CN105555714B - Activated carbon for water purifier - Google Patents
Activated carbon for water purifier Download PDFInfo
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- CN105555714B CN105555714B CN201580001883.0A CN201580001883A CN105555714B CN 105555714 B CN105555714 B CN 105555714B CN 201580001883 A CN201580001883 A CN 201580001883A CN 105555714 B CN105555714 B CN 105555714B
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
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- B01J20/28088—Pore-size distribution
- B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/14—Pore volume
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The powdery or granular activated carbon for a water purifier of the present invention has a BET specific surface area of 700m2More than/g and less than 1250m2(ii) a pore volume ratio of 2nm or less in pore diameter to 30nm or less in pore volume of 50% or more and less than 80%, and a pore volume ratio of 10% or more and less than 40% in pore diameter of more than 2nm and 10nm or less to 30nm or less in pore volume of pore diameter.
Description
Technical Field
The present invention relates to an activated carbon for water purifiers, and more particularly, to an activated carbon for water purifiers having excellent adsorption capacity for organic halides.
Background
Raw water for tap water must be treated with chlorine, and the treated tap water contains a certain amount of residual chlorine. On the other hand, the residual chlorine has not only a bactericidal action but also an oxidative decomposition action of organic substances, and generates organic halides such as trihalomethanes, which are carcinogenic substances. The residual organic halide in the tap water has a small molecular weight and an extremely low concentration in the tap water. Therefore, it is very difficult to sufficiently remove such organic halides with conventional activated carbon.
In order to solve such problems, a method of optimizing the pore size distribution of activated carbon has been proposed. Various proposals have been made in view of the fact that increasing the proportion of medium pore volume contributes to increasing the adsorption of the organic halide.
For example, patent document 1 proposes a granular carbon molded product formed by carbonizing a phenol resin powder and binding it to activated particles, and discloses a technique for improving the adsorption ability to a low-boiling-point organic chlorine compound by adjusting the specific surface area, the relationship between the pore diameter and the pore volume, the particle volume density, and the packing density.
In addition, patent document 2 discloses adjusting the diameter of pores
Pore volume, pore diameter
Pore volume ratio and pore diameter of
The adsorption ability to trihalomethanes is improved by the following pore volume ratio.
Documents of the prior art
Patent document
JP-A9-110409 in patent document 1
Japanese patent application laid-open No. 2006-247527 of patent document 2
Disclosure of Invention
In recent years, with the increase of demand for water, it has been required to improve the adsorption performance of activated carbon to organic halides under water delivery conditions. However, conventional activated carbon does not have sufficient adsorption performance under water transport conditions.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an activated carbon for a water purifier which has an excellent adsorption capacity of an organic halide in equilibrium and also has an excellent adsorption performance under water transport conditions.
The powdery or granular activated carbon for a water purifier according to the present invention, which solves the above-mentioned problems, has a BET specific surface area of 700m2More than/g and 1250m2(ii)/g or less, the pore volume ratio of pore diameter 2nm or less is 50% or more and less than 80% with respect to the pore volume of pore diameter 30nm or less, and the pore volume ratio of pore diameter more than 2nm and 10nm or less is 10% or more and 40% or less with respect to the pore volume of pore diameter 30nm or less.
The activated carbon for a water purifier according to the present invention has an embodiment in which the average pore diameter of the activated carbon is preferably 2.0nm or more and 4.0nm or less, and the pore volume ratio of 10nm or less is preferably 80% or more with respect to the pore volume of the activated carbon having a pore diameter of 30nm or less.
The activated carbon for a water purifier according to the present invention is preferably one in which the carbide of the paper-phenol resin laminate is activated so that the BET specific surface area falls within the above range, and more preferably, the activation treatment is a steam activation treatment.
The activated carbon for water purifiers of the present invention can exhibit excellent adsorption performance even under water transport conditions in addition to excellent equilibrium adsorption capacity for organic halides because the specific surface area and pore structure are optimized.
Drawings
FIG. 1 is a graph showing the relationship between the equilibrium adsorption amount of 1,1, 1-trichloroethane and the specific surface area in the equilibrium test of each activated carbon in the examples.
FIG. 2 is a graph showing the relationship between the water transport amount of 1,1, 1-trichloroethane and the specific surface area in the water transport test of each activated carbon in the examples.
FIG. 3 is a graph showing the pore size distribution of each activated carbon in examples.
Detailed Description
The organic halide is adsorbed in micropores having a pore diameter of 2nm or less, and in order to improve the adsorption performance of the organic halide under water transport conditions, it is necessary to increase the diffusion rate of the organic halide in the particles. It is therefore necessary to consider increasing the number of mesopores having a pore diameter of more than 2nm and 50nm or less as an input path leading to the micropores. However, the specific surface area and pore volume of conventional activated carbon cannot be strictly controlled, and organic halides cannot be efficiently removed under water transport conditions.
For example, in patent document 1, the ratio of pore volume of 0.6 to 0.8nm in pore diameter in a spherical phenolic resin is increased. However, in patent document 1, the large pores contributing to the increase in the diffusion rate of the organic halide in the pores are not considered sufficiently, and therefore, the adsorption performance under water transport conditions cannot be improved.
In addition, in patent document 2, it is desired to improve the adsorption performance of an organic halide under water transport conditions by improving the pore volume ratio of 2 to 10nm in pore diameter in an activated carbon using a fullerene as a raw material. However, from the viewpoint of satisfying both a higher adsorption amount and a diffusion rate of the organic halide under water transport conditions, there is still room for studying the relationship between the pore diameter and the pore volume. In particular, patent document 2 has a problem that the production cost is high by using fullerene as an activated carbon raw material, and the activated carbon using fullerene as a raw material is difficult to adjust in terms of specific surface area and pore volume in accordance with the improvement of the adsorption performance for organic halides under water transport conditions.
The inventors of the present invention have made studies on an activated carbon having not only an excellent equilibrium adsorption amount of an organic halide but also an excellent adsorption property under water transport conditions. As a result, they have found that the relationship between pore diameter and pore volume and the specific surface area can be well balanced between the adsorption amount and the diffusion rate of the organic halide.
That is, the powdery or granular activated carbon for water purifiers of the present invention can improve the equilibrium adsorption amount of an organic halide and the adsorption performance under water transport conditions by strictly adjusting the pore volume ratio of pores having a pore diameter of more than 2nm and not more than 10nm (hereinafter also referred to as "pore volume ratio of 2 to 10 nm") among mesopores contributing to the improvement of the diffusion rate of an organic halide, and the pore volume ratio of pores having a pore diameter of not more than 2nm contributing to the improvement of the adsorption amount of an organic halide (hereinafter also referred to as "pore volume ratio of not more than 2 nm"), and further strictly adjusting the specific surface area of the activated carbon.
The activated carbon for a water purifier of the present invention is characterized by having a BET specific surface area of 700m2More than/g and less than 1250m2(ii)/g, the pore volume ratio of 2nm or less is 50% or more and less than 80% with respect to the pore volume of 30nm or less in pore diameter (hereinafter also referred to as "total pore volume"), and the pore volume ratio of 2 to 10nm is 10% or more and less than 40% with respect to the total pore volume.
The activated carbon for water purifiers according to the present invention having the above-described configuration has a high rate of movement and diffusion of the organic halide in the activated carbon, and a large number of adsorption sites. Therefore, the activated carbon of the present invention is excellent in adsorption performance under water transport conditions.
The activated carbon of the present invention will be specifically described below.
[ BET specific surface area 700m2More than/g and less than 1250m2/g]
When the BET specific surface area of the activated carbon is too small, a sufficient adsorption amount cannot be obtained. Accordingly, the BET specific surface area is 700m2A ratio of 800m or more, preferably 800m2More preferably 900 m/g or more2More than g. On the other hand, when the BET specific surface area is too large, the packing density of the activated carbon decreases, and it is not possible to ensure a good balance between the pore volume ratio of 2nm or less, which contributes to an increase in the adsorption amount, and the pore volume ratio of 2 to 10nm, which contributes to an increase in the diffusion rate. Therefore, the BET specific surface area is less than 1250m2Per g, preferably 1100m2(ii) less than g, more preferably 1050m2A ratio of the total amount of the components to the total amount of the components is less than or equal to 1000m2/g。
[ the proportion of pore volume of pores having a pore diameter of 2nm or less to the total pore volume is 50% or more and less than 80% ]
Pores having a pore diameter of 2nm or less in the activated carbon are effective pores for increasing the adsorption amount of the organic halide, and when the pore volume ratio of 2nm or less is too small, a sufficient adsorption amount cannot be secured. Therefore, the pore volume ratio of 2nm or less is 50% or more, preferably 60% or more, and more preferably 70% or more, with respect to the total pore volume. On the other hand, when the pore volume ratio of 2nm or less is too large, the pore volume ratio of 2 to 10nm contributing to the increase of the diffusion rate cannot be sufficiently secured, and the adsorption performance under the water transport condition is lowered. Therefore, the pore volume ratio of 2nm or less is less than 80%, preferably 75% or less, with respect to the total pore volume.
[ the ratio of pore volume of pores having a pore diameter of more than 2nm and not more than 10nm to less than 40% based on the total pore volume ]
Pores having a pore diameter of more than 2nm and not more than 10nm in the activated carbon are effective in increasing the diffusion rate of the organic halide in the activated carbon to effectively improve the adsorption performance under water transport conditions. When the pore volume ratio of 2 to 10nm is too small, the diffusion rate becomes slow, and the adsorption performance under the water transport condition is lowered. Therefore, the pore volume ratio of 2 to 10nm to the total pore volume is 10% or more, preferably 15% or more, more preferably 20% or more, and still more preferably 25% or more. On the other hand, when the pore volume ratio of 2 to 10nm is too large, the pore volume ratio of 2nm or less decreases, and the adsorption amount decreases. Therefore, the pore volume ratio of 2 to 10nm is less than 40%, preferably 35% or less, with respect to the total pore volume.
In order to further improve the adsorption performance of the organic halide under water transport conditions, the following conditions are preferably satisfied.
[ pore volume ratio of 10nm or less to the total pore volume ]
As described above, pores having a pore diameter of 10nm or less in the activated carbon contribute to an increase in the adsorption amount and the diffusion rate, and by ensuring that the pore diameter is a certain amount or more, the adsorption performance of the activated carbon can be further improved. Therefore, the total volume ratio of the pore volume ratio of 2nm or less and the pore volume ratio of 2 to 10nm (hereinafter referred to as "pore volume ratio of 10nm or less") is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more, based on the total pore volume of the activated carbon. Although the upper limit is not particularly limited, when the pore volume ratio of 10nm or less is too large, mesopores or micropores having a large pore diameter, in which the pore diameter of the organic halide input passage is larger than 10nm, are reduced, and the rate of movement and diffusion of the organic halide in the activated carbon is reduced, thereby degrading the adsorption performance under water transport conditions. Therefore, the pore volume ratio of 10nm or less is preferably 98% or less, more preferably 96% or less, and still more preferably 95% or less, with respect to the total pore volume.
[ Total pore volume of activated carbon ]
The activated carbon of the present invention may satisfy the pore volume ratio, and the pore volume of pores having a pore diameter of 30nm or less, that is, the total pore volume is not limited. When the total pore volume is too small, a sufficient adsorption amount cannot be secured. Therefore, the total pore volume is preferably 0.30cm3A value of at least g, more preferably 0.40cm3A value of at least one gram, more preferably 0.50cm3More than g. The upper limit of the total pore volume is not particularly limited, but is preferably 0.80cm3A value of less than or equal to g, more preferably 0.70cm3The ratio of the carbon atoms to the carbon atoms is less than g.
[ average pore diameter of activated carbon ]
The average pore diameter of the activated carbon is not particularly limited, but is preferably 2.0nm or more, more preferably 2.1nm or more, further preferably 2.2nm or more, and further preferably 2.3nm or more, from the viewpoint of improving the efficiency of introducing the organic halide into the activated carbon. On the other hand, since the packing density decreases when the average pore diameter is too large, the average pore diameter of the activated carbon is preferably 4.0nm or less, more preferably 3.5nm or less, and still more preferably 3.0nm or less.
[ average particle diameter of activated carbon ]
The activated carbon of the present invention may be in the form of powder or granules, and the average particle size is not particularly limited, but is preferably 20 μm or more, more preferably 30 μm or more, further preferably 40 μm or more, preferably 300 μm or less, more preferably 150 μm or less, and further preferably 100 μm or less.
The activated carbon of the present invention has excellent adsorption performance for trihalomethanes such as trichloromethane, trifluoromethane, difluorochloromethane, dichlorobromomethane, dibromochloromethane, tribromomethane, etc., organic halides such as trichloroethane, trichloroethylene, etc., and preferably has excellent adsorption performance for 1,1, 1-trichloroethane which has a small molecular weight and is difficult to adsorb.
The activated carbon of the present invention is suitable for removing the above-mentioned substances contained in tap water or industrial wastewater.
The activated carbon of the present invention can preferably have an equilibrium adsorption amount of 20mg/g or more, more preferably 25mg/g or more, based on the equilibrium test in examples described later. The activated carbon of the present invention is suitable as an activated carbon for removing trihalide under water transport conditions, and the removal rate of organic halide by the water transport test in the examples described later can be maintained at 80% or more of the water transport amount, preferably 52L/g or more, more preferably 60L/g or more, still more preferably 70L/g or more, and still more preferably 80L/g or more.
The form of the water purifier using the activated carbon of the present invention is not particularly limited, and the water purifier can be used in various known water purifiers.
Next, a method for producing the activated carbon of the present invention will be specifically described, but the method for producing the activated carbon of the present invention is not limited to the following production examples, and can be appropriately modified, and such modifications are included in the scope of the present invention.
The activated carbon of the present invention can be produced by subjecting an activating raw material to an activating treatment. The "activation treatment" is a treatment of forming pores on the surface of the activation raw material to increase the specific surface area and pore volume. As the activation treatment, steam activation is preferably performed. The activation treatment may be performed once or more. The activating material may be a raw material of general activated carbon, and the following raw materials are particularly preferable.
The activating material is preferably a composite of an activating material that easily forms relatively large pores (hereinafter also referred to as a "medium pore-forming material") and an activating material that easily forms relatively small pores (hereinafter also referred to as a "fine pore-forming material"). When a composite of the mesoporous raw material and the microporous raw material is used as the activating raw material, activated carbon having a pore volume ratio corresponding to each pore diameter specified above can be obtained by one activating treatment without performing a plurality of activating treatments.
Examples of the medium pore-forming raw material include cellulose-based raw materials such as paper, cotton fiber, and wood material. Examples of the raw material for forming the micropores include synthetic resin-based raw materials such as phenol resins and furan resins. At least one of these medium pore-forming raw materials and fine pore-forming raw materials is used. The ratio of the medium pore-forming raw material to the fine pore-forming raw material may be appropriately changed according to the desired physical properties of the activated carbon. As the composite of the intermediate pore-forming raw material and the fine pore-forming raw material, for example, a paper-phenolic resin laminate is preferable.
The formation of mesopores or micropores can be strictly controlled by adjusting the activation conditions of the paper-phenol resin laminate as compared with activated carbon used as a raw material such as a phenol resin or a fullerene in patent document 1 or patent document 2. Therefore, precise control of the specific surface area, pore volume ratio, and the like of the activated carbon can be achieved. Thereby obtaining the activated carbon with excellent organic halide adsorption performance under the water delivery condition.
The mixture or composite of the medium pore-forming raw material and the fine pore-forming raw material is preferably used after being carbonized. The carbonization treatment may be generally performed by heating the carbon material in an inert gas atmosphere such as nitrogen, helium, or argon at a temperature and for a time at which the carbon material does not burn. The temperature of the carbonization treatment is preferably 500 ℃ or more, more preferably 550 ℃ or more, preferably 850 ℃ or less, and more preferably 800 ℃ or less. The holding time is not particularly limited, and the carbonized product may be held at the temperature for about 5 to 10 minutes or more.
The activation treatment is not particularly limited as long as the BET specific surface area and pore volume ratio of the activated carbon of the present invention are obtained. From the viewpoint of more convenient and accurate control of the BET specific surface area and the pore volume ratio, water vapor activation is preferable.
In the steam activation, the activating raw material is heated to a predetermined temperature, and then subjected to an activation treatment by supplying steam so that the BET specific surface area and the pore volume ratio are within the predetermined ranges. The heating of the activation raw material is preferably performed in an inert gas atmosphere such as nitrogen, argon, helium, or the like.
The temperature (furnace temperature) at the time of activation treatment is preferably 400 ℃ or higher, more preferably 450 ℃ or higher, preferably 1500 ℃ or lower, and more preferably 1300 ℃ or lower. The heating time in the activation treatment is preferably 0.5 hours or more, more preferably 1.0 hour or more, preferably 10 hours or less, and more preferably 5 hours or less.
The total amount of the water vapor supplied in the activation treatment is not particularly limited.
The supply form of the steam is not particularly limited, and may be any form in which the steam is supplied undiluted or in which the steam is diluted with an inert gas and supplied as a mixed gas, for example. For efficient activation, the solution is preferably diluted with an inert gas and supplied. When the water vapor is diluted with the inert gas and supplied, the partial pressure of the water vapor in the mixed gas (total pressure 101.3kPa) is preferably 30kPa or more, more preferably 40kPa or more.
The activated carbon activated with steam may be subjected to washing, heat treatment, or pulverization as needed. The activated carbon after the steam activation is washed with a known solvent such as water, an acid solution, or an alkali solution. By washing the activated carbon, impurities such as ash can be removed. The heat treatment is to heat the activated carbon after the steam activation or after the washing in an inert gas atmosphere. By heat-treating the activated carbon, water contained in the activated carbon can be removed. The pulverization treatment is carried out using a disk mill, a ball mill, a bead mill, or the like. The particle size of the activated carbon can be appropriately adjusted as necessary.
The present application claims benefit based on priority of japanese invention patent application No. 2014-76685, applied on 3/4/2014. The entire contents of the specification of japanese invention patent application No. 2014-76685, which was filed 4/3/2014, are incorporated by reference into this application.
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples, and can be modified appropriately within the spirit and scope of the present invention.
(measurement conditions, etc.)
1. Specific surface area, total pore volume
After 0.2g of activated carbon was heated at 250 ℃ in vacuum, an adsorption isotherm was obtained using a nitrogen adsorption apparatus ("ASAP-2400" manufactured by Micromeritics), and the specific surface area (m) was calculated by the BET method2(g), the total pore volume (V) of pores having a pore diameter of 30nm or less was calculated from the adsorption isothermtotal：cm3/g)。
2. Average pore diameter and pore volume of each pore diameter
The average pore diameter was calculated assuming that the shape of the pores formed by the activated carbon was cylindrical. The pore volume of each pore diameter was analyzed by the BJH method, and the pore volume of each pore diameter was calculated. Based on the specific surface area and the total pore volume calculated above, the following expressions (1) to (4) were calculated. Also, the pore size distribution is shown in FIG. 3.
Average pore diameter (nm) (4 × total pore volume) (V)total：cm3In terms of/g))/specific surface area (m)2/g)···(1)
Pore volume (V less than or equal to V) of pore diameter less than 2nm2nm：cm3(iv) — (V) total pore volumetotal：cm3Pore volume (V) of: (2-10 nm)2-10nm：cm3(V) g) + pore volume greater than 10nm10nm＜：cm3/g))···(2)
Pore volume (V) of pore diameter of more than 2nm and 10nm or less2-10nm：cm3(iv) — (V) total pore volumetotal：cm3Volume of pores (V) of ≤ g to (2 nm)2nm：cm3Per g) + fines greater than 10nmPore volume (V)10nm＜：cm3/g))···(3)
Pore volume (V) greater than 10nm10nm＜：cm3(iv) — (V) total pore volumetotal：cm3Volume of pores (V) of ≤ g to (2 nm)2nm：cm3(V) pore volume of 2-10nm in g + solution2-10nm：cm3/g))···(4)
3. Relative to total pore volume (V)total) Diameter of each pore (less than or equal to V)2nm、V2-10nm、V10nm<) pore volume ratio
The pore volume ratio (%) of each pore diameter was calculated by dividing the pore volume by the total pore volume.
4. Water delivery test
A water transport test was carried out in accordance with JIS S3201 (2010: test method for household water purifier) by packing 2.0g of activated carbon (diameter: 15mm) having a particle diameter adjusted to fall within the range of 53 to 250 μm in a column. Specifically, raw water with the concentration of 1,1, 1-trichloroethane adjusted to 0.3 +/-0.06 mg/L is used for 500h at Space Velocity (SV)-1Through the column. The concentration of 1,1, 1-trichloroethane before and after passing through the column was quantitatively determined by headspace gas chromatography. The inflection point (point of water vapor) was the concentration of 1,1, 1-trichloroethane in the effluent water relative to 20% of the column influent water, and the amount of 1,1, 1-trichloroethane water transported at the inflection point (total filtered water amount (L)/activated carbon mass (g) at the inflection point) was calculated]) As a filtration performance. The headspace gas chromatograph sample injector used was TurboMatrix HS manufactured by PerkinElmer, and the gas chromatograph mass spectrometer used was QP2010 manufactured by Shimadzu corporation.
5. Balance test
A stock solution was prepared by diluting 0.5g of 1,1, 1-trichloroethane with 50mL of methanol and then diluting the resulting solution 10 times with methanol. 5mL of the stock solution was diluted with pure water to prepare a 5mg/L aqueous solution of 1,1, 1-trichloroethane. A brown flask having a capacity of 100mL was charged with a stirrer and activated carbon having a particle size adjusted to a range of 53 to 250 μm, and then filled with an aqueous solution of 1,1, 1-trichloroethane and sealed. Thereafter, the flask was placed in a constant temperature bath maintained at 20 ℃ and stirred for 14 hours. After 14 hours, the aqueous solution in the flask was passed through a syringe filter. The equilibrium concentration (mg/L) of the 1,1, 1-trichloroethane aqueous solution in the filtrate was determined by headspace gas chromatography, the equilibrium adsorption amount (mg/g) of the 1,1, 1-trichloroethane aqueous solution divided by the mass of the activated carbon was determined, an adsorption isotherm curve was prepared, and the equilibrium adsorption amount of 1,1, 1-trichloroethane at an equilibrium concentration of 0.3mg/L was calculated as the adsorption amount of 1,1, 1-trichloroethane.
Activated carbon No.1
Carbon powder obtained by carbonizing a paper-phenolic resin laminate as a carbon raw material was heated at 870 ℃ and charged into a heating furnace adjusted to an inert atmosphere. While the paper-phenolic resin laminate was being charged, steam (partial pressure of steam: 40kPa) was supplied into a heating furnace, and steam activation treatment was carried out in an inert gas atmosphere for 2.0 hours to obtain activated carbon No. 1. The amount of steam supplied was 300 parts by weight per 100 parts by weight of the paper-phenol resin laminate.
Activated carbon No.2-4
Activated carbon Nos. 2 to 4 were prepared in the same manner as in activated carbon No.1, except that the activation time was changed.
Activated carbon No.5
As the activated carbon No.5, commercially available coconut shell steam-activated carbon (manufactured by MC Evave Technologies Corporation) was prepared.
Activated carbon No.6
Potassium hydroxide as an activating agent in an amount of 0.64 times by mass was added to 30g of the carbonized paper-phenol resin laminate, and the mixture was put into a heating furnace and activated at 800 ℃ for 2 hours in a nitrogen atmosphere. The obtained activated carbon was washed with water in warm water at 60 ℃ and then with hydrochloric acid (hydrochloric acid concentration: 5.25% by mass), and then washed with warm water at 60 ℃. Then, the activated carbon was placed in a muffle furnace, and the temperature in the furnace was raised to 750 ℃ under a nitrogen flow (2L/min) (rate of temperature rise: 10 ℃/min), and kept at 750 ℃ for 2 hours to prepare activated carbon No. 6.
TABLE 1
FIG. 1 shows the relationship between the equilibrium adsorption amount of 1,1, 1-trichloroethane and the specific surface area in the equilibrium test for each activated carbon. FIG. 2 shows the water transport amount of 1,1, 1-trichloroethane as a function of the specific surface area in the water transport test for each of the activated carbons. FIG. 3 shows the pore size distribution of activated carbon Nos. 1 to 6.
As shown in FIG. 1, activated carbon Nos. 1 to 4 using a paper-phenolic resin laminate had more excellent adsorption performance in the equilibrium test than activated carbon No.5 using coconut shells. Further, as shown in FIG. 2, activated carbon Nos. 1 to 4 had more excellent adsorption performance than activated carbon No.6 in the water transfer experiment.
As shown in FIG. 3, the activated carbon Nos. 1 to 4 have a larger pore volume ratio of 2 to 10nm than the activated carbon Nos. 5 and 6. Therefore, as shown in FIGS. 1 and 2, activated carbon Nos. 1 to 4 satisfying the requirements of the present invention exhibited excellent adsorption performance for 1,1, 1-trichloroethane in both the equilibrium test and the water transport test.
Claims (6)
1. An active carbon for a water purifier in the form of powder or granules, which is characterized in that,
BET specific surface area of 700m2More than g and less than 1000m2/g，
The pore volume ratio of pore volume of pore diameter 2nm or less to pore volume of pore diameter 30nm or less is 60% or more and less than 80%, and,
the ratio of pore volume of pores having diameters of more than 2nm and not more than 10nm to pore volume of pores having diameters of 30nm or less is 10% or more and less than 40%, and the average particle diameter is 20 μm or more.
2. The activated carbon for a water purifier according to claim 1, wherein the activated carbon has an average pore diameter of 2.0nm or more and 4.0nm or less.
3. The activated carbon for a water purifier as claimed in claim 1, wherein a pore volume ratio of 10nm or less is 80% or more with respect to a pore volume of 30nm or less in pore diameter in the activated carbon.
4. The activated carbon for a water purifier as claimed in claim 2, wherein a pore volume ratio of 10nm or less is 80% or more with respect to a pore volume of 30nm or less in pore diameter in the activated carbon.
5. The activated carbon for a water purifier as claimed in any one of claims 1 to 4, wherein the activated carbon is one in which a carbide of a paper-phenol resin laminate is subjected to an activation treatment so that a BET specific surface area is in the range.
6. The activated carbon for a water purifier as claimed in claim 5, wherein the activation treatment is a water vapor activation treatment.
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| EP3812349A4 (en) * | 2018-06-19 | 2022-02-09 | Ad'All Co., Ltd. | Activated carbon |
| JP6683969B1 (en) * | 2018-06-19 | 2020-04-22 | 株式会社アドール | Activated carbon |
| CN109012581B (en) * | 2018-07-24 | 2021-12-17 | 北海和荣活性炭科技有限责任公司 | Production method of composite carbon rod filter element for water purification |
| CN111247097B (en) * | 2018-09-28 | 2024-03-05 | 关西热化学株式会社 | Activated carbon and preparation method thereof |
| JP6542968B1 (en) * | 2018-09-28 | 2019-07-10 | 関西熱化学株式会社 | Activated carbon and method for producing the same |
| GB2584615C (en) * | 2019-05-20 | 2023-10-25 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| WO2022004594A1 (en) * | 2020-06-30 | 2022-01-06 | 株式会社クラレ | Carbonaceous material and method for producing same, water purification filter, and water purifier |
| DE102020117667B4 (en) * | 2020-07-03 | 2022-03-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | A manufacturing process of an impregnated sorbent for oxidizing and sorbing mercury |
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