WO2023032633A1 - 活性炭 - Google Patents

活性炭 Download PDF

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Publication number
WO2023032633A1
WO2023032633A1 PCT/JP2022/030637 JP2022030637W WO2023032633A1 WO 2023032633 A1 WO2023032633 A1 WO 2023032633A1 JP 2022030637 W JP2022030637 W JP 2022030637W WO 2023032633 A1 WO2023032633 A1 WO 2023032633A1
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Prior art keywords
activated carbon
pore
less
pore volume
chloroform
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PCT/JP2022/030637
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English (en)
French (fr)
Japanese (ja)
Inventor
一臣 菅原
智康 中野
弘和 清水
啓二 堺
拓哉 浅田
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AD'ALL Co Ltd
Osaka Gas Chemicals Co Ltd
Unitika Ltd
Original Assignee
AD'ALL Co Ltd
Osaka Gas Chemicals Co Ltd
Unitika Ltd
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Application filed by AD'ALL Co Ltd, Osaka Gas Chemicals Co Ltd, Unitika Ltd filed Critical AD'ALL Co Ltd
Priority to EP22864218.7A priority Critical patent/EP4400478A4/en
Priority to JP2023545408A priority patent/JPWO2023032633A1/ja
Priority to US18/683,802 priority patent/US20250121353A1/en
Publication of WO2023032633A1 publication Critical patent/WO2023032633A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28023—Fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • 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
    • C01B32/336—Preparation characterised by gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

Definitions

  • the present invention relates to activated carbon having high mechanical strength and excellent trihalomethane filtration ability.
  • chlorine is added to tap water for drinking purposes for the purpose of sterilization.
  • chlorine contained in tap water reacts with organic substances contained in tap water to produce organic halogen compounds.
  • organic substances contained in tap water For example, it is known that when humic substances, which are natural organic substances, react with chlorine in tap water, trihalomethanes such as chloroform, which are carcinogenic substances, are produced. Therefore, in recent years, activated carbon has been proposed that has an excellent ability to filter trihalomethanes contained in tap water.
  • Patent Document 1 as an activated carbon excellent in trihalomethane filtration ability, among the pore volumes calculated by the QSDFT method, the pore volume of pore diameters in the range of 1.0 nm or less is 0.3 cc / g or more. And, of the pore volume calculated by the QSDFT method, the pore volume of pore diameters in the range of 3.0 nm or more and 3.5 nm or less is 0.009 cc/g or more.
  • the activated carbon described in Patent Document 1 exhibits excellent trihalomethane filtration ability even in water flow treatment at a high superficial velocity (SV), and is highly useful.
  • the inventors of the present invention have studied to further improve the functionality of activated carbon, and have learned that the activated carbon described in Patent Document 1 has room for further improvement in terms of mechanical strength. .
  • the main object of the present invention is to provide an activated carbon having high mechanical strength and excellent trihalomethane filtration ability.
  • the inventors of the present invention thought that in order to further improve the mechanical strength of the activated carbon described in Patent Document 1, it was necessary to reduce the pore volume A with a pore diameter in the range of 1.0 nm or less. That is, the activated carbon described in Patent Document 1 has a pore volume A of 0.3 cc/g or more with a pore diameter in the range of 1.0 nm or less, which is a barrier to further improvement in mechanical strength. I thought it was. However, it is believed that trihalomethanes are likely to be adsorbed in pores with a pore diameter in the range of 1.0 nm or less, and simply reducing the pore volume A of the pore diameter in question leads to a decrease in the filtering ability of trihalomethanes. Therefore, it becomes impossible to achieve both high mechanical strength and excellent trihalomethane filtration ability.
  • the inventors of the present invention conducted further studies and found that by controlling the pore diameter, pore volume, and specific surface area of activated carbon, both high mechanical strength and excellent trihalomethane filtration ability can be achieved. I got Specifically, the present inventors found that (1) among the pore volumes calculated by the QSDFT method from the nitrogen desorption isotherm, the pore volume A of pore diameters in the range of 1.0 nm or less is 0.230 cc/ (2) of the pore volume calculated by the QSDFT method from the nitrogen desorption isotherm, the pore volume B of the pore diameter in the range of 1.5 nm to 2.5 nm is 0.8.
  • Activated carbon satisfying more than 12 cc/g and 0.19 cc/g or less and (3) having a specific surface area of 1000 m 2 /g or more and 1200 m 2 /g or less can have high mechanical strength and excellent trihalomethane filtration ability. Found it.
  • the present invention has been completed through further studies based on such findings.
  • the present invention provides inventions in the following aspects.
  • Section 1 Among the pore volumes calculated by the QSDFT method from the nitrogen desorption isotherm, the pore volume A of pore diameters in the range of 1.0 nm or less is 0.230 cc / g or more and 0.250 cc / g or less, Among the pore volumes calculated by the QSDFT method from the nitrogen desorption isotherm, the pore volume B with a pore diameter in the range of 1.5 nm or more and 2.5 nm or less is more than 0.120 cc / g and 0.190 cc / g or less can be, Activated carbon having a specific surface area of 1000 m 2 /g or more and 1200 m 2 /g or less.
  • Item 2. The activated carbon according to Item 1, which is fibrous activated carbon.
  • Item 3. Item 3.
  • the activated carbon according to item 1 or 2 which has a chloroform filtration capacity of 40 L/g or more in water flow treatment at a superficial velocity of 3000 h -1 shown below. ⁇ Method for measuring chloroform filtration ability in water flow treatment at superficial velocity of 3000 h -1 > 3.0 g of dried activated carbon is beaten and packed into a glass column (diameter: 25 mm) to prepare an activated carbon column (filled height of activated carbon: 41 mm).
  • Raw water for testing with a chloroform concentration of 60 ⁇ 12 ppb is prepared, the water temperature is controlled at 20° C. ⁇ 1° C., and the water is passed through the activated carbon column at a superficial velocity of 3000 h ⁇ 1 .
  • the chloroform concentration of the test raw water and filtered water was measured by the headspace method using a non-radioactive electron capture detector, and the water flow rate (L / g) when the chloroform removal rate reached 80%. is obtained as the chloroform filtration capacity.
  • the activated carbon according to Item 2 which has a tensile strength of 0.15 GPa or more as measured according to "7.3.2 Tensile strength" of JIS K 1477:2007 "Testing methods for fibrous activated carbon”.
  • Item 5 A method for producing activated carbon according to any one of Items 1 to 4, The method for producing activated carbon, comprising the step of activating an activated carbon precursor containing 0.1 to 1.0% by mass of yttrium at a temperature of 925 to 940° C. in an atmosphere having a CO 2 concentration of 90% by volume or more.
  • a water purification filter comprising the activated carbon according to any one of items 1 to 4.
  • Item 5. A method for filtering water using the activated carbon according to any one of Items 1 to 4.
  • the pore size, pore volume, and specific surface area of the activated carbon satisfy predetermined ranges, so that high mechanical strength and excellent trihalomethane filtration ability can be provided.
  • the activated carbon of the present invention can exhibit excellent trihalomethane filtration ability even in water treatment at high superficial velocity, and therefore can be suitably used for removing trihalomethane from tap water.
  • FIG. 4 is a graph showing the pore size distribution calculated by the QSDFT method from the nitrogen desorption isotherm of the activated carbon of Example 1.
  • FIG. 4 is a graph showing the pore size distribution calculated by the QSDFT method from the nitrogen desorption isotherm of the activated carbon of Example 2.
  • FIG. 4 is a graph showing the pore size distribution calculated by the QSDFT method from the nitrogen desorption isotherm of the activated carbon of Example 3.
  • FIG. 4 is a graph showing the pore size distribution calculated by the QSDFT method from the nitrogen desorption isotherm of activated carbon of Comparative Example 1.
  • FIG. 4 is a graph showing the pore size distribution calculated by the QSDFT method from the nitrogen desorption isotherm of activated carbon of Comparative Example 2.
  • FIG. 4 is a graph showing the pore size distribution calculated by the QSDFT method from the nitrogen desorption isotherm of activated carbon of Comparative Example 3.
  • FIG. 4 is a graph showing the pore size distribution calculated by the QSDFT method from the nitrogen
  • the activated carbon of the present invention has a pore volume A of 0.230 cc/g or more and 0.250 cc/g or less with a pore diameter in the range of 1.0 nm or less in the pore volume calculated by the QSDFT method from the nitrogen desorption isotherm. , and a pore volume B of more than 0.12 cc/g and 0.19 cc/g or less with a pore diameter in the range of 1.5 nm to 2.5 nm, and a specific surface area of 1000 m 2 /g to 1200 m 2 /g It is characterized by the following.
  • the activated carbon of the present invention will be described in detail below.
  • the pore diameter and pore volume of activated carbon are calculated by the QSDFT method (quenched solid density functional theory) from the nitrogen desorption isotherm (relative pressure 0.02 to 0.995) measured at a temperature of 77 K. value.
  • the QSDFT method is an analysis method that can calculate the pore size distribution from about 0.5 nm to about 40 nm, targeting the pore size analysis of geometrically and chemically irregular microporous/mesoporous carbon.
  • the QSDFT method clearly takes into account the effects of pore surface roughness and non-uniformity, and is therefore a technique that greatly improves the accuracy of pore size distribution analysis.
  • the measurement of the nitrogen desorption isotherm may be performed by using a gas adsorption amount measuring device such as "AUTOSORB-1-MP" manufactured by Quantachrome, and the pore size distribution analysis by the QSDFT method uses N as a calculation model. 2 at 77K on carbon [slit pore, QSDFT equilibrium model] may be applied.
  • a gas adsorption amount measuring device such as "AUTOSORB-1-MP” manufactured by Quantachrome
  • the activated carbon of the present invention has a pore volume A of 0.230 cc/g or more and 0.250 cc/g or less with a pore diameter in the range of 1.0 nm or less in the pore volume calculated by the QSDFT method from the nitrogen desorption isotherm. is.
  • the activated carbon can be provided with high mechanical strength.
  • the pore volume A it is possible to provide excellent trihalomethane filtration performance, particularly excellent trihalomethane filtration performance even at high superficial velocity.
  • the pore volume A is preferably 0.230 cc/g or more and 0.245 cc/g or less, more preferably 0.230 cc/g or more and 0.245 cc/g or less.
  • the pore volume B of pore diameters in the range of 1.5 nm or more and 2.5 nm or less exceeds 0.120 cc / g and 0 .190 cc/g or less.
  • the pore volume B By setting the pore volume B to more than 0.120 cc/g, it is possible to provide excellent trihalomethane filtration performance, particularly excellent trihalomethane filtration performance even at high superficial velocity. Further, by setting the pore volume B to 0.19 cc/g or less, the pore volume A described above can be easily satisfied in the range of 0.230 cc/g or more.
  • pores having a pore diameter in the range of 1.5 nm or more and 2.5 nm or less have the function of diffusing trihalomethane into the pores, and have a function of 3.0 nm or more and 3.5 nm or less. It is thought that trihalomethanes are more likely to be adsorbed than pores having a pore diameter in the range of . Therefore, it is considered that the activated carbon of the present invention can exhibit excellent trihalomethane adsorption performance even if the pore volume A of pores with a diameter of 1.0 nm or less, which is responsible for the trihalomethane adsorption performance, is reduced to 0.250 cc/g or less. be done.
  • the pore volume B is preferably 0.121 cc/g or more and 0.180 cc from the viewpoint of providing an excellent trihalomethane filtration ability, particularly an excellent trihalomethane filtration ability even at a high superficial velocity. /g or less, more preferably 0.145 cc/g or more and 0.175 cc/g or less, still more preferably 0.150 cc/g or more and 0.170 cc/g or less, particularly preferably 0.153 cc/g or more and 0.169 cc/g or less
  • these include:
  • the pore volumes A and B are in the range described above. Although it is not particularly limited as long as it satisfies the 0.077 cc/g or less. By satisfying such a range, it becomes easier to achieve both high mechanical strength and excellent trihalomethane filtration ability more preferably.
  • the pore volumes A and B are in the range described above. Although it is not particularly limited as long as it satisfies, for example, it is 0.140 cc/g or more and 0.150 cc/g or less, preferably 0.144 cc/g or more and 0.150 cc/g or less. By satisfying such a range, it becomes easier to achieve both high mechanical strength and excellent trihalomethane filtration ability more preferably.
  • the pore volumes A and B are in the range described above. Although it is not particularly limited as long as it satisfies, for example, it is 0.300 cc/g or more and 0.400 cc/g or less, preferably 0.300 cc/g or more and 0.350 cc/g or less. By satisfying such a range, it becomes easier to achieve both high mechanical strength and excellent trihalomethane filtration ability more preferably.
  • the pore volumes A and B are within the ranges described above. Although it is not particularly limited as long as it satisfies the 0.425 cc/g or less. By satisfying such a range, it becomes easier to achieve both high mechanical strength and excellent trihalomethane filtration ability more preferably.
  • the pore volumes A and B are within the ranges described above. Although it is not particularly limited as long as it satisfies the is mentioned.
  • the pore volumes A and B are in the range described above. Although it is not particularly limited as long as it satisfies, for example, it is 0.010 cc/g or less, preferably 0.005 cc/g or less. By satisfying such a range, the trihalomethane filtration ability can be further improved.
  • the total pore volume calculated by the QSDFT method from the nitrogen desorption isotherm is not particularly limited as long as the pore volumes A and B satisfy the above-described range.
  • the activated carbon of the present invention has a specific surface area of 1000 m 2 /g or more and 1200 m 2 /g or less.
  • the specific surface area By setting the specific surface area to 1,000 m 2 /g or more, it is possible to provide excellent trihalomethane filtration performance, particularly excellent trihalomethane filtration performance even at high superficial velocity. Further, by setting the specific surface area to 1200 m 2 /g or less, it is possible to easily satisfy the pore volume A described above in the range of 0.230 cc/g or more.
  • the specific surface area of the activated carbon of the present invention is preferably 1000 m 2 /g or more and 1180 m 2 /g or less, more preferably 1000 m 2 /g or more and 1180 m 2 /g or less, from the viewpoint of further improving the trihalomethane filtration performance, particularly the trihalomethane filtration performance under high superficial velocity. 1050 m 2 /g or more and 1180 m 2 /g or less, more preferably 1080 m 2 /g or more and 1160 m 2 /g or less.
  • the specific surface area of activated carbon is a value determined by the BET method (one-point method with a relative pressure of 0.1 as a measuring point) using nitrogen as a substance to be adsorbed.
  • the raw material from which the activated carbon of the present invention is derived is not particularly limited. plant-derived materials such as fruit shells and fruit seeds), mineral-based carbonaceous precursors (e.g., peat, lignite, lignite, bituminous coal, anthracite, coke, coal tar, and other mineral-derived materials), infusible or Examples thereof include carbonized organic materials and infusible resins such as phenolic resins. Specific examples of the organic material include polyacrylonitrile, pitch, polyvinyl alcohol, and cellulose. Among these, the activated carbon of the present invention is preferably derived from pitch, and more preferably derived from coal pitch.
  • the preferred method for producing activated carbon of the present invention includes a step of activating an activated carbon precursor containing an yttrium compound. It contains yttrium derived from Yttrium contained in one embodiment of the activated carbon of the present invention may be in the form of yttrium alone, in the form of an yttrium compound, or in a mixed form. In one embodiment of the activated carbon of the present invention, the yttrium content is, for example, 0.001 to 1.0% by mass, preferably 0.01 to 0.8% by mass, more preferably 0.4 to 0.8% by mass.
  • the yttrium content in the activated carbon is determined by measuring the yttrium element content with an energy dispersive X-ray fluorescence spectrometer. Also, when the activated carbon of the present invention contains yttrium, washing can reduce the yttrium content. Reducing the yttrium content by washing does not affect the mechanical strength of the activated carbon of the present invention and its ability to filter trihalomethanes.
  • the activated carbon does not substantially contain iron (elemental iron and/or iron compounds).
  • substantially contains no iron means that the content of iron element is below the detection limit when the activated carbon is ashed, the ash is dissolved in acid, and measured with an ICP emission spectrometer.
  • the form of the activated carbon of the present invention is not particularly limited, but examples thereof include fibrous, granular and powdery forms. Fibrous activated carbon is preferred from the viewpoints of workability when processed into a filter for use and trihalomethane adsorption rate when used in a water purifier.
  • the average fiber diameter of the fibrous activated carbon is obtained by observing a lateral image of a test piece of fibrous activated carbon with an optical microscope and photographing it with a microscope camera system attached to the microscope. The photographed image is imported into image analysis software, and the width at any position in the length direction of the test piece is measured. This is done for 50 fibrous activated carbon fibers, and the average value of the widths of the 50 fibers is taken as the average fiber diameter.
  • the activated carbon of the present invention is in the form of granules or powder
  • its particle diameter is, for example, an integrated volume percentage D50 measured by a laser diffraction/scattering method of 0.01 to 5 mm.
  • the activated carbon of the present invention has an excellent trihalomethane filtration ability, particularly an excellent trihalomethane filtration ability even at a high superficial velocity, because the pore volume A, the pore volume B, and the specific surface area satisfy the predetermined ranges. can be provided.
  • the chloroform filtration ability in water flow treatment at a superficial velocity of 3000 h ⁇ 1 shown below is 40 L/g or more, preferably 40 to 90 L/g, more preferably 40 to 60 L/g, more preferably 42 to 45 L/g.
  • Raw water for testing with a chloroform concentration of 60 ⁇ 12 ppb is prepared, the water temperature is controlled at 20° C. ⁇ 1° C., and the water is passed through the activated carbon column at a superficial velocity of 3000 h ⁇ 1 .
  • the chloroform concentration of the test raw water and filtered water was measured by the headspace method using a non-radioactive electron capture detector, and the water flow rate (L / g) when the chloroform removal rate reached 80%. is obtained as the chloroform filtration capacity.
  • the chloroform removal rate (%) is calculated according to the following formula.
  • the water flow rate at the time when the chloroform removal rate reaches 80% is the total amount of the filtered liquid that flows out from the activated carbon column and is collected until the chloroform removal rate decreases to 80%.
  • the details of the method for measuring the chloroform filtering ability are as described in the Examples section.
  • the activated carbon of the present invention can have high mechanical strength by satisfying the above-described pore volume A, pore volume B, and specific surface area within the predetermined ranges.
  • an example of the mechanical strength that can be provided when the activated carbon of the present invention is a fibrous activated carbon is a tensile strength of 0.15 GPa or more, preferably 0.15 to 0.40 GPa, more preferably 0.16 to 0.25 GPa. mentioned.
  • the tensile strength of fibrous activated carbon is a value measured according to "7.3.2 Tensile strength" of Japanese Industrial Standards JIS K 1477:2007 "Fibrous activated carbon test method". Specific measurement conditions are as described in Examples.
  • the use of the activated carbon of the present invention is not particularly limited, but it is preferably used for water purification.
  • the activated carbon of the present invention has an excellent ability to filter trihalomethanes, and is therefore suitable as a water purification filter for removing trihalomethanes from liquids containing trihalomethanes or liquids that may contain trihalomethanes. used.
  • the activated carbon of the present invention may be molded into a desired shape as necessary.
  • the activated carbon of the present invention when used as a water purification filter for a water purifier, it is preferable to have a cylindrical shape. good.
  • the activated carbon of the present invention when used as a water purification filter, the activated carbon of the present invention can be provided as it is or molded into a desired shape and filled in a housing to provide a cartridge.
  • the trihalomethane to be removed by the activated carbon of the present invention may be at least one of chloroform, bromodichloromethane, dibromochloromethane, and bromoform, preferably chloroform.
  • the liquid to be treated with the activated carbon of the present invention may be a liquid containing trihalomethane or a liquid that may contain trihalomethane.
  • a liquid containing trihalomethane for example, tap water, industrial water, preferably tap water. mentioned.
  • the activated carbon of the present invention since the activated carbon of the present invention has an excellent trihalomethane filtration ability even at high superficial velocity, it can be suitably used as a water purification filter for water flow treatment (filtration treatment) at high superficial velocity. In addition, it goes without saying that it can be used as a water purification filter for water flow treatment not only at high superficial velocity but also at low superficial velocity.
  • the superficial velocity applied to the activated carbon of the present invention during water flow treatment is, for example, 500 h -1 or more, preferably 1000 to 4000 h -1 .
  • the applied high superficial velocity is preferably 2000 to 4000 h -1 , more preferably 2000 to 3500 h -1 .
  • the method for producing activated carbon of the present invention is not particularly limited as long as the activated carbon satisfying the above-described pore volume A, pore volume B, and specific surface area satisfies the predetermined ranges.
  • a manufacturing method includes a step of activating an activated carbon precursor containing 0.1 to 1.0% by mass of yttrium at a temperature of 925 to 940° C. in an atmosphere having a CO 2 concentration of 90% by volume or more.
  • the production method will be described in detail by referring to it as "the production method of activated carbon of the present invention”.
  • an activated carbon precursor containing 0.1 to 1.0% by mass of yttrium is heated at 925 to 940° C. using an activation gas containing 90% by volume or more of CO 2 , which reacts more slowly than steam.
  • an activation gas containing 90% by volume or more of CO 2 which reacts more slowly than steam.
  • the main raw material of the activated carbon precursor is not particularly limited, but examples include infusibilized or carbonized organic materials, infusible resins such as phenolic resins, and the like.
  • examples of the organic material include polyacrylonitrile, pitch, polyvinyl alcohol, and cellulose.
  • pitch is preferred from the viewpoint of the theoretical carbonization yield during carbonization, and coal pitch is particularly preferred among pitches.
  • the yttrium to be contained in the activated carbon precursor may be yttrium alone, yttrium compounds, or mixtures thereof, preferably yttrium compounds.
  • the yttrium compound examples include inorganic yttrium compounds such as yttrium oxide, yttrium hydroxide, yttrium halide, and yttrium sulfate; yttrium organic acid salts such as yttrium acetate; and organic yttrium compounds. mentioned. Among these yttrium compounds, the dispersibility of the yttrium compound in the activated carbon precursor is increased, and the pore volume A, pore volume B, and specific surface area described above are satisfied within suitable ranges for the obtained activated carbon. Organic yttrium compounds are preferred from the standpoint of ease of use.
  • a suitable example of the organic yttrium compound is an yttrium complex having a ⁇ -diketone compound as a ligand. Examples of ⁇ -diketone type compounds include those having structures represented by the following formulas (1) to (3).
  • R 12 and R 13 are the same or different and are an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 11 carbon atoms or It represents an alkenyl group of 1 to 11, more preferably an alkyl group of 1 to 8 carbon atoms, and still more preferably a methyl group.
  • R 11 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 1 to 22 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 11 carbon atoms or an alkyl group having 1 to 11 carbon atoms.
  • 11 alkenyl groups more preferably hydrogen atoms.
  • R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 1 to 22 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 11 carbon atoms or an alkyl group having 1 to 11 carbon atoms.
  • 11 alkenyl groups more preferably hydrogen atoms.
  • R 22 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 1 to 22 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 11 carbon atoms or an alkyl group having 1 to 11 carbon atoms.
  • 11 alkenyl groups more preferably hydrogen atoms.
  • R 23 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 11 carbon atoms or an alkenyl group having 1 to 11 carbon atoms, and An alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is more preferred.
  • R 31 and R 33 are the same or different and are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 1 to 22 carbon atoms, preferably a hydrogen atom or 1 to 11 carbon atoms. or an alkenyl group having 1 to 11 carbon atoms, more preferably a hydrogen atom.
  • R 32 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 1 to 22 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 11 carbon atoms or an alkyl group having 1 to 11 carbon atoms. 11 alkenyl groups, more preferably hydrogen atoms.
  • yttrium complexes having a ⁇ -diketone type compound as a ligand yttrium complexes having a ⁇ -diketone type compound represented by the above formula (1) as a ligand are preferred, more preferably trisacetylacetonatoitrium [acetylacetone ( and a compound in which R 11 and R 13 are methyl groups and R 12 is a hydrogen atom in the formula (1); and a yttrium complex in which three molecules are coordinated.
  • the content of yttrium in the activated carbon precursor may be 0.1 to 1.0% by mass, preferably 0.15 to 1.0% by mass, more preferably 0.15 to 0.5% by mass, more preferably 0.20 to 0.25% by mass.
  • the yttrium content in the activated carbon precursor is the yttrium element equivalent amount measured by an energy dispersive X-ray fluorescence spectrometer.
  • the CO 2 concentration of the atmosphere for activation may be 90% by volume or higher, preferably 95% by volume or higher, more preferably 99% by volume or higher.
  • the reaction progresses slowly. Therefore, the higher the CO 2 concentration, the easier it is to adjust the pore size distribution, and the easier to obtain the activated carbon of the present invention.
  • Components other than CO2 in the activation atmosphere include N2 , O2 , H2 , H2O and CO.
  • the ambient temperature for activation may be 925 to 940°C, preferably 928 to 938°C, and more preferably 930 to 935°C.
  • the activation time may be adjusted according to the main raw material of the activated carbon precursor, the content of the yttrium compound, the CO 2 concentration in the activation gas, etc. so as to obtain a predetermined pore size distribution and specific surface area.
  • pitch having a softening point of 275° C. to 288° C. is used as the main raw material of the activated carbon precursor, and the content of the yttrium compound in the activated carbon precursor is 0.1 to 1.0 parts by mass. is 100% by volume
  • the activation may be performed at an ambient temperature of 925 to 940° C. and for an activation time of 30 to 50 minutes.
  • the activated carbon obtained after activation may, if necessary, be subjected to a cleaning treatment using an acid such as sulfuric acid.
  • an acid such as sulfuric acid.
  • Test method Yttrium content (% by mass) of activated carbon precursor (infusible pitch fiber) The pitch fiber was pulverized, and the yttrium content was determined as the yttrium element conversion ratio measured by an energy dispersive X-ray fluorescence spectrometer (NEX DE manufactured by Rigaku Corporation).
  • Iron content (% by mass) of activated carbon precursor (infusible pitch fiber) Pitch fibers were subjected to ashing treatment, the ash was dissolved in acid, and the ratio of iron element conversion measured by an ICP emission spectrometer (manufactured by Varian, model 715-ES) was determined as the iron content.
  • Yttrium content of activated carbon (% by mass)
  • the fibrous activated carbon was pulverized, and the ratio of yttrium element conversion measured by an energy dispersive X-ray fluorescence spectrometer (NEX DE manufactured by Rigaku Corporation) was determined as the yttrium content.
  • Iron content of activated carbon (% by mass) The fibrous activated carbon was subjected to ashing treatment, the ash was dissolved in acid, and the ratio of iron element conversion measured by an ICP emission spectrometer (manufactured by Varian, model 715-ES) was determined as the iron content.
  • Pore volume (cc/g) and specific surface area (m 2 /g) The pore physical properties were measured from the nitrogen adsorption isotherm (relative pressure 0.02 to 0.995) at 77K using Quantachrome "AUTOSORB-1-MP". The specific surface area was calculated from the measurement point at a relative pressure of 0.1 by the BET method.
  • the total pore volume and the pore volume in each pore size range described in Table 1 were obtained by applying N at 77K on carbon [slit pore, QSDFT equilibrium model] as a calculation model to the measured nitrogen desorption isotherm. Analysis was performed by calculating the pore size distribution.
  • the pore volume in each pore size range shown in Table 1 is the read value of the graph showing the pore size distribution shown in FIGS. 1 to 6 or the value calculated from the read value. More specifically, the pore volume with a pore diameter of 0.65 nm or less is the read value of Cumulative Pore Volume (cc/g) when the horizontal axis Pore Width of the pore diameter distribution diagram is 0.65 nm.
  • pore volume with a pore diameter of 0.8 nm or less, pore volume A with a pore diameter of 1.0 nm or less, pore volume with a pore diameter of 1.5 nm or less, pore volume with a pore diameter of 2.0 nm or less, fine A pore volume with a pore diameter of 2.5 nm or less, a pore volume with a pore diameter of 3.0 nm or less, and a pore volume with a pore diameter of 3.5 nm or less were obtained.
  • the pore volume B with a pore diameter in the range of 1.5 nm or more and 2.5 nm or less was calculated by subtracting the pore volume with a pore diameter of 1.5 nm or less from the pore volume with a pore diameter of 2.5 nm or less.
  • the total pore volume the total pore volume obtained by the QSDFT method was used.
  • the pore volume with a pore diameter of 2.0 nm or more was calculated by subtracting the pore volume with a pore diameter of 2.0 nm or less from the total pore volume obtained by the QSDFT method.
  • the pore volume with a pore diameter of 2.5 nm or more was calculated by subtracting the pore volume with a pore diameter of 2.5 nm or less from the total pore volume obtained by the QSDFT method.
  • the pore volume with a pore diameter of 3.5 nm or more was calculated by subtracting the pore volume with a pore diameter of 3.5 nm or less from the total pore volume obtained by the QSDFT method.
  • the pore volume with a pore diameter in the range of 1.0 nm or more and 1.5 nm or less was calculated by subtracting the pore volume A with a pore diameter of 1.0 nm or less from the pore volume with a pore diameter of 1.5 nm or less.
  • the pore volume with a pore diameter in the range of 1.0 nm or more and 2.0 nm or less was calculated by subtracting the pore volume A with a pore diameter of 1.0 nm or less from the pore volume with a pore diameter of 2.0 nm or less.
  • the pore volume with a pore diameter in the range of 0.65 nm or more and 0.8 nm or less was calculated by subtracting the pore volume with a pore diameter of 0.65 nm or less from the pore volume with a pore diameter of 0.8 nm or less.
  • the pore volume with a pore diameter in the range of 0.65 nm or more and 1.0 nm or less was calculated by subtracting the pore volume with a pore diameter of 0.65 nm or less from the pore volume A with a pore diameter of 1.0 nm or less.
  • the pore volume with a pore diameter in the range of 0.8 nm or more and 1.5 nm or less was calculated by subtracting the pore volume with a pore diameter of 0.8 nm or less from the pore volume with a pore diameter of 1.5 nm or less.
  • the pore volume with a pore diameter in the range of 2.0 nm or more and 3.0 nm or less was calculated by subtracting the pore volume with a pore diameter of 2.0 nm or less from the pore volume with a pore diameter of 3.0 nm or less.
  • Fiber diameter of fibrous activated carbon ( ⁇ m) An image of a test piece of fibrous activated carbon viewed from the side was observed with an optical microscope (ECLIPSE E600 manufactured by Nikon Corporation) at a magnification of 40 times. ) (512 ⁇ 384). The photographed image was imported into image analysis software (Image-Pro Plus), and the width of the test piece was measured at an arbitrary position in the longitudinal direction. This was performed on 50 fibrous activated carbon fibers, and the average value of the widths of the 50 fibers was taken as the average fiber diameter.
  • Chloroform filtration capacity (L/g) After drying the fibrous activated carbon in a dryer at 105°C for 2 hours or more, 3.0 g was sampled, beaten with a mixer, packed in a glass column (25 mm in diameter), and placed in an activated carbon column (filled height of activated carbon: 41 mm). made. Prepare test raw water with a chloroform concentration of 60 ⁇ 12 ppb based on the method specified in "6.4.4.1 Individual test" of JIS S 3201: 2019 "Household water purifier test method", water temperature 20 C. ⁇ 1.degree. C., and water was passed through the activated carbon column at a superficial velocity of 3000 h.sup. -1 .
  • the chloroform concentrations in the test raw water and filtered water were measured by the headspace method using a non-radioactive electron capture detector (GC7000EN, manufactured by J Science Lab Co., Ltd.).
  • the raw water for testing was continuously passed until the chloroform removal rate of the filtered water fell below 80%, and the water flow rate (L / g) at the time when the chloroform removal rate reached 80% was defined as the chloroform filtration capacity of the activated carbon. . If the water flow rate is 40 L/g or more at the time when the chloroform removal rate reaches 80%, it can be evaluated as having excellent chloroform filtering ability.
  • the chloroform removal rate (%) was calculated according to the following formula. Further, the water flow amount at the time when the chloroform removal rate reaches 80% is the total amount of the filtered liquid which flows out from the activated carbon column and is collected by the time when the chloroform removal rate decreases to 80%.
  • Tensile strength of fibrous activated carbon was measured according to "7.3.2 Tensile strength" of JIS K 1477:2007 “Fibrous activated carbon test method", using a tensile tester manufactured by Shimadzu Corporation (trade name SIMADZU EZ-SX) as a measuring instrument. was measured using Specifically, first, a test piece was produced by fixing both ends of one fibrous activated carbon to a test mount. A tensile test of the fibrous activated carbon was performed by attaching the test piece to a tensile tester and cutting the test mount of the test piece.
  • the length of the test piece was set to 10.0 ⁇ 0.2 mm, and the tensile speed was set to 1 mm/min.
  • the tensile strength was calculated by When the fibrous activated carbon has a tensile strength of 0.15 GPa or more, it can be evaluated as having high mechanical strength.
  • Example 1 As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280° C. and 1.0 part by mass of trisacetylacetonatoitrium (CAS number: 15554-47-9) is supplied to the melt extruder. Then, they were melt-blended at a melting temperature of 325° C. and spun to obtain pitch fibers. The obtained pitch fibers were heated in air from room temperature to 360° C. at a rate of 1 to 30° C./min for 70 minutes to obtain an infusible pitch fiber as an activated carbon precursor. In the activated carbon precursor, the yttrium content was 0.228% by mass and the iron content was 0% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into an activation furnace and heat-treating it at an atmospheric temperature of 935° C. for 40 minutes to obtain a fibrous activated carbon.
  • Table 1 shows the results of measuring the metal content, pore volume, specific surface area, fiber diameter of fibrous activated carbon, chloroform filtering capacity and tensile strength of the obtained activated carbon.
  • the obtained activated carbon has a pore volume A of 0.238 cc/g for pore diameters in the range of 1.0 nm or less, and a pore volume B of 0.169 cc/g for pore diameters in the range of 1.5 nm to 2.5 nm.
  • the specific surface area was 1151 m 2 /g
  • the yttrium content was 0.57% by mass
  • the iron content was 0% by mass
  • the average fiber diameter was 14.0 ⁇ m.
  • the obtained activated carbon was washed with sulfuric acid.
  • the yttrium content of the activated carbon after washing was 0.038% by mass. Moreover, the pore volume and specific surface area of the activated carbon after washing, the fiber diameter of the fibrous activated carbon, the chloroform filtering capacity and the tensile strength did not change from those before washing.
  • Example 2 As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280° C. and 1.0 part by mass of trisacetylacetonatoitrium (CAS number: 15554-47-9) is supplied to the melt extruder. Then, they were melt-blended at a melting temperature of 325° C. and spun to obtain pitch fibers. The obtained pitch fibers were heated in air from room temperature to 360° C. at a rate of 1 to 30° C./min for 70 minutes to obtain an infusible pitch fiber as an activated carbon precursor. The yttrium content in the activated carbon precursor was 0.228% by mass. The iron content was 0% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into an activation furnace and heat-treating it at an atmospheric temperature of 930° C. for 40 minutes to obtain a fibrous activated carbon.
  • Table 1 shows the results of measuring the metal content, pore volume, specific surface area, fiber diameter of fibrous activated carbon, chloroform filtering capacity and tensile strength of the obtained activated carbon.
  • the obtained activated carbon has a pore volume A of 0.240 cc/g for pore diameters in the range of 1.0 nm or less, and a pore volume B of 0.153 cc/g for pore diameters in the range of 1.5 nm to 2.5 nm.
  • specific surface area 1097 m 2 /g
  • yttrium content 0.53% by mass
  • iron content of 0% by mass and average fiber diameter of 14.0 ⁇ m.
  • the obtained activated carbon was washed with sulfuric acid.
  • the yttrium content of the activated carbon after washing was 0.038% by mass. Moreover, the pore volume and specific surface area of the activated carbon after washing, the fiber diameter of the fibrous activated carbon, the chloroform filtering capacity and the tensile strength did not change from those before washing.
  • Example 3 As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280° C. and 1.0 part by mass of trisacetylacetonatoitrium (CAS number: 15554-47-9) is supplied to the melt extruder. Then, they were melt-blended at a melting temperature of 325° C. and spun to obtain pitch fibers. The obtained pitch fibers were heated in air from room temperature to 360° C. at a rate of 1 to 30° C./min for 70 minutes to obtain an infusible pitch fiber as an activated carbon precursor. The yttrium content in the activated carbon precursor was 0.232% by mass. The iron content was 0% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into an activation furnace and heat-treating it at an atmospheric temperature of 930° C. for 40 minutes to obtain a fibrous activated carbon.
  • Table 1 shows the results of measuring the metal content, pore volume, specific surface area, fiber diameter of fibrous activated carbon, chloroform filtering capacity and tensile strength of the obtained activated carbon.
  • the obtained activated carbon has a pore volume A of 0.239 cc/g for pore diameters in the range of 1.0 nm or less, and a pore volume B of 0.122 cc/g for pore diameters in the range of 1.5 nm to 2.5 nm.
  • g a specific surface area of 1005 m 2 /g, an yttrium content of 0.44% by mass, an iron content of 0% by mass, and an average fiber diameter of 14.6 ⁇ m.
  • the obtained activated carbon was washed with sulfuric acid.
  • the yttrium content of the activated carbon after washing was 0.038% by mass. Moreover, the pore volume and specific surface area of the activated carbon after washing, the fiber diameter of the fibrous activated carbon, the chloroform filtering capacity and the tensile strength did not change from those before washing.
  • Comparative example 1 As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280° C. and 1.3 parts by mass of trisacetylacetonatoitrium (CAS number: 15554-47-9) is supplied to the melt extruder. Then, they were melt-blended at a melting temperature of 325° C. and spun to obtain pitch fibers. The obtained pitch fibers were heated in air from room temperature to 370° C. at a rate of 1 to 30° C./min for 60 minutes to perform an infusibilization treatment, thereby obtaining an activated carbon precursor as infusible pitch fibers. The yttrium content in the activated carbon precursor was 0.285 mass %. The iron content was 0% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into an activation furnace and heat-treating it at an ambient temperature of 896° C. for 32 minutes to obtain a fibrous activated carbon. .
  • Table 1 shows the results of measuring the metal content, pore volume, specific surface area, fiber diameter of fibrous activated carbon, chloroform filtering capacity and tensile strength of the obtained activated carbon.
  • the obtained activated carbon has a pore volume A of 0.212 cc/g for pore diameters in the range of 1.0 nm or less, and a pore volume B of 0.124 cc/g for pore diameters in the range of 1.5 nm to 2.5 nm.
  • g a specific surface area of 993 m 2 /g, a yttrium content of 0.59% by mass, an iron content of 0% by mass, and an average fiber diameter of 17.4 ⁇ m.
  • the obtained activated carbon was washed with sulfuric acid.
  • the yttrium content of the activated carbon after washing was 0.038% by mass. Moreover, the pore volume and specific surface area of the activated carbon after washing, the fiber diameter of the fibrous activated carbon, the chloroform filtering capacity and the tensile strength did not change from those before washing.
  • Comparative example 2 As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280° C. and 1.0 part by mass of trisacetylacetonatoitrium (CAS number: 15554-47-9) is supplied to the melt extruder. Then, they were melt-blended at a melting temperature of 325° C. and spun to obtain pitch fibers. The obtained pitch fibers were heated in air from room temperature to 360° C. at a rate of 1 to 30° C./min for 70 minutes to obtain an infusible pitch fiber as an activated carbon precursor. The yttrium content in the activated carbon precursor was 0.234% by mass. The iron content was 0% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into an activation furnace and heat-treating it at an atmospheric temperature of 915° C. for 40 minutes to obtain a fibrous activated carbon.
  • Table 1 shows the results of measuring the metal content, pore volume, specific surface area, fiber diameter of fibrous activated carbon, chloroform filtering capacity and tensile strength of the obtained activated carbon.
  • the obtained activated carbon has a pore volume A of 0.239 cc/g for pore diameters in the range of 1.0 nm or less, and a pore volume B of 0.112 cc/g for pore diameters in the range of 1.5 nm to 2.5 nm.
  • the specific surface area was 960 m 2 /g
  • the yttrium content was 0.45% by mass
  • the iron content was 0% by mass
  • the average fiber diameter was 14.0 ⁇ m.
  • the obtained activated carbon was washed with sulfuric acid.
  • the yttrium content of the activated carbon after washing was 0.038% by mass. Moreover, the pore volume and specific surface area of the activated carbon after washing, the fiber diameter of the fibrous activated carbon, the chloroform filtering capacity and the tensile strength did not change from those before washing.
  • Comparative example 3 As an organic material, a mixture of 100 parts by mass of granular coal pitch having a softening point of 280° C. and 0.9 parts by mass of tris(2,4-pentanedionato)iron (III) (metal type Fe) was melted. The mixture was supplied to an extruder, melt-mixed at a melting temperature of 320° C., and spun to obtain pitch fibers. The obtained pitch fibers were heated in air from normal temperature to 354° C. at a rate of 1 to 30° C./min for 54 minutes to perform an infusibilization treatment, thereby obtaining an activated carbon precursor as infusible pitch fibers. The content of iron (Fe) in the activated carbon precursor was 0.110% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into an activation furnace and heat-treating it at an ambient temperature of 950° C. for 25 minutes to obtain a fibrous activated carbon.
  • Table 1 shows the results of measuring the metal content, pore volume, specific surface area, fiber diameter of fibrous activated carbon, chloroform filtering capacity and tensile strength of the obtained activated carbon.
  • the obtained activated carbon has a pore volume A of 0.350 cc/g with pore diameters in the range of 1.0 nm or less, and a pore volume B of 0.002 cc/g with pore diameters in the range of 1.5 nm or more and 2.5 nm or less.
  • g a specific surface area of 988 m 2 /g, a yttrium content of 0% by mass, an iron content of 0.18% by mass, and an average fiber diameter of 13.9 ⁇ m.
  • the obtained activated carbon was washed with sulfuric acid.
  • the iron content of the activated carbon after washing was 0.038% by mass.
  • the pore volume and specific surface area of the activated carbon after washing, the fiber diameter of the fibrous activated carbon, the chloroform filtering capacity and the tensile strength did not change from those before washing.
  • Table 1 shows the physical properties of each fibrous activated carbon obtained.
  • 1 to 6 show pore size distribution maps calculated by the QSDFT method for each activated carbon.
  • the activated carbons of Examples 1 to 3 have a tensile strength of 0.15 GPa or more, have high mechanical strength, and further have a chloroform filtration capacity at a superficial velocity of 3000 h (80% chloroform removal rate The water flow rate at the time when it became low) was 40 L/g or more, and the chloroform filtration capacity under high superficial velocity was excellent.
  • the pore volume with a pore diameter in the range of 1.0 nm or less among the pore volumes calculated by the SDFT method A is 0.23 cc/g or more and 0.25 cc/g or less; .12 cc/g to 0.19 cc/g and (3) a specific surface area of 1000 m 2 /g to 1200 m 2 /g, so that both high mechanical strength and excellent chloroform filtration ability can be achieved. Do you get it.
  • the activated carbon of Comparative Example 1 has a pore volume A of pore diameters in the range of 1.0 nm or less of less than 0.23 cc/g and a specific surface area of less than 1000 m 2 /g. , the filtration capacity of chloroform under high superficial velocity was inferior.
  • the activated carbon of Comparative Example 2 has a pore volume B of less than 0.12 cc/g with a pore diameter in the range of 1.5 nm or more and 2.5 nm or less, and a specific surface area of less than 1000 m 2 /g. Therefore, the filtration capacity of chloroform under high superficial velocity was inferior.
  • the activated carbon of Comparative Example 3 was inferior in mechanical strength due to the pore volume A of pore diameters in the range of 1.0 nm or less exceeding 0.25 cc/g.

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PCT/JP2022/030637 2021-09-06 2022-08-10 活性炭 Ceased WO2023032633A1 (ja)

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EP22864218.7A EP4400478A4 (en) 2021-09-06 2022-08-10 ACTIVATED CARBON
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7580864B1 (ja) * 2023-01-25 2024-11-12 ユニチカ株式会社 フィルター

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105217625A (zh) * 2015-09-16 2016-01-06 中国矿业大学(北京) 以弱粘结性煤为主料配煤制备的压块活性炭及制法和应用
WO2017213057A1 (ja) * 2016-06-06 2017-12-14 住友電気工業株式会社 電気二重層キャパシタ電極用の多孔質炭素材料、その製造方法および電気二重層キャパシタ電極
WO2018116859A1 (ja) * 2016-12-19 2018-06-28 株式会社アドール 活性炭及びその製造方法
WO2019244903A1 (ja) 2018-06-19 2019-12-26 株式会社アドール 活性炭

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7223985B2 (ja) * 2018-03-22 2023-02-17 株式会社アドール 活性炭及びその製造方法
JP6719709B2 (ja) * 2018-06-19 2020-07-08 株式会社アドール 活性炭

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105217625A (zh) * 2015-09-16 2016-01-06 中国矿业大学(北京) 以弱粘结性煤为主料配煤制备的压块活性炭及制法和应用
WO2017213057A1 (ja) * 2016-06-06 2017-12-14 住友電気工業株式会社 電気二重層キャパシタ電極用の多孔質炭素材料、その製造方法および電気二重層キャパシタ電極
WO2018116859A1 (ja) * 2016-12-19 2018-06-28 株式会社アドール 活性炭及びその製造方法
WO2019244903A1 (ja) 2018-06-19 2019-12-26 株式会社アドール 活性炭

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
no. 15554-47-9
See also references of EP4400478A4
VELASCO LETICIA F.; GUILLET-NICOLAS RéMY; DOBOS GáBOR; THOMMES MATTHIAS; LODEWYCKX PETER: "Towards a better understanding of water adsorption hysteresis in activated carbons by scanning isotherms", CARBON, ELSEVIER OXFORD, GB, vol. 96, 20 October 2015 (2015-10-20), GB , pages 753 - 758, XP029314433, ISSN: 0008-6223, DOI: 10.1016/j.carbon.2015.10.017 *
YOSHIKAWA YASUNORI; TESHIMA KATSUYA; FUTAMURA RYUSUKE; TANAKA HIDEKI; IIYAMA TAKU; KANEKO KATSUMI: "Structural adsorption mechanism of chloroform in narrow micropores of pitch-based activated carbon fibres", CARBON, ELSEVIER OXFORD, GB, vol. 171, 18 August 2020 (2020-08-18), GB , pages 681 - 688, XP086397843, ISSN: 0008-6223, DOI: 10.1016/j.carbon.2020.08.020 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7580864B1 (ja) * 2023-01-25 2024-11-12 ユニチカ株式会社 フィルター

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