • the organic solvent recovery system 1 includes an organic solvent adsorption/desorption processing device 22 having adsorption tanks 2A and 2B, and inside the adsorption tanks 2A and 2B, an activated carbon fiber nonwoven fabric 9 (adsorbent) is arranged in a cylindrical cage-shaped winding core. It has a hollow cylindrical structure in which layers are wound around each other, and an element 8 whose outer peripheral surface is fixed with a wire mesh is removably provided.
  • FIG. 1 illustrates an organic solvent recovery system 1 having two adsorption tanks, the system may have one or three or more adsorption tanks. Note that the bottom of the element 8 is closed.
  • a solvent mixed gas (gas to be treated) 3 containing an organic solvent passes through a pre-filter 4, is sent to an adsorption tank 2A via a lower damper 6 by a blower 5, and is removed by the activated carbon fiber nonwoven fabric 9 of an element 8.
  • the organic solvent is adsorbed, and is discharged as clean air through the upper damper 10 to the outside of the system through the exhaust port 12 of the adsorption tank 2A.
  • the automatic valve 14 of the steam supply line 13 is in a closed state.
  • the organic solvent recovery device in the organic solvent recovery system includes, for example, the condenser 17, the cooling water supply line 18, and the separator 19 in FIG. 1, but is not limited thereto.
  • the organic solvent adsorption/desorption treatment device, organic solvent recovery system, organic solvent adsorption/desorption treatment method, and organic solvent recovery method of the present invention are performed using known treatment devices and systems, except for using the activated carbon fiber nonwoven fabric of the present invention as an adsorbent.
  • processing method, and recovery method for example, processing apparatuses, systems, and processing methods described in Japanese Patent Publication No. 6-55254, Japanese Patent Application Publication No. 2004-105806, and Japanese Patent Application Publication No. 2013-111552. , and recovery methods can be adopted.
  • Fiber diameter of activated carbon fiber A microscopic image was observed using a scanning electron microscope (product name: SU1510, manufactured by Hitachi High-Technologies), and the diameters of 100 or more fibers were read from the microscopic image, and the read fiber diameters were averaged. Note that the fiber diameter means the fiber diameter.
  • the sample was vacuum-dried at 200°C for 16 hours, weighed, and then vacuum-dried at 300°C for 1 hour, using a high-precision gas/vapor adsorption measurement device (product name: BELSORP-MAXII, manufactured by Microtrac Bell). It was measured by The amount of nitrogen adsorption at the boiling point (77K) of liquid nitrogen was measured in the relative pressure range of 10 -7 to 0.99, and the nitrogen adsorption isotherm of the sample was obtained.
  • a high-precision gas/vapor adsorption measurement device product name: BELSORP-MAXII, manufactured by Microtrac Bell. It was measured by The amount of nitrogen adsorption at the boiling point (77K) of liquid nitrogen was measured in the relative pressure range of 10 -7 to 0.99, and the nitrogen adsorption isotherm of the sample was obtained.
  • This nitrogen adsorption isotherm was analyzed by the BET method in which the analytical relative pressure range was determined under the conditions of adsorption isotherm type I (ISO9277), and the BET specific surface area per weight (unit: m 2 /g) was determined.
  • the sample was vacuum-dried at 200°C for 16 hours, weighed, and then vacuum-dried at 300°C for 1 hour, using a high-precision gas/vapor adsorption measurement device (product name: BELSORP-MAXII, manufactured by Microtrac Bell). It was measured by The amount of nitrogen adsorbed at the boiling point (77K) of liquid nitrogen was measured at a relative pressure in the range of 10 -7 to 0.99, and the pore size distribution was obtained using the GCMC method.
  • the model of the GCMC method was Slit, the adsorbent type was Graphic Carbon, and the fitting method was Tikhnov regularization.
  • the pore volume V 0.7 with a pore diameter of 0 to 0.7 nm and the total pore volume V a were determined. Furthermore, the ratio of the pore volume V 0.7 to the total pore volume V a (V 0.7 /V a ) was determined.
  • Load durability in thickness direction (%) t 200 ⁇ t 0 ⁇ 100
  • the relative ratio (B/A x 100) between the packing density A (kg/m 3 ) of the element using the activated carbon fiber nonwoven fabric and the bulk density B (kg/m 3 ) of the activated carbon fiber nonwoven fabric is preferably 95% or more.
  • the load durability of activated carbon fiber nonwoven fabric is 95% or more. is preferred.
  • the activated carbon fiber nonwoven fabric was wound around a cylindrical structure having an inner diameter of 100 mm and a length of 575 mm until the mass of the activated carbon fiber was 5 kg. Adjust the winding tension so that the relative ratio (B/A x 100) between the packing density A (kg/m 3 ) of the element and the bulk density B (kg/m 3 ) of the activated carbon fiber nonwoven fabric is 95%, I got the element. Next, the element was mounted on the organic solvent-containing gas treatment device shown in Fig.
  • the gas to be treated containing 1000 ppm of ethyl acetate at a temperature of 45°C was supplied from the blower 5 to the adsorption tank 2A for 18 minutes at an air flow rate of 10 Nm 3 /min. Air was blown to adsorb ethyl acetate in the gas to be treated onto the activated carbon fiber nonwoven fabric 9.
  • the ethyl acetate concentration of the gas to be treated and the gas discharged outside the system is measured at the outlet of the blower 5 and the exhaust port 12 of the adsorption tank 2A using a total hydrocarbon meter (product name: HCM-1B, manufactured by Shimadzu Corporation). did.
  • the removal performance (%) of ethyl acetate is determined by the following formula.
  • Ethyl acetate removal performance (%) average concentration of ethyl acetate in gas discharged outside the system (ppm) ⁇ Average concentration of gas to be treated at the outlet of blower 5 (ppm) x 100
  • Example 1 A polyphenylene ether fiber obtained by melt spinning poly(2,6-dimethyl-1,4-phenylene ether) (PPO646, manufactured by SABIC Innovative Plastic) was cut into a length of 51 mm. Subsequently, front and back treatments were performed using a needle punch machine under the conditions of a needle density of 350 pieces/cm 2 and a needle depth of 15 mm (front) and 9 mm (back) to obtain a precursor fiber nonwoven fabric. The obtained precursor fiber nonwoven fabric was heated to a water vapor concentration of 4 vol. % air atmosphere at 190°C for 40 hours, the temperature was further raised to 320°C, and heat treatment was performed for 2 hours.
  • Example 2 An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1 except that the activation treatment time was changed to 15 minutes. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
  • Example 3 An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1 except that the activation treatment time was changed to 23 minutes. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
  • Example 4 Water vapor concentration 25vol. % and oxygen 2 vol.
  • An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1, except that the activation treatment was performed at 950° C. for 7 minutes in a nitrogen atmosphere of 50%. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
  • Example 5 Poly(2,6-dimethyl-1,4-phenylene ether) (PPO640, manufactured by SABIC Innovative Plastic) and poly(2,6-dimethyl-1,4-phenylene ether) (PPO SA120, manufactured by SABIC Innovative Plastic) at 60%
  • An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 2, except that polyphenylene ether fiber obtained by melt spinning at a mass ratio of :30 was used as the precursor fiber.
  • Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
  • the activated carbon fiber nonwoven fabrics of Examples 1 to 5 all have high ethyl acetate removal performance, and also have superior load durability in the thickness direction compared to Comparative Examples 1 to 4. Excellent long-term shape stability of the element. Since Comparative Example 1 had a low bulk density, its load durability in the thickness direction was low. Comparative Example 2 had a low graphite-like crystallinity Xg in X-ray diffraction, so the load durability in the thickness direction was low. Comparative Example 3 had a small R value in Raman spectroscopy, so the load durability in the thickness direction was low. Comparative Example 4 had a large half-width of the D band in Raman spectroscopy, so the load durability in the thickness direction was low.
  • Comparative Example 5 had a small BET specific surface area, so its ethyl acetate removal performance was poor.
  • Comparative Example 6 had a large BET specific surface area, a small graphite-like crystallinity Xg in X-ray diffraction, and a small R value in Raman spectroscopy, so the load durability in the thickness direction was low.
  • the activated carbon fiber nonwoven fabric of the present invention can be suitably used as an activated carbon fiber nonwoven fabric that has excellent adsorption performance and long-term shape stability in place of conventional activated carbon fiber nonwoven fabrics, and can greatly contribute to industry.
  • Organic solvent recovery system 2A Adsorption tank 2B: Adsorption tank 3: Solvent mixed gas containing organic solvent (gas to be treated) 4: Pre-filter 5: Blower 6: Lower damper 7: Lower damper 8: Element 9: Activated carbon fiber nonwoven fabric 10: Upper damper 11: Upper damper 12: Exhaust port 13: Steam supply line 14: Automatic valve 15: Automatic valve 16 :Desorption gas line 17:Condenser 18:Cooling water supply line 19:Separator 20:Return gas line 22:Organic solvent adsorption/desorption treatment device

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Abstract

The purpose of the present invention is to provide an activated carbon fiber non-woven fabric having a superior absorption/desorption performance and a high load-durability in the thickness direction. This activated carbon fiber non-woven fabric has: a BET specific surface area of at least 1000 m2/g and no more than 2000m2/g; a bulk density greater than 100kg/m3; a graphite crystallinity Xg of at least 0.35 in X-ray diffraction; an R value of at least 1.20 in Raman spectroscopy; and a full width at half maximum of no more than 145cm-1 for the D band in Raman spectroscopy.

Description

活性炭素繊維不織布、活性炭素繊維不織布の製造方法、エレメント、有機溶剤吸脱着処理装置、有機溶剤回収システム、有機溶剤吸脱着処理方法、及び有機溶剤回収方法Activated carbon fiber nonwoven fabric, method for producing activated carbon fiber nonwoven fabric, element, organic solvent adsorption/desorption treatment device, organic solvent recovery system, organic solvent adsorption/desorption treatment method, and organic solvent recovery method
　本発明は、活性炭素繊維不織布、その製造方法等に関する。 The present invention relates to an activated carbon fiber nonwoven fabric, a method for producing the same, and the like.
　活性炭素繊維は有機溶剤に対する吸着容量が大きく、吸着速度及び脱着速度が速い等の優れた吸脱着性能を有している。活性炭素繊維不織布は主にビスコースレーヨン等のセルロース系、ピッチ系等の前駆体繊維からなる不織布を炭化、賦活処理することにより得られる。 Activated carbon fibers have excellent adsorption and desorption performance, such as a large adsorption capacity for organic solvents and fast adsorption and desorption rates. Activated carbon fiber nonwoven fabrics are obtained by carbonizing and activating nonwoven fabrics mainly composed of cellulose-based, pitch-based, and other precursor fibers such as viscose rayon.
　活性炭素繊維はその優れた吸脱着特性により、被処理ガスに含まれる有機溶剤を吸脱着する有機溶剤吸脱着処理装置を小型化できることから、シート状の活性炭素繊維不織布を円筒状のエレメントに加工し、有機溶剤吸脱着処理装置の吸着剤として用いられている。例えば、特許文献１では連続式のガス吸着処理装置に用いるため、嵩密度６８ｋｇ／ｍ３以上の活性炭素繊維不織布を巻き付けて構成される円筒エレメントが開示されている。 Due to the excellent adsorption and desorption properties of activated carbon fibers, it is possible to miniaturize organic solvent adsorption and desorption processing equipment that adsorbs and desorbs organic solvents contained in the gas to be treated, so sheet-like activated carbon fiber nonwoven fabric is processed into cylindrical elements. However, it is used as an adsorbent in organic solvent adsorption/desorption treatment equipment. For example, Patent Document 1 discloses a cylindrical element formed by wrapping an activated carbon fiber nonwoven fabric having a bulk density of 68 kg/m 3 or more for use in a continuous gas adsorption treatment device.
特開２００２－１６１４３９号公報Japanese Patent Application Publication No. 2002-161439
　しかしながら、活性炭素繊維不織布は一般的な有機繊維不織布に比べて厚さ方向に対する荷重耐久性が低く、厚さ方向へ繰り返し荷重（又は圧力）を与えることで活性炭素繊維が徐々に破断されて不織布の形状が崩れ、結果として厚さが徐々に薄くなる。これは活性炭素繊維不織布に被処理ガスを通風する場合に起きる現象であり、被処理ガスの供給と供給停止を繰り返し行うことで厚さ方向に対する圧力の負荷状態と無負荷状態が繰り返され、活性炭素繊維不織布の厚さが徐々に薄くなる。その結果、有機溶剤吸脱着処理装置を長期運転する場合に活性炭素繊維不織布を円筒状に巻き付けたエレメントの巻き付け力が低下し、重力によって活性炭素繊維不織布が下方にずれてしまう。エレメントの形状安定性が損なわれると被処理ガスが活性炭素繊維不織布をショートパスしてしまい、有機溶剤吸脱着処理装置の吸着性能が低下する。 However, activated carbon fiber nonwoven fabrics have lower load durability in the thickness direction than general organic fiber nonwoven fabrics, and when repeated loads (or pressure) are applied in the thickness direction, the activated carbon fibers gradually break and become nonwoven. The shape of the material collapses, and as a result, the thickness gradually decreases. This is a phenomenon that occurs when a gas to be treated is passed through activated carbon fiber nonwoven fabric, and by repeatedly supplying and stopping the supply of gas to be treated, the pressure in the thickness direction is repeatedly applied and unloaded, and the activated carbon fiber nonwoven fabric is activated. The thickness of the carbon fiber nonwoven fabric gradually becomes thinner. As a result, when the organic solvent adsorption/desorption treatment apparatus is operated for a long period of time, the winding force of the element in which the activated carbon fiber nonwoven fabric is wrapped in a cylindrical shape decreases, and the activated carbon fiber nonwoven fabric is displaced downward due to gravity. If the shape stability of the element is impaired, the gas to be treated will make a short pass through the activated carbon fiber nonwoven fabric, and the adsorption performance of the organic solvent adsorption/desorption treatment device will deteriorate.
　エレメントの形状安定性を保つため、より強い張力で円筒状に巻き付ける対策等が考えられるが、過剰な巻き付け張力により活性炭素繊維不織布の破断が生じる等の問題があり、工業的に困難である。また、活性炭素繊維不織布の厚さが経時的に薄くなると活性炭素繊維不織布の圧力損失が上昇し、エレメントへ供給する被処理ガスの風量が経時的に低下する問題がある。 In order to maintain the shape stability of the element, measures such as wrapping it in a cylindrical shape with stronger tension can be considered, but this is industrially difficult because there are problems such as the activated carbon fiber nonwoven fabric breaking due to excessive winding tension. Further, when the thickness of the activated carbon fiber nonwoven fabric becomes thinner over time, the pressure loss of the activated carbon fiber nonwoven fabric increases, and there is a problem that the air volume of the gas to be treated to be supplied to the element decreases over time.
　これらの問題を理由に、活性炭素繊維不織布は細孔閉塞等の劣化が進行していないにも関わらず、吸着性能の維持や被処理ガスの風量安定性の観点から、エレメントの形状安定性が損なわれる前に活性炭素繊維不織布を交換する場合がある。しかし近年、産業廃棄物の削減の観点から活性炭素繊維不織布の長寿命化が望まれている。 Due to these problems, although the activated carbon fiber nonwoven fabric has not undergone any deterioration such as pore clogging, the shape stability of the element is difficult to maintain in terms of adsorption performance and airflow stability of the gas to be treated. The activated carbon fiber nonwoven fabric may be replaced before it is damaged. However, in recent years, from the perspective of reducing industrial waste, it has been desired to extend the life of activated carbon fiber nonwoven fabrics.
　そこで本発明は、上記問題を解決するためになされ、その目的は、有機溶剤に対する吸脱着性能が高く、厚さ方向の荷重耐久性を向上させた活性炭素繊維不織布を提供することにある。 Therefore, the present invention was made to solve the above problems, and its purpose is to provide an activated carbon fiber nonwoven fabric that has high adsorption/desorption performance for organic solvents and improved load durability in the thickness direction.
　本発明者らは鋭意検討を進めたところ、所定のＢＥＴ比表面積、嵩密度、及び炭素構造を有する活性炭素繊維不織布は、吸脱着性能が高いだけでなく、厚さ方向の荷重耐久性を高くできることを見出し、本発明を完成させるに至った。 The inventors of the present invention conducted extensive studies and found that an activated carbon fiber nonwoven fabric having a predetermined BET specific surface area, bulk density, and carbon structure not only has high adsorption/desorption performance but also has high load durability in the thickness direction. We have discovered that this can be done, and have completed the present invention.
　すなわち、本発明は、ＢＥＴ比表面積が１０００ｍ２／ｇ以上２０００ｍ２／ｇ以下、
　嵩密度が１００ｋｇ／ｍ３よりも大きく、Ｘ線回折におけるグラファイト状結晶化度Ｘｇが０．３５以上、ラマン分光測定におけるＲ値が１．２０以上、及び、ラマン分光測定におけるＤバンドの半値幅が１４５ｃｍ－１以下である、ことを特徴とする活性炭素繊維不織布、である。 That is, the present invention has a BET specific surface area of 1000 m 2 /g or more and 2000 m 2 /g or less,
Bulk density is greater than 100 kg/ m3 , graphite crystallinity Xg in X-ray diffraction is 0.35 or more, R value in Raman spectroscopy is 1.20 or more, and half width of D band in Raman spectroscopy. is 145 cm −1 or less.
　上記した本発明の活性炭素繊維不織布は、細孔直径が０．７ｎｍ以下の細孔容積Ｖ０．７が０．２２ｃｍ３／ｇ以上であることが好ましい。 The activated carbon fiber nonwoven fabric of the present invention described above preferably has a pore diameter of 0.7 nm or less and a pore volume V 0.7 of 0.22 cm 3 /g or more.
　上記した本発明の活性炭素繊維不織布は、全細孔容積Ｖaに対する細孔直径が０．７ｎｍ以下の細孔容積Ｖ０．７が占める割合（Ｖ０．７／Ｖａ）が０．３０以上であることが好ましい。 The activated carbon fiber nonwoven fabric of the present invention described above has a ratio (V 0.7 /V a ) of pore volume V 0.7 with a pore diameter of 0.7 nm or less to the total pore volume V a of 0.30. It is preferable that it is above.
　さらに、本発明は、前駆体繊維不織布を炭素化処理して炭素繊維不織布を得る工程と、前記炭素繊維不織布を賦活処理する工程と含み、前記賦活処理は水蒸気賦活法によって行われる、上記した本発明の活性炭素繊維不織布を製造する製造方法、である。 Furthermore, the present invention includes a step of carbonizing a precursor fiber nonwoven fabric to obtain a carbon fiber nonwoven fabric, and an activation treatment of the carbon fiber nonwoven fabric, wherein the activation treatment is performed by a steam activation method. A manufacturing method for manufacturing an activated carbon fiber nonwoven fabric of the invention.
　さらに、本発明は、上記した本発明の活性炭素繊維不織布を用いて構成されるエレメント、である。 Furthermore, the present invention is an element constructed using the activated carbon fiber nonwoven fabric of the present invention described above.
　さらに、本発明は、吸着材を充填した吸着槽を備え、前記吸着材に、被処理ガスを接触させることで有機溶剤を吸着し清浄化ガスを排出し、かつ、水蒸気又は加熱ガスを接触させることで吸着した有機溶剤を脱着し脱着ガスを排出する、有機溶剤吸脱着装置であって、前記吸着材が、上記した本発明の活性炭素繊維不織布を含む有機溶剤吸脱着処理装置、である。 Furthermore, the present invention includes an adsorption tank filled with an adsorbent, and the adsorbent is brought into contact with a gas to be treated to adsorb an organic solvent and discharge a cleaning gas, and is brought into contact with water vapor or heated gas. This is an organic solvent adsorption/desorption device that desorbs the adsorbed organic solvent and discharges the desorption gas, the organic solvent adsorption/desorption processing device including the above-described activated carbon fiber nonwoven fabric of the present invention as the adsorbent.
　さらに、本発明は、上記した本発明の有機溶剤吸脱着処理装置、及び当該有機溶剤吸脱着処理装置から排出された脱着ガスを凝縮して有機溶剤を回収する有機溶剤回収装置を含む有機溶剤回収システム、である。 Furthermore, the present invention provides an organic solvent recovery device that includes the above-described organic solvent adsorption/desorption processing device of the present invention and an organic solvent recovery device that recovers an organic solvent by condensing the desorption gas discharged from the organic solvent adsorption/desorption processing device. It is a system.
　さらに、本発明は、被処理ガスを吸着材に接触させることで有機溶剤を吸着させ清浄化ガスを排出し、水蒸気又は加熱ガスを前記吸着材に接触させることで吸着した有機溶剤を脱着させ脱着ガスを排出する有機溶剤吸脱着処理方法であって、前記吸着材が、上記した本発明の活性炭素繊維不織布を含む有機溶剤吸脱着処理方法、である。 Furthermore, the present invention allows the organic solvent to be adsorbed by bringing the gas to be treated into contact with an adsorbent and the cleaning gas is discharged, and the adsorbed organic solvent is desorbed by bringing water vapor or heated gas into contact with the adsorbent. The present invention is an organic solvent adsorption/desorption treatment method for discharging gas, wherein the adsorbent comprises the above-described activated carbon fiber nonwoven fabric of the present invention.
　さらに、本発明は、被処理ガスを吸着材に接触させることで有機溶剤を吸着させ清浄化ガスを排出し、水蒸気又は加熱ガスを前記吸着材に接触させることで吸着した有機溶剤を脱着させ脱着ガスを排出し、排出された前記脱着ガスを凝縮して有機溶剤を回収する、有機溶剤回収方法であって、前記吸着材が上記した本発明の活性炭素繊維不織布を含む有機溶剤回収方方法、である。 Furthermore, the present invention allows the organic solvent to be adsorbed by bringing the gas to be treated into contact with an adsorbent and the cleaning gas is discharged, and the adsorbed organic solvent is desorbed by bringing water vapor or heated gas into contact with the adsorbent. An organic solvent recovery method comprising discharging a gas and condensing the discharged desorption gas to recover an organic solvent, the method comprising: the adsorbent comprising the above-described activated carbon fiber nonwoven fabric of the present invention; It is.
　本発明の活性炭素繊維不織布は、上記した所定のＢＥＴ比表面積、嵩密度、及び炭素構造を有するため、吸脱着性能が高いだけでなく、厚さ方向の荷重耐久性を高くできる。よって、優れた吸着性能の活性炭素繊維不織布の長寿命化を図ることができ、産業廃棄物の削減に繋がり、環境負荷を低減できる。また、本発明の活性炭素繊維不織布を用いたエレメントは形状安定性に優れている。また、本発明の活性炭素繊維不織布を用いた、有機溶剤吸脱着処理装置及び有機溶剤回収システム、並びに、有機溶剤吸脱着処理方法及び有機溶剤回収方法は、吸着性能の長期安定性に優れている。 Since the activated carbon fiber nonwoven fabric of the present invention has the above-described predetermined BET specific surface area, bulk density, and carbon structure, it not only has high adsorption/desorption performance but also can have high load durability in the thickness direction. Therefore, it is possible to extend the life of the activated carbon fiber nonwoven fabric with excellent adsorption performance, leading to a reduction in industrial waste and reducing environmental burden. Furthermore, the element using the activated carbon fiber nonwoven fabric of the present invention has excellent shape stability. Furthermore, the organic solvent adsorption/desorption treatment device and organic solvent recovery system, as well as the organic solvent adsorption/desorption treatment method and organic solvent recovery method using the activated carbon fiber nonwoven fabric of the present invention, have excellent long-term stability of adsorption performance. .
本発明の有機溶剤回収システムの一実施形態を示す概略図である。1 is a schematic diagram showing an embodiment of an organic solvent recovery system of the present invention.
＜活性炭素繊維不織布＞
　本発明の活性炭素繊維不織布は、ＢＥＴ比表面積が１０００ｍ２／ｇ以上２０００ｍ２／ｇ以下である。ＢＥＴ比表面積が前記範囲にあることで、少量の活性炭素繊維でも十分な吸着性能を発揮することができる。またＢＥＴ比表面積は１１００ｍ２／ｇ以上１９５０ｍ２／ｇ以下がより好ましく、１２００ｍ２／ｇ以上１９００ｍ２／ｇ以下がさらに好ましい。 <Activated carbon fiber nonwoven fabric>
The activated carbon fiber nonwoven fabric of the present invention has a BET specific surface area of 1000 m 2 /g or more and 2000 m 2 /g or less. When the BET specific surface area is within the above range, sufficient adsorption performance can be exhibited even with a small amount of activated carbon fiber. Further, the BET specific surface area is more preferably 1100 m 2 /g or more and 1950 m 2 /g or less, and even more preferably 1200 m 2 /g or more and 1900 m 2 /g or less.
　本発明の活性炭素繊維不織布の嵩密度は１００ｋｇ／ｍ３よりも大きい。嵩密度が１００ｋｇ／ｍ３よりも大きければ、厚さ方向に荷重を与えた際も単繊維が破断し難いため、厚さ安定性に優れ、長期の形状安定性に優れたエレメントを得ることができる。また嵩密度は１０１ｋｇ／ｍ３以上がより好ましく、１０５ｋｇ／ｍ３以上がさらに好ましい。また、当該嵩密度の上限は特に限定されるものではないが、４００ｋｇ／ｍ３を超える嵩密度を実現するのは難しい。 The bulk density of the activated carbon fiber nonwoven fabric of the present invention is greater than 100 kg/m 3 . If the bulk density is greater than 100 kg/ m3 , the single fibers are difficult to break even when a load is applied in the thickness direction, making it possible to obtain an element with excellent thickness stability and long-term shape stability. can. Further, the bulk density is more preferably 101 kg/m 3 or more, and even more preferably 105 kg/m 3 or more. Further, although the upper limit of the bulk density is not particularly limited, it is difficult to achieve a bulk density exceeding 400 kg/m 3 .
　本発明の活性炭素繊維不織布のＸ線回折におけるグラファイト状結晶化度Ｘｇは０．３５以上である。グラファイト状結晶化度ＸｇはＸ線回折ピークプロファイルの回折角２θ＝２３～２８°付近に存在する（００２）面ピーク強度から以下の式で求められる。
　Ｘｇ＝Ｘｐ÷Ｘａ
　ここで、Ｘｐとは、Ｘ線回折ピークプロファイルの（００２）面ピークの両裾に接線を引き、その接線より上部の強度の最大値と接線との差の値であり、Ｘａとは（００２）面ピーク強度から空気散乱強度を差し引いた残りの強度である。空気散乱強度は試料がない状態で走査して求められる。Ｘｐはグラファイト状の結晶構造に起因するピーク強度であり、グラファイト状結晶化度Ｘｇはグラファイト状の結晶構造の発達度合の指標である。一般的にグラファイト状結晶化度Ｘｇの値が大きいほどグラファイト状の結晶化度は大きくなる。 The graphite crystallinity Xg of the activated carbon fiber nonwoven fabric of the present invention in X-ray diffraction is 0.35 or more. The graphite crystallinity Xg is determined by the following formula from the intensity of the (002) plane peak present around the diffraction angle 2θ=23 to 28° in the X-ray diffraction peak profile.
Xg=Xp÷Xa
Here, Xp is the value of the difference between the tangent line and the maximum intensity above the tangent line drawn at both ends of the (002) plane peak of the X-ray diffraction peak profile, and Xa is the value of the difference between the tangent line and the maximum intensity value above the tangent line. ) is the remaining intensity after subtracting the air scattering intensity from the surface peak intensity. Air scattering intensity is determined by scanning without a sample. Xp is the peak intensity resulting from the graphite-like crystal structure, and graphite-like crystallinity Xg is an index of the degree of development of the graphite-like crystal structure. Generally, the larger the value of graphite crystallinity Xg, the greater the graphite crystallinity.
　例えば、ほぼ完全なグラファイト結晶で構成される炭素繊維は極めて機械強度が高い特徴を有する。本発明の活性炭素繊維不織布はグラファイト状結晶化度Ｘｇが０．３５以上のため、機械強度に優れ、厚さ方向に荷重を与えた際も単繊維が破断し難いため、厚さ安定性に優れ、長期の形状安定性に優れたエレメントを得ることができる。また、グラファイト状結晶化度Ｘｇは０．３６以上がより好ましく、０．３７以上がさらに好ましい。また、当該グラファイト状結晶化度Ｘｇの上限は特に限定されるものではないが、０．８５を超えるグラファイト状結晶化度Ｘｇで本発明のＢＥＴ比表面積を発現することは難しい。 For example, carbon fiber composed of almost perfect graphite crystals is characterized by extremely high mechanical strength. The activated carbon fiber nonwoven fabric of the present invention has a graphite crystallinity Xg of 0.35 or more, so it has excellent mechanical strength, and single fibers are difficult to break even when a load is applied in the thickness direction, so it has excellent thickness stability. It is possible to obtain an element with excellent long-term shape stability. Further, the graphite crystallinity Xg is more preferably 0.36 or more, and even more preferably 0.37 or more. Further, although the upper limit of the graphite-like crystallinity Xg is not particularly limited, it is difficult to express the BET specific surface area of the present invention with a graphite-like crystallinity Xg exceeding 0.85.
　本発明の活性炭素繊維不織布のラマン分光測定におけるＲ値は１．２０以上である。Ｒ値はラマンスペクトルにおけるＧバンドのピーク強度（Ｉｇ）とＤバンドのピーク強度（Ｉｄ）の相対比であり、以下の式で求められる。
　Ｒ値＝Ｉｄ÷Ｉｇ
　ラマンスペクトルにおけるＧバンドとは波長１５８０ｃｍ－１付近にみられるピークであり、グラファイトの結晶構造に由来する。また、Ｄバンドとは波長１３６０ｃｍ－１付近に見られるピークであり、ダイヤモンドの結晶構造に由来する。 The activated carbon fiber nonwoven fabric of the present invention has an R value of 1.20 or more in Raman spectroscopy. The R value is a relative ratio between the peak intensity of the G band (Ig) and the peak intensity of the D band (Id) in the Raman spectrum, and is determined by the following formula.
R value=Id÷Ig
The G band in the Raman spectrum is a peak seen at a wavelength of around 1580 cm −1 and is derived from the crystal structure of graphite. Further, the D band is a peak seen at a wavelength of around 1360 cm −1 and is derived from the crystal structure of diamond.
　Ｒ値が大きいほどダイヤモンドの結晶構造に起因するＤバンドの強度が大きくなり、ダイヤモンドのような性質を高められる。ダイヤモンドは一般的に硬度が高いことで知られる。本発明の活性炭素繊維不織布はラマン分光測定におけるＲ値が１．２０以上のため、機械強度に優れ、厚さ方向に荷重を与えた際も単繊維が破断し難いため、厚さ安定性に優れ、長期の形状安定性に優れたエレメントを得ることができる。また、Ｒ値は１．２３以上がより好ましく、１．２５以上がさらに好ましい。また、当該Ｒ値の上限は特に限定されるものではないが、３．０を超えるＲ値で本発明のＢＥＴ比表面積を発現することは難しい。 The larger the R value, the greater the intensity of the D band caused by the crystal structure of diamond, and the diamond-like properties can be enhanced. Diamond is generally known for its high hardness. The activated carbon fiber nonwoven fabric of the present invention has an R value of 1.20 or more in Raman spectroscopy, so it has excellent mechanical strength, and single fibers are difficult to break even when a load is applied in the thickness direction, so it has excellent thickness stability. It is possible to obtain an element with excellent long-term shape stability. Further, the R value is more preferably 1.23 or more, and even more preferably 1.25 or more. Further, although the upper limit of the R value is not particularly limited, it is difficult to express the BET specific surface area of the present invention with an R value exceeding 3.0.
　本発明の活性炭素繊維不織布のラマン分光測定におけるＤバンドの半値幅は１４５ｃｍ－１以下である。ラマンスペクトルのピークのシャープさは一般的に結晶状態と関連があり、半値幅が狭いほど結晶性が高いといえる。そのため、Ｄバンドの半値幅はダイヤモンド状の結晶構造の結晶化度の指標となる。 The half width of the D band in Raman spectroscopy of the activated carbon fiber nonwoven fabric of the present invention is 145 cm -1 or less. The sharpness of the peak in a Raman spectrum is generally related to the crystalline state, and it can be said that the narrower the half-width, the higher the crystallinity. Therefore, the half-width of the D band is an index of the degree of crystallinity of the diamond-like crystal structure.
　本発明の活性炭素繊維不織布はラマン分光測定Ｄバンドの半値幅が１４５ｃｍ－１以下のため、機械強度に優れ、厚さ方向に荷重を与えた際も単繊維が破断し難いため、厚さ安定性に優れ、長期の形状安定性に優れたエレメントを得ることができる。また、Ｄバンドの半値幅は１４０ｃｍ－１以下がより好ましい。また、当該Ｄバンドの半値幅の下限は特に限定されるものではないが、５０ｃｍ－１を下回る半値幅で本発明のＢＥＴ比表面積を発現することは難しい。 The activated carbon fiber nonwoven fabric of the present invention has a half width of D band measured by Raman spectroscopy of 145 cm -1 or less, so it has excellent mechanical strength, and even when a load is applied in the thickness direction, single fibers are difficult to break, so the thickness is stable. It is possible to obtain an element with excellent properties and long-term shape stability. Further, the half width of the D band is more preferably 140 cm −1 or less. Further, although the lower limit of the half-value width of the D band is not particularly limited, it is difficult to express the BET specific surface area of the present invention with a half-value width of less than 50 cm −1 .
　本発明者らは、ＢＥＴ比表面積が１０００～２０００ｍ２／ｇの活性炭素繊維不織布において、嵩密度、Ｘ線回折におけるグラファイト状結晶化度Ｘｇ、ラマン分光測定におけるＲ値、及びラマン分光測定におけるＤバンドの半値幅が上述した範囲となることで、有機溶剤に対する高い吸着性能を維持しながら、厚さ方向に対する荷重耐久性が著しく向上することを見出した。より具体的にはグラファイト状の結晶化度、ダイヤモンド状の結晶化度、及びＲ値の均衡が厚さ方向の荷重耐久性にとって重要であることを見出した。 The present inventors investigated the bulk density, the graphite-like crystallinity Xg in X -ray diffraction, the R value in Raman spectroscopy, and the D It has been found that when the half width of the band falls within the above range, the load durability in the thickness direction can be significantly improved while maintaining high adsorption performance for organic solvents. More specifically, it has been found that the balance between graphite-like crystallinity, diamond-like crystallinity, and R value is important for load durability in the thickness direction.
　本発明の活性炭素繊維不織布は、細孔直径が０．７以下の細孔容積Ｖ０．７が０．２０ｃｍ３／ｇ以上であることが好ましい。細孔容積Ｖ０．７が０．２０ｃｍ３／ｇ以上であることで、より少量の活性炭素繊維でも十分な吸着性能を発揮することができる。また細孔容積Ｖ０．７は０．２１ｃｍ３／ｇ以上がより好ましく、０．２２ｃｍ３／ｇ以上がさらに好ましい。また、当該細孔容積Ｖ０．７の上限値は特に限定されるものではないが、０．５０ｃｍ３／ｇを超える細孔容積Ｖ０．７を実現するのは難しい。 The activated carbon fiber nonwoven fabric of the present invention preferably has a pore diameter of 0.7 or less and a pore volume V 0.7 of 0.20 cm 3 /g or more. When the pore volume V 0.7 is 0.20 cm 3 /g or more, sufficient adsorption performance can be exhibited even with a smaller amount of activated carbon fiber. Further, the pore volume V 0.7 is more preferably 0.21 cm 3 /g or more, and even more preferably 0.22 cm 3 /g or more. Further, although the upper limit of the pore volume V 0.7 is not particularly limited, it is difficult to achieve a pore volume V 0.7 exceeding 0.50 cm 3 /g.
　本発明の活性炭素繊維不織布は、全細孔容積Ｖaに対する細孔直径０．７ｎｍ以下の細孔容積Ｖ０．７が占める割合（Ｖ０．７／Ｖａ）が０．２８以上であることが好ましい。有機溶剤の吸着には特に細孔直径０．７ｎｍ以下の細孔が機能する一方で、０．７ｎｍより大きな細孔は有機溶剤の吸着に機能しない場合がある。また、細孔直径２～５０ｎｍのメソ孔や細孔直径５０ｎｍを超えるマクロ孔の存在は活性炭素繊維不織布の機械強度を低下させる要因にもなる。そのため、Ｖ０．７／Ｖａが０．２８以上であることで、活性炭素繊維不織布の細孔が有機溶剤の吸着に対して効率的に機能し、さらに機械強度に優れる。その結果、厚さ方向に荷重を与えた際も単繊維が破断し難いため、厚さ安定性に優れ、長期の形状安定性に優れたエレメントを得ることができる。またＶ０．７／Ｖａは０．２９以上がより好ましく、０．３０以上がさらに好ましい。また、当該細孔容積Ｖ０．７／Ｖａの上限値は特に限定されるものではないが、０．９５を超える活性炭素繊維不織布を実現するのは難しい。 In the activated carbon fiber nonwoven fabric of the present invention, the ratio (V 0.7 /V a ) of the pore volume V 0.7 with a pore diameter of 0.7 nm or less to the total pore volume V a is 0.28 or more. It is preferable. While pores with a pore diameter of 0.7 nm or less particularly function for adsorption of organic solvents, pores larger than 0.7 nm may not function for adsorption of organic solvents. Furthermore, the presence of mesopores with a pore diameter of 2 to 50 nm and macropores with a pore diameter of more than 50 nm is a factor that reduces the mechanical strength of the activated carbon fiber nonwoven fabric. Therefore, when V 0.7 /V a is 0.28 or more, the pores of the activated carbon fiber nonwoven fabric function efficiently for adsorption of organic solvents, and furthermore, the fabric has excellent mechanical strength. As a result, the single fibers are difficult to break even when a load is applied in the thickness direction, making it possible to obtain an element with excellent thickness stability and long-term shape stability. Further, V 0.7 /V a is more preferably 0.29 or more, and even more preferably 0.30 or more. Further, although the upper limit of the pore volume V 0.7 /V a is not particularly limited, it is difficult to realize an activated carbon fiber nonwoven fabric having a value exceeding 0.95.
＜活性炭素繊維不織布の製造方法＞
　本発明の活性炭素繊維不織布の前駆体繊維は特に限定されず、例えば、ビスコースレーヨン等のセルロース系繊維、フェノール樹脂系繊維、ポリアクリロニトリル系繊維、ピッチ系繊維、ポリフェニレンエーテル系繊維、ポリビニルアルコール系繊維等が挙げられる。これらの中でもポリフェニレンエーテル系繊維が好ましい。 <Method for producing activated carbon fiber nonwoven fabric>
The precursor fibers of the activated carbon fiber nonwoven fabric of the present invention are not particularly limited, and include, for example, cellulose fibers such as viscose rayon, phenolic resin fibers, polyacrylonitrile fibers, pitch fibers, polyphenylene ether fibers, and polyvinyl alcohol fibers. Examples include fibers. Among these, polyphenylene ether fibers are preferred.
　ポリフェニレンエーテル系繊維を構成するポリフェニレンエーテルとしては、具体的には、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）、ポリ（２，６－ジエチル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－エチル－１，４－フェニレンエーテル）、ポリ（２，６－ジプロピル－１，４－フェニレンエーテル）等を挙げることができるが、これらの中でも、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）がより好ましい。 Specifically, the polyphenylene ether constituting the polyphenylene ether fiber includes poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), and polyphenylene ether. (2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dipropyl-1,4-phenylene ether), etc. Among these, poly(2,6- dimethyl-1,4-phenylene ether) is more preferred.
　前記ポリ（２，６－ジメチル－１，４－フェニレンエーテル）としては、市販品も好適に用いることができ、具体的は、例えば、ＳＡＢＩＣ　Ｉｎｎｏｖａｔｉｖｅ　Ｐｌａｓｔｉｃ製のＰＰＯ６４０、ＰＰＯ６４６、ＰＰＯＳＡ１２０、旭化成ケミカルズ（株）製のザイロンＳ２０１Ａ、ザイロンＳ２０２Ａ等を挙げることができる。 As the poly(2,6-dimethyl-1,4-phenylene ether), commercially available products can also be suitably used. Specifically, for example, PPO640, PPO646, PPOSA120 manufactured by SABIC Innovative Plastic, Asahi Kasei Chemicals Co., Ltd. Examples include Zylon S201A and Zylon S202A manufactured by ).
　前記ポリフェニレンエーテルのガラス転移点温度は、特に限定されないが、１７０℃以上であることが好ましく、２００℃以上であることがより好ましく、２１０℃以上であることさらに好ましい。また、ガラス転移点温度の上限値は特に限定されないが、２３０℃以下であることが好ましい。 The glass transition temperature of the polyphenylene ether is not particularly limited, but is preferably 170°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher. Further, the upper limit of the glass transition point temperature is not particularly limited, but is preferably 230° C. or lower.
　また、本発明で用いるポリフェニレンエーテルとしては、異なるガラス転移点温度を有するポリフェニレンエーテルを２種以上含んでいてもよく、具体的には、前記ガラス転移点温度が１７０℃以上であるポリフェニレンエーテルに加えて、ガラス転移点温度が１７０℃未満のポリフェニレンエーテルを含むことができる。この場合、ガラス転移点温度が１７０℃以上であるポリフェニレンエーテルの含有量は、特に限定されないが、使用するポリフェニレンエーテル全量に対して、５０質量％以上であることが好ましく、６５質量％以上であることがより好ましく、７０質量％以上であることがさらに好ましい。また、上限値は特に限定されず、１００質量％以下であることが好ましい。本発明においては、ガラス転移点温度が高い（すなわち高分子量）のポリフェニレンエーテルを前記範囲で含むことで、得られる活性炭素繊維不織布の吸脱着性能、厚さ方向の荷重耐久性の観点から好ましい。 Further, the polyphenylene ether used in the present invention may contain two or more types of polyphenylene ethers having different glass transition temperatures, and specifically, in addition to the polyphenylene ether having a glass transition temperature of 170°C or higher, It may contain polyphenylene ether having a glass transition point temperature of less than 170°C. In this case, the content of polyphenylene ether having a glass transition point temperature of 170°C or higher is not particularly limited, but is preferably 50% by mass or higher, and 65% by mass or higher based on the total amount of polyphenylene ether used. It is more preferable that the amount is 70% by mass or more. Moreover, the upper limit is not particularly limited, and is preferably 100% by mass or less. In the present invention, it is preferable to include polyphenylene ether having a high glass transition point temperature (that is, high molecular weight) in the above range from the viewpoint of adsorption/desorption performance and load durability in the thickness direction of the obtained activated carbon fiber nonwoven fabric.
　本発明では前駆体繊維を不織布化した後に不融化処理、炭化処理、及び賦活処理の順に加工を行い、活性炭素繊維不織布を得ることが好ましい。また、炭化処理と賦活処理とを同時に実施してもよい。前駆体繊維の不織布の製造方法は特に限定されるものではなく、本分野において通常用いられる方法を適宜採用することができる。本発明の好ましい成形体の一例である不織布の製造方法としては、例えば、スパンボンド法、メルトブロー法、スパンレース法、ニードルパンチ法、サーマルボンド法、ケミカルボンド法等を挙げることができる。これらの中でも、短繊維不織布の製造方法であるニードルパンチ法が好ましい。 In the present invention, it is preferable to process the precursor fibers in the order of infusibility treatment, carbonization treatment, and activation treatment after forming them into a nonwoven fabric to obtain an activated carbon fiber nonwoven fabric. Further, the carbonization treatment and the activation treatment may be performed simultaneously. The method for producing the nonwoven fabric of the precursor fibers is not particularly limited, and any method commonly used in this field can be appropriately employed. Examples of the method for producing the nonwoven fabric, which is a preferred example of the molded article of the present invention, include a spunbond method, a melt blow method, a spunlace method, a needle punch method, a thermal bond method, a chemical bond method, and the like. Among these, the needle punch method, which is a method for producing short fiber nonwoven fabrics, is preferred.
　前駆体繊維にポリフェニレンエーテル系繊維を用いた場合の不融化処理は、ポリフェニレンエーテル系繊維から形成された不織布を、水蒸気濃度０．５～２０ｖｏｌ．％の空気雰囲気下で、１２０～４００℃で、０．１～１００時間熱処理して不融化処理することにより行うことができる。ここで、空気中とは、特に調整されていない環境のことである。また、水蒸気濃度は１～１５ｖｏｌ．％であることがより好ましく、さらに２～１３ｖｏｌ．％であることがさらに好ましい。また、不融化処理の温度は、１４０～３７０℃であることがより好ましく、１６０～３５０℃であることがさらに好ましい。また、不融化処理の時間は、１～８０時間であることがより好ましく、２～６０時間であることがさらに好ましい。また、不融化処理は、多段階で行ってもよく、例えば、１２０～２３０℃で０．１～５０時間処理し、その後、２３０～３５０℃で０．１～１０時間処理する２段階での処理方法を採用することができる。不融化処理の水蒸気濃度、温度、及び時間を前記範囲とすることで、炭化及び賦活して得られる活性炭素繊維不織布の機械強度に優れ、厚さ方向に荷重を与えた際も単繊維が破断し難いため、厚さ安定性に優れ、長期の形状安定性に優れたエレメントを得ることができるため好ましい。 In the case of using polyphenylene ether fibers as the precursor fibers, the infusibility treatment is performed by heating a nonwoven fabric formed from polyphenylene ether fibers at a water vapor concentration of 0.5 to 20 vol. % air atmosphere at 120 to 400° C. for 0.1 to 100 hours to make it infusible. Here, in the air refers to an environment that is not particularly adjusted. In addition, the water vapor concentration is 1 to 15 vol. %, more preferably 2 to 13 vol. % is more preferable. Further, the temperature of the infusibility treatment is more preferably 140 to 370°C, and even more preferably 160 to 350°C. Further, the time for the infusibility treatment is more preferably 1 to 80 hours, and even more preferably 2 to 60 hours. In addition, the infusibility treatment may be performed in multiple stages, for example, in two stages of treatment at 120 to 230°C for 0.1 to 50 hours, and then treatment at 230 to 350°C for 0.1 to 10 hours. A processing method can be adopted. By setting the water vapor concentration, temperature, and time of the infusibility treatment within the above ranges, the activated carbon fiber nonwoven fabric obtained by carbonization and activation has excellent mechanical strength, and even when a load is applied in the thickness direction, single fibers do not break. This is preferable because it is difficult to form an element, so it is possible to obtain an element with excellent thickness stability and long-term shape stability.
　本発明の活性炭素繊維不織布は、前駆体繊維不織布を炭素化（炭素化処理）した炭素繊維不織布、を賦活（賦活処理）することにより製造することができる。前記炭素化（炭素化処理）は、公知の方法で行うことができ、具体的には、不活性ガスの存在下で加熱することにより行われる。不活性ガスとしては、例えば、窒素、及びアルゴン等が挙げられる。加熱温度は、通常、８００～２５００℃であり、好ましくは９５０～１５００℃である。加熱時間は、通常、０．１～４０時間であり、好ましくは０．１～３０時間であり、より好ましくは０．１～１０時間であり、さらに好ましくは０．５～５時間である。なお、炭化処理と賦活処理とを同時に実施してもよい。 The activated carbon fiber nonwoven fabric of the present invention can be produced by activating (activation treatment) a carbon fiber nonwoven fabric obtained by carbonizing (carbonization treatment) a precursor fiber nonwoven fabric. The carbonization (carbonization treatment) can be performed by a known method, and specifically, by heating in the presence of an inert gas. Examples of the inert gas include nitrogen and argon. The heating temperature is usually 800 to 2500°C, preferably 950 to 1500°C. The heating time is usually 0.1 to 40 hours, preferably 0.1 to 30 hours, more preferably 0.1 to 10 hours, and even more preferably 0.5 to 5 hours. Note that the carbonization treatment and the activation treatment may be performed simultaneously.
　前記賦活処理は、公知の方法で行うことができ、具体的には、ガス賦活法、及び薬品賦活法等が挙げられるが、繊維強度及び不織布の厚さ安定性の観点から、水蒸気賦活法が好ましい。水蒸気賦活の温度は、通常、６００～１３００℃であり、好ましくは８００～１０００℃であり、より好ましくは８８０～１０００℃である。水蒸気賦活の時間は、通常、０．０５～６時間であり、好ましくは０．１～５時間であり、より好ましくは０．１～３時間であり、さらに好ましくは０．１～１時間であり、特に好ましくは０．１～０．５時間である。前記水蒸気賦活は、特に限定されないが、例えば、水蒸気濃度１～４０ｖｏｌ．％の窒素雰囲気下で行うことが好ましく、前記水蒸気濃度は５～３０ｖｏｌ．％であることがより好ましい。また、水蒸気賦活においては、酸素濃度が低い環境下において行うことが好ましく、５ｖｏｌ．％以下であることが好ましく、２ｖｏｌ．％以下であることがより好ましく、酸素が存在しない環境で行うことがさらに好ましい。 The activation treatment can be performed by a known method, and specific examples include a gas activation method and a chemical activation method. However, from the viewpoint of fiber strength and thickness stability of the nonwoven fabric, a steam activation method is preferred. preferable. The temperature for steam activation is usually 600 to 1300°C, preferably 800 to 1000°C, more preferably 880 to 1000°C. The time for steam activation is usually 0.05 to 6 hours, preferably 0.1 to 5 hours, more preferably 0.1 to 3 hours, even more preferably 0.1 to 1 hour. The time is particularly preferably 0.1 to 0.5 hours. The water vapor activation is not particularly limited, but for example, the water vapor concentration is 1 to 40 vol. % nitrogen atmosphere, and the water vapor concentration is 5 to 30 vol. % is more preferable. In addition, in steam activation, it is preferable to perform it in an environment with a low oxygen concentration, and 5 vol. % or less, preferably 2 vol. % or less, and even more preferably in an oxygen-free environment.
　本発明では活性炭素繊維不織布の機械強度及び厚さ安定性の観点から、炭化処理温度が賦活処理温度より高いことが好ましい。より具体的には炭化温度は賦活温度より５０℃以上高いことが好ましく、６０℃以上高いことがより好ましく、７０℃以上高いことがさらに好ましい。 In the present invention, from the viewpoint of mechanical strength and thickness stability of the activated carbon fiber nonwoven fabric, it is preferable that the carbonization treatment temperature is higher than the activation treatment temperature. More specifically, the carbonization temperature is preferably 50°C or more higher than the activation temperature, more preferably 60°C or more higher, and even more preferably 70°C or more higher.
　本発明の活性炭素繊維不織布は、例えば、酢酸エチル等の有機溶剤の回収；トリハロメタン等の塩素化合物の除去；悪臭ガス、ＮＯｘ、及びＳＯｘ等の有害ガスの除去；鉛、ヒ素、及びマンガン等の重金属の除去、等に好適に用いられる。ただし、ここで記載された用途に限定されることはない。 The activated carbon fiber nonwoven fabric of the present invention can, for example, recover organic solvents such as ethyl acetate; remove chlorine compounds such as trihalomethane; remove harmful gases such as malodorous gases, NOx, and SOx; and remove organic solvents such as lead, arsenic, and manganese. Suitable for use in removing heavy metals, etc. However, the applications are not limited to those described here.
＜エレメント＞
　本発明のエレメントは、上記工程を経て得られた活性炭素繊維不織布を円筒に巻き付けることによって製造することができる。活性炭素繊維不織布の巻き付けは活性炭素繊維不織布を厚さ方向に潰して活性炭素繊維を破断しないように巻き付け張力を調整しながら行う必要があり、エレメント加工後の充填密度Ａ（ｋｇ／ｍ３）と活性炭素繊維不織布の嵩密度Ｂ（ｋｇ／ｍ３）との相対比率（Ｂ／Ａ×１００）が９５％以上にすることが好ましい。なお、エレメント加工後の充填密度Ａは以下の式で求められる。
　　　　充填密度Ａ＝巻き付けた活性炭素繊維不織布の重量
　　　÷（円筒高さ×（（円筒外径）２－（円筒内径）２）×円周率π÷４）
　ここでの円筒高さは円筒状に巻き付けた活性炭素繊維不織布の高さ、円筒外径は円筒状に巻き付けた活性炭素繊維不織布の外径、円筒内径は円筒状に巻き付けた活性炭素繊維不織布の内径を示す。 <Element>
The element of the present invention can be manufactured by winding the activated carbon fiber nonwoven fabric obtained through the above steps around a cylinder. It is necessary to wrap the activated carbon fiber nonwoven fabric while adjusting the winding tension so as not to crush the activated carbon fiber nonwoven fabric in the thickness direction and break the activated carbon fibers, and the packing density after element processing is A (kg/m 3 ). It is preferable that the relative ratio (B/A×100) of the active carbon fiber nonwoven fabric and the bulk density B (kg/m 3 ) of the activated carbon fiber nonwoven fabric is 95% or more. In addition, the packing density A after element processing is calculated|required by the following formula.
Packing density A = Weight of rolled activated carbon fiber nonwoven fabric ÷ (Cylinder height x ((Cylinder outer diameter) 2 - (Cylinder inner diameter) 2 ) x Pi ÷ 4)
The cylinder height here is the height of the activated carbon fiber nonwoven fabric wrapped in a cylindrical shape, the cylinder outer diameter is the outer diameter of the activated carbon fiber nonwoven fabric wrapped in a cylindrical shape, and the cylinder inner diameter is the height of the activated carbon fiber nonwoven fabric wrapped in a cylindrical shape. Indicates inner diameter.
　＜有機溶剤吸脱着処理装置、有機溶剤回収システム、有機溶剤吸脱着処理方法、及び有機溶剤回収方法＞
　本発明の有機溶剤回収システムの一実施形態を図１にて説明する。有機溶剤回収システム１は、吸着槽２Ａ及び２Ｂを有する有機溶剤吸脱着処理装置２２を備え、吸着槽２Ａ及び２Ｂの内部には円筒状かご型の巻芯に活性炭素繊維不織布９（吸着材）を層状に巻き付けた中空円筒構造で、その外周面を金網で固定したエレメント８を着脱可能に設けている。図１では、２つの吸着槽を有する有機溶剤回収システム１を例示しているが、吸着槽は１つでもよく、３つ以上有していてもよい。なお、エレメント８の底部は閉鎖されている。 <Organic solvent adsorption/desorption treatment device, organic solvent recovery system, organic solvent adsorption/desorption treatment method, and organic solvent recovery method>
An embodiment of the organic solvent recovery system of the present invention will be described with reference to FIG. The organic solvent recovery system 1 includes an organic solvent adsorption/desorption processing device 22 having adsorption tanks 2A and 2B, and inside the adsorption tanks 2A and 2B, an activated carbon fiber nonwoven fabric 9 (adsorbent) is arranged in a cylindrical cage-shaped winding core. It has a hollow cylindrical structure in which layers are wound around each other, and an element 8 whose outer peripheral surface is fixed with a wire mesh is removably provided. Although FIG. 1 illustrates an organic solvent recovery system 1 having two adsorption tanks, the system may have one or three or more adsorption tanks. Note that the bottom of the element 8 is closed.
　図１の吸着槽２Ａが吸着処理中、吸着槽２Ｂが脱着処理中の場合について説明する。まず吸着工程について説明する。有機溶剤を含有する溶剤混合ガス（被処理ガス）３はプレフィルター４を通り、送風機５により下ダンパー６を経て吸着槽２Ａに送られ、エレメント８の活性炭素繊維不織布９で被処理ガス中の有機溶剤の吸着が行われ、上ダンパー１０を経て清浄空気として吸着槽２Ａの排気口１２より系外に排出される。この時、水蒸気供給ライン１３の自動弁１４は閉の状態である。 A case will be described in which the adsorption tank 2A in FIG. 1 is in the process of adsorption processing and the adsorption tank 2B is in the process of desorption processing. First, the adsorption process will be explained. A solvent mixed gas (gas to be treated) 3 containing an organic solvent passes through a pre-filter 4, is sent to an adsorption tank 2A via a lower damper 6 by a blower 5, and is removed by the activated carbon fiber nonwoven fabric 9 of an element 8. The organic solvent is adsorbed, and is discharged as clean air through the upper damper 10 to the outside of the system through the exhaust port 12 of the adsorption tank 2A. At this time, the automatic valve 14 of the steam supply line 13 is in a closed state.
　次に脱着工程について説明する。水蒸気供給ライン１３より供給された水蒸気は自動弁１５を経て吸着槽２Ｂに供給され、エレメント８の活性炭素繊維不織布９に吸着された被処理ガス中の有機溶剤を脱着し再生させる。凝縮液、及び被処理ガス中の有機溶剤成分を含む未凝縮の水蒸気は、脱着ガスライン１６を通って、コンデンサー１７へ送られ被処理ガス中の有機溶剤成分を含む未凝縮の水蒸気が凝縮される。コンデンサー１７より高濃度の有機溶剤を含んだ凝縮液がセパレーター１９へ送られる。この時、下ダンパー７及び上ダンパー１１は閉の状態である。なお、セパレーター１９内に滞留している有機溶剤成分を含むガスは、戻りガスライン２０により再度被処理ガス３に戻される。有機溶剤回収システムにおける有機溶剤回収装置は、例えば、図１中のコンデンサー１７、冷却水供給ライン１８、及びセパレーター１９を含むものであるが、これらに限定されない。 Next, the desorption process will be explained. Steam supplied from the steam supply line 13 is supplied to the adsorption tank 2B via an automatic valve 15, and the organic solvent in the gas to be treated adsorbed to the activated carbon fiber nonwoven fabric 9 of the element 8 is desorbed and regenerated. The condensate and the uncondensed water vapor containing the organic solvent component in the gas to be treated are sent to the condenser 17 through the desorption gas line 16, where the uncondensed water vapor including the organic solvent component in the gas to be treated is condensed. Ru. A condensate containing a highly concentrated organic solvent is sent from the condenser 17 to the separator 19. At this time, the lower damper 7 and the upper damper 11 are in a closed state. Note that the gas containing the organic solvent component remaining in the separator 19 is returned to the gas to be treated 3 again through the return gas line 20. The organic solvent recovery device in the organic solvent recovery system includes, for example, the condenser 17, the cooling water supply line 18, and the separator 19 in FIG. 1, but is not limited thereto.
　本発明の有機溶剤吸脱着処理装置、有機溶剤回収システム、有機溶剤吸脱着処理方法、及び有機溶剤回収方法は、吸着材として本発明の活性炭素繊維不織布を用いる以外は、公知の処理装置、システム、処理方法、及び回収方法を採用することができ、例えば、特公平６－５５２５４号公報、特開２００４－１０５８０６号公報、及び特開２０１３－１１１５５２号公報に記載の処理装置、システム、処理方法、及び回収方法を採用することができる。 The organic solvent adsorption/desorption treatment device, organic solvent recovery system, organic solvent adsorption/desorption treatment method, and organic solvent recovery method of the present invention are performed using known treatment devices and systems, except for using the activated carbon fiber nonwoven fabric of the present invention as an adsorbent. , processing method, and recovery method, for example, processing apparatuses, systems, and processing methods described in Japanese Patent Publication No. 6-55254, Japanese Patent Application Publication No. 2004-105806, and Japanese Patent Application Publication No. 2013-111552. , and recovery methods can be adopted.
　以下、実施例及び比較例を示して本発明をより具体的に説明するが、本発明は以下の実施例によって限定されるものではない。なお、以下の実施例における物性等の評価方法は以下の通りである。 Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the evaluation method of physical properties etc. in the following examples is as follows.
（活性炭素繊維の繊維径）
　走査電子顕微鏡（製品名：ＳＵ１５１０、日立ハイテクノロジーズ社製）を用いて顕微鏡画像を観察し、その顕微鏡画像から１００本以上の繊維径を読み取り、読み取った繊維径を平均して求めた。なお、繊維径とは繊維直径を意味する。 (Fiber diameter of activated carbon fiber)
A microscopic image was observed using a scanning electron microscope (product name: SU1510, manufactured by Hitachi High-Technologies), and the diameters of 100 or more fibers were read from the microscopic image, and the read fiber diameters were averaged. Note that the fiber diameter means the fiber diameter.
　（ＢＥＴ比表面積）
　試料を２００℃で１６時間真空乾燥して秤量し、さらに３００℃で１時間真空乾燥した後に高精度ガス／蒸気吸着量測定装置（製品名：ＢＥＬＳＯＲＰ－ＭＡＸII、マイクロトラック・ベル社製）を使用して測定した。液体窒素の沸点（７７Ｋ）における窒素吸着量を相対圧１０－7～０．９９の範囲で測定し、試料の窒素吸着等温線を得た。この窒素吸着等温線を、解析相対圧範囲を吸着等温線Ｉ型（ＩＳＯ９２７７）の条件で決定したＢＥＴ法により解析し、重量当たりのＢＥＴ比表面積（単位：ｍ２／ｇ）を求めた。 (BET specific surface area)
The sample was vacuum-dried at 200°C for 16 hours, weighed, and then vacuum-dried at 300°C for 1 hour, using a high-precision gas/vapor adsorption measurement device (product name: BELSORP-MAXII, manufactured by Microtrac Bell). It was measured by The amount of nitrogen adsorption at the boiling point (77K) of liquid nitrogen was measured in the relative pressure range of 10 -7 to 0.99, and the nitrogen adsorption isotherm of the sample was obtained. This nitrogen adsorption isotherm was analyzed by the BET method in which the analytical relative pressure range was determined under the conditions of adsorption isotherm type I (ISO9277), and the BET specific surface area per weight (unit: m 2 /g) was determined.
（活性炭素繊維不織布の嵩密度）
　試料をＪＩＳ　Ｋ１４７７　７．５（乾燥減量）に準じて１２０℃で３時間乾燥させた後、単位面積当たりの重量（ｇ／ｍ２）を測定した。さらに単位面積当たりの重量を厚さで割り、嵩密度（ｋｇ／ｍ３）を求めた。なお、厚さは面積４ｃｍ２の円盤を用いて、試料にかかる荷重を１．５ｇｆ／ｃｍ２に調整して測定した。 (Bulk density of activated carbon fiber nonwoven fabric)
After drying the sample at 120° C. for 3 hours according to JIS K1477 7.5 (loss on drying), the weight per unit area (g/m 2 ) was measured. Furthermore, the weight per unit area was divided by the thickness to determine the bulk density (kg/m 3 ). The thickness was measured using a disk with an area of 4 cm 2 and adjusting the load applied to the sample to 1.5 gf/cm 2 .
（Ｘ線回折におけるグラファイト状結晶化度Ｘｇ）
　試料をメノウ乳鉢で粉状にすりつぶした後、リガク社製の標準アルミ試料ホルダーに詰め、Ｘ線回折装置（製品名：ＳｍａｒｔＬａｂ、リガク社製）を使用して以下の条件にてＸ線回折ピークプロファイルを測定した。
　　ターゲット：Ｃｕ
　　電圧：４０ｋＶ
　　電流：３０ｍＡ
　　試料測定時のスリット条件：ＲＳ１＝２／３ｄｅｇ、Ｓｏｌｌａｒ＝５．０ｄｅｇ、Ｓ２＝０．３ｍｍ
　　試料が無い状態で測定する時のスリット条件：Ｓｏｌｌａｒ＝５．０ｄｅｇ、ＩＳ＝２／３ｄｅｇ
　　受光部：Ｎｉフィルタ（ Ｄｔｅｘ／Ｕｌｔｒａ）
　　走査範囲：２θ＝１０～４０ｄｅｇ (Graphite-like crystallinity Xg in X-ray diffraction)
After grinding the sample into powder in an agate mortar, it was packed into a standard aluminum sample holder manufactured by Rigaku Co., Ltd., and the X-ray diffraction peak was measured using an X-ray diffraction device (product name: SmartLab, manufactured by Rigaku Co., Ltd.) under the following conditions. The profile was measured.
Target: Cu
Voltage: 40kV
Current: 30mA
Slit conditions during sample measurement: RS1=2/3deg, Solar=5.0deg, S2=0.3mm
Slit conditions when measuring without a sample: Solar=5.0deg, IS=2/3deg
Light receiving part: Ni filter (Dtex/Ultra)
Scanning range: 2θ=10~40deg
（ラマン分光測定におけるＲ値及びＤバンドの半値幅）
　レーザーラマン顕微鏡（製品名：ＲＡＭＡＮ－１１、ナノフォトン社製）を使用し、以下の条件で試料の繊維表面のラマンスペクトルを測定した。
　　励起波長：５３２ｎｍ
　　対物レンズ：５０倍
　　回折格子：３００ｇｒ／ｍｍ
　　露光時間：１５秒
　　積算回数：１０回
　得られたスペクトルに対して、７００ｃｍ－１～２，０００ｃｍ－１の波数域を直線でベースライン補正した後、Ｄバンド（１３６０±３０ｃｍ－１付近）、Ｇバンド（１５８０±３０ｃｍ－１付近）のピーク分離を行った。なお、フィッティング関数にはローレンツ関数とガウス関数を用い、上記２つのピーク以外の補正として２つの関数を加え、フィッティング後の曲線が実測したラマンスペクトルとほぼ一致するようにピーク分離解析を実施した。分離されたピーク曲線からＤバンドのピーク強度ＩｄとＧバンドのピーク強度Ｉｇを求め、Ｒ値（Ｉｄ／Ｉｇ）を求めた。さらに分離されたＤバンドのピーク曲線からＤバンドの半値幅（ｃｍ－１）を求めた。 (R value and half width of D band in Raman spectrometry)
Using a laser Raman microscope (product name: RAMAN-11, manufactured by Nanophoton), the Raman spectrum of the fiber surface of the sample was measured under the following conditions.
Excitation wavelength: 532nm
Objective lens: 50x Diffraction grating: 300gr/mm
Exposure time: 15 seconds Number of integrations: 10 times For the obtained spectrum, after baseline correction in the wave number range of 700 cm -1 to 2,000 cm -1 with a straight line, the D band (around 1360 ± 30 cm -1 ), Peak separation of the G band (around 1580±30 cm −1 ) was performed. Note that a Lorentz function and a Gaussian function were used as fitting functions, two functions were added as corrections for the peaks other than the above two, and peak separation analysis was performed so that the curve after fitting almost matched the actually measured Raman spectrum. The peak intensity Id of the D band and the peak intensity Ig of the G band were determined from the separated peak curves, and the R value (Id/Ig) was determined. Furthermore, the half width (cm −1 ) of the D band was determined from the separated peak curve of the D band.
（細孔容積）
　試料を２００℃で１６時間真空乾燥して秤量し、さらに３００℃で１時間真空乾燥した後に高精度ガス／蒸気吸着量測定装置（製品名：ＢＥＬＳＯＲＰ－ＭＡＸII、マイクロトラック・ベル社製）を使用して測定した。液体窒素の沸点（７７Ｋ）における窒素吸着量を相対圧１０－7～０．９９の範囲で測定し、ＧＣＭＣ法にて細孔径分布を得た。ＧＣＭＣ法のモデルはＳｌｉｔ、吸着剤タイプはＧｒａｐｈｉｔｉｃ　Ｃａｒｂｏｎ、フィッティング方法はＴｉｋｈｎｏｖ正則化で解析した。得られた細孔径分布から細孔直径が０～０．７ｎｍの細孔容積Ｖ０．７、及び全細孔容積Ｖaを求めた。さらに全細孔容積Ｖaに対する細孔容積Ｖ０．７が占める割合（Ｖ０．７／Ｖａ）を求めた。 (pore volume)
The sample was vacuum-dried at 200°C for 16 hours, weighed, and then vacuum-dried at 300°C for 1 hour, using a high-precision gas/vapor adsorption measurement device (product name: BELSORP-MAXII, manufactured by Microtrac Bell). It was measured by The amount of nitrogen adsorbed at the boiling point (77K) of liquid nitrogen was measured at a relative pressure in the range of 10 -7 to 0.99, and the pore size distribution was obtained using the GCMC method. The model of the GCMC method was Slit, the adsorbent type was Graphic Carbon, and the fitting method was Tikhnov regularization. From the obtained pore size distribution, the pore volume V 0.7 with a pore diameter of 0 to 0.7 nm and the total pore volume V a were determined. Furthermore, the ratio of the pore volume V 0.7 to the total pore volume V a (V 0.7 /V a ) was determined.
（活性炭素繊維不織布の厚さ方向の荷重耐久性）
　０．１５ｋＰａの荷重で試料の初期厚さｔ０を測定した後、５．０ｋＰａの荷重を１分間与えた。つづいて試料に荷重を与えない状態で１分間静置した後、再び０．１５ｋＰａの荷重で厚さを測定した。その後、５．０ｋＰａ荷重→荷重を与えない状態で静置→０．１５ｋＰａ荷重で厚さ測定、の順で上述した作業を２００回繰り返し、２００回目の厚さｔ２００を測定した。厚さ方向の荷重耐久性（％）を以下の式で求めた。
　厚さ方向の荷重耐久性（％）＝ｔ２００÷ｔ０×１００
　活性炭素繊維不織布を用いたエレメントの充填密度Ａ（ｋｇ／ｍ３）と活性炭素繊維不織布の嵩密度Ｂ（ｋｇ／ｍ３）との相対比率（Ｂ／Ａ×１００）は９５％以上が好ましく、さらに有機溶剤吸脱着処理装置でエレメントに供給される被処理ガスの圧力損失は約５ｋＰａであることから、エレメントの長期の形状安定性の観点より活性炭素繊維不織布の荷重耐久性は９５％以上が好ましい。 (Load durability in the thickness direction of activated carbon fiber nonwoven fabric)
After measuring the initial thickness t 0 of the sample under a load of 0.15 kPa, a load of 5.0 kPa was applied for 1 minute. Subsequently, after allowing the sample to stand for 1 minute without applying any load, the thickness was measured again under a load of 0.15 kPa. Thereafter, the above-mentioned operation was repeated 200 times in the order of 5.0 kPa load → standing still without applying any load → thickness measurement under 0.15 kPa load, and the 200th thickness t 200 was measured. The load durability (%) in the thickness direction was determined using the following formula.
Load durability in thickness direction (%) = t 200 ÷ t 0 × 100
The relative ratio (B/A x 100) between the packing density A (kg/m 3 ) of the element using the activated carbon fiber nonwoven fabric and the bulk density B (kg/m 3 ) of the activated carbon fiber nonwoven fabric is preferably 95% or more. Furthermore, since the pressure loss of the gas to be treated that is supplied to the element in an organic solvent adsorption/desorption treatment device is approximately 5 kPa, from the viewpoint of long-term shape stability of the element, the load durability of activated carbon fiber nonwoven fabric is 95% or more. is preferred.
（エレメントの有機溶剤除去性能）
　活性炭素繊維不織布を、内径１００ｍｍ、長さ５７５ｍｍの円筒構造体に活性炭素繊維の質量が５ｋｇになるまで巻き付けた。エレメントの充填密度Ａ（ｋｇ／ｍ３）と活性炭素繊維不織布の嵩密度Ｂ（ｋｇ／ｍ３）との相対比率（Ｂ／Ａ×１００）が９５％となるように巻き付け張力を調整し、エレメントを得た。次に、当該エレメントを図１に示した有機溶剤含有ガス処理装置に搭載し、酢酸エチル１０００ｐｐｍを含む温度４５℃の被処理ガスを、風量１０Ｎｍ３／分で送風機５より吸着槽２Ａに１８分間送風し、被処理ガス中の酢酸エチルを活性炭素繊維不織布９に吸着させた。被処理ガス及び系外に排出されるガスの酢酸エチル濃度は、全炭化水素計（製品名：ＨＣＭ－１Ｂ、島津製作所製）を用いて送風機５の出口と吸着槽２Ａの排気口１２で測定した。吸着槽２Ａに被処理ガスを供給してから１８分が経過した時点でダンパーの開閉を切り替え、続いて被処理ガスを吸着槽２Ｂに供給した。一方で水蒸気を、水蒸気供給ライン１３より吸着槽２Ａに供給してエレメント８の活性炭素繊維不織布９に吸着された酢酸エチルを脱着して再生させた。酢酸エチルの吸着と脱着を１０回繰り返し、系外に排出されるガスの酢酸エチル平均濃度が安定した時点で酢酸エチルの除去性能（％）を求めた。酢酸エチルの除去性能（％）は以下の式で求められる。
　　酢酸エチルの除去性能（％）＝系外に排出されるガスの酢酸エチル平均濃度（ｐｐｍ）
　÷送風機５の出口の被処理ガス平均濃度（ｐｐｍ）×１００ (Element's organic solvent removal performance)
The activated carbon fiber nonwoven fabric was wound around a cylindrical structure having an inner diameter of 100 mm and a length of 575 mm until the mass of the activated carbon fiber was 5 kg. Adjust the winding tension so that the relative ratio (B/A x 100) between the packing density A (kg/m 3 ) of the element and the bulk density B (kg/m 3 ) of the activated carbon fiber nonwoven fabric is 95%, I got the element. Next, the element was mounted on the organic solvent-containing gas treatment device shown in Fig. 1, and the gas to be treated containing 1000 ppm of ethyl acetate at a temperature of 45°C was supplied from the blower 5 to the adsorption tank 2A for 18 minutes at an air flow rate of 10 Nm 3 /min. Air was blown to adsorb ethyl acetate in the gas to be treated onto the activated carbon fiber nonwoven fabric 9. The ethyl acetate concentration of the gas to be treated and the gas discharged outside the system is measured at the outlet of the blower 5 and the exhaust port 12 of the adsorption tank 2A using a total hydrocarbon meter (product name: HCM-1B, manufactured by Shimadzu Corporation). did. When 18 minutes had elapsed since the gas to be treated was supplied to the adsorption tank 2A, the damper was switched between opening and closing, and then the gas to be treated was supplied to the adsorption tank 2B. On the other hand, water vapor was supplied from the water vapor supply line 13 to the adsorption tank 2A to desorb and regenerate the ethyl acetate adsorbed on the activated carbon fiber nonwoven fabric 9 of the element 8. Adsorption and desorption of ethyl acetate was repeated 10 times, and when the average concentration of ethyl acetate in the gas discharged outside the system became stable, the removal performance (%) of ethyl acetate was determined. The removal performance (%) of ethyl acetate is determined by the following formula.
Ethyl acetate removal performance (%) = average concentration of ethyl acetate in gas discharged outside the system (ppm)
÷ Average concentration of gas to be treated at the outlet of blower 5 (ppm) x 100
＜実施例１＞
　ポリ（２，６－ジメチル－１，４－フェニレンエーテル）（ＰＰＯ６４６、ＳＡＢＩＣＩｎｎｏｖａｔｉｖｅ Ｐｌａｓ ｔｉｃ製）を溶融紡糸して得られたポリフェニレンエーテル系繊維を長さ５１ｍｍにカットした。続いてニードルパンチ機により、針密度３５０本／ｃｍ２、針深度１５ｍｍ（表）、９ｍｍ（裏）の条件で表裏処理を行い、前駆体繊維不織布を得た。得られた前駆体繊維不織布を水蒸気濃度４ｖｏｌ．％の空気雰囲気下にて１９０℃で４０時間熱処理をしたあと、さらに３２０℃まで昇温して２時間熱処理をした。続けて窒素中にて１０２０℃で３０時間の炭素化処理を行った。さらに続けて水蒸気濃度２５ｖｏｌ．％の窒素雰囲気下にて９５０℃で８分間の賦活処理を行い、繊維径３０μｍの活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Example 1>
A polyphenylene ether fiber obtained by melt spinning poly(2,6-dimethyl-1,4-phenylene ether) (PPO646, manufactured by SABIC Innovative Plastic) was cut into a length of 51 mm. Subsequently, front and back treatments were performed using a needle punch machine under the conditions of a needle density of 350 pieces/cm 2 and a needle depth of 15 mm (front) and 9 mm (back) to obtain a precursor fiber nonwoven fabric. The obtained precursor fiber nonwoven fabric was heated to a water vapor concentration of 4 vol. % air atmosphere at 190°C for 40 hours, the temperature was further raised to 320°C, and heat treatment was performed for 2 hours. Subsequently, carbonization treatment was performed at 1020° C. for 30 hours in nitrogen. Furthermore, the water vapor concentration is 25 vol. % of nitrogen atmosphere at 950° C. for 8 minutes to obtain an activated carbon fiber nonwoven fabric with a fiber diameter of 30 μm. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜実施例２＞
　賦活処理の時間を１５分に変更した以外は実施例１と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Example 2>
An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1 except that the activation treatment time was changed to 15 minutes. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜実施例３＞
　賦活処理の時間を２３分に変更した以外は実施例１と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Example 3>
An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1 except that the activation treatment time was changed to 23 minutes. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜実施例４＞
　水蒸気濃度２５ｖｏｌ．％及び酸素２ｖｏｌ．％の窒素雰囲気下にて９５０℃で７分間の賦活処理を行った以外は実施例１と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Example 4>
Water vapor concentration 25vol. % and oxygen 2 vol. An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1, except that the activation treatment was performed at 950° C. for 7 minutes in a nitrogen atmosphere of 50%. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜実施例５＞
　ポリ（２，６－ジメチル－１，４－フェニレンエーテル）（ＰＰＯ６４０、ＳＡＢＩＣＩｎｎｏｖａｔｉｖｅ Ｐｌａｓ ｔｉｃ製）とポリ（２，６－ジメチル－１，４－フェニレンエーテル）（ＰＰＯ ＳＡ１２０、ＳＡＢＩＣＩｎｎｏｖａｔｉｖｅ Ｐｌａｓ ｔｉｃ製）を６０：３０の質量比で溶融紡糸して得られたポリフェニレンエーテル系繊維を前駆体繊維として用いた以外は実施例２と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Example 5>
Poly(2,6-dimethyl-1,4-phenylene ether) (PPO640, manufactured by SABIC Innovative Plastic) and poly(2,6-dimethyl-1,4-phenylene ether) (PPO SA120, manufactured by SABIC Innovative Plastic) at 60% An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 2, except that polyphenylene ether fiber obtained by melt spinning at a mass ratio of :30 was used as the precursor fiber. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜比較例１＞
　ニードルパンチ機の針密度を２００本／ｃｍ２に変更した以外は実施例２と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Comparative example 1>
An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 2, except that the needle density of the needle punch machine was changed to 200 needles/cm 2 . Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜比較例２＞
　炭素化処理の温度を８５０℃に変更し、さらに賦活処理の温度を８５０℃、時間を７０分に変更した以外は実施例１と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Comparative example 2>
An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1, except that the temperature of the carbonization treatment was changed to 850° C., and the temperature of the activation treatment was changed to 850° C. and the time was changed to 70 minutes. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜比較例３＞
　前駆体繊維不織布を水蒸気濃度４ｖｏｌ．％の空気雰囲気下にて１９０℃で４０時間熱処理をしたあと炭素化処理を行った以外は実施例２と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Comparative example 3>
The precursor fiber nonwoven fabric was heated to a water vapor concentration of 4 vol. An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 2, except that the carbonization treatment was performed after heat treatment at 190° C. for 40 hours in an air atmosphere of 10%. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜比較例４＞
　リン酸２アンモニウムを８ｗｔ．％添着したビスコースレーヨン繊維（ダイワボウレーヨン社製）を長さ５１ｍｍにカットした。続いてニードルパンチ機により、針密度２５０本／ｃｍ２、針深度１５ｍｍ（表）、９ｍｍ（裏）の条件で表裏処理を行い、前駆体繊維不織布を得た。得られた前駆体繊維不織布を４００℃の窒素雰囲気下にて１時間の難燃化処理をした。続けて窒素中にて１０２０℃で３０時間の炭素化処理を行った。さらに続けて水蒸気濃度２５ｖｏｌ．％の窒素雰囲気下にて９５０℃で１５分間の賦活処理を行い、活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Comparative example 4>
8 wt. diammonium phosphate. % impregnated viscose rayon fiber (manufactured by Daiwabo Rayon Co., Ltd.) was cut into a length of 51 mm. Subsequently, front and back treatments were performed using a needle punch machine under the conditions of a needle density of 250 pieces/cm 2 and a needle depth of 15 mm (front) and 9 mm (back) to obtain a precursor fiber nonwoven fabric. The obtained precursor fiber nonwoven fabric was subjected to flame retardant treatment for 1 hour in a nitrogen atmosphere at 400°C. Subsequently, carbonization treatment was performed at 1020° C. for 30 hours in nitrogen. Furthermore, the water vapor concentration is 25 vol. % of nitrogen atmosphere at 950° C. for 15 minutes to obtain an activated carbon fiber nonwoven fabric. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜比較例５＞
　賦活処理の時間を３分間に変更した以外は実施例１と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Comparative example 5>
An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1 except that the activation treatment time was changed to 3 minutes. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
＜比較例６＞
　賦活処理の時間を３１分間に変更した以外は実施例１と同様にして活性炭素繊維不織布を得た。得られた活性炭素繊維不織布の各評価結果を表１に示す。 <Comparative example 6>
An activated carbon fiber nonwoven fabric was obtained in the same manner as in Example 1 except that the activation treatment time was changed to 31 minutes. Table 1 shows the evaluation results of the obtained activated carbon fiber nonwoven fabric.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１からわかるように、実施例１～５の活性炭素繊維不織布はいずれも酢酸エチルの除去性能が高く、しかも比較例１～４に比べて厚さ方向の荷重耐久性が優れていることからエレメントの長期の形状安定性に優れる。比較例１は嵩密度が小さいため、厚さ方向の荷重耐久性が低かった。比較例２はＸ線回折におけるグラファイト状結晶化度Ｘｇが小さいため、厚さ方向の荷重耐久性が低かった。比較例３はラマン分光測定におけるＲ値が小さいため、厚さ方向の荷重耐久性が低かった。比較例４はラマン分光測定におけるＤバンドの半値幅が大きいため、厚さ方向の荷重耐久性が低かった。比較例５はＢＥＴ比表面積が小さいため、酢酸エチル除去性能が劣るものであった。比較例６は、ＢＥＴ比表面積が大きく、Ｘ線回折におけるグラファイト状結晶化度Ｘｇが小さく、ラマン分光測定におけるＲ値が小さいため、厚さ方向の荷重耐久性が低かった。 As can be seen from Table 1, the activated carbon fiber nonwoven fabrics of Examples 1 to 5 all have high ethyl acetate removal performance, and also have superior load durability in the thickness direction compared to Comparative Examples 1 to 4. Excellent long-term shape stability of the element. Since Comparative Example 1 had a low bulk density, its load durability in the thickness direction was low. Comparative Example 2 had a low graphite-like crystallinity Xg in X-ray diffraction, so the load durability in the thickness direction was low. Comparative Example 3 had a small R value in Raman spectroscopy, so the load durability in the thickness direction was low. Comparative Example 4 had a large half-width of the D band in Raman spectroscopy, so the load durability in the thickness direction was low. Comparative Example 5 had a small BET specific surface area, so its ethyl acetate removal performance was poor. Comparative Example 6 had a large BET specific surface area, a small graphite-like crystallinity Xg in X-ray diffraction, and a small R value in Raman spectroscopy, so the load durability in the thickness direction was low.
　本発明の活性炭素繊維不織布は、従来の活性炭素繊維不織布に替わる、優れた吸着性能と長期の形状安定性を有する活性炭素繊維不織布として好適に用いることができ、産業に大いに貢献できる。 The activated carbon fiber nonwoven fabric of the present invention can be suitably used as an activated carbon fiber nonwoven fabric that has excellent adsorption performance and long-term shape stability in place of conventional activated carbon fiber nonwoven fabrics, and can greatly contribute to industry.
１　：有機溶剤回収システム
２Ａ：吸着槽
２Ｂ：吸着槽
３　：有機溶剤を含有した溶剤混合ガス（被処理ガス）
４　：プレフィルター
５　：送風機
６　：下ダンパー
７　：下ダンパー
８　：エレメント
９　：活性炭素繊維不織布
１０：上ダンパー
１１：上ダンパー
１２：排気口
１３：水蒸気供給ライン
１４：自動弁
１５：自動弁
１６：脱着ガスライン
１７：コンデンサー
１８：冷却水供給ライン
１９：セパレーター
２０：戻りガスライン
２２：有機溶剤吸脱着処理装置 1: Organic solvent recovery system 2A: Adsorption tank 2B: Adsorption tank 3: Solvent mixed gas containing organic solvent (gas to be treated)
4: Pre-filter 5: Blower 6: Lower damper 7: Lower damper 8: Element 9: Activated carbon fiber nonwoven fabric 10: Upper damper 11: Upper damper 12: Exhaust port 13: Steam supply line 14: Automatic valve 15: Automatic valve 16 :Desorption gas line 17:Condenser 18:Cooling water supply line 19:Separator 20:Return gas line 22:Organic solvent adsorption/desorption treatment device

Claims (9)

  1. 　ＢＥＴ比表面積が１０００ｍ２／ｇ以上２０００ｍ２／ｇ以下、
    　嵩密度が１００ｋｇ／ｍ３よりも大きく、
    　Ｘ線回折におけるグラファイト状結晶化度Ｘｇが０．３５以上、
    　ラマン分光測定におけるＲ値が１．２０以上、及び、
    　ラマン分光測定におけるＤバンドの半値幅が１４５ｃｍ－１以下、であることを特徴とする活性炭素繊維不織布。     BET specific surface area is 1000 m 2 /g or more and 2000 m 2 /g or less,
    The bulk density is greater than 100 kg/ m3 ,
    Graphite crystallinity Xg in X-ray diffraction is 0.35 or more,
    R value in Raman spectroscopy measurement is 1.20 or more, and
    An activated carbon fiber nonwoven fabric characterized in that the half width of the D band in Raman spectroscopy is 145 cm -1 or less.
  2. 　細孔直径が０．７ｎｍ以下の細孔容積Ｖ０．７が０．２２ｃｍ３／ｇ以上である、請求項１に記載の活性炭素繊維不織布。 The activated carbon fiber nonwoven fabric according to claim 1, having a pore diameter of 0.7 nm or less and a pore volume V 0.7 of 0.22 cm 3 /g or more.
  3. 　全細孔容積Ｖaに対する細孔直径０．７ｎｍ以下の細孔容積Ｖ０．７が占める割合（Ｖ０．７／Ｖａ）が０．３０以上である、請求項１又は２に記載の活性炭素繊維不織布。 3. The ratio of the pore volume V 0.7 having a pore diameter of 0.7 nm or less to the total pore volume V a (V 0.7 /V a ) is 0.30 or more. Activated carbon fiber non-woven fabric.
  4. 　前駆体繊維不織布を炭素化処理して炭素繊維不織布を得る工程と、前記炭素繊維不織布を賦活処理する工程と含み、
    　前記賦活処理は水蒸気賦活法によって行われる、請求項１又は２に記載の活性炭素繊維不織布を製造する製造方法。     A step of carbonizing a precursor fiber nonwoven fabric to obtain a carbon fiber nonwoven fabric, and an activation treatment of the carbon fiber nonwoven fabric,
    The manufacturing method for manufacturing an activated carbon fiber nonwoven fabric according to claim 1 or 2, wherein the activation treatment is performed by a steam activation method.
  5. 　請求項１又は２に記載の活性炭素繊維不織布を用いて構成されるエレメント。 An element constructed using the activated carbon fiber nonwoven fabric according to claim 1 or 2.
  6. 　吸着材を充填した吸着槽を備え、
    　前記吸着材に、被処理ガスを接触させることで有機溶剤を吸着し清浄化ガスを排出し、かつ、水蒸気又は加熱ガスを接触させることで吸着した有機溶剤を脱着し脱着ガスを排出する、有機溶剤吸脱着装置であって、
    　前記吸着材が請求項１又は２に記載の活性炭素繊維不織布を含む、有機溶剤吸脱着処理装置。     Equipped with an adsorption tank filled with adsorbent,
    An organic solvent that adsorbs an organic solvent and discharges a cleaning gas by contacting the adsorbent with a gas to be treated, and desorbs the adsorbed organic solvent and discharges a desorbed gas by contacting the adsorbent with water vapor or heated gas. A solvent adsorption/desorption device,
    An organic solvent adsorption/desorption treatment device, wherein the adsorbent comprises the activated carbon fiber nonwoven fabric according to claim 1 or 2.
  7. 　請求項６に記載の有機溶剤吸脱着処理装置、及び当該有機溶剤吸脱着処理装置から排出された脱着ガスを凝縮して有機溶剤を回収する有機溶剤回収装置を含む、有機溶剤回収システム。 An organic solvent recovery system comprising the organic solvent adsorption/desorption processing device according to claim 6 and an organic solvent recovery device that recovers the organic solvent by condensing the desorption gas discharged from the organic solvent adsorption/desorption processing device.
  8. 　被処理ガスを吸着材に接触させることで有機溶剤を吸着させ清浄化ガスを排出し、水蒸気又は加熱ガスを前記吸着材に接触させることで吸着した有機溶剤を脱着させ脱着ガスを排出する有機溶剤吸脱着処理方法であって、
    　前記吸着材が、請求項１又は２に記載の活性炭素繊維不織布を含む、有機溶剤吸脱着処理方法。     An organic solvent that adsorbs an organic solvent and discharges a cleaning gas by bringing the gas to be treated into contact with an adsorbent, and desorbs the adsorbed organic solvent by bringing water vapor or heated gas into contact with the adsorbent, and discharges the desorbed gas. An adsorption/desorption treatment method, comprising:
    An organic solvent adsorption/desorption treatment method, wherein the adsorbent comprises the activated carbon fiber nonwoven fabric according to claim 1 or 2.
  9. 　被処理ガスを吸着材に接触させることで有機溶剤を吸着させ清浄化ガスを排出し、水蒸気又は加熱ガスを前記吸着材に接触させることで吸着した有機溶剤を脱着させ脱着ガスを排出し、排出された前記脱着ガスを凝縮して有機溶剤を回収する、有機溶剤回収方法であって、
    　前記吸着材が請求項１又は２に記載の活性炭素繊維不織布を含む、有機溶剤回収方法。
          By bringing the gas to be treated into contact with an adsorbent, an organic solvent is adsorbed and a cleaning gas is discharged, and by bringing water vapor or heated gas into contact with the adsorbent, the adsorbed organic solvent is desorbed and the desorbed gas is discharged. An organic solvent recovery method for recovering an organic solvent by condensing the desorbed gas, the method comprising:
    An organic solvent recovery method, wherein the adsorbent comprises the activated carbon fiber nonwoven fabric according to claim 1 or 2.
PCT/JP2023/030472 2022-08-31 2023-08-24 Activated carbon fiber non-woven fabric, activated carbon fiber non-woven fabric manufacturing method, element, organic solvent absorpbtion/desorption treatment device, organic solvent recovery system, organic solvent absorption/desorption treatment method, and organic solvent recovery method WO2024048410A1 (en)

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JP2020029376A (en) * 2018-08-21 2020-02-27 日本製紙株式会社 Activated carbon fiber material
WO2021200223A1 (en) * 2020-03-31 2021-10-07 東洋紡株式会社 Infusibilized polyphenylene ether fibers, infusibilized polyphenylene ether molded article, carbon fibers, activated carbon fibers, carbon fiber molded article, activated carbon fiber molded article, and method for manufacturing same
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JP2004033891A (en) * 2002-07-02 2004-02-05 Toyobo Co Ltd Carbon carrier for carrying metal catalyst
JP2004299928A (en) * 2003-03-28 2004-10-28 Kuraray Chem Corp Hardly ignitable activated carbon and its manufacturing method, and method for processing waste gas
JP2020029376A (en) * 2018-08-21 2020-02-27 日本製紙株式会社 Activated carbon fiber material
WO2021200223A1 (en) * 2020-03-31 2021-10-07 東洋紡株式会社 Infusibilized polyphenylene ether fibers, infusibilized polyphenylene ether molded article, carbon fibers, activated carbon fibers, carbon fiber molded article, activated carbon fiber molded article, and method for manufacturing same
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