WO2018116859A1 - Charbon actif et sa méthode de production - Google Patents

Charbon actif et sa méthode de production Download PDF

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WO2018116859A1
WO2018116859A1 PCT/JP2017/044097 JP2017044097W WO2018116859A1 WO 2018116859 A1 WO2018116859 A1 WO 2018116859A1 JP 2017044097 W JP2017044097 W JP 2017044097W WO 2018116859 A1 WO2018116859 A1 WO 2018116859A1
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activated carbon
pore
pore volume
less
range
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PCT/JP2017/044097
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English (en)
Japanese (ja)
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中野　智康
弘和 清水
昭典 河内
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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Priority to JP2018525488A priority Critical patent/JP6379325B1/ja
Publication of WO2018116859A1 publication Critical patent/WO2018116859A1/fr

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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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • 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
    • 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

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 excellent in trihalomethane filtering ability under high empty space velocity.
  • chlorine is added to tap water or the like used for beverages for the purpose of sterilization.
  • chlorine contained in tap water reacts with organic substances contained in tap water to produce an organic halogen compound.
  • organic substances contained in tap water For example, it is known that when humic substances that are natural organic substances react with chlorine in tap water, trihalomethanes that are carcinogenic substances are produced. And the activated carbon excellent in the filtration capability of these organic halogen compounds contained in tap water is proposed.
  • the pore volume ratio of the pore diameter of 20 to 100 mm (2 nm to 10 nm) to the pore volume of the pore diameter of 100 mm (10 nm) or less is 5 to 50%.
  • an adsorbent containing porous carbon having a pore volume ratio of 45% or more with a pore diameter of 10 mm (1 nm) or less see, for example, Patent Document 1).
  • the ratio of the pore volume of the pore diameter of 20 to 100 mm to 5 to 50% is to increase the proportion of relatively large pores and This is to increase the attractive adsorption force.
  • the pore volume ratio with a pore diameter of 10 mm or less effective for the static equilibrium adsorption amount may be 45% or more. It is disclosed. And it is supposed that this adsorbent can make static adsorption force and dynamic adsorption force compatible by setting it as such a structure.
  • the mesopore volume in the range of pore diameters of 30 mm or more and less than 50 mm in the pore diameter distribution determined by the BJH method from the nitrogen adsorption isotherm at 77.4 K is 0.02 to 0.40 cc / g
  • Activated carbon is known in which the ratio of the mesopore volume in the above range to the pore volume is 5 to 45% (see, for example, Patent Document 2).
  • the activated carbon by controlling the volume of the mesopores (pores having a diameter of 2 to 50 nm) and the ratio within such a range, a material suitable for adsorption of various substances to be adsorbed (particularly trihalomethanes) It is supposed to be possible.
  • the water purification filter has been required to have a large amount of total trihalomethane filtrate (the amount of water until the total trihalomethane removal rate is reduced to 80%) in the JIS S3201 “Volatile Organic Compound Filtration Capability Test”. ing. The larger the total amount of filtered water, the longer the usable period (replacement period) of the purified water filter.
  • the water purification filter when the water purification filter is for a faucet integrated water purifier, the water purification filter needs to be downsized. As the water filter becomes smaller, the superficial velocity (SV) increases and it becomes difficult to maintain a high total trihalomethane filtration capacity.
  • SV superficial velocity
  • the main object of the present invention is to solve the above problems and to provide an activated carbon having a high total trihalomethane filtration capacity and a method for producing the same even in water treatment at a high superficial velocity (SV).
  • trihalomethane molecules are likely to be adsorbed in pores of 1.5 nm or less.
  • the present inventors considered that the rate at which trihalomethane molecules diffuse into the pores is also an important factor when considering the filtration of total trihalomethane molecules under high SV. Therefore, the present inventors have repeatedly studied from these viewpoints, control the pore diameter and the pore volume of the activated carbon, make the pore volume of 1.5 nm or less a specific range, and 1.5 nm or more and 2.5 nm It has been found that by setting the pore volume of the following pore diameters within a specific range, it has a high total trihalomethane filtration ability even under high SV.
  • the invention disclosed in Patent Document 1 aims to increase the dynamic adsorption force by controlling the pore volume of 2 to 10 nm, which is a wide pore diameter range among mesopores.
  • it is considered to improve the filtration ability under high SV such as 3000 h ⁇ 1 and to control the pore volume of the pore diameter in the range of 1.5 nm to 2.5 nm.
  • the activated carbon specifically disclosed as an example in the same document has a small pore volume in the range of 1.5 nm to 2.5 nm, and filtration of total trihalomethanes under high superficial velocity conditions. The ability cannot be fully demonstrated.
  • the invention disclosed in Patent Document 2 discloses that the pore volume in a relatively large pore diameter range of 3 to 5 nm is controlled. Further, as a control method, a pitch containing 0.01 to 5% by weight of at least one metal component of Mg, Mn, Fe, Y, Pt and Gd is used as an activated carbon precursor, and the precursor is infusible. Alternatively, in the method of carbonization treatment and activation treatment, the mesopore mode diameter of the obtained activated carbon is controlled by changing the type of the metal component, and when producing activated carbon for adsorption of trihalomethanes, Fe It is disclosed that the added activated carbon exhibits the most excellent effect as an adsorbent for removing organic compounds in water.
  • the pore volume in the range can be increased, the pore volume in the range of the pore diameter of 1.5 nm or less and the pore volume in the range of 1.5 to 2.5 nm are sufficiently large. It was found that the total trihalomethane filtration capacity under high superficial velocity conditions could not be fully demonstrated.
  • the present invention is an invention that has been completed through further studies based on these findings.
  • this invention provides the invention of the aspect hung up below.
  • Item 1 Among the pore volumes calculated by the QSDFT method, the pore volume A having a pore diameter in the range of 1.5 nm or less is 0.3 cc / g or more and 0.5 cc / g or less, And the activated carbon whose pore volume B of the pore diameter of the range of 1.5 nm or more and 2.5 nm or less is 0.03 cc / g or more and 0.12 cc / g or less among the pore volumes calculated by the QSDFT method.
  • Item 2. Item 2.
  • Activated carbon according to Item 1 wherein, among the pore volumes calculated by the QSDFT method, the pore volume C having a pore diameter in the range of 2.5 nm or more is 0.03 cc / g or less.
  • Item 3. Item 3. The activated carbon according to Item 1 or 2, wherein a ratio of the pore volume B to the pore volume A (pore volume B / pore volume A) is 0.1 to 0.3.
  • the specific surface area is 900 m 2 / g or more and 1500 m 2 / g or less, and among the pore volumes calculated by the QSDFT method, the total pore volume is 0.33 cc / g or more and 0.70 cc / g or less.
  • Item 5. The activated carbon according to any one of Items 1 to 4, wherein the total trihalomethane filtration capacity is 45 L / g or more.
  • Item 6. The activated carbon according to any one of Items 1 to 5, wherein the activated carbon is fibrous activated carbon.
  • Item 7. Item 6. The method according to any one of Items 1 to 6, comprising a step of activating an activated carbon precursor containing 0.1 to 1.0% by mass of yttrium at a temperature of 900 to 1000 ° C. in an atmosphere having a CO 2 concentration of 50% by volume or more. The manufacturing method of activated carbon as described in any one of.
  • Item 8. A water purification filter comprising the activated carbon according to any one of Items 1 to 6.
  • Item 9. Item 7. A method for filtering water using the activated carbon according to any one of Items 1 to 6.
  • the pore volume A having a pore diameter in the range of 1.5 nm or less is 0.3 cc / g or more and 0.5 cc / g or less
  • the pore volume B having a pore diameter in the range of 1.5 nm to 2.5 nm is 0.03 cc / g to 0.12 cc / g
  • FIG. 2 is a graph showing the pore size distribution calculated by the QSDFT method for activated carbon of Example 1.
  • FIG. It is a graph which shows the pore size distribution calculated by the QSDFT method of the activated carbon of Example 2. It is a graph which shows the pore diameter distribution calculated by the QSDFT method of the activated carbon of Example 3. It is a graph which shows the pore diameter distribution calculated by the QSDFT method of the activated carbon of Example 4. It is a graph which shows the pore size distribution calculated by the QSDFT method of the activated carbon of Example 5.
  • 6 is a graph showing a pore size distribution calculated by the QSDFT method of activated carbon of Comparative Example 1.
  • the activated carbon of the present invention has a pore volume A with a pore diameter in the range of 1.5 nm or less of the pore volume calculated by the QSDFT method of 0.3 to 0.5 cc / g, and the QSDFT method.
  • the pore volume B having a pore diameter in the range of 1.5 nm to 2.5 nm is 0.03 cc / g to 0.12 cc / g.
  • a pore volume having a pore diameter in the range of 1.5 nm or less is set to a specific range, and a pore having a pore diameter of 1.5 nm to 2.5 nm is used. It is important that the volume is in a specific range.
  • pores of 1.5 nm or less tend to adsorb trihalomethane molecules, and pores of 1.5 nm or more and 2.5 nm or less are adsorbed within the pores of trihalomethane molecules in addition to adsorption of trihalomethane molecules. It is thought that it also contributes to diffusion.
  • the pore volume of pores of 1.5 nm or less and the pore volume of pores of 1.5 nm or more and 2.5 nm or less are simply increased.
  • the pore volume in a specific pore diameter range is calculated by the QSDFT method.
  • QSDFT method quenched solid density functional method
  • measurement of nitrogen adsorption isotherm and pore size distribution analysis by QSDFT method are performed using “AUTOSORB-1-MP” manufactured by Quantachrome.
  • the pore size distribution is calculated to obtain a fine pore size range.
  • the pore volume can be calculated.
  • the activated carbon of the present invention has a pore volume A having a pore diameter in the range of 1.5 nm or less in the pore volume calculated by the QSDFT method of 0.3 cc / g to 0.5 cc / g,
  • the pore volume A is preferably 0.4 cc / g or more and 0.5 cc / g or less from the viewpoint of easily having higher total trihalomethane filtration ability.
  • the pore volume A having a pore diameter in the range of 1.5 nm or less is 0.4 cc / g or more and 0.5 cc / g or less, and the pore diameter is in the range of 0.65 nm or more and 0.8 nm or less.
  • the volume is 0.05 cc / g or more, preferably 0.06 cc / g or more and 0.12 cc / g or less
  • the activated carbon of the present invention can be used even in water flow treatment at a large superficial velocity (SV). It tends to have high total trihalomethane filtration capacity.
  • the activated carbon of the present invention has a pore volume calculated by the QSDFT method of 1
  • the pore volume having a pore diameter in the range of 0.0 nm or less is preferably 0.2 cc / g or more and 0.4 cc / g or less.
  • the activated carbon of the present invention has a pore volume in the range of 1.0 nm or more and 1.5 nm or less in the pore volume calculated by the QSDFT method of 0.03 cc / g or more and 0 or less. .15 cc / g or less is preferable.
  • the activated carbon of the present invention has a pore volume B having a pore diameter in the range of 1.5 nm to 2.5 nm of the pore volume calculated by the QSDFT method of 0.03 cc / g to 0.12 cc / g.
  • the pore volume B is 0.06 cc / g or more and 0.12 cc / g or less. preferable.
  • the activated carbon of the present invention is 2.5 nm out of the pore volume calculated by the QSDFT method from the viewpoint of easily having a higher total trihalomethane filtration capacity even in water flow treatment at a high superficial velocity (SV).
  • the pore volume C having a pore diameter in the above range is preferably 0.03 cc / g or less.
  • the ratio of the pore volume B to the pore volume A (from the viewpoint of easily having a higher total trihalomethane filtration capacity even in water flow treatment at a high superficial velocity (SV) (
  • the pore volume B / pore volume A) is preferably 0.1 to 0.3, more preferably 0.15 to 0.3, and particularly preferably 0.15 to 0.20. preferable.
  • the activated carbon of the present invention preferably has a specific surface area of the activated carbon (value measured by the BET method using nitrogen as an adsorbed substance (one-point method)) of about 700 to 2500 m 2 / g, more preferably 1000 to For example, about 2000 m 2 / g.
  • the total pore volume of the activated carbon calculated by the QSDFT method is preferably about 0.35 to 1.50 cc / g, more preferably about 0.35 to 1.00 cc / g.
  • the activated carbon of the present invention is further improved in that it has a better balance between adsorption and diffusion of trihalomethane, and has a higher total trihalomethane filtration capability.
  • the ratio of the pore volume A is preferably about 70 to 90%, more preferably about 75 to 85%, and particularly preferably about 82 to 84%. It is done.
  • the proportion of the pore volume B in the total pore volume (100%) is preferably about 10 to 30%, more preferably about 12 to 19%, and particularly preferably 13 to 15%. Degree.
  • 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.
  • an infusible or carbonized organic material phenol
  • 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 one containing an yttrium compound as an activated carbon precursor is used in order to obtain the specific pore size distribution.
  • the activated carbon of this invention may contain the yttrium single-piece
  • Examples of the ratio (total) of the mass of the yttrium simple substance and the yttrium compound contained in the activated carbon in the total mass of the activated carbon of the present invention include 0.2 to 1.0% by mass, and 0.21 to 0%. 0.5% by mass is preferred.
  • the above ratio is a ratio in terms of yttrium element (that is, yttrium content) measured by an ICP emission spectroscopic analyzer (model 715-ES manufactured by Varian).
  • the form of the activated carbon of this invention is not specifically limited, For example, granular activated carbon, powdered activated carbon, fibrous activated carbon, etc. are mentioned. It is more preferable to use fibrous activated carbon from the viewpoint of processability when used after filtering and adsorption rate when used in a water purifier.
  • 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 of the fibrous activated carbon of the present invention is a value measured by an image processing fiber diameter measuring device (based on JIS K 1477).
  • Examples of the particle sizes of the granular activated carbon and the powdered activated carbon include an integrated volume percentage D 50 measured by a laser diffraction / scattering method of 0.01 to 5 mm.
  • the activated carbon of the present invention has a pore volume A having a pore diameter in the range of 1.5 nm or less of the pore volume calculated by the QSDFT method of 0.3 cc / g to 0.5 cc / g, and Among the pore volumes calculated by the QSDFT method, the pore volume B having a pore diameter in the range of 1.5 nm or more and 2.5 nm or less is 0.03 cc / g or more and 0.12 cc / g or less.
  • Activated carbon having a high total trihalomethane filtration capacity can also be obtained in the water flow treatment at the tower speed (SV).
  • Examples of the total trihalomethane filtration capacity in the water flow treatment at a high superficial velocity (SV) provided in the activated carbon of the present invention include 45 to 90 L / g in the case of SV3000h ⁇ 1 , preferably 50 to 70 L / g. Can be mentioned.
  • the method for producing activated carbon of the present invention includes a step of activating an activated carbon precursor containing 0.1 to 1.0% by mass of yttrium at a temperature of 900 to 1000 ° C. in an atmosphere having a CO 2 concentration of 50% by volume or more. Is preferred.
  • the activated carbon disclosed in Patent Document 1 has a small pore volume in the range of 1.5 nm to 2.5 nm.
  • Patent Document 2 discloses an activated carbon precursor containing at least one metal component of Mg, Mn, Fe, Y, Pt, and Gd in order to make the volume of pores having a pore diameter of 30 mm or more and less than 50 mm within a specific range.
  • a method for activating a body in an atmosphere containing nitrogen and saturated water vapor is disclosed.
  • the pore volume having a pore diameter in the range of 1.5 nm or less and the pore volume having a pore diameter in the range of 1.5 nm to 2.5 nm are sufficiently large. It cannot be assumed.
  • the activated carbon precursor containing yttrium 0.1-1.0 wt% by activation with slowly reactive activating gas of CO 2 containing 50% by volume or more than the water vapor
  • the pore volume in the range of 1.5 nm or less can be controlled to be in a specific range.
  • the main raw material for 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 theoretical carbonization yield at the time of carbonization, pitch is preferable, and coal pitch is particularly preferable among pitches.
  • the yttrium content of the activated carbon precursor is preferably 0.1 to 1.0% by mass, more preferably 0.1 to 0.5% by mass.
  • Yttrium can be contained by mixing yttrium alone or an yttrium compound with a raw material.
  • the yttrium compound include yttrium as a constituent metal element, metal oxide, metal hydroxide, metal halide, inorganic metal compound such as metal sulfate, salt of organic acid and metal such as acetic acid, organometallic compound, etc. Is mentioned.
  • the organometallic compound include metal acetylacetonate and aromatic metal compounds.
  • the activation atmosphere has a CO 2 concentration of 50% by volume or more, preferably 95% by volume or more, more preferably 99% by volume or more.
  • CO 2 when used as the activation gas, the reaction proceeds slowly. Therefore, the higher the CO 2 concentration, the easier the adjustment of the pore size distribution, and the easier it is to obtain the activated carbon of the present invention.
  • the activation ambient temperature is usually about 800 to 1000 ° C., preferably about 900 to 980 ° 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, the content of the yttrium compound, the CO 2 concentration in the activation gas, and the like. For example, assuming that the softening point as the main raw material of the activated carbon precursor using a pitch of 275 ° C. ⁇ 288 ° C., from 0.1 to 5.0 parts by mass as the amount of the yttrium compound of the activated carbon precursor, CO 2 concentration Is 100% by volume, the activation atmosphere temperature is 900 to 1000 ° C. and the activation time is 10 to 50 minutes.
  • Example and Comparative Example were evaluated by the following methods.
  • Yttrium content (mass%) of activated carbon precursor (infusible pitch fiber) The pitch fiber was incinerated, the ash was dissolved in an acid, and the ratio in terms of yttrium element measured by an ICP emission spectroscopic analyzer (model 715-ES manufactured by Varian) was defined as the yttrium content.
  • the yttrium content was defined as the ratio of yttrium element measured by dissolving fibrous activated carbon in an acid and measuring with an ICP emission spectroscopic analyzer (model 715-ES manufactured by Varian).
  • Pore volume (cc / g), specific surface area (m 2 / g), fiber diameter of fibrous activated carbon ( ⁇ m) The pore physical properties were measured from a nitrogen adsorption isotherm at 77K using “AUTOSORB-1-MP” manufactured by Quantachrome. The specific surface area was calculated from the measurement point of relative pressure 0.1 by the BET method. Pore volume in the pore diameter range described total pore volume and Table 1, compared the measured nitrogen desorption isotherm, by applying N 2 at 77K on carbon [slit pore, QSDFT equilibrium model] as Calculation model Analysis was performed by calculating the pore size distribution.
  • the pore volume in each pore diameter range shown in Table 1 is a reading value of a graph showing the pore diameter distribution shown in FIGS. 1 to 12, or a value calculated from the reading value. More specifically, the pore volume having a pore diameter of 0.65 nm or less is a reading value of Cumulative Pore Volume (cc / g) when the horizontal axis Pore Width of the pore diameter distribution chart is 0.65 nm.
  • a pore volume having a pore diameter of 0.8 nm or less, a pore volume having a pore diameter of 1.0 nm or less, a pore volume A having a pore diameter of 1.5 nm or less, and a pore volume having a pore diameter of 2.5 nm or less are obtained. It was.
  • the pore volume C having a pore diameter of 2.5 nm or more was calculated by subtracting the pore volume having a pore diameter of 2.5 nm or less from the total pore volume T obtained by the QSDFT method.
  • the pore volume in the pore diameter range of 0.65 to 0.8 nm was calculated by subtracting the pore volume having the pore diameter of 0.65 nm or less from the pore volume having the pore diameter of 0.8 nm or less.
  • the pore volume within the pore diameter range of 1.0 nm to 1.5 nm was calculated by subtracting the pore volume having the pore diameter of 1.0 nm or less from the pore volume A having the pore diameter of 1.5 nm or less.
  • the pore volume B in the pore diameter range of 1.5 nm to 2.5 nm was calculated by subtracting the pore volume A having a pore diameter of 1.5 nm or less from the pore volume having a pore diameter of 2.5 nm or less.
  • Example 1 As an organic material, a mixture of 1.0 part by mass of trisacetylacetonatoyttrium (metal type Y) with 100 parts by mass of a granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder, and a melting temperature of 320 Pitch fibers were obtained by melt-mixing at 0 ° C. and spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the content of yttrium (Y) was 0.16% 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 heat-treating it at an ambient temperature of 950 ° C. for 25 minutes to obtain activated carbon of Example 1. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.33 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.04 cc / g. g,
  • the content of yttrium was 0.30% by mass, and the average fiber diameter was 14.2 ⁇ m.
  • Example 2 As an organic material, a mixture of 1.0 part by mass of trisacetylacetonatoyttrium with 100 parts by mass of granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C. A pitch fiber was obtained by spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the yttrium content was 0.16% 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 heat-treating it at an ambient temperature of 950 ° C. for 32 minutes to obtain activated carbon of Example 2. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.42 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.07 cc / g. g,
  • the content of yttrium was 0.35% by mass, and the average fiber diameter was 14.2 ⁇ m.
  • Example 3 As an organic material, a mixture of 1.0 part by mass of trisacetylacetonatoyttrium with 100 parts by mass of granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C. A pitch fiber was obtained by spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the yttrium content was 0.16% by mass.
  • the activated carbon precursor 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 ambient temperature of 950 ° C. for 40 minutes to obtain activated carbon of Example 3. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.47 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.11 cc / g. g,
  • the content of yttrium was 0.41% by mass, and the average fiber diameter was 13.9 ⁇ m.
  • Example 4 As an organic material, a mixture of 1.0 part by mass of trisacetylacetonatoyttrium with 100 parts by mass of granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C. A pitch fiber was obtained by spinning at a discharge rate of 19 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the yttrium content was 0.16% 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 heat-treating it at an ambient temperature of 950 ° C. for 32 minutes to obtain activated carbon of Example 4. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.41 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.09 cc / g. g,
  • the content of yttrium in the obtained activated carbon was 0.37% by mass, and the average fiber diameter was 15.5 ⁇ m.
  • Example 5 As an organic material, a mixture of 1.0 part by mass of trisacetylacetonatoyttrium with 100 parts by mass of granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C. A pitch fiber was obtained by spinning at a discharge rate of 16 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the yttrium content was 0.16% by mass.
  • the activated carbon precursor thus obtained was activated by continuously introducing a gas having a CO 2 concentration of 50% by volume and an H 2 O concentration of 50% by volume into an activation furnace and heat-treating it at an ambient temperature of 950 ° C. for 15 minutes.
  • the activated carbon of Example 5 was obtained.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.32 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.09 cc / g. g,
  • the content of yttrium was 0.33% by mass, and the average fiber diameter was 14.6 ⁇ m.
  • Example 1 A test simulating Example 5 of Patent Document 2 was conducted. Specifically, an organic material obtained by mixing 1.3 parts by mass of trisacetylacetonatoyttrium with 100 parts by mass of a granular pitch having a softening point of 280 ° C. is supplied to a melt extruder at a melting temperature of 320 ° C. Pitch fibers were obtained by melt mixing and spinning at a discharge rate of 20 g / min. The obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber. In the activated carbon precursor, the yttrium content was 0.25% by mass.
  • the activated carbon precursor obtained 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 900 ° C. for 20 minutes. Obtained.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.34 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.13 cc / g. g,
  • the content of yttrium was 0.66% by mass, and the average fiber diameter was 16.5 ⁇ m.
  • the activated carbon precursor obtained 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 875 ° C. for 40 minutes. Obtained.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.47 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.01 cc / g. g,
  • the content of yttrium was 0% by mass, and the average fiber diameter was 16.7 ⁇ m.
  • 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 ambient temperature of 950 ° C. for 60 minutes to obtain activated carbon of Comparative Example 3. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.32 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.00 cc / g. g,
  • the content of yttrium was 0% by mass, and the average fiber diameter was 18.5 ⁇ m.
  • 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 ambient temperature of 950 ° C. for 67 minutes to obtain activated carbon of Comparative Example 4. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.61 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.11 cc / g. g,
  • the content of yttrium was 0.17% by mass, and the average fiber diameter was 16.8 ⁇ m.
  • 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 atmospheric temperature of 950 ° C. for 70 minutes to obtain activated carbon of Comparative Example 5. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.64 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.12 cc / g. g,
  • the content of yttrium was 0.18% by mass, and the average fiber diameter was 16.8 ⁇ m.
  • 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 atmospheric temperature of 950 ° C. for 60 minutes to obtain activated carbon of Comparative Example 6. It was.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.58 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.06 cc / g. g.
  • the content of yttrium was 0.15% by mass, and the fiber diameter was 18.2 ⁇ m.
  • a mixture of 1.0 part by mass of trisacetylacetonatoyttrium with 100 parts by mass of granular coal pitch having a softening point of 280 ° C. is supplied to a melt extruder and melt-mixed at a melting temperature of 320 ° C.
  • a pitch fiber was obtained by spinning at a discharge rate of 19 g / min.
  • the obtained pitch fiber was heated from normal temperature to 354 ° C. in air at a rate of 1 to 30 ° C./min for 54 minutes to effect infusibilization to obtain an activated carbon precursor as an infusible pitch fiber.
  • the yttrium content was 0.16% by mass.
  • the activated carbon precursor obtained was activated by continuously introducing a gas having a CO 2 concentration of 50% by volume and an H 2 O concentration of 50% by volume into an activation furnace and heat-treating it at an ambient temperature of 950 ° C. for 20 minutes.
  • the activated carbon of Comparative Example 7 was obtained.
  • the obtained activated carbon has a pore volume A having a pore diameter in the range of 1.5 nm or less of 0.35 cc / g, and a pore volume B having a pore diameter in the range of 1.5 to 2.5 nm of 0.15 cc / g. g,
  • the content of yttrium was 0.46% by mass, and the average fiber diameter was 14.6 ⁇ m.
  • the pore volume A having a pore diameter in the range of 1.5 nm or less is 0.3 cc / g or more and 0.5 cc / g or less.
  • the pore volume B having a pore diameter in the range of 1.5 nm to 2.5 nm is 0.03 cc / g to 0.12 cc / g.
  • the activated carbon of Example 2 has a pore volume A having a pore diameter in the range of 1.5 nm or less of the pore volume calculated by the QSDFT method of 0.4 cc / g or more and 0.5 cc / g or less.
  • the pore volume B having a pore diameter in the range of 1.5 nm to 2.5 nm is 0.06 cc / g to 0.12 cc / g, and the ratio of the pore volume B to the pore volume A ( Since the pore volume B / pore volume A) was 0.15 to 0.20, the total trihalomethane filtration ability was particularly excellent.
  • the pore volume B having a pore diameter in the range of 1.5 nm to 2.5 nm exceeds 0.12 cc / g. Therefore, the total trihalomethane filtration capacity was inferior.
  • the pore volume B having a pore diameter in the range of 1.5 nm to 2.5 nm was less than 0.03 cc / g. Therefore, the total trihalomethane filtration capacity was inferior.
  • the pore volume A having a pore diameter in the range of 1.5 nm or less out of the pore volumes calculated by the QSDFT method exceeded 0.5 cc / g.
  • the total trihalomethane filtration capacity was inferior.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

L'invention concerne également un charbon actif qui a une capacité de filtration de trihalométhane totale élevée même dans un traitement par passage d'eau avec une vitesse superficielle élevée (Vs). Du volume poreux calculé par la méthode QSDFT, le volume poreux A dans ce carbone actif de pores ayant un diamètre inférieur ou égal à 1,5 nm est de 0,3 à 0,5 cc/g, et, du volume de pore calculé par le procédé QSDFT, le volume de pore B des pores ayant un diamètre dans la plage allant de 1,5 à 2,5 nm est de 0,03 à 0,12 cc/g.
PCT/JP2017/044097 2016-12-19 2017-12-07 Charbon actif et sa méthode de production WO2018116859A1 (fr)

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CN110354805A (zh) * 2019-07-29 2019-10-22 江西师范大学 一种p-6型碱式碳酸钇/碳复合材料及其制备方法和应用
JP2020121288A (ja) * 2019-01-31 2020-08-13 株式会社タカギ トリハロメタン除去用活性炭およびその製造方法
JP2020157242A (ja) * 2019-03-27 2020-10-01 株式会社Ｌｉｘｉｌ 活性炭及び浄水カートリッジ
WO2023032633A1 (fr) * 2021-09-06 2023-03-09 株式会社アドール Charbon actif

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JP6471256B1 (ja) * 2018-05-18 2019-02-13 ユニチカ株式会社 脱臭材及び脱臭シート
EP3929153A4 (fr) * 2019-02-18 2022-11-23 Kuraray Co., Ltd. Charbon actif et sa méthode de production
KR102678135B1 (ko) * 2023-12-01 2024-06-25 주식회사 퓨어스피어 수처리용 활성탄소 및 이를 포함하는 수처리용 필터

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JP2020121288A (ja) * 2019-01-31 2020-08-13 株式会社タカギ トリハロメタン除去用活性炭およびその製造方法
JP7300124B2 (ja) 2019-01-31 2023-06-29 株式会社タカギ トリハロメタン除去用活性炭およびその製造方法
JP2020157242A (ja) * 2019-03-27 2020-10-01 株式会社Ｌｉｘｉｌ 活性炭及び浄水カートリッジ
WO2020195116A1 (fr) * 2019-03-27 2020-10-01 株式会社Ｌｉｘｉｌ Cartouche de purification d'eau et de charbon actif
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WO2023032633A1 (fr) * 2021-09-06 2023-03-09 株式会社アドール Charbon actif

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