WO2019244904A1 - 活性炭 - Google Patents

活性炭 Download PDF

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Publication number
WO2019244904A1
WO2019244904A1 PCT/JP2019/024170 JP2019024170W WO2019244904A1 WO 2019244904 A1 WO2019244904 A1 WO 2019244904A1 JP 2019024170 W JP2019024170 W JP 2019024170W WO 2019244904 A1 WO2019244904 A1 WO 2019244904A1
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Prior art keywords
pore
pore volume
activated carbon
less
calculated
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PCT/JP2019/024170
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English (en)
French (fr)
Japanese (ja)
Inventor
中野　智康
弘和 清水
啓二 堺
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株式会社アドール
ユニチカ株式会社
大阪ガスケミカル株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=68984068&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2019244904(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 株式会社アドール, ユニチカ株式会社, 大阪ガスケミカル株式会社 filed Critical 株式会社アドール
Priority to CN201980033693.5A priority Critical patent/CN112135794B/zh
Priority to KR1020207033202A priority patent/KR102545878B1/ko
Priority to JP2019563309A priority patent/JP6683969B1/ja
Publication of WO2019244904A1 publication Critical patent/WO2019244904A1/ja

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    • 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
    • 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
    • C01B32/336—Preparation characterised by gaseous activating agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the present invention relates to activated carbon and a method for producing the same, and more particularly to activated carbon and a method for producing the same, which are suitable for adsorbing dichloromethane in a gas phase.
  • an adsorption removal technique for adsorbing components present in a gas phase or a liquid phase with activated carbon and removing these components Conventionally, the adsorption removal technique using activated carbon has also been used for solvent recovery from a gas containing an organic solvent.
  • Activated carbon fibers having particularly excellent adsorption performance for organic compounds such as dichloromethane have a BET specific surface area of 700 to 1500 m 2 / g, a total pore volume of 0.3 to 0.7 cc / g, and a pore diameter of 1 nm.
  • Activated carbon fibers having a micropore pore volume (micropore) of 95% or more of the total micropore pore volume and a water adsorption rate of 15% or less at a temperature of 25 ° C. and a relative humidity of 52% are known. (For example, see Patent Document 1).
  • the BET specific surface area is less than 700 m 2 / g, the adsorption area is too small, and organic compounds such as dichloromethane having a boiling point in the range of ⁇ 30 to 70 ° C. are not sufficiently adsorbed. It is described that there is a problem that, when it exceeds 1500 m 2 / g, the pores become large, and there is a problem that an organic compound such as dichloromethane having a boiling point in the range of ⁇ 30 to 70 ° C. is not sufficiently adsorbed. I have.
  • the micropore volume having a pore diameter of 1 nm or less is less than 95% of the total micropore volume, the pores become too large and the boiling point is in the range of ⁇ 30 to 70 ° C.
  • an organic compound such as dichloromethane is not sufficiently adsorbed.
  • the document states that when the water adsorption rate at a temperature of 25 ° C. and a relative humidity of 52% exceeds 15%, water molecules are first adsorbed around the pores. It is described that the amount of adsorption is not adsorbed and is reduced accordingly.
  • the activated carbon disclosed in Patent Document 1 has a problem that the equilibrium adsorption amount of dichloromethane is insufficient.
  • An object of the present invention is to solve the above problems and to provide an activated carbon having an excellent equilibrium adsorption amount of dichloromethane.
  • the present inventors have studied the realization of a pore structure suitable for adsorption of a low-boiling organic compound such as dichloromethane. More specifically, it maintains or increases the volume of micropores having a pore diameter of 1 nm or less, which is considered to be suitable for the adsorption of low-boiling organic compounds such as dichloromethane, and further increases the fineness of the pores so as to be less affected by coexisting moisture. It was considered effective to provide an appropriate amount of holes.
  • a specific amount of an yttrium compound and / or a vanadium compound is contained as an activated carbon precursor, and the activation gas is activated as carbon dioxide, and for the first time, the activation gas is reduced to 1 nm or less. While maintaining the volume of the pores, the present inventors succeeded in providing an appropriate amount of another pore having a relatively large pore diameter exceeding 1 nm.
  • a pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less and a fine pore volume B in a range of 0.65 nm or more and 1.0 nm or less are used.
  • the pore volume E (cc / g) of the pore diameter is set to a specific range, and the pore volume calculated by the QSDFT method is 1.5 nm with respect to the pore volume C having a pore diameter of 2.0 nm or less. It has been found that the activated carbon obtained by controlling the ratio (B / C) of the pore volume B having the pore diameter in the following range to a specific range is excellent in the equilibrium adsorption amount of dichloromethane.
  • the present invention has been completed by further study based on these findings.
  • the present invention provides the following aspects of the invention.
  • Item 1 Among the pore volumes calculated by the QSDFT method, the pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less is 0.4 cc / g or more, Among the pore volumes calculated by the QSDFT method, the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.2 cc / g or more, and In the pore volume calculated by the QSDFT method, the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in a range of 2.0 nm or less is 0.880 to 0.985.
  • Activated carbon Item 2.
  • the ratio of the pore volume A (cc / g) having a pore diameter of 1.0 nm or less to the pore volume C (cc / g) with respect to the pore volume calculated by the QSDFT method pore volume A Item 2.
  • Item 3. Item 3.
  • the activated carbon according to item 1 or 2 wherein the ratio of the pore volume B to the pore volume C (pore volume B / pore volume C) is 0.90 to 0.99.
  • Item 4. The activated carbon according to any one of items 1 to 3, wherein the activated carbon is fibrous activated carbon.
  • Item 5. Item 5.
  • Item 6. Item 6.
  • Item 7. Item 7.
  • the pore volume B (cc / g) having a pore diameter in the range of 1.5 nm or less is 0.4 cc / g or more.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.2 cc / g or more, and the pore volume is calculated by the QSDFT method. Since the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less is 0.880 to 0.985, the equilibrium adsorption amount of dichloromethane Excellent.
  • 3 is a graph showing the pore size distribution of the activated carbon of Example 1 calculated by the QSDFT method.
  • 4 is a graph showing the pore size distribution of the activated carbon of Example 2 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Example 3 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Example 4 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Example 5 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Example 6 calculated by the QSDFT method.
  • 11 is a graph showing the pore size distribution of the activated carbon of Example 7 calculated by the QSDFT method.
  • 15 is a graph showing the pore size distribution of the activated carbon of Example 8 calculated by the QSDFT method.
  • 14 is a graph showing the pore size distribution of the activated carbon of Example 9 calculated by the QSDFT method.
  • 14 is a graph showing the pore size distribution of the activated carbon of Example 10 calculated by the QSDFT method.
  • 19 is a graph showing the pore size distribution of the activated carbon of Example 11 calculated by the QSDFT method.
  • 19 is a graph showing the pore size distribution of the activated carbon of Example 12 calculated by the QSDFT method.
  • 19 is a graph showing the pore size distribution of the activated carbon of Example 13 calculated by the QSDFT method.
  • 19 is a graph showing the pore size distribution of the activated carbon of Example 14 calculated by the QSDFT method.
  • 19 is a graph showing the pore size distribution of the activated carbon of Example 15 calculated by the QSDFT method.
  • 19 is a graph showing the pore size distribution of the activated carbon of Example 16 calculated by the QSDFT method.
  • 18 is a graph showing the pore size distribution of the activated carbon of Example 17 calculated by the QSDFT method.
  • 19 is a graph showing the pore size distribution of the activated carbon of Example 18 calculated by the QSDFT method.
  • 5 is a graph showing the pore size distribution of the activated carbon of Comparative Example 1 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Comparative Example 2 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Comparative Example 3 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Comparative Example 4 calculated by the QSDFT method.
  • 11 is a graph showing the pore size distribution of the activated carbon of Comparative Example 5 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Comparative Example 6 calculated by the QSDFT method.
  • 9 is a graph showing the pore size distribution of the activated carbon of Comparative Example 7 calculated by the QSDFT method.
  • the activated carbon of the present invention has a pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less of 0.4 cc / g or more among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) of the pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.2 cc / g or more and the pore volume calculated by the QSDFT method is
  • the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less is 0.880 to 0.985.
  • the pore volume refers to a pore volume calculated by a QSDFT method (quenched solid density functional theory).
  • the QSDFT method is an analysis method capable of calculating the pore size distribution from about 0.5 nm to about 40 nm for the analysis of the pore size of microporous and mesoporous carbon that is irregular geometrically and chemically.
  • the QSDFT method is a method in which the accuracy of the pore diameter distribution analysis has been greatly improved because the influence of the roughness and unevenness of the pore surface is clearly considered.
  • measurement of a nitrogen adsorption isotherm is performed using “AUTOSORB-1-MP” manufactured by Quantachrome, and pore size distribution analysis is performed by a QSDFT method.
  • a specific pore size range is calculated by calculating a pore size distribution by applying N 2 at 77 K on carbon [slit pore, QSDFT equilibrium model] as a calculation model.
  • the pore volume can be calculated.
  • the activated carbon of the present invention has a pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less of 0.4 cc / g or more among pore volumes calculated by the QSDFT method, and the equilibrium of dichloromethane.
  • the pore volume B is preferably equal to or greater than 0.525 cc / g, and more preferably equal to or greater than 0.535 cc / g.
  • the upper limit of the pore volume B is not particularly limited, but is, for example, 1.0 cc / g or less, and preferably 0.7 cc / g or less.
  • the activated carbon of the present invention has a pore volume having a pore diameter of 0.65 nm or less in the pore volume calculated by the QSDFT method, which is 0.10 cc / g. Or more and 0.40 cc / g or less, preferably 0.10 cc / g or more and 0.28 cc / g or less, more preferably 0.15 cc / g or more and 0.25 cc / g or less, and still more preferably 0.17 cc / g.
  • cc / g or less particularly preferably 0.17 cc / g or more and 0.195 cc / g or less.
  • the pore volume of the pore diameter in the range of 0.65 nm or less is 0.10 cc / g or more and 0.40 cc / g or less (excluding the range of 0.15 cc / g or more and 0.166 or less), 0.10 cc / g or more and 0.28 cc / g or less (excluding the range of 0.15 cc / g or more and 0.166 or less), 0.170 cc / g or more and 0.25 cc / g or 0.170 cc / g. g or more and 0.195 cc / g or less.
  • the activated carbon of the present invention has a pore volume having a pore diameter of 0.8 nm or less among pore volumes calculated by the QSDFT method, which is 0.20 cc / g. 0.50 cc / g or less, preferably 0.20 cc / g or more and 0.40 cc / g or less, more preferably 0.21 cc / g or more and 0.40 cc / g or less.
  • the activated carbon of the present invention has a pore volume A having a pore diameter of 1.0 nm or less in a pore volume calculated by the QSDFT method, of 0.35 cc /. g and 0.55 cc / g or less, preferably 0.35 cc / g or more and 0.48 cc / g or less, more preferably 0.40 cc / g or more and 0.48 cc / g or less.
  • the activated carbon of the present invention has a pore volume C having a pore diameter of 2.0 nm or less among pore volumes calculated by the QSDFT method, of 0.25 cc /. g to 0.85 cc / g, preferably 0.45 cc / g to 0.80 cc / g, more preferably 0.45 cc / g to 0.80 cc / g, and particularly preferably 0.555 cc / g. g and 0.77 cc / g or less.
  • the activated carbon of the present invention has a pore volume having a pore diameter of 2.0 nm or more among pore volumes calculated by the QSDFT method, which is 0.10 cc / g.
  • the following may be mentioned, preferably 0.05 cc / g or less, more preferably 0.001 cc / g or more and 0.05 cc / g or less.
  • the activated carbon of the present invention has a pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less in the pore volume calculated by the QSDFT method, which is 0.2 cc / g or more.
  • the pore volume E is preferably 0.21 cc / g or more, and more preferably 0.23 cc / g or more.
  • the upper limit of the pore volume E is not particularly limited, but is, for example, 0.4 cc / g or less, and preferably 0.33 cc / g or less.
  • the activated carbon of the present invention has a pore volume of 1.0 nm or more and 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0%. 0.01 cc / g or more and 0.3 cc / g or less, preferably 0.04 cc / g or more and 0.3 cc / g or less, more preferably 0.04 cc / g or more and 0.3 cc / g or less, and even more preferably 0 or more. 0.08 cc / g or more and 0.25 cc / g or less, particularly preferably 0.125 cc / g or more and 0.25 cc / g or less.
  • the activated carbon of the present invention has a pore volume having a pore diameter in a range of 1.0 nm or more and 2.0 nm or less in a pore volume calculated by the QSDFT method, which is 0%. 0.01 cc / g or more and 0.35 cc / g or less, preferably 0.05 cc / g or more and 0.35 cc / g or less, more preferably 0.10 cc / g or more and 0.35 cc / g or less, and particularly preferably 0 or less. 0.21 cc / g or more and 0.35 cc / g or less.
  • the activated carbon of the present invention has a pore volume having a pore diameter in the range of 0.65 nm or more and 0.8 nm or less in the pore volume calculated by the QSDFT method, which is 0%. It is preferably from 0.05 cc / g to 0.18 cc / g, more preferably from 0.1 cc / g to 0.15 cc / g.
  • the activated carbon of the present invention has a pore volume of 0.8 nm or more and 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0%. 0.08 cc / g or more and 0.60 cc / g or less, preferably 0.12 cc / g or more and 0.50 cc / g or less, more preferably 0.18 cc / g or more and 0.50 cc / g or less, particularly preferably 0 or more. .20 cc / g or more and 0.50 cc / g or less.
  • the activated carbon of the present invention has a pore volume D having a pore diameter in a range of 1.5 nm or more and 2.0 nm or less among pore volumes calculated by the QSDFT method, It is preferably from 0.01 cc / g to 0.1 cc / g, and more preferably from 0.013 cc / g to 0.065 cc / g.
  • the activated carbon of the present invention has a specific surface area (value measured by a BET method (one-point method) using nitrogen as a substance to be adsorbed) of activated carbon of about 1000 to 2000 m 2 / g, preferably 1300 to 2000 m 2 / g. About 1900 m 2 / g, more preferably about 1400 to 1900 m 2 / g. Further, the total pore volume of the activated carbon calculated by the QSDFT method is about 0.35 to 1.00 cc / g, preferably about 0.40 to 1.00 cc / g, more preferably about 0.50 cc / g. About 0.80 cc / g, more preferably about 0.55 to 0.80 cc / g.
  • the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter of 2.0 nm or less in the pore volume calculated by the QSDFT method is 0.880. From the viewpoint of further improving the equilibrium adsorption amount of dichloromethane, the ratio is preferably from 0.880 to 0.965.
  • the setting of the upper limit of B / C means that the activated carbon of the present invention has pores having a pore diameter in the range of 1.5 nm or more and 2.0 nm or less in the pore volume calculated by the QSDFT method. This indicates that it is necessary to distribute the substance appropriately.
  • the pores having a pore diameter in the range of 1.5 nm or more and 2.0 nm or less assist in the diffusion of the substance to be adsorbed into the pores so that the B / C falls within a specific range, thereby equilibrating adsorption of dichloromethane. It is believed that the amount will be further improved.
  • the activated carbon of the present invention has a ratio of the pore volume A to the pore volume B (pore volume A / pore volume B) of 0.600 to 0. 900, preferably 0.600 to 0.830.
  • the ratio of the pore volume A to the pore volume C is 0.560 to 0. 890, preferably 0.560 to 0.820, more preferably 0.560 to 0.795.
  • the ratio of the pore volume A to the pore volume D is from 0.010 to 0. 220, preferably 0.030 to 0.220, more preferably 0.05 to 0.220.
  • the ratio of the pore volume A to the total pore volume is from 0.530 to 0.5 from the viewpoint of further improving the equilibrium adsorption amount of dichloromethane. 900, preferably 0.530 to 0.800, more preferably 0.530 to 0.789.
  • the ratio of the pore volume B to the total pore volume is from 0.800 to 0. 990, preferably 0.800 to 0.970, more preferably 0.800 to 0.955.
  • the ratio of the pore volume C to the total pore volume is from 0.930 to 1. 000, preferably 0.930 to 0.998.
  • the ratio of the pore volume D to the total pore volume is from 0.010 to 0.1 from the viewpoint of further improving the equilibrium adsorption amount of dichloromethane. 130, preferably 0.030 to 0.130, more preferably 0.035 to 0.130.
  • the activated carbon of the present invention has a pore volume having a pore diameter in a range of 0.65 nm or less among pore volumes calculated by the QSDFT method with respect to the total pore volume.
  • the ratio (pore volume of pore diameter in the range of 0.65 nm or less / total pore volume) is 0.120 to 0.520.
  • the activated carbon of the present invention has a pore volume having a pore diameter of 0.8 nm or less among the pore volumes calculated by the QSDFT method with respect to the total pore volume.
  • the ratio pore volume of pore diameter in the range of 0.8 nm or less / total pore volume
  • 0.200 to 0.800 preferably 0.350 to 0.650, and 0.200 to 0.650.
  • 0.590 is more preferably mentioned.
  • the main raw material of the activated carbon precursor (that is, the raw material from which the activated carbon of the present invention is derived) is not particularly limited.
  • infusible or carbonized organic material phenol
  • the material include infusible resins such as resins
  • examples of the organic material include polyacrylonitrile, pitch, polyvinyl alcohol, and cellulose.
  • the activated carbon of the present invention is preferably derived from pitch, and more preferably derived from coal pitch.
  • the activated carbon of the present invention uses an activated carbon precursor containing an yttrium compound and / or a vanadium compound in order to obtain the above-mentioned specific pore size distribution.
  • the activated carbon of the present invention contains at least one selected from the group consisting of yttrium simple substance, yttrium compound, simple vanadium substance, and vanadium compound derived from the yttrium compound and / or vanadium compound contained in the activated carbon precursor. You may.
  • the ratio (total) of the mass of yttrium alone, the yttrium compound, the vanadium alone and the vanadium compound contained in the activated carbon in the total mass of the activated carbon of the present invention is, for example, 0.001 to 5.0% by mass. And preferably 0.001 to 3.0% by mass, more preferably 0.001 to 0.35% by mass.
  • the above ratio is the ratio in terms of yttrium element and vanadium element (that is, the content of yttrium and vanadium) measured by an ICP emission spectrometer (Model 715-ES manufactured by Varian).
  • the activated carbon of the present invention contains an yttrium compound and a vanadium compound
  • the micropore volume of 1 nm or less is largely maintained by the effect of vanadium, and the somewhat large pores are appropriately distributed by the effect of yttrium.
  • These slightly large pores are preferable in that the equilibrium adsorption amount of dichloromethane is further improved because the somewhat large pores assist the diffusion of the substance to be adsorbed in the pores.
  • the ratio of the total content of the simple substance and the yttrium compound contained in the activated carbon to the total content of the simple substance and the vanadium compound contained in the activated carbon in the range of 4 to 16.
  • the activated carbon of the present invention has a pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less of 0.4 cc / g or more among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) of the pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.2 cc / g or more and the pore volume calculated by the QSDFT method is Of these, the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less is 0.880 to 0.985, so that the equilibrium adsorption amount of dichloromethane is excellent. .
  • the equilibrium adsorption amount (% by mass) of dichloromethane included in the activated carbon of the present invention is, for example, 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more.
  • the form of the activated carbon of the present invention is not particularly limited, and examples thereof include granular activated carbon, powdered activated carbon, and fibrous activated carbon. From the viewpoint of further improving the dichloromethane adsorption rate, it is more preferable to use fibrous activated carbon which is fibrous.
  • the average fiber diameter of the fibrous activated carbon is preferably 30 ⁇ m or less, more preferably about 5 to 20 ⁇ m.
  • the average fiber diameter in the present invention is a value measured by an image processing fiber diameter measuring device (based on JIS K 1477).
  • an integrated volume percentage D 50 measured by a laser diffraction / scattering method is 0.01 to 5 mm.
  • the activated carbon of the present invention can be used in either a gas phase or a liquid phase.
  • the activated carbon of the present invention is suitably used for adsorbing dichloromethane in a gas phase.
  • the method for producing activated carbon of the present invention includes a step of activating a activated carbon precursor containing an yttrium compound and / or a vanadium compound in an atmosphere having a CO 2 concentration of 90% by volume or more at a temperature of 600 to 1200 ° C.
  • the ratio (B / C) of the pore volume B can be in a specific range, and the activated carbon of the invention can be obtained.
  • the pore volume E having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less and the pore volume B having a pore diameter in the range of 1.5 nm or less B (Cc / g)
  • the activated carbon precursor does not contain an yttrium compound and / or a vanadium compound, it is difficult to obtain the pore distribution of the activated carbon of the present invention.
  • the main raw material of the activated carbon precursor is not particularly limited.
  • an infusible or carbonized organic material an infusible resin such as a phenol resin, and the like can be mentioned.
  • the organic material include polyacrylonitrile, pitch, polyvinyl alcohol, and cellulose. From the viewpoint of the theoretical carbonization yield during carbonization, pitch is preferable, and among the pitches, coal pitch is particularly preferable.
  • the total content of yttrium and vanadium in the activated carbon precursor is preferably 0.01 to 5.0% by mass, more preferably 0.03 to 1.0% by mass, and furthermore Preferably, the content is 0.03 to 0.3% by mass.
  • Yttrium can be contained by mixing yttrium alone or an yttrium compound with a raw material.
  • the yttrium compound include inorganic metal compounds such as metal oxides, metal hydroxides, metal halides, and metal sulfates containing yttrium as a constituent metal element, salts of organic acids and metals such as acetic acid, and organic metal compounds. Is mentioned.
  • the organic metal compound examples include metal acetylacetonate, an aromatic metal compound, and the like.
  • vanadium can be contained by mixing vanadium alone or a vanadium compound with a raw material.
  • a metal oxide, a metal hydroxide, a metal halide, an inorganic metal compound such as a metal sulfate, a salt of an organic acid and a metal such as acetic acid, an organic metal compound, and the like containing vanadium as a constituent metal element Is mentioned.
  • the yttrium compounds and / or vanadium compounds among them, from the viewpoint of highly dispersing the metal in the activated carbon precursor, it is preferable to use an organometallic compound.
  • a ⁇ -diketone type compound is used as a ligand. More preferred are metal complexes. Examples of the ⁇ -diketone type compound include those having a structure represented by the following formulas (1) to (3), and specific examples include acetylacetone.
  • the activated carbon of the present invention further contains yttrium alone and / or an yttrium compound, it may be obtained by mixing vanadium alone or a vanadium compound with yttrium alone and / or an yttrium compound with a main raw material of an activated carbon precursor. What is necessary is just to contain.
  • the yttrium compound to be mixed with the main raw material of the activated carbon precursor similarly to the vanadium compound, inorganic metal compounds such as metal oxides, metal hydroxides, metal halides, and metal sulfates containing yttrium as a constituent metal element. And salts of metals with organic acids such as acetic acid and the like, and organic metal compounds.
  • the organic metal compound include metal acetylacetonate, an aromatic metal compound, and the like.
  • an organic metal compound is preferable, and as the organic metal compound, a metal complex having a ⁇ -diketone type compound as a ligand is more preferable.
  • the ⁇ -diketone type compound include those having a structure represented by the following formulas (1) to (3), and specific examples include acetylacetone.
  • the activated carbon precursor contains an yttrium compound and a vanadium compound
  • the micropore volume of 1 nm or less is largely maintained by the effect of vanadium, and the somewhat large pores are appropriately distributed by the effect of yttrium.
  • These slightly large pores are preferable in that the equilibrium adsorption amount of dichloromethane is further improved because the somewhat large pores assist the diffusion of the substance to be adsorbed in the pores.
  • the ratio of the content of the yttrium compound to the content of the vanadium compound in the activated carbon precursor is as follows: 4 to 15 are preferred.
  • the activation atmosphere has a CO 2 concentration of 90% by volume or more, preferably 95% by volume or more, more preferably 99% by volume or more.
  • the activation atmosphere temperature is usually about 600 to 1200 ° C., preferably about 800 to 1000 ° C., and more preferably about 900 to 1000 ° C.
  • the activation time may be adjusted so as to have a predetermined pore size distribution according to the main raw material of the activated carbon precursor. For example, when a pitch having a softening point of 275 ° C. to 288 ° C. is used as the main raw material of the activated carbon precursor, the activation atmosphere temperature is 900 to 1000 ° C., and the activation time is 10 to 80 minutes, more preferably 30 to 80 minutes. Activating as a part.
  • the pitch fiber is incinerated, the ash is dissolved in acid, and the vanadium element-converted ratio and the yttrium element-converted ratio measured by an ICP emission spectrometer (Model 715-ES manufactured by Varian) are respectively defined as vanadium content and vanadium content.
  • the yttrium content was determined.
  • Pore volume (cc / g), specific surface area (m 2 / g), fiber diameter of fibrous activated carbon ( ⁇ m) The pore physical property values were measured from a nitrogen adsorption isotherm at 77 K using “AUTOSORB-1-MP” manufactured by Quantachrome. 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 diameter range described in Table 1 were determined by applying N 2 at 77K on carbon [slit pore, QSDFT equilibrium model] as a calculation model to the measured nitrogen desorption isotherm. It was analyzed by calculating the pore size distribution.
  • the pore volume in each pore diameter range described in Table 1 is a value read from a graph showing the pore diameter distribution shown in FIGS. 1 to 20 or a value calculated from the read value. More specifically, the pore volume with a pore diameter of 0.65 nm or less is a reading of Cumulative Pore Volume (cc / g) when the horizontal axis Pore Width of the pore diameter distribution diagram is 0.65 nm.
  • the pore volume with a pore diameter of 2.0 nm or more was calculated by subtracting the pore volume C with a pore diameter of 2.0 nm or less from the total pore volume obtained by the QSDFT method.
  • the pore volume in the range of the pore diameter of 1.0 nm or more and 1.5 nm or less was calculated by subtracting the pore volume A of the pore diameter of 1.0 nm or less from the pore volume B of the pore diameter of 1.5 nm or less.
  • the pore volume in the range of the pore diameter of 1.0 nm or more and 2.0 nm or less was calculated by subtracting the pore volume A of the pore diameter of 1.0 nm or less from the pore volume C of the pore diameter of 2.0 nm or less.
  • the pore volume of the pore diameter in the range of 0.65 nm or more and 0.8 nm or less was calculated by subtracting the pore volume of the pore diameter of 0.65 nm or less from the pore volume of 0.8 nm or less.
  • the pore volume E of the pore diameter in the range of 0.65 nm or more and 1.0 nm or less was calculated by subtracting the pore volume of 0.65 nm or less from the pore volume A of 1.0 nm or less. .
  • the pore volume of the pore diameter in the range of 0.8 nm to 1.5 nm was calculated by subtracting the pore volume of the pore diameter of 0.8 nm or less from the pore volume B of the pore diameter of 1.5 nm or less.
  • the pore volume having a pore diameter in the range of 1.5 nm or more and 2.0 nm or less was calculated by subtracting the pore volume B having the pore diameter of 1.5 nm or less from the pore volume C having the pore diameter of 2.0 nm or less. .
  • Fiber diameter of fibrous activated carbon ( ⁇ m) It was measured by an image processing fiber diameter measuring device (based on JIS K1277).
  • Example 1 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. , And 0.1 parts by mass of trisacetylacetonatoittrium (CAS number: 15554-47-9) are supplied to a melt extruder, melt-mixed at a melting temperature of 320 ° C., and a discharge amount of 16 g / The pitch fiber was obtained by spinning at min. The obtained pitch fibers were heated in the air from room temperature to 354 ° C.
  • an activated carbon precursor as infusible pitch fibers was obtained.
  • the content of vanadium was 0.11% by mass
  • the content of yttrium was 0.022% by mass.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into the activation furnace and performing a heat treatment at an atmosphere temperature of 950 ° C. for 32 minutes to obtain the activated carbon of Example 1. .
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.456 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.216 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.970, the vanadium content is 0.220% by mass, and the yttrium content is 0.040. % By mass, and the average fiber diameter was 13.5 ⁇ m.
  • Example 2 Activated carbon of Example 2 was obtained in the same manner as in Example 1 except that the activation time was changed to 40 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) of a pore diameter in a range of 1.5 nm or less of 0.558 cc / g among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.256 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.947, the vanadium content is 0.270% by mass, and the yttrium content is 0.050. % By mass, and the average fiber diameter was 13.3 ⁇ m.
  • Example 3 Activated carbon of Example 3 was obtained in the same manner as in Example 1 except that the activation time was 45 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) of a pore diameter in a range of 1.5 nm or less of 0.621 cc / g among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.274 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 0 nm or less is 0.917, the vanadium content is 0.310% by mass, and the yttrium content is 0.060. % By mass, and the average fiber diameter was 13.5 ⁇ m.
  • Example 4 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. , And 0.06 parts by mass of trisacetylacetonatoittrium (CAS number: 15554-47-9) are supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C., and a discharge amount of 16 g / The pitch fiber was obtained by spinning at min. The obtained pitch fibers were heated in the air from room temperature to 354 ° C.
  • an activated carbon precursor as infusible pitch fibers was obtained.
  • the content of vanadium was 0.09% by mass
  • the content of yttrium was 0.01% by mass.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into the activation furnace and heat-treating it at 950 ° C. for 38 minutes to obtain activated carbon of Example 4. .
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less of 0.482 cc / g among the pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.204 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.980, the content of vanadium is 0.190% by mass, and the content of yttrium is 0.020. % By mass, and the average fiber diameter was 13.1 ⁇ m.
  • Example 5 Activated carbon of Example 5 was obtained in the same manner as in Example 4, except that the activation time was changed to 44 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.535 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.239 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.961, the vanadium content is 0.220% by mass, and the yttrium content is 0.030. % By mass, and the average fiber diameter was 13.0 ⁇ m.
  • Example 6 Activated carbon of Example 6 was obtained in the same manner as in Example 4, except that the activation time was changed to 50 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less of 0.600 cc / g among the pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.262 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.932, the vanadium content is 0.250% by mass, and the yttrium content is 0.030. % By mass, and the average fiber diameter was 13.2 ⁇ m.
  • Example 7 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. , And 0.03 parts by mass of trisacetylacetonatoittrium (CAS number: 15554-47-9) are supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C., and a discharge amount of 16 g / The pitch fiber was obtained by spinning at min. The obtained pitch fibers were heated in the air from room temperature to 354 ° C.
  • an activated carbon precursor as infusible pitch fibers was obtained.
  • the content of vanadium was 0.095% by mass
  • the content of yttrium was 0.007% 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 950 ° C. for 37 minutes to obtain activated carbon of Example 7. .
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.517 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.211 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.981, the vanadium content is 0.210% by mass, and the yttrium content is 0.020. % By mass, and the average fiber diameter was 13.5 ⁇ m.
  • Example 8 Activated carbon of Example 8 was obtained in the same manner as in Example 7, except that the activation time was changed to 40 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) of a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.548 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.233 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.945, the vanadium content is 0.230% by mass, and the yttrium content is 0.020. % By mass, and the average fiber diameter was 13.0 ⁇ m.
  • Example 9 Activated carbon of Example 9 was obtained in the same manner as in Example 7, except that the activation time was changed to 50 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) of a pore diameter of 1.5 nm or less of 0.641 cc / g among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.277 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.926, the vanadium content is 0.290% by mass, and the yttrium content is 0.020. % By mass, and the average fiber diameter was 13.2 ⁇ m.
  • Example 10 As an organic material, a mixture obtained by mixing 0.3 parts by mass of trisacetylacetonatoittrium (CAS number: 15554-47-9) with 100 parts by mass of granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder. Then, the mixture was melt-mixed at a melting temperature of 320 ° C. and spun at a discharge rate of 20 g / min to obtain pitch fibers. The obtained pitch fibers were heated in the air from room temperature to 354 ° C. at a rate of 1 to 30 ° C./min for 54 minutes to perform infusibilization treatment, and an activated carbon precursor as infusible pitch fibers was obtained. In the activated carbon precursor, the content of yttrium was 0.06% by mass.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into the activation furnace and performing a heat treatment at an atmosphere temperature of 950 ° C. for 67 minutes to obtain the activated carbon of Example 10.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less of 0.613 cc / g among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.262 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.890, the yttrium content is 0.170% by mass, and the average fiber diameter is 16.8 ⁇ m. there were.
  • Example 11 Activated carbon of Example 11 was obtained in the same manner as in Example 10, except that the activation time was 70 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) of a pore diameter in a range of 1.5 nm or less of 0.636 cc / g among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.269 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.880, the yttrium content is 0.180% by mass, and the average fiber diameter is 16.8 ⁇ m. there were.
  • Example 12 Activated carbon of Example 12 was obtained in the same manner as in Example 10, except that the activation time was 65 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.594 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.256 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.907, the yttrium content is 0.150% by mass, and the average fiber diameter is 18.2 ⁇ m. there were.
  • Example 13 Activated carbon of Example 13 was obtained in the same manner as in Example 10, except that the activation time was 55 minutes.
  • the obtained activated carbon has a pore volume B (cc / g) of 0.532 cc / g having a pore diameter in a range of 1.5 nm or less among the pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.241 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.942, the yttrium content is 0.140% by mass, and the average fiber diameter is 18.4 ⁇ m. there were.
  • Example 14 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. The mixture was supplied to a melt extruder, melt-mixed at a melting temperature of 325 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was heated stepwise to 355 ° C. in the air and held for a total of 87 minutes to perform infusibilization treatment, thereby obtaining an activated carbon precursor as an infusibilized pitch fiber. In the activated carbon precursor, the content of vanadium was 0.076% by mass.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into an activation furnace and performing a heat treatment at an atmosphere temperature of 950 ° C. for 50 minutes to obtain an activated carbon of Example 14. .
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.581 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.245 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.965, the content of vanadium is 0.230% by mass, and the average fiber diameter is 13.2 ⁇ m. there were.
  • Example 15 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. The mixture was supplied to a melt extruder, melt-mixed at a melting temperature of 325 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was gradually heated to 335 ° C. in the air and held for 87 minutes in total to perform an infusibilization treatment to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the content of vanadium was 0.076% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into the activation furnace and heat-treating it at an atmosphere temperature of 950 ° C. for 50 minutes to obtain an activated carbon of Example 15. .
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.287 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.958, the vanadium content is 0.281% by mass, and the average fiber diameter is 13.7 ⁇ m. there were.
  • Example 16 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. The mixture was supplied to a melt extruder, melt-mixed at a melting temperature of 325 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was gradually heated to 364 ° C. in the air and held for a total of 87 minutes to perform infusibilization treatment, thereby obtaining an activated carbon precursor as an infusibilized pitch fiber. In the activated carbon precursor, the content of vanadium was 0.100% by mass.
  • the obtained activated carbon precursor was activated by continuously introducing a gas having a CO 2 concentration of 100% by volume into the activation furnace and performing heat treatment at an atmosphere temperature of 950 ° C. for 50 minutes to obtain an activated carbon of Example 17. .
  • the obtained activated carbon has a pore volume B (cc / g) of a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.553 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.280 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.955, the vanadium content is 0.286% by mass, and the average fiber diameter is 13.8 ⁇ m. there were.
  • Example 17 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. The mixture was supplied to a melt extruder, melt-mixed at a melting temperature of 325 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The obtained pitch fiber was heated stepwise to 333 ° C. in the air and held for a total of 87 minutes to carry out infusibility treatment, thereby obtaining an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the content of vanadium was 0.095% by mass.
  • the obtained activated carbon precursor is activated by continuously introducing a mixed gas having a CO 2 concentration of 63% by volume and a N 2 concentration of 37% by volume into an activation furnace and performing a heat treatment at an atmosphere temperature of 950 ° C. for 50 minutes.
  • Activated carbon of Example 18 was obtained.
  • the obtained activated carbon has a pore volume B (cc / g) of a pore diameter of 1.5 nm or less of 0.462 cc / g among pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.227 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.996, the vanadium content is 0.257% by mass, and the average fiber diameter is 13.9 ⁇ m. there were.
  • Example 18 As an organic material, bis (2,4-pentanedionato) vanadium (IV) oxide (CAS number: 3153-26-2) 0.6 part by mass per 100 parts by mass of granular coal pitch having a softening point of 280 ° C. The mixture was supplied to a melt extruder, melt-mixed at a melting temperature of 325 ° C., and spun at a discharge rate of 16 g / min to obtain pitch fibers. The pitch fibers thus obtained were heated stepwise to 339 ° C. in the air and maintained for a total of 87 minutes to carry out infusibility treatment, thereby obtaining an activated carbon precursor as infusible pitch fibers. In the activated carbon precursor, the content of vanadium was 0.093% 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 performing heat treatment at an atmosphere temperature of 950 ° C. for 50 minutes to obtain an activated carbon of Example 19. .
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.556 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.287 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0 nm or less is 0.954, the vanadium content is 0.344% by mass, and the average fiber diameter is 13.6 ⁇ m. there were.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into an activation furnace and performing a heat treatment at an atmosphere temperature of 875 ° C. for 25 minutes to obtain the activated carbon of Comparative Example 1. Obtained.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.314 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.112 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.997, the content of yttrium and vanadium is 0.00% by mass, and the average fiber diameter is 16. It was 8 ⁇ m.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into the activation furnace and performing a heat treatment at an atmosphere temperature of 875 ° C. for 40 minutes to obtain the activated carbon of Comparative Example 2. Obtained.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less of 0.465 cc / g among the pore volumes calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.180 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.977, the content of yttrium and vanadium is 0.00% by mass, and the average fiber diameter is 16. It was 7 ⁇ m.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into an activation furnace and performing a heat treatment at an ambient temperature of 900 ° C. for 20 minutes. Obtained.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.339 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.166 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.827, the yttrium content is 0.66% by mass, and the average fiber diameter is 16.5 ⁇ m. there were.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having an H 2 O concentration of 100% by volume into the activation furnace and performing heat treatment at 900 ° C. for 25 minutes to obtain the activated carbon of Comparative Example 4. Obtained.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is 0.312 cc / g, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.137 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.790, the yttrium content is 0.83% by mass, and the average fiber diameter is 15.8 ⁇ m. there were.
  • the activated carbon precursor thus obtained 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 atmosphere temperature of 950 ° C. for 90 minutes to obtain an activated carbon of Comparative Example 5.
  • the obtained activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less of 0.496 cc / g in the pore volume calculated by the QSDFT method, and is calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.223 cc / g, and among the pore volumes calculated by the QSDFT method, 2.
  • the ratio (B / C) of the pore volume B to the pore volume C in the pore diameter range of 0 nm or less is 0.998, the content of vanadium and yttrium is 0.00% by mass, and the average fiber diameter is 18. It was 1 ⁇ m.
  • the activated carbon As the activated carbon, a commercially available phenolic activated carbon was used.
  • the activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less of 0.364 cc / g among pore volumes calculated by the QSDFT method, and a pore volume calculated by the QSDFT method.
  • the pore volume E (cc / g) having a pore diameter in the range of 0.65 nm to 1.0 nm is 0.110 cc / g
  • the pore volume calculated by the QSDFT method is 2.0 nm or less.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 1.000, the content of vanadium and yttrium is 0.00% by mass, and the average fiber diameter is 12.6 ⁇ m. there were.
  • the activated carbon As the activated carbon, a commercially available phenolic activated carbon was used.
  • the activated carbon has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less of 0.542 cc / g among pore volumes calculated by the QSDFT method, and a pore volume calculated by the QSDFT method.
  • the pore volume E (cc / g) of the pore diameter in the range of 0.65 nm to 1.0 nm is 0.167 cc / g
  • the pore volume calculated by the QSDFT method is 2.0 nm or less.
  • the ratio (B / C) of the pore volume B to the pore volume C of the pore diameter in the range of 0.989 is 0.989, the content of vanadium and yttrium is 0.00% by mass, and the average fiber diameter is 12.8 ⁇ m. there were.
  • the pore volume B (cc / g) having a pore diameter in the range of 1.5 nm or less was 0.4 cc / g or more.
  • the pore volume E (cc / g) of the pore diameter in the range of 0.65 nm or more and 1.0 nm or less is 0.2 cc / g or more and the fine volume calculated by the QSDFT method. Since the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less in the pore volume is 0.880 to 0.985, equilibrium adsorption of dichloromethane is performed. The quantity was excellent.
  • the activated carbon of Comparative Example 1 has a pore volume B (cc / g) having a pore diameter of 1.5 nm or less in the pore volume calculated by the QSDFT method, which is less than 0.4 cc / g.
  • the pore volume E (cc / g) of the pore diameter in the range of 0.65 nm or more and 1.0 nm or less is less than 0.2 cc / g, and is calculated by the QSDFT method.
  • the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less is more than 0.985. The amount of adsorption was poor.
  • the activated carbon of Comparative Example 2 has a pore volume E (cc / g) of a pore diameter in the range of 0.65 nm or more and 1.0 nm or less in the pore volume calculated by the QSDFT method, which is less than 0.2 cc / g. For this reason, the equilibrium adsorption amount of dichloromethane was poor.
  • the pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less is less than 0.4 cc / g
  • the pore volume E (cc / g) of the pore diameter in the range of 0.65 nm or more and 1.0 nm or less is less than 0.2 cc / g
  • the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less is less than 0.880. The amount of adsorption was poor.
  • the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter of 2.0 nm or less in the pore volume calculated by the QSDFT method was 0.1%. Since it exceeded 985, the equilibrium adsorption amount of dichloromethane was inferior.
  • the pore volume B (cc / g) having a pore diameter in a range of 1.5 nm or less is less than 0.4 cc / g, among the pore volumes calculated by the QSDFT method,
  • the pore volume E (cc / g) of the pore diameter in the range of 0.65 nm or more and 1.0 nm or less is less than 0.2 cc / g, and is calculated by the QSDFT method.
  • the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less is more than 0.985. The amount of adsorption was poor.
  • the activated carbon of Comparative Example 7 has a pore volume E (cc / g) of a pore diameter in a range of 0.65 nm or more and 1.0 nm or less in a pore volume calculated by the QSDFT method of less than 0.2 cc / g. And the ratio (B / C) of the pore volume B to the pore volume C having a pore diameter in the range of 2.0 nm or less in the pore volume calculated by the QSDFT method exceeds 0.985. Therefore, the equilibrium adsorption amount of dichloromethane was poor.

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