JP2019018202A - Air purification device, filter for purifying air, water purification device, and cartridge for purifying water - Google Patents

Abstract

To provide a water purification device which can exhibit a water purification function sufficiently even when a filtration flow rate is high and in which such a problem is hardly caused that a porous carbon material leaks from a water purifier together with purified water.SOLUTION: The water purification device includes a column or a cartridge in which the porous carbon material is packed, which material has 1×10m/g or larger specific surface area when measured by a nitrogen BET method, 0.3 cm/g or higher pore volume when measured by the BJH method, and 75 μm or larger particle diameter. The bulk density of the porous carbon material is from 0.1 g/cmto 0.8 g/cm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a contaminant removing agent, a carbon / polymer composite, a contaminant removing sheet member, and a filter medium.

  As a water purifier for purifying water, activated carbon is often used as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2001-205253 and 06-106161. Moreover, the water purifier is often used by being directly attached to a faucet, for example.

JP 2001-205253 A JP-A-06-106161

  In such a conventional water purifier, there is a problem that if the flow rate of filtration is large, that is, if the flow rate of water flowing through the water purifier is high, the water purifying function may not be sufficiently exhibited. Moreover, although the pulverized product of activated carbon is often used for the purpose of increasing the specific surface area, there may be a problem that the pulverized activated carbon leaks from the water purifier together with the purified water. Furthermore, there is a strong demand for contaminant removers, carbon / polymer composites, and contaminant removal sheet members that can more effectively remove contaminants. In addition, there is a demand for controlling the hardness of water by passing through a filter medium, but a technique that can achieve such a demand is not known as long as the present inventors have investigated.

  Accordingly, a first object of the present invention is to provide a pollutant removing agent, a carbon / polymer composite, a pollutant removing sheet member, and a filter medium that can more effectively remove pollutants. A second object of the present invention is to provide a filter medium that can sufficiently perform the purification function even when the filtration flow rate is large and that does not easily cause a problem of flowing out with the purified fluid. Furthermore, the third object of the present invention is to provide a filter medium that can control the hardness of water.

The pollutant removing agent according to the first aspect of the present invention for achieving the first object has a specific surface area value of 1 × 10 ² m ² / gram or more by the nitrogen BET method and pores by the BJH method. Is made of a porous carbon material having a volume of 0.3 cm ³ / gram or more, preferably 0.4 cm ³ / gram or more, more preferably 0.5 cm ³ / gram or more, and a particle size of 75 μm or more. Such a porous carbon material may be referred to as “a porous carbon material according to the first aspect of the present invention” for convenience. Here, a porous carbon material having a particle diameter of 75 μm or more obtained by granulating a porous carbon material having a particle diameter of less than 75 μm, or a porous carbon material having a particle diameter of less than 75 μm and 75 μm or more. A porous carbon material having a particle diameter of 75 μm or more obtained by granulating a porous carbon material mixed with a porous carbon material is also referred to as a “porous carbon material having a particle diameter of 75 μm or more” in the present invention. Is included. The same applies to the following description.

The pollutant removing agent according to the second aspect of the present invention for achieving the first object described above has a specific surface area value of 1 × 10 ² m ² / gram or more according to the nitrogen BET method, a delocalization density It is made of a porous carbon material having a total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by a functional method of 1.0 cm ³ / gram or more and a particle size of 75 μm or more. . Such a porous carbon material may be referred to as “a porous carbon material according to the second aspect of the present invention” for convenience.

The pollutant removing agent according to the third aspect of the present invention for achieving the first object described above has a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method, and a delocalization density In the pore size distribution obtained by the functional method, the ratio of the total volume of pores having at least one peak in the range of 3 nm to 20 nm and having the pore size in the range of 3 nm to 20 nm is completely fine. It is made of a porous carbon material having a total pore volume of 0.2 or more and a particle size of 75 μm or more. Such a porous carbon material may be referred to as “a porous carbon material according to the third aspect of the present invention” for convenience.

The pollutant removing agent according to the fourth aspect of the present invention for achieving the first object described above has a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method and a fine particle size by mercury intrusion method. It is made of a porous carbon material having a pore volume of 1.0 cm ³ / gram or more and a particle size of 75 μm or more. Such a porous carbon material may be referred to as “a porous carbon material according to the fourth aspect of the present invention” for convenience.

  The carbon / polymer composite according to the first aspect of the present invention for achieving the first object comprises the porous carbon material according to the first aspect of the present invention and a binder.

  The carbon / polymer composite according to the second aspect of the present invention for achieving the first object comprises the porous carbon material according to the second aspect of the present invention and a binder.

  The carbon / polymer composite according to the third aspect of the present invention for achieving the first object comprises the porous carbon material according to the third aspect of the present invention and a binder.

  The carbon / polymer composite according to the fourth aspect of the present invention for achieving the first object comprises the porous carbon material according to the fourth aspect of the present invention and a binder.

  The pollutant removal sheet member according to the first aspect of the present invention for achieving the first object comprises the porous carbon material according to the first aspect of the present invention and a support member.

  The pollutant removal sheet member according to the second aspect of the present invention for achieving the first object comprises the porous carbon material according to the second aspect of the present invention and a support member.

  The pollutant removal sheet member according to the third aspect of the present invention for achieving the first object comprises the porous carbon material according to the third aspect of the present invention and a support member.

  The pollutant removal sheet member according to the fourth aspect of the present invention for achieving the first object comprises the porous carbon material according to the fourth aspect of the present invention and a support member.

  The filter medium according to the first aspect of the present invention for achieving the second object is composed of the porous carbon material according to the first aspect of the present invention.

  The filter medium according to the second aspect of the present invention for achieving the second object is composed of the porous carbon material according to the second aspect of the present invention.

  The filter medium according to the third aspect of the present invention for achieving the second object is composed of the porous carbon material according to the third aspect of the present invention.

  The filter medium according to the fourth aspect of the present invention for achieving the second object is composed of the porous carbon material according to the fourth aspect of the present invention.

The filter medium according to the fifth aspect of the present invention for achieving the above third object has a specific surface area value of 1 × 10 ² m ² / gram or more by the nitrogen BET method and a pore volume by the BJH method. It consists of a porous carbon material made from a plant that is at least 0.1 cm ³ / gram and contains at least one component selected from the group consisting of sodium, magnesium, potassium and calcium.

The filter medium according to the sixth aspect of the present invention for achieving the above third object has a specific surface area value of 1 × 10 ² m ² / gram or more by a nitrogen BET method, and a delocalized density functional method. The total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the above is 0.1 cm ³ / gram or more, preferably 0.2 cm ³ / gram or more, sodium, magnesium, It consists of a porous carbon material made from a plant containing at least one component selected from the group consisting of potassium and calcium.

The filter medium according to the seventh aspect of the present invention for achieving the third object described above has a specific surface area value of 1 × 10 ² m ² / gram or more by a nitrogen BET method, and a delocalized density functional method. In the pore size distribution obtained by the above, the ratio of the total volume of pores having at least one peak in the range of 3 nm to 20 nm and having the pore size in the range of 3 nm to 20 nm is the volume of all pores The total is 0.1 or more, and is made of a porous carbon material made from a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium and calcium.

The filter medium according to the eighth aspect of the present invention for achieving the above third object has a specific surface area value of 1 × 10 ² m ² / gram or more by the nitrogen BET method, and the pore volume by the mercury intrusion method. There is a 1.0 cm ³ / g or more, comprising sodium, magnesium, a plant comprising at least one component selected from the group consisting of potassium and calcium from the porous carbon material as a raw material.

The filter medium according to the ninth to fifteenth aspects of the present invention for achieving the first object described above,
It consists of a porous carbon material according to the first aspect of the present invention, or
It consists of a porous carbon material according to the second aspect of the present invention, or
It consists of a porous carbon material according to the third aspect of the present invention, or
It consists of the porous carbon material which concerns on the 4th aspect of this invention.

The filter medium according to the ninth aspect of the present invention continuously passes water containing 1 microgram / liter of a substance having a molecular weight of 1 × 10 ^{2 to} 1 × 10 ⁵ at a space velocity of 1200 hours- ¹ for 48 hours. When the liquid is applied, the time until the removal rate of the substance reaches 80% is more than twice the time until the removal rate of the substance reaches 80% when coconut shell activated carbon is used. Here, Kuraray Chemical Co., Ltd. Kuraray Coal GW is used as coconut shell activated carbon.

Moreover, when the filter medium according to the tenth aspect of the present invention was continuously passed through water containing 0.9 mg / liter of dodecylbenzenesulfonate at a space velocity of 1200 hours ^-1 for 25 hours, The removal rate of dodecylbenzene sulfonate is 10% or more.

In addition, when the filter medium according to the eleventh aspect of the present invention was continuously passed through water containing 6 microgram / liter of chlorothalonil at a space velocity of 1200 hr- ¹ for 50 hours, the removal rate of chlorothalonil was 60% or more.

The filter medium according to the twelfth aspect of the present invention removes dichloroboss when water containing 6 microgram / liter of dichloroboss is continuously passed for 25 hours at a space velocity of 1200 hours- ¹ . The rate is 60% or more.

Further, the filter medium according to the thirteenth aspect of the present invention is a soluble lead when water containing 6 microgram / liter of soluble lead is continuously passed through at a space velocity of 1200 hours- ¹ for 25 hours. The removal rate is 30% or more.

The filter medium according to the fourteenth aspect of the present invention, when water containing 0.2 milligram / liter of free chlorine is continuously passed for 50 hours at a space velocity of 1200 hours- ¹ , The removal rate is 70% or more.

The filter medium according to the fifteenth aspect of the present invention, when water containing 130 μg / liter of all organic halogens in terms of chlorine was continuously passed for 5 hours at a space velocity of 1200 hours- ¹ , The removal rate of all organic halogens is 45% or more.

Contaminant remover according to first to fourth aspects of the present invention, carbon / polymer composite according to first to fourth aspects of the present invention, first to fourth aspects of the present invention In the pollutant removal sheet member according to the aspect or the filter medium according to the first aspect to the fourth aspect and the ninth aspect to the fifteenth aspect of the present invention, the value of the specific surface area of the porous carbon material to be used Since the volume value and pore distribution of various pores are regulated, it is possible to remove pollutants with high efficiency, and to purify fluid with high filtration flow rate, and high efficiency. The desired material can be removed. Further, since the particle size of the porous carbon material is regulated, it is difficult for the problem that the porous carbon material flows out with the fluid. The contaminant removing agent according to the first to fourth aspects of the present invention, the carbon / polymer composite according to the first to fourth aspects of the present invention, and the first to fourth aspects of the present invention. In the contaminant removal sheet member according to the aspect 4 or the filter medium according to the first aspect to the fourth aspect of the present invention, in addition to the adsorption of the contaminant, for example,
HClO + C (porous carbon material) → CO (surface of porous carbon material)
⁺ H + + Cl ^-
The chlorine content is removed based on the chemical reaction. Further, in the filter medium according to the fifth aspect to the eighth aspect of the present invention, the specific surface area value of the porous carbon material to be used, the value of the pore volume, and the pore distribution are defined, And since the raw material is prescribed | regulated, the hardness of the water which passed the filter medium can be controlled.

FIGS. 1A and 1B are graphs showing the relationship between the test time of the filter medium of Example 1A, the filter medium of Comparative Example 1A and Comparative Example 1B, and the amounts of methylene blue and black 5 adsorbed per gram of the filter medium, respectively. It is. FIG. 2 shows the results of measuring the concentration of methylene blue in the water flowing out of the cartridge by filling the cartridge with the samples of Example 1B, Reference Example 1, Comparative Example 1C, and Comparative Example 1D, and flowing the methylene blue aqueous solution into the cartridge. It is a graph which shows. FIG. 3 is a schematic cross-sectional view of the water purifier according to the first embodiment. 4 is a schematic cross-sectional view of the contaminant removal sheet member of Example 1. FIG. FIG. 5 is a graph showing the chlorine removal rate in the filter medium made of the porous carbon material of Example 2, the filter mediums of Comparative Example 2A, Comparative Example 2B, and Comparative Example 2C. (A), (B) and (C) in FIG. 6 show the removal rates of chlorine, 1,1,1-trichloroethane and CAT in the filter medium made of the porous carbon material of Example 3 and the filter medium of Comparative Example 3, respectively. It is a graph which shows. FIG. 7 is a graph showing the removal rate of microcystin LR in the filter medium made of the porous carbon material of Example 4 and the filter medium of Comparative Example 4. FIG. 8 is a graph showing the high-speed adsorption characteristics and particle size dependence of the filter medium made of the porous carbon material of Example 5 and the filter medium of Comparative Example 5. (A) to (D) of FIG. 9 respectively show Example 6a, Example 6a ′, Example 6b, Example 6b ′, Example 6c, Example 6c ′, Example 6d, and Example 6d ′. It is a graph which shows the X-ray-diffraction result of a sample. 10A and 10B are graphs showing the measurement results of the pore volume of Example 6A, Example 6B, Example 6C and Example 6D, and Comparative Example 6. FIG. FIG. 11 is a graph showing the measurement results of the pore size distribution obtained by the filter media of Example 6A, Example 6B, Example 6C and Example 6D, and the delocalized density functional method of Comparative Example 6. is there. 12A and 12B are graphs showing the measurement results of the removal rate of sodium dodecylbenzenesulfonate in the samples of Example 7 and Comparative Example 7. FIG. FIGS. 13A and 13B are graphs showing the results of measuring the chlorothalonil removal rate of the samples of Example 7 and Comparative Example 7. FIG. FIG. 14 is a graph showing the results of measuring the dichloroboss removal rate of the samples of Example 7 and Comparative Example 7. FIG. 15 is a graph showing the measurement results of the removal rate of soluble lead in the samples of Example 7 and Comparative Example 7. 16A and 16B are graphs showing the results of measuring the free chlorine removal rate of the samples of Example 7 and Comparative Example 7. FIG. FIG. 17 is a graph showing the measurement results of the total organic halogen removal rate of the samples of Example 7 and Comparative Example 7. 18A and 18B are a schematic partial cross-sectional view and a schematic cross-sectional view of a bottle in Example 8. FIG. FIGS. 19A and 19B are a schematic partial cross-sectional view of a modified example of the bottle in Example 8 and a schematic surface with a part cut away.

Hereinafter, the present invention will be described based on examples with reference to the drawings. However, the present invention is not limited to the examples, and various numerical values and materials in the examples are examples. The description will be given in the following order.
1. Contaminant remover according to first to fourth aspects of the present invention, carbon / polymer composite according to first to fourth aspects of the present invention, first to fourth aspects of the present invention 1. General description of the contaminant removing sheet member according to the aspect and the filter medium according to the first to fifteenth aspects of the present invention. Example 1 (pollutant removing agent according to the first to fourth aspects of the present invention, carbon / polymer composite according to the first to fourth aspects of the present invention, the first aspect of the present invention) -Contaminant removing sheet member according to fourth aspect and filter medium according to first aspect-fourth aspect of the present invention)
3. Example 2 (Modification of Example 1)
4). Example 3 (another modification of Example 1)
5. Example 4 (another modification of Example 1)
6). Example 5 (another modification of Example 1)
7). Example 6 (filter medium according to the fifth to eighth aspects of the present invention)
8). Example 7 (filter medium according to ninth to fifteenth aspects of the present invention)
9. Example 8 (modification of Example 1 to Example 7), others

[Contaminant removing agent according to first to fourth aspects of the present invention, carbon / polymer composite according to first to fourth aspects of the present invention, and first to fourth aspects of the present invention] Contaminant Removal Sheet Member According to Aspect of Aspect and Filter Media According to First to Fifteenth Aspects of the Present Invention, General Description]
In the following description, the pollutant removing agents according to the first to fourth aspects of the present invention may be collectively referred to simply as “pollutant removing agent of the present invention”. The carbon / polymer composite according to the first aspect to the fourth aspect may be collectively referred to simply as “the carbon / polymer composite of the present invention”, or the first to fourth aspects of the present invention may be referred to. The pollutant removal sheet member according to the embodiment may be collectively referred to simply as “pollutant removal sheet member of the present invention”, or the filter media according to the first to fifteenth embodiments of the present invention may be collectively referred to. In some cases, it is simply referred to as “the filter medium of the present invention”. Further, the pollutant removing agent of the present invention, the carbon / polymer composite of the present invention, the pollutant removing sheet member of the present invention and the filter medium of the present invention may be collectively referred to simply as “the present invention”, The pollutant removing agent of the present invention, the carbon / polymer composite of the present invention, the pollutant removing sheet member of the present invention, and the first to fourth aspects and the ninth to fifteenth aspects of the present invention. The porous carbon materials constituting the filter medium may be collectively referred to as “porous carbon material in the present invention”.

The pollutant removing agent according to the first aspect of the present invention, the carbon / polymer composite according to the first aspect of the present invention, the contaminant removing sheet member according to the first aspect of the present invention, or the first of the present invention Although it does not limit in the porous carbon material which comprises the filter medium which concerns on an aspect, It is preferable that the volume of the pore by a mercury intrusion method is 1.5 cm < ³ > / gram or more. Moreover, it is preferable that the volume of the pore by MP method is 0.1 cm < ³ > / gram or more.

Contaminant remover according to the first to fourth aspects of the present invention including the above preferred embodiments, or the filter medium according to the first to fourth and ninth to fifteenth aspects of the present invention. In the porous carbon material constituting the material, the bulk density of the porous carbon material is preferably 0.1 gram / cm ^{3 to} 0.8 gram / cm ³ , although not limited thereto. By defining the bulk density of the porous carbon material within the above range, there is no possibility that the flow of fluid is hindered by the porous carbon material. That is, the pressure loss of the fluid resulting from the porous carbon material can be suppressed.

  In the filter medium according to the fifth to eighth aspects of the present invention including the preferred embodiments described above, the porous carbon material is sodium (Na), magnesium (Mg), potassium (K) and When a plant containing at least one component selected from the group consisting of calcium (Ca) is used as a raw material, and using such a plant raw material as a filter medium, a mineral component is contained in the filtered water from the porous carbon material. As a result of elution, the hardness of filtered water can be controlled. In this case, 1 gram of the filter medium is added to 50 ml of water having a hardness of 0.1 or less (test water), and the hardness after 5 hours can be 5 or more. In addition, it is preferable that sodium (Na), magnesium (Mg), potassium (K), and calcium (Ca) contain 0.4 mass% or more in total in a porous carbon material. Here, specific examples of plant raw materials include citrus peels such as mandarin orange peel, orange peel and grapefruit peel, and banana peel.

  Moreover, from the porous carbon material which comprises the filter medium which concerns on such a 5th aspect of this invention-the 8th aspect, various functional foods including the functional food as a mineral adjustment material for the purpose of mineral supplementation Cosmetics including cosmetics as mineral adjusting materials for the purpose of supplementing minerals, cosmetics, and the like can be configured. In addition, in the functional food, for example, excipients, binders, disintegrants, lubricants, diluents, flavoring agents, preservatives, stabilizers, coloring agents, fragrances, vitamins, coloring agents, Brighteners, sweeteners, bitters, acidulants, umami seasonings, fermented seasonings, antioxidants, enzymes, yeast extracts, and nutrient enhancers may be included. Examples of the functional food include powder, solid, tablet, granule, granule, capsule, cream, sol, gel, and colloid. Examples of cosmetics include cleansing agents that remove dirt components such as lotion, lotion-impregnated packs, sweat, oils and fats, and lipsticks, and have other cosmetic components that are hydrophobic. Substances (for example, daidzein, genistein) can be mentioned, and examples of ingredients having a moisturizing effect and / or antioxidant effect include active ingredients contained in lotions such as hyaluronic acid, astaxanthin, tocopherol, Trolox, and coenzyme Q10. be able to.

  The porous carbon material in the present invention is specified to have a particle size of 75 μm or more, and the specification is based on JIS Z8801-1: 2006 “Test sieve—Part 1: Metal mesh sieve”. That is, when a test is performed using a wire mesh having a nominal opening of 75 μm (so-called 200 mesh wire mesh) and the porous carbon material not passing through the wire mesh is 90% by mass or more, the particle size is defined as 75 μm or more. To do. In the following description, such a porous carbon material is referred to as a “200 mesh-on product”, and a porous carbon material that has passed through a 200-mesh wire mesh is referred to as a “200 mesh pass product”. When measuring the particle size, the measurement is performed in a state where the porous carbon material in the present invention is used, that is, primary particles and secondary particles in which a plurality of primary particles are aggregated.

  The measurement of pores by the mercury intrusion method conforms to JIS R1655: 2003 “Method for testing pore size distribution of compacts by mercury intrusion method of fine ceramics”. Specifically, mercury porosimetry was performed using a mercury porosimeter (PASCAL 440: manufactured by Thermo Electron). The pore measurement area was 15 μm to 2 nm.

  The pollutant removing agent of the present invention can be used, for example, for water purification or air purification, and broadly for fluid purification. Alternatively, the contaminant removal agent of the present invention can be used as a removal agent for the purpose of removing harmful substances and waste products, for example. As a usage form of the contaminant removing agent of the present invention, it is used in a sheet form, in a state where it is packed in a column or a cartridge, in a state of being contained in a water-permeable bag, and a binder (binder). The use in the state shape | molded to the desired shape using etc., and the use in a powder form can be illustrated. When used as a contaminant removal agent dispersed in a solution, the surface can be used after being subjected to a hydrophilic treatment or a hydrophobic treatment. For example, a filter, a mask, a protective glove, and a protective shoe of an air purification device can be configured from the carbon / polymer composite and the contaminant removing sheet member of the present invention.

  In the pollutant removal sheet member of the present invention including the preferred embodiments described above, examples of the support member include woven fabric and nonwoven fabric, and examples of the material constituting the support member include cellulose, polypropylene, and polyester. And as a form of a pollutant removal sheet member, the form in which the porous carbon material in the present invention is sandwiched between the support member and the support member, and the form in which the porous carbon material is kneaded into the support member can be mentioned. it can. Alternatively, as a form of the contaminant removing sheet member, the carbon / polymer composite of the present invention is sandwiched between the support member and the carbon / polymer composite of the present invention is kneaded into the support member. Can be mentioned. Examples of the binder constituting the carbon / polymer composite include carboxynitrocellulose.

  In a purification device suitable for incorporating the filter medium of the present invention including the above preferred form, specifically, in a water purifier (hereinafter sometimes referred to as “water purifier in the present invention”), a filtration membrane ( For example, a hollow fiber membrane or flat membrane having a hole of 0.4 μm to 0.01 μm can be provided (a combination of the filter medium and the filtration membrane of the present invention), and a reverse osmosis membrane (RO) Furthermore, it can be set as the structure (combination of the filter medium of this invention and a reverse osmosis membrane), and also has the structure (the filter medium of this invention, and the product made from ceramics) which further has the filter material made of ceramics (the filter medium made of ceramics which has a fine hole) A combination of a filter medium) and a configuration further including an ion exchange resin (a combination of the filter medium of the present invention and an ion exchange resin). In general, the filtered water that has passed through the reverse osmosis membrane (RO) contains almost no mineral components, but after passing through the reverse osmosis membrane (RO), the filtered water of the present invention is passed through to pass the filtered water. Can contain mineral components.

  Examples of the water purifier in the present invention include a continuous water purifier, a batch water purifier, and a reverse osmosis membrane water purifier, or a faucet direct connection type in which a water purifier main body is directly attached to the tip of a water faucet. , Stationary type (also called top sink type or tabletop type), faucet integrated type with water purifier built into the faucet, under sink type (built-in type) installed in the kitchen sink, pots and jugs Examples include a pot type (pitcher type) incorporating a water purifier inside, a central type directly attached to a water pipe after a water meter, a portable type, and a straw type. The configuration and structure of the water purifier in the present invention can be the same configuration and structure as a conventional water purifier. In the water purifier of the present invention, the filter medium (porous carbon material) of the present invention can be used, for example, in a cartridge, and the cartridge may be provided with a water inflow portion and a water discharge portion. The “water” to be purified in the water purifier of the present invention is not limited to “water” defined in “3. Terms and Definitions” of JIS S3201: 2010 “Home Water Purifier Test Method”. .

  Alternatively, as a member suitable for incorporating the filter medium of the present invention, a cap in a cap or lid, a straw member, a bottle with a spray member (so-called PET bottle), a laminate container, a plastic container, a glass container, a glass bottle, or the like, A lid can be mentioned. Here, the filter medium of the present invention is arranged inside the cap or lid, and the liquid or water (drinking water, lotion, etc.) in the bottle, laminate container, plastic container, glass container, glass bottle, etc. Mineral components can be contained in the filtered water by passing through the filter medium of the present invention disposed inside and drinking or using the filter medium. Alternatively, the filter medium of the present invention is stored in a bag having water permeability, and liquid or water in various containers such as bottles (so-called PET bottles), laminate containers, plastic containers, glass containers, glass bottles, pot jugs, etc. It is also possible to adopt a form in which this bag is put into drinking water or lotion.

  When the raw material of the porous carbon material in the present invention is a plant-derived material containing silicon (Si), specifically, although not limited, an ignition residue (residual ash content) in the porous carbon material ) Content is preferably 15% by mass or less. Further, the content of the ignition residue (residual ash) in the porous carbon material precursor or carbonaceous material described below is preferably 20% by mass or more. Here, the ignition residue (residual ash) is the mass% of the substance left when a sample dried at 120 ° C. for 12 hours is heated to 800 ° C. in air (dry air). Specifically, it can be measured based on a thermogravimetry (TG) method.

  The porous carbon material in the present invention or the porous carbon material constituting the filter medium according to the fifth to eighth aspects of the present invention is, for example, a plant-derived material at 400 ° C to 1400 ° C. After carbonization, it can be obtained by treatment with acid or alkali. In such a method for producing a porous carbon material (hereinafter sometimes simply referred to as “a method for producing a porous carbon material”), the plant-derived material is carbonized at 400 ° C. to 1400 ° C. The material obtained by the above process and before the treatment with acid or alkali is referred to as “porous carbon material precursor” or “carbonaceous substance”.

  In the manufacturing method of a porous carbon material, the process of performing an activation process can be included after the process with an acid or an alkali, and after performing an activation process, you may perform the process with an acid or an alkali. Further, in the method for producing a porous carbon material including such a preferable form, depending on the plant-derived material to be used, before carbonizing the plant-derived material, the temperature for carbonization is determined. Alternatively, the plant-derived material may be subjected to a heat treatment (preliminary carbonization treatment) at a low temperature (for example, 400 ° C. to 700 ° C.) in a state where oxygen is blocked. As a result, the tar component that will be generated in the carbonization process can be extracted. As a result, the tar component that will be generated in the carbonization process can be reduced or eliminated. The state in which oxygen is shut off is, for example, an inert gas atmosphere such as nitrogen gas or argon gas, or a vacuum atmosphere, or a plant-derived material is in a kind of steamed state. Can be achieved. Further, in the method for producing a porous carbon material, depending on the plant-derived material used, depending on the case, in order to reduce mineral components and moisture contained in the plant-derived material, In order to prevent the generation of a strange odor during the conversion process, the plant-derived material may be immersed in an acid or alkali, or in an alcohol (for example, methyl alcohol, ethyl alcohol, or isopropyl alcohol). In addition, in the manufacturing method of a porous carbon material, you may perform a preliminary carbonization process after that. As a material that is preferably heat-treated in an inert gas, for example, a plant that generates a large amount of wood vinegar liquid (tar or light oil) can be mentioned. In addition, examples of materials that are preferably pretreated with alcohol include seaweeds that contain a large amount of iodine and various minerals.

  In the method for producing a porous carbon material, a plant-derived material is carbonized at 400 ° C. to 1400 ° C. Here, carbonization is generally an organic substance (porous carbon in the present invention). In the case of the porous carbon material constituting the filter medium according to the fifth aspect to the eighth aspect of the present invention or the material of the present invention, it means that the plant-derived material) is heat-treated and converted into a carbonaceous substance. (For example, see JIS M0104-1984). The atmosphere for carbonization can include an atmosphere in which oxygen is shut off. Specifically, a vacuum atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas, and a plant-derived material as a kind of steamed state. The atmosphere to do can be mentioned. The rate of temperature rise until reaching the carbonization temperature is not limited, but in such an atmosphere, 1 ° C / min or more, preferably 3 ° C / min or more, more preferably 5 ° C / min or more. be able to. The upper limit of the carbonization time can be 10 hours, preferably 7 hours, more preferably 5 hours, but is not limited thereto. The lower limit of the carbonization time may be a time during which the plant-derived material is reliably carbonized. Moreover, the plant-derived material may be pulverized as desired to obtain a desired particle size, or may be classified. Plant-derived materials may be washed in advance. Alternatively, the obtained porous carbon material precursor or porous carbon material may be pulverized as desired to obtain a desired particle size or classified. Alternatively, the porous carbon material after the activation treatment may be pulverized as desired to obtain a desired particle size or may be classified. Further, the porous carbon material finally obtained may be sterilized. There is no restriction | limiting in the form, structure, and structure of the furnace used for carbonization, It can also be set as a continuous furnace and can also be set as a batch furnace (batch furnace).

  In the method for producing a porous carbon material, as described above, when the activation treatment is performed, micropores (described later) having a pore diameter smaller than 2 nm can be increased. Examples of the activation treatment method include a gas activation method and a chemical activation method. Here, the gas activation method uses oxygen, water vapor, carbon dioxide gas, air or the like as an activator, and in such a gas atmosphere, at 700 ° C. to 1400 ° C., preferably at 700 ° C. to 1000 ° C. More preferably, by heating the porous carbon material at 800 ° C. to 950 ° C. for several tens of minutes to several hours, the microstructure is developed by the volatile components and carbon molecules in the porous carbon material. is there. More specifically, the heating temperature may be appropriately selected based on the type of plant-derived material, the type and concentration of gas, and the like. The chemical activation method is activated with zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, sulfuric acid, etc. instead of oxygen and water vapor used in the gas activation method, washed with hydrochloric acid, alkaline In this method, the pH is adjusted with an aqueous solution and dried.

  Chemical treatment or molecular modification may be performed on the surface of the porous carbon material in the present invention or the surface of the porous carbon material constituting the filter medium according to the fifth to eighth aspects of the present invention. . Examples of the chemical treatment include a treatment for generating a carboxy group on the surface by nitric acid treatment. Moreover, various functional groups, such as a hydroxyl group, a carboxy group, a ketone group, an ester group, can also be produced | generated on the surface of a porous carbon material by performing the process similar to the activation process by water vapor | steam, oxygen, an alkali. Furthermore, molecular modification can also be achieved by chemically reacting a chemical species or protein having a hydroxyl group, a carboxy group, an amino group or the like that can react with the porous carbon material.

  In the method for producing a porous carbon material, the silicon component in the plant-derived material after carbonization is removed by treatment with acid or alkali. Here, examples of the silicon component include silicon oxides such as silicon dioxide, silicon oxide, and silicon oxide salts. Thus, the porous carbon material which has a high specific surface area can be obtained by removing the silicon component in the plant-derived material after carbonization. In some cases, the silicon component in the plant-derived material after carbonization may be removed based on a dry etching method. For example, it is possible to remove the mineral component contained in the plant-derived material after carbonization by immersing in an inorganic acid such as hydrochloric acid, nitric acid, and sulfuric acid.

  The porous carbon material in the present invention can be made from a plant-derived material. Here, as plant-derived materials, rice husks and straws such as rice (rice), barley, wheat, rye, rice husk and millet, rice beans, tea leaves (for example, leaves such as green tea and tea), Sugar cane (more specifically, sugar cane squeezed straw), corn (more specifically, corn core), the above-mentioned fruit skin (for example, citrus skin such as mandarin orange, banana skin, etc.) ), Or cocoons and stem wakame, but is not limited to these, and other examples include vascular plants, fern plants, moss plants, algae, and seaweeds that are vegetated on land. . In addition, these materials may be used independently as a raw material, and multiple types may be mixed and used. Further, the shape and form of the plant-derived material are not particularly limited, and may be, for example, rice husk or straw itself, or may be a dried product. Furthermore, what processed various processes, such as a fermentation process, a roasting process, an extraction process, can also be used in food-drinks processing, such as beer and western liquor. In particular, it is preferable to use straws and rice husks after processing such as threshing from the viewpoint of recycling industrial waste. These processed straws and rice husks can be easily obtained in large quantities from, for example, agricultural cooperatives, liquor manufacturers, food companies, and food processing companies.

  The porous carbon material in the present invention includes magnesium (Mg), potassium (K), calcium (Ca), nonmetallic elements such as phosphorus (P) and sulfur (S), and metal elements such as transition elements. It may be. Magnesium (Mg) content of 0.01% by mass to 3% by mass, potassium (K) content of 0.01% by mass to 3% by mass, calcium (Ca) content of 0.05% by mass % To 3% by mass, phosphorus (P) content of 0.01% to 3% by mass, and sulfur (S) content of 0.01% to 3% by mass. The content of these elements is preferably smaller from the viewpoint of increasing the specific surface area. Needless to say, the porous carbon material may contain elements other than the above-described elements, and the range of the content of each of the above-mentioned various elements can be changed.

  In the porous carbon material according to the present invention or the porous carbon material constituting the filter medium according to the fifth to eighth aspects of the present invention, various elements are analyzed, for example, energy dispersive X-rays. An analysis apparatus (for example, JED-2200F manufactured by JEOL Ltd.) can be used, and can be performed by an energy dispersion method (EDS). Here, the measurement conditions may be, for example, a scanning voltage of 15 kV and an irradiation current of 10 μA.

The porous carbon material in the present invention or the porous carbon material constituting the filter medium according to the fifth to eighth aspects of the present invention has many pores. The pore includes “mesopore” having a pore diameter of 2 nm to 50 nm, “micropore” having a pore diameter smaller than 2 nm, and “macropore” having a pore diameter exceeding 50 nm. In the porous carbon material of the present invention, the pore volume by the MP method is preferably 0.1 cm ³ / gram or more as described above.

In the porous carbon material according to the present invention or the porous carbon material constituting the filter medium according to the fifth to eighth aspects of the present invention, the specific surface area value by the nitrogen BET method (hereinafter simply referred to as “specific surface area”). Is preferably 4 × 10 ² m ² / gram or more in order to obtain even better functionality.

The nitrogen BET method is an adsorption isotherm measured by adsorbing and desorbing nitrogen as an adsorbed molecule on an adsorbent (here, a porous carbon material), and the measured data is converted into a BET equation represented by equation (1). Based on this method, the specific surface area, pore volume, and the like can be calculated. Specifically, when calculating the value of the specific surface area by the nitrogen BET method, first, an adsorption isotherm is obtained by adsorbing and desorbing nitrogen as an adsorbed molecule on the porous carbon material. Then, [p / {V _a (p ₀ −p)}] is calculated from the obtained adsorption isotherm based on the formula (1) or the formula (1 ′) obtained by modifying the formula (1), and the equilibrium relative pressure is calculated. Plot against (p / p ₀ ). Then, this plot is regarded as a straight line, and based on the least square method, the slope s (= [(C-1) / (C · V _m )]) and the intercept i (= [1 / (C · V _m )]) Is calculated. Then, V _m and C are calculated from the obtained slope s and intercept i based on the equations (2-1) and (2-2). Furthermore, the specific surface area a _sBET is calculated from V _m based on the formula (3) (see BELSORP-mini and BELSORP analysis software manual, pages 62 to 66, manufactured by Bell Japan Co., Ltd.). The nitrogen BET method is a measurement method according to JIS R 1626-1996 “Measurement method of specific surface area of fine ceramic powder by gas adsorption BET method”.

_{V a = (V m · C} · p) / [(p 0 -p) {1+ (C-1) (p / p 0)}] (1)
[P / {V _a (p ₀ −p)}]
= [(C-1) / (C · V _m )] (p / p ₀ ) + [1 / (C · V _m )] (1 ′)
V _m = 1 / (s + i) (2-1)
C = (s / i) +1 (2-2)
_{a sBET = (V m · L} · σ) / 22414 (3)

However,
V _a : Adsorption amount V _m : Adsorption amount of monolayer p: Nitrogen equilibrium pressure p ₀ : Nitrogen saturated vapor pressure L: Avogadro number σ: Nitrogen adsorption cross section.

When the pore volume V _p is calculated by the nitrogen BET method, for example, the adsorption data of the obtained adsorption isotherm is linearly interpolated to obtain the adsorption amount V at the relative pressure set by the pore volume calculation relative pressure. The pore volume V _p can be calculated from this adsorption amount V based on the formula (4) (see BELSORP-mini and BELSORP analysis software manual, page 62 to page 65, manufactured by Bell Japan Co., Ltd.). Hereinafter, the pore volume based on the nitrogen BET method may be simply referred to as “pore volume”.

V _p = (V / 22414) × (M _g / ρ _g ) (4)

However,
V: Adsorption amount at relative pressure M _g : Nitrogen molecular weight ρ _g : Nitrogen density.

The pore diameter of the mesopores can be calculated as a pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the BJH method. The BJH method is widely used as a pore distribution analysis method. When pore distribution analysis is performed based on the BJH method, first, desorption isotherms are obtained by adsorbing and desorbing nitrogen as adsorbed molecules on the porous carbon material. Then, based on the obtained desorption isotherm, the thickness of the adsorption layer when the adsorption molecules are attached and detached in stages from the state where the pores are filled with the adsorption molecules (for example, nitrogen), and the pores generated at that time obtains an inner diameter (twice the core radius) of calculating the pore radius r _p based on equation (5) to calculate the pore volume based on the equation (6). Then, the pore radius and the pore volume variation rate relative to the pore diameter (2r _p) from the pore volume (dV _p / dr _p) pore distribution curve is obtained by plotting the (Nippon Bel Co. Ltd. BELSORP-mini And BELSORP analysis software manual, pages 85-88).

r _p = t + r _k (5)
V _pn = R _n · dV _n -R _n · dt _n · c · ΣA _pj (6)
However,
R _n = r _pn ² / (r _kn −1 + dt _n ) ² (7)

here,
r _p : pore radius r _k : core radius (inner diameter / 2) when the adsorption layer having a thickness t is adsorbed on the inner wall of the pore having the pore radius r _p at that pressure
V _pn : pore volume dV _n when the nth attachment / detachment of nitrogen occurs: change amount dt _{n at} that time: change in the thickness t _n of the adsorption layer when the nth attachment / detachment of nitrogen occurs Amount r _kn : Core radius c at that time c: Fixed value r _pn : Pore radius when the nth attachment / detachment of nitrogen occurs. ΣA _pj represents the integrated value of the area of the wall surfaces of the pores from j = 1 to j = n−1.

  The pore diameter of the micropores can be calculated as a pore distribution from the pore volume change rate with respect to the pore diameter, for example, based on the MP method. When performing pore distribution analysis by the MP method, first, an adsorption isotherm is obtained by adsorbing nitrogen to a porous carbon material. Then, this adsorption isotherm is converted into a pore volume with respect to the thickness t of the adsorption layer (t plotted). A pore distribution curve can be obtained based on the curvature of this plot (the amount of change in pore volume with respect to the amount of change in the thickness t of the adsorption layer) (BELSORP-mini and BELSORP analysis software manuals manufactured by Bell Japan Co., Ltd.). 72 to 73 and 82).

  JIS Z8831-2: 2010 “Pore size distribution and pore characteristics of powder (solid) —Part 2: Method for measuring mesopores and macropores by gas adsorption” and JIS Z8831-3: 2010 “Powder” Analysis software for the delocalized density functional method (NLDFT method) defined in "Particle size distribution and pore characteristics of solid bodies (solid)-Part 3: Method for measuring micropores by gas adsorption" As an example, software attached to an automatic specific surface area / pore distribution measuring device “BELSORP-MAX” manufactured by Nippon Bell Co., Ltd. is used. As a precondition, the model is assumed to be a cylinder shape and carbon black (CB) is assumed, the distribution function of the pore distribution parameter is “no-assumtion”, and the obtained distribution data is smoothed 10 times.

The porous carbon material precursor is treated with an acid or alkali. Specific treatment methods include, for example, a method of immersing the porous carbon material precursor in an acid or alkali aqueous solution, or a porous carbon material precursor and an acid. Or the method of making it react with an alkali by a gaseous phase can be mentioned. More specifically, when treating with an acid, examples of the acid include fluorine compounds exhibiting acidity such as hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, and sodium fluoride. When a fluorine compound is used, it is sufficient that the amount of fluorine element is 4 times the amount of silicon element in the silicon component contained in the porous carbon material precursor, and the concentration of the fluorine compound aqueous solution is preferably 10% by mass or more. When the silicon component (for example, silicon dioxide) contained in the porous carbon material precursor is removed by hydrofluoric acid, the silicon dioxide is mixed with hydrofluoric acid as shown in chemical formula (A) or chemical formula (B). It reacts and is removed as hexafluorosilicic acid (H ₂ SiF ₆ ) or silicon tetrafluoride (SiF ₄ ) to obtain a porous carbon material. Thereafter, washing and drying may be performed. In the case of treating with an acid, for example, the mineral component contained in the porous carbon material precursor can be removed by treating with an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid.

SiO ₂ + 6HF → H ₂ SiF ₆ + 2H ₂ O (A)
SiO ₂ + 4HF → SiF ₄ + 2H ₂ O (B)

Moreover, when processing with an alkali (base), sodium hydroxide can be mentioned as an alkali, for example. When an alkaline aqueous solution is used, the pH of the aqueous solution may be 11 or more. When the silicon component (for example, silicon dioxide) contained in the porous carbon material precursor is removed with the aqueous sodium hydroxide solution, the silicon dioxide is heated as shown in the chemical formula (C) by heating the aqueous sodium hydroxide solution. It reacts and is removed as sodium silicate (Na ₂ SiO ₃ ) to obtain a porous carbon material. In addition, when processing by reacting sodium hydroxide in the gas phase, the sodium hydroxide solid is heated to react as shown in the chemical formula (C) and is removed as sodium silicate (Na ₂ SiO ₃ ). A porous carbon material can be obtained. Thereafter, washing and drying may be performed.

SiO ₂ + 2NaOH → Na ₂ SiO ₃ + H ₂ O (C)

Alternatively, as the porous carbon material in the present invention or the porous carbon material constituting the filter medium according to the fifth to eighth aspects of the present invention, for example, pores disclosed in JP 2010-106007 A Is a porous carbon material having a three-dimensional regularity (so-called porous carbon material having an inverse opal structure), specifically, an average diameter of 3 × 10 ⁻⁹ m to 1 × 10 ⁻⁵ m. Porous carbon material having dimensionally arranged spherical holes and a surface area of 3 × 10 ² m ² / gram or more, preferably macroscopically arranged in an arrangement corresponding to the crystal structure Alternatively, it is possible to use a porous carbon material in which pores are arranged on the surface in an arrangement state corresponding to the (111) plane orientation in the face-centered cubic structure macroscopically.

  Example 1 is a contaminant removing agent according to the first to fourth aspects of the present invention, the carbon / polymer composite according to the first to fourth aspects of the present invention, and the first of the present invention. The present invention relates to a pollutant removing sheet member according to the fourth to fourth aspects and the filter medium according to the first to fourth aspects of the present invention.

When the contaminant removal agent or filter medium of Example 1 is expressed according to the contaminant removal agent or filter medium according to the first aspect of the present invention, the specific surface area value by the nitrogen BET method is 1 × 10 ² m ² / gram. As described above, a porous carbon material having a pore volume by the BJH method of 0.3 cm ³ / gram or more, preferably 0.4 cm ³ / gram or more, more preferably 0.5 cm ³ / gram or more and a particle size of 75 μm or more. Consists of. Further, when expressed in accordance with the contaminant removing agent or filter medium according to the second aspect of the present invention, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / gram or more, the delocalized density functional method The total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m obtained by (NLDFT method, Non Localized Density Functional Theory method) (referred to as “volume A” for convenience) is 1.0 cm. ³ / gram or more and a porous carbon material having a particle size of 75 μm or more. Furthermore, when expressed in accordance with the contaminant removal agent or filter medium according to the third aspect of the present invention, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / gram or more, the delocalized density functional In the pore size distribution obtained by the method, the proportion of the total volume of pores having at least one peak in the range of 3 nm to 20 nm and having the pore size in the range of 3 nm to 20 nm is the total pore size. It is made of a porous carbon material having a volume total of 0.2 or more and a particle size of 75 μm or more. Further, when expressed in accordance with the contaminant removing agent or filter medium according to the fourth aspect of the present invention, the specific surface area value by the nitrogen BET method is 1 × 10 ² m ² / gram or more, and the pore volume by the mercury intrusion method. Is made of a porous carbon material having a diameter of 1.0 cm ³ / gram or more and a particle diameter of 75 μm or more.

Incidentally, the pores by the BJH method (mesopores), the pores by the MP method (micropores), and the pores by the mercury intrusion method are at least due to the removal of silicon from the plant-derived material containing silicon. can get. The pore volume of the porous carbon material by mercury porosimetry is more preferably 2.0 cm ³ / gram or more, and the pore volume by MP method is preferably 0.1 cm ³ / gram or more. The bulk density of the porous carbon material is preferably 0.1 gram / cm ^{3 to} 0.8 gram / cm ³ .

  In Example 1, rice (rice) rice husk was used as the plant-derived material that is the raw material of the porous carbon material. And the porous carbon material in Example 1 is obtained by carbonizing the chaff as a raw material, converting it into a carbonaceous substance (porous carbon material precursor), and then performing an acid treatment. Hereinafter, the manufacturing method of the porous carbon material in Example 1 is demonstrated.

  In the production of the porous carbon material in Example 1, the plant-derived material was carbonized at 400 ° C. to 1400 ° C. and then treated with an acid or an alkali to obtain a porous carbon material. That is, first, heat treatment (preliminary carbonization treatment) is performed on the rice husk in an inert gas. Specifically, the rice husk was carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain a carbide. In addition, by performing such a process, the tar component which will be produced | generated at the time of the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was put in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonized at 800 degreeC for 1 hour, after converting into a carbonaceous substance (porous carbon material precursor), it cooled to room temperature. In addition, nitrogen gas was continued to flow during carbonization and cooling. Next, this porous carbon material precursor was subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed with water and ethyl alcohol until pH 7 was reached. Next, after drying at 120 ° C, the porous carbon material of Example 1 is obtained by performing activation treatment by heating at 900 ° C in a water vapor stream (5 liters / minute) for 3 hours. I was able to. And Example 1A was able to be obtained by grind | pulverizing the porous carbon material of Example 1, passing through a sieve, and extract | collecting the part of 60 mesh pass and 200 mesh on.

  The filter medium used in a commercially available water purifier was passed through a sieve to collect a portion of 60 mesh pass / 200 mesh on to be Comparative Example 1A and Comparative Example 1B. The filter medium in Comparative Example 1A is made of silica, and the filter medium in Comparative Example 1B is made of bamboo charcoal.

A nitrogen adsorption / desorption test was performed using BELSORP-mini (manufactured by Nippon Bell Co., Ltd.) as a measuring instrument for determining the specific surface area and pore volume. As measurement conditions, the measurement equilibrium relative pressure (p / p ₀ ) was set to 0.01 to 0.99. The specific surface area and pore volume were calculated based on BELSORP analysis software. In addition, the pore size distribution of mesopores and micropores was calculated based on the BJH method and the MP method using BELSORP analysis software after performing a nitrogen adsorption / desorption test using the above-described measuring instrument. Furthermore, in the measurement based on the delocalized density functional method (NLDFT method), an automatic specific surface area / pore distribution measuring device “BELSORP-MAX” manufactured by Nippon Bell Co., Ltd. was used. In the measurement, the sample was dried at 200 ° C. for 3 hours as a pretreatment.

When the specific surface area and pore volume were measured for the filter media of Example 1A, Comparative Example 1A, and Comparative Example 1B, the results shown in Table 1 were obtained. In Table 1, “specific surface area” refers to the value of the specific surface area by the nitrogen BET method, and the unit is m ² / gram. “MP method” and “BJH method” indicate the volume measurement results of pores (micropores) by the MP method and the volume measurement results of pores (mesopores to macropores) by the BJH method. Is cm ³ / gram. In Table 1, “total pore volume” refers to the value of the total pore volume according to the nitrogen BET method, and the unit is cm ³ / gram. Furthermore, the total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m based on the delocalized density functional method (NLDFT method) (volume A, total volume of all pores) Table 2 shows the ratio (volume ratio) of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm with respect to. In addition, although the pore volume measurement result based on the BJH method in Comparative Example 1A and the volume total (volume A) measurement result of all pores based on the NLDFT method show large values, this is the same as in Comparative Example 1A. This is because the filter medium is not made of a porous carbon material but is made of silica.

  To measure the amount of adsorption, an aqueous solution of 0.03 mol / liter of methylene blue and 0.5 mmol / liter of black 5 was prepared, and 10 milligrams of the sample was added to each 40 milliliter of the aqueous solution. And it stirs at 100 rpm using a mix rotor (stirrer), stirs as 0.5 minutes, 1 minute, 3 minutes, 5 minutes, 15 minutes, 30 minutes, 60 minutes, 180 minutes, and filters. Based on the test method for measuring the change in absorbance of the obtained filtrate, the relationship between the stirring time and the amount of adsorption of methylene blue and black 5 per gram of the filter medium is determined from the value of the calibration curve obtained from the absorbance per unit mass. Calculated.

  The results are shown in FIG. 1 (A) and (B), the amount of adsorption of methylene blue and black 5 of the filter medium of Example 1A is much larger than the amount of adsorption of the filter medium of Comparative Example 1A and Comparative Example 1B, This is considered to be an effect of large-volume mesopores and macropores that are not observed in the comparative example. In addition, the vertical axis | shaft of FIG. 1 is adsorption amount (unit: milligram / gram), and a horizontal axis is a test time (Time which immersed the filter medium in the test solution, and a unit is a minute). Further, the triangle mark indicates data of Example 1A, the square mark indicates data of Comparative Example 1A, and the circle mark indicates data of Comparative Example 1B.

  In addition, the filter medium of Example 1 in another production lot was manually pulverized using a mortar to obtain the filter medium of Example 1B. However, the filter medium of Example 1B was a 200 mesh-on product, and the particle size was 0.50 mm to 0.85 mm. Also, a 200-mesh pass filter medium obtained at the same time was used as Reference Example 1. When the specific surface area and pore volume were measured, the results shown in Table 1 were obtained. Furthermore, activated carbon was taken out from a commercially available water purifier, and those having a particle size of 0.50 mm to 0.85 mm were collected from these activated carbons and evaluated as Comparative Example 1C and Comparative Example 1D.

  Furthermore, 200 mg of the sample of Example 1B, Reference Example 1, Comparative Example 1C, and Comparative Example 1D was filled in the cartridge, respectively, and the methylene blue aqueous solution was flowed through the cartridge at a flow rate of 50 ml / min, and was discharged from the cartridge. The methylene blue concentration of water was measured. The result is shown in FIG. The vertical axis in FIG. 2 is the methylene blue adsorption rate (removal rate), which is a value normalized with the adsorption amount (removal rate) of the filter medium of Reference Example 1 as 100%. The horizontal axis represents the flow rate of the methylene blue aqueous solution. Also from FIG. 2, the amount of methylene blue adsorbed on the filter media of Example 1B (indicated by square marks) and Reference Example 1 (indicated by rhombus marks) is Comparative Example 1C (indicated by triangular marks) or Comparative Example 1D (indicated by circular marks). ) Is much higher than

  A sectional view of the water purifier of Example 1 is shown in FIG. The water purifier of Example 1 is a continuous water purifier, and is a faucet-directly connected water purifier in which a water purifier body is directly attached to the tip of a water faucet. The water purifier of Example 1 is disposed inside the water purifier main body 10 and the water purifier main body 10, and is filled with the porous carbon material 11 of Example 1A or Example 1B and Reference Example 1, A second filling portion 14 filled with cotton 13 is provided. The tap water discharged from the tap is discharged from the inlet 15 provided in the water purifier main body 10 through the porous carbon material 11 and cotton 13 and discharged from the outlet 16 provided in the water purifier main body 10. Is done.

  A schematic diagram showing the cross-sectional structure of the contaminant removal sheet member of Example 1 is shown in FIG. The contaminant removal sheet member of Example 1 includes Example 1A or Example 1B, the porous carbon material of Reference Example 1, and a support member. Specifically, the pollutant removal sheet member of Example 1 is a porous carbon material formed into a sheet between a support member (nonwoven fabric 2) and a support member (nonwoven fabric 2) made of cellulose, that is, carbon / It has a structure in which the polymer composite 1 is sandwiched. The carbon / polymer composite 1 is composed of the porous carbon material of Example 1A or Example 1B and Reference Example 1, and a binder, and the binder is composed of, for example, carboxynitrocellulose. In addition, the porous carbon material of Example 1A or Example 1B and Reference Example 1 is applied to the support member, or the porous carbon material of Example 1 is kneaded into the support member. It can also be made into a form.

  The second embodiment is a modification of the first embodiment. In Example 2, an evaluation test on the removal rate of chlorine was performed.

  In the production of the porous carbon material in Example 2, the plant-derived material was carbonized at 400 ° C. to 1400 ° C. and then treated with an acid or alkali to obtain a porous carbon material. That is, first, heat treatment (preliminary carbonization treatment) is performed on the rice husk in an inert gas. Specifically, the rice husk was carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain a carbide. In addition, by performing such a process, the tar component which will be produced | generated at the time of the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was put in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonized at 800 degreeC for 1 hour, after converting into a carbonaceous substance (porous carbon material precursor), it cooled to room temperature. In addition, nitrogen gas was continued to flow during carbonization and cooling. Next, this porous carbon material precursor was subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed with water and ethyl alcohol until pH 7 was reached. Next, after drying at 120 ° C., the activation treatment is performed by heating at 900 ° C. in a steam stream (3.5 liter / min) for 3 hours, so that the porous carbon material of Example 2 is used. Could get.

When the specific surface area and pore volume of the filter medium in Example 2 were measured, the results shown in Table 1 were obtained. The filter medium of Example 2 was pulverized to adjust the particle size to obtain a 200 mesh-on product. Samples of Example 2A and Example 2B having two types of particle size distributions were prepared. Table 3 shows the particle size distribution measurement results using a sieve. Furthermore, activated carbon was taken out from a commercially available water purifier, and these activated carbons were evaluated as Comparative Example 2A, Comparative Example 2B, and Comparative Example 2C. In addition, the mass (unit: grams) when each sample is filled in the first filling portion 12 having the same volume (2.0 cm ³ ) is shown in Table 1, and when the first filling portion 12 is filled with each sample, The filling rate may be called “filling rate”. Furthermore, a fine pore having a pore diameter within a range of 3 nm to 20 nm based on the total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m (total volume of all pores) based on the NLDFT method. Table 2 shows the volume ratio of the total pore volume. Moreover, the measurement result of the mercury intrusion method is shown below. Furthermore, a sample obtained by drying at 120 ° C. for 12 hours was heated to 800 ° C. with 300 ml / min of dry air based on the thermogravimetry (TG) method. The measurement results of residual ash) are shown below. In addition, the measurement result of the ignition residue (residual ash content) in the porous carbon material of Example 1 and Example 7, the measurement of the ignition residue (residual ash content) in the porous carbon material precursor before the acid treatment. The results are also shown.

[Measurement results of mercury intrusion method]
Example 2 4.12 cm ³ / gram Comparative Example 2A 0.26 cm ³ / gram Comparative Example 2B 0.35 cm ³ / gram Comparative Example 2C 0.24 cm ³ / gram

[Still heat]
Example 1 5.83%
Example 2 3.49%
Example 7 7.29%
Porous carbon material precursor 43.27%

In the test, a glass tube having an inner diameter of 7.0 mm was filled with each sample having a volume of 2 ml, and chlorine water having a concentration of 2.0 mg / liter was caused to flow through the glass tube at a flow rate of 400 ml / min. And
Removal rate based on DPD spectrophotometry (%)
= (Raw water measured value-passing water measured value) / raw water measured value x 100
FIG. 5 shows the chlorine removal rate measurement results obtained based on the above method. The flow rate of 400 ml / min is converted into space velocity (SV) as follows.

SV = 400 × 60 (milliliter / hour) / 2 cm ³ = 12000 hour ⁻¹

  From FIG. 5, the filter medium made of the porous carbon material of Example 2A and Example 2B has a remarkably high chlorine removal rate as compared with Comparative Example 2A, Comparative Example 2B, and Comparative Example 2C.

The third embodiment is also a modification of the first embodiment. In Example 3, the removal rate of chlorine, the removal rate of 1,1,1-trichloroethane, and the removal rate of 2-chloro-4,6 bisethylamino-1,3,5-triazine (CAT) A test was conducted. The removal rate was calculated from the following equation by gas chromatography analysis. As the porous carbon material constituting the filter medium of Example 3, the porous carbon material (200 mesh-on product) of Example 2A was used. As Comparative Example 3, the same filter medium as Comparative Example 2C was used.
Removal rate (%) = (raw water measured value−passing water measured value) / raw water measured value × 100

  Using the filter medium of Example 3 and Comparative Example 3, a glass tube having an inner diameter of 10.0 mm was filled with each sample having a volume of 10 milliliters, chlorine water having a concentration of 2.0 milligrams / liter, 0.3 milligrams / liter of chlorine water. A 1,1,1-trichloroethane aqueous solution having a concentration and a CAT aqueous solution having a concentration of 0.003 milligram / liter were allowed to flow through the glass tube at a flow rate of 400 ml / min. The removal rates of chlorine, 1,1,1-trichloroethane and CAT are shown in FIGS. 6 (A), (B) and (C). 6 (A), (B) and (C), it can be seen that the filter medium made of the porous carbon material of Example 3 has a remarkably high removal rate as compared with Comparative Example 3. It was. The flow rate of 400 ml / min is converted into space velocity (SV) as follows.

SV = 400 × 60 (milliliter / hour) / 10 cm ³ = 2400 hour ⁻¹

  In eutrophied lakes and ponds, cyanobacteria (microkistis, etc.) grow abnormally, especially in the summer, and a thick layer of water is covered with green powder. Is called Aoko. This cyanobacteria is known to generate toxins that are harmful to the human body. Among many toxins, a toxin called microcystin LR is particularly wary. When microcystin LR enters the living body, the liver is severely damaged, and its toxicity has been reported in experiments with mice. Toxic sea cucumbers that produce microcystin LR occur in Australia, Europe, American lakes, and other parts of Asia. In the devastated lakes of China, large-sized blue-tailed sea cucumbers do not disappear throughout the year. And since lake water is used for drinking water and agricultural water, the toxins produced by cyanobacteria in the lake become a problem in securing human drinking water, and there is a strong demand for a solution.

In Example 4, the adsorption of microcystin LR (number average molecular weight: 994) was evaluated. A porous carbon material constituting the filter medium of Example 4 was obtained by a method substantially similar to the method described in Example 1. Specifically, in Example 4, the activation process was a process of heating at 900 ° C. in a steam stream (2.5 liters / minute) for 3 hours. Except this point, it was obtained by the same method as described in Example 1. When the specific surface area and pore volume of the filter medium in Example 4 were measured, the results shown in Table 1 were obtained. Further, the pore diameter is within a range of 3 nm to 20 nm with respect to the total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m (volume A, total volume of all pores) based on the NLDFT method. Table 2 shows the volume ratio of the total pore volume. The filter medium in Example 4 is a 60 mesh pass / 200 mesh on product. Further, as Comparative Example 4, granular activated carbon (60 mesh pass / 200 mesh on product) manufactured by Wako Pure Chemical Industries, Ltd. was used.

  Using the filter media of Example 4 and Comparative Example 4, the microcystin concentration of the solution before and after the reaction was determined by a colorimetric method using an ultraviolet / visible spectrophotometer, and the removal rate was calculated. The result is shown in FIG. 7, and it was found that the filter medium made of the porous carbon material of Example 4 had a remarkably higher removal rate than that of Comparative Example 4.

  In Example 5, the particle size dependency was evaluated. The porous carbon material (60 mesh pass / 200 mesh on product) in Example 1 was used as the porous carbon material constituting the filter medium of Example 5. Further, although it is a porous carbon material in Example 1, a 200 mesh pass product was used as Reference Example 5. Furthermore, as the comparative example 5A, the granular activated carbon (60 mesh pass / 200 mesh on product) of the comparative example 4 was used, and as the comparative example 5B, the 200 mesh pass product obtained by pulverizing the granular activated carbon of the comparative example 4 was used.

Using the filter media of Example 5, Reference Example 5, Comparative Example 5A and Comparative Example 5B as samples, 10 milligrams of sample and 50 milliliters of indole solution (3 × 10 ⁻⁴ mol / liter) were placed in a 50 milliliter screw tube. The particle size dependence was evaluated based on the method of quantifying the amount of adsorbed indole after 1 hour. The results are shown in FIG. 8, and it was found that the filter medium made of the porous carbon material of Example 5 and Reference Example 5 has no particle size dependency as compared with Comparative Example 5A and Comparative Example 5B.

  Conventional activated carbon made from coconut husk and petroleum pitch is used in filter materials for water purification, functional foods, cosmetics, etc., but these activated carbons have a low mineral content and are minerals in water. It is not suitable for the purpose of adjusting the amount of release.

Example 6 relates to the filter medium according to the fifth to eighth aspects of the present invention. The filter medium of Example 6 has a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method, a pore volume of 0.1 cm ³ / gram or more by BJH method, sodium, magnesium, potassium, and It consists of a porous carbon material made from a plant containing at least one component selected from the group consisting of calcium. Alternatively, the filter medium of Example 6 has a specific surface area value of 1 × 10 ² m ² / gram or more by the nitrogen BET method and a diameter of 1 × 10 ⁻⁹ m to 5 determined by the delocalized density functional method. The total volume of pores of × 10 ⁻⁷ m is at least 0.1 cm ³ / gram, preferably at least 0.2 cm ³ / gram, and at least one selected from the group consisting of sodium, magnesium, potassium and calcium It consists of a porous carbon material made from a plant containing these components. Alternatively, the filter medium of Example 6 has a specific surface area value of 1 × 10 ² m ² / gram or more according to the nitrogen BET method, and a pore size distribution determined by the delocalized density functional method is 3 nm to 20 nm. The proportion of the total volume of pores having at least one peak in the range and having a pore diameter in the range of 3 nm to 20 nm is 0.1 or more of the total volume of all pores, sodium, magnesium, It consists of a porous carbon material made from a plant containing at least one component selected from the group consisting of potassium and calcium. Alternatively, the filter medium of Example 6 has a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method, and a pore volume of 1.0 cm ³ / gram or more by mercury intrusion method, sodium, It consists of a porous carbon material made from a plant containing at least one component selected from the group consisting of magnesium, potassium and calcium.

  In Example 6, the porous carbon material is made from a plant containing at least one component selected from the group consisting of sodium (Na), magnesium (Mg), potassium (K), and calcium (Ca). By using such a plant raw material, when used as a filter medium, a large amount of mineral components are eluted from the porous carbon material into the filtered water, so that the hardness of the water can be controlled. In this case, 1 gram of the filter medium is added to 50 ml of water having a hardness of 0.1 or less (test water), and the hardness after 5 hours is 5 or more.

  More specifically, in Example 6, citrus peel such as mandarin peel (Example 6A), orange peel (Example 6B), grapefruit peel (Example 6C), banana peel (implementation) Example 6D) was used as a raw material. As Comparative Example 6, Kuraray Coal GW manufactured by Kuraray Chemical Co., Ltd. was used.

  In the production of the porous carbon material constituting the filter medium of Example 6, the above-mentioned various plant materials were dried at 120 ° C. for 24 hours. Thereafter, a preliminary carbonization treatment was performed in a nitrogen stream at 500 ° C. for 3 hours. Subsequently, after baking at 800 degreeC for 1 hour, it cooled to room temperature and grind | pulverized using the mortar. The samples (carbonaceous material and porous carbon material precursor) thus obtained are referred to as samples of Example 6a, Example 6b, Example 6c, and Example 6d for convenience. Then, after immersing each sample in concentrated hydrochloric acid for 24 hours and washing until the cleaning solution becomes neutral, the samples of Example 6a ′, Example 6b ′, Example 6c ′ and Example 6d ′ are obtained. It was. Next, the samples of Example 6a ′, Example 6b ′, Example 6c ′, and Example 6d ′ were subjected to activation treatment at 900 ° C. in a steam stream for 1 hour, thereby causing Example 6A and Example 6B. A filter medium composed of the porous carbon material of Example 6C and Example 6D could be obtained.

Table 4 below shows the composition analysis results of the samples of Example 6A, Example 6B, Example 6C, and Example 6D, and the sample of Comparative Example 6. Also, X-ray diffraction of the samples of Example 6a, Example 6b, Example 6c and Example 6d, and the porous carbon materials of Example 6a ′, Example 6b ′, Example 6c ′ and Example 6d ′. A result is shown to (A)-(D) of FIG. In addition, all the filter media of Example 6A, Example 6B, Example 6C, and Example 6D were 200 mesh pass products. Moreover, when the specific surface area and the pore volume were measured, the results shown in Table 1 and FIGS. 10A and 10B were obtained. Further, the pore diameter is within a range of 3 nm to 20 nm with respect to the total volume of pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m (volume A, total volume of all pores) based on the NLDFT method. Table 2 shows the volume ratio of the total pore volume. Furthermore, the graph which shows the measurement result of the pore diameter distribution calculated | required by the filter material of Example 6A, Example 6B, Example 6C, and Example 6D and the delocalization density functional method of the comparative example 6 is shown. 11 shows.

  From Table 4, it was found that the samples of Example 6A, Example 6B, Example 6C, and Example 6D contained more mineral components than the sample of Comparative Example 6. Further, from the results of X-ray diffraction, the filter media of Example 6a ′, Example 6b ′, Example 6c ′ and Example 6d ′ were converted into samples of Example 6a, Example 6b, Example 6c and Example 6d. The crystallinity peak derived from the mineral component was not observed. From this, the mineral content is partly removed once by acid treatment with concentrated hydrochloric acid, but it is considered that the mineral content inside the filter medium becomes obvious again by the activation treatment.

Using the samples of Example 6A, Example 6B, Example 6C and Example 6D, and the sample of Comparative Example 6, each sample was added to test water (hardness: <0.066) as pure water at 1 gram / The mixture was added at a rate of 50 ml, stirred for 6 hours, filtered, and the amounts of various minerals contained in the filtrate were quantified by ICP-AES. Table 5 shows the mineral amount in the filtrate obtained from each sample and the hardness of the filtrate. The hardness (milligram / liter) is
Calcium concentration (milligram / liter) x 2.5
+ Magnesium concentration (milligram / liter) x 4.1
Calculated as For reference, World Health Organization (WHO) standards (soft water: 0 or more, less than 60, moderate soft water (medium hard water): 60 or more, less than 120, hard water: 120 or more, less than 180, very hard water: 180 or more) The classification of water according to

  From Table 5, in each sample of Example 6, the mineral elution characteristic higher than Comparative Example 6 can be confirmed, and the filter medium made of the porous carbon material of Example 6 is suitable for adjusting the hardness of the filtrate. It has been shown. Moreover, it turned out that the hardness of the obtained filtrate can be adjusted with soft water-medium hard water-hard water-very hard water by the plant raw material to be used.

[Table 1]
Specific surface area Total pore volume MP method BJH method Mass Example 1A 1753 1.65 0.66 1.19
Example 1B 2056 1.83 0.73 1.37
Reference Example 1 1804 1.64 0.67 1.27
Comparative Example 1A 1015 1.04 0.80 1.12.
Comparative Example 1B 375 0.21 0.16 0.07
Comparative Example 1C 848 0.43 0.40 0.08
Comparative Example 1D 1109 0.62 0.49 0.21
Example 2 1612 1.51 0.51 1.13 0.16
Comparative Example 2A 1099 0.57 0.50 0.14 1.00
Comparative Example 2B 908 0.48 0.42 0.12 0.85
Comparative Example 2C 1090 0.54 0.50 0.18 1.00
Example 4 1321 1.13 0.70 0.56
Example 6A 802 0.434 0.40 0.15
Example 6B 372 0.223 0.20 0.096
Example 6C 605 0.402 0.33 0.21
Example 6D 843 0.396 0.33 0.080
Comparative Example 6 929 0.414 0.40 0.061

[Table 2]
Volume ratio Total volume of all pores (volume A)
Example 1A 0.5354 2.0168 cm ³ / gram Example 1B 0.4820 2.2389 cm ³ / gram Reference Example 1 0.4774 2.0595 cm ³ / gram Comparative Example 1A 0.2755 1.8993 cm ³ / gram Comparative Example 1B 0.0951 0.3228 cm ³ / gram Comparative Example 1C 0.0526 0.7105 cm ³ / gram Comparative Example 1D 0.1125 0.8427 cm ³ / gram Example 2 0.5036 1.8934 cm ³ / gram Comparative Example 2A 0 .1170 0.8836cm ³ / g Comparative example 2B 0.0818 0.7869cm ³ / g Comparative example 2C 0.0300 0.8765cm ³ / g example 4 0.4661 1.4396cm ³ / g Comparative example 4 0.1340 0.7557 cm ³ / gram Example 6A 0.4006 0.556 7 cm ³ / g EXAMPLE 6B 0.0553 0.3038cm ³ / g Example 6C 0.1566 0.7171cm ³ / g Example 6D 0.2597 0.5044cm ³ / g Comparative Example 6 0.0216 0.6935cm ³ / G

[Table 3]

[Table 4]

[Table 5]

Example 7 relates to the filter medium according to the ninth to fifteenth aspects of the present disclosure. In Example 7, dodecylbenzenesulfonate (specifically sodium linear dodecylbenzenesulfonate), a synthetic detergent component that is discharged in a large amount in the water environment, pesticides used in large amounts. Disinfectant chlorothalonil (TPN, C ₈ Cl ₄ N) and insecticide dichlorovos (DDVP, C ₄ H ₇ Cl ₂ O ₄ P), soluble lead eluted from water pipes, etc., is a typical pollutant in tap water The purpose is to remove free residual chlorine and various organic halogen compounds (including organic halogen compounds generated from humic substances) by-produced by chlorine disinfection.

  In Example 7, a porous carbon material was produced by the following method. As Comparative Example 7, Kuraray Coal GW was used.

  In the production of the porous carbon material in Example 7, the plant-derived material was carbonized at 400 ° C. to 1400 ° C. and then treated with an alkali to obtain a porous carbon material. That is, first, heat treatment (preliminary carbonization treatment) is performed on the rice husk in an inert gas. Specifically, the rice husk was carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain a carbide. In addition, by performing such a process, the tar component which will be produced | generated at the time of the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was put in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonized at 800 degreeC for 1 hour, after converting into a carbonaceous substance (porous carbon material precursor), it cooled to room temperature. In addition, nitrogen gas was continued to flow during carbonization and cooling. Next, this porous carbon material precursor was subjected to an alkali treatment by immersing it in a 10% by mass aqueous sodium hydroxide solution at 80 ° C. overnight, and then washed with water and ethyl alcohol until the pH reached 7. . Next, after drying at 120 ° C., the porous carbon material of Example 7 was subjected to activation treatment by heating at 900 ° C. in a steam stream (2.5 liters / minute) for 3 hours. Could get.

  Table 3 shows the particle size distribution measurement results of the samples of Example 7 and Comparative Example 7. The measurement results of the specific surface area and pore volume of the samples of Example 7 and Comparative Example 7 are shown in Tables 6 and 7 below. The measurement items and units in Tables 6 and 7 are the same as those in Tables 1 and 2. Furthermore, Table 8 shows the measurement results of the mercury intrusion method.

[Table 6]
Specific surface area Total pore volume MP method BJH method Mass Example 7 1280 0.93 0.44 0.52 0.30
Comparative Example 7 820 0.41 0.39 0.08 1.15

[Table 7]
Volume ratio Total volume of all pores (volume A)
Example 7 0.3723 1.2534 cm < ³ > / gram Comparative Example 7 0.0219 0.6935 cm < ³ > / gram

[Table 8]
Example 7 1.94 cm ³ / gram Comparative Example 7 0.26 cm ³ / gram

Samples 2 cm ³ of Example 7 and Comparative Example 7 were sampled and stored in a column with a stainless steel net. And per liter of water,
(A) Sodium dodecylbenzenesulfonate 0.9 milligrams (B) Chlorotalonyl 6.0 micrograms (C) Dichlorobos 6.0 micrograms (D) Dissolvable lead (specifically lead acetate) 6 micrograms (lead Conversion)
(E) 0.2 mg of sodium hypochlorite as free chlorine (chlorine conversion)
(F) TOX concentration of 130 ± 20 micrograms as total organic halogen (chlorine conversion)
Each solution was dissolved, and 2 cm ³ of each sample was passed at a flow rate of 40 ml / min. And the density | concentration before and behind water flow was measured, and the removal rate was computed. A flow rate of 40 ml / min corresponds to the following space velocity (SV).

Also, per liter of water,
(A) 0.9 mg of sodium dodecylbenzenesulfonate (B) 6 micrograms of chlorothalonil (E) 2.0 mg of sodium hypochlorite as free chlorine (chlorine conversion)
Each solution was dissolved, and 2 cm ³ of each sample was passed at a flow rate of 240 ml / min. And the density | concentration before and behind water flow was measured, and the removal rate was computed. The flow rate of 240 ml / min corresponds to the following space velocity (SV).

Flow rate 40ml / min:
SV = 40 × 60 (milliliter / hour) / 2 cm ³ = 1200 hour ⁻¹
Flow rate 240ml / min:
SV = 240 × 60 (milliliter / hour) / 2 cm ³ = 7200 hour ⁻¹

  Then, the removal rate of sodium dodecylbenzenesulfonate is measured based on the cell absorbance method, and the removal rate of chlorothalonil and dichloroboss is measured based on the gas chromatograph (ECO-GC) method with an electron capture detector to remove soluble lead. The rate measurement was performed based on the inductively coupled plasma-mass spectrometry (IPC / MS) method, the free chlorine removal rate measurement was performed based on the cell absorbance method, and the total organic halogen removal rate measurement was performed based on the ion chromatograph method.

  The removal rate measurement results of sodium dodecylbenzenesulfonate (DBS) are shown in FIGS. 12 (A) and (B), and the removal rate measurement results of chlorothalonil (TPN) are shown in FIGS. 13 (A) and (B). The removal rate measurement result of dichloroboss (DDVP) is shown in FIG. 14, the removal rate measurement result of soluble lead is shown in FIG. 15, and the removal rate measurement result of free chlorine is shown in (A) and (B) of FIG. FIG. 17 shows the measurement results of the removal rate of all organic halogens. In all, it was shown that the removal rate of Example 7 was higher than that of Comparative Example 7.

That is, in the filter medium of Example 7, water containing 1 microgram / liter of a substance having a molecular weight of 1 × 10 ^{2 to} 1 × 10 ⁵ was continuously passed for 48 hours at a space velocity of 1200 hours ⁻¹ . When performed, the time until the removal rate of the substance reaches 80% is more than twice the time until the removal rate of the substance reaches 80% when coconut shell activated carbon is used.

In the filter medium of Example 7, when water containing 0.9 mg / liter of dodecylbenzenesulfonate was continuously passed through at a space velocity of 1200 hours- ¹ for 25 hours, dodecylbenzene was used. The removal rate of sulfonate is 10% or more.

In the filter medium of Example 7, when water containing 6 microgram / liter of chlorothalonil was continuously passed for 50 hours at a space velocity of 1200 hr- ¹ , the removal rate of chlorothalonil was 60%. That's it.

In the filter medium of Example 7, when water containing 6 microgram / liter of dichloroboss was continuously passed through at a space velocity of 1200 hours- ¹ for 25 hours, the removal rate of dichloroboss was 60% or more.

In the filter medium of Example 7, when lead containing 6 microgram / liter of soluble lead was continuously passed for 25 hours at a space velocity of 1200 hr- ¹ , removal of soluble lead was achieved. The rate is 30% or more.

Moreover, in the filter medium of Example 7, when water containing 0.2 mg / liter of free chlorine was continuously passed through at a space velocity of 1200 hours- ¹ for 50 hours, the free chlorine removal rate. Is 70% or more.

Further, in the filter medium of Example 7, when water containing 130 micrograms / liter of all organic halogens in terms of chlorine was continuously passed for 5 hours at a space velocity of 1200 hours- ¹ , all organic halogens were obtained. The halogen removal rate is 45% or more.

From the results of measuring the removal rate of sodium dodecylbenzenesulfonate (DBS), at SV = 1200 hr- ¹ , the filter medium of Example 7 had a packing rate of only about 27% of the activated carbon of Comparative Example 7. The removal rate higher than that of the activated carbon of Comparative Example 7 was maintained, and the removal rate was 100% at about 5 hours of water flow and 50% or more at about 27 hours of water flow. On the other hand, the removal rate of the activated carbon of Comparative Example 7 decreases rapidly soon after passing water. This is probably because the adsorption rate of DBS having a large molecular weight is slow in the activated carbon of Comparative Example 7 having only small pores. From the results of the test, in Example 7, using a stationary water purifier containing 150 ml of the filter medium of Example 7 (hereinafter referred to as “stationary water purifier-A” for convenience), 0. When water containing 2 milligrams / liter of DBS was used, it was estimated that 100% of DBS could be removed for about 18 months, assuming 25 liters per day at a flow rate of 3.0 liters / minute. Further, even at SV = 7200 hr ⁻¹ , a higher removal rate than the activated carbon of Comparative Example 7 was maintained. Then, assuming that water containing 0.2 milligram / liter of DBS is filtered at a flow rate of 1.8 liter / minute for 15 liters a day, a stationary water purifier containing 15 milliliters of the filter medium of Example 7 ( Hereinafter, for convenience, it is estimated that 50% or more of DBS can be removed for about 4 months using “stationary water purifier-B”.

In addition, from the measurement result of the removal rate of chlorothalonil (TPN), at SV = 1200 hr- ¹ , the filter medium of Example 7 maintains a higher removal rate of TPN than the activated carbon of Comparative Example 7, and the passage of the activated carbon of Comparative Example 7 The removal rate was 80% or more up to about 50 hours, which is 2.05 times the value of 20 hours of water. This is because the molecular weight of TPN is as large as 265.9, so the filter medium of Example 7, which has a high adsorption rate, is more advantageous than the activated carbon of Comparative Example 7, and because TPN has a low solubility in water, it has an adsorptivity. Since it is high, it is considered that a high removal rate was maintained for a long time. From the results of the test, in Example 7, using stationary water purifier-A, water containing 6.0 microgram / liter of TPN was added at a flow rate of 3.0 liter / minute. Assuming 25 liters per day for filtration, it was estimated that more than 80% of TNP could be removed for about 1 year. On the other hand, at SV = 7200 hr- ¹ , the removal rate is lower than that at SV = 1200 hr- ¹ , but water containing 6.0 microgram / liter TPN is 1 at a flow rate of 1.8 liter / min. Assuming 15 liters per day for filtration, it was estimated that 50% or more of TNP could be removed using stationary water purifier-B for about 7 months.

Moreover, from the removal rate measurement result of dichloro boss (DDVP), at SV = 1200 hr- ¹ , the removal rate of the filter medium of Example 7 is maintained higher than that of the activated carbon of Comparative Example 7, and the removal rate is up to about 32 hours. 80% or more. This is because the molecular weight 221 of DDVP is slightly larger, so the filter medium of Example 7 having a higher adsorption rate is considered to be more advantageous than the activated carbon of Comparative Example 7. Since DDVP has a very high water solubility of 10 grams / liter, the equilibrium adsorption amount is small, so the removal rate was 80% or more until about 32 hours of water flow, but the removal rate decreased thereafter. In about 43 hours, the removal rate was 50%. For about 32 hours, the water containing 6.0 micrograms / liter of DDVP is filtered at a flow rate of 3.0 liters / minute for 25 liters a day using the stationary water purifier-A. Assuming that it is used for about 8 months, about 43 hours of water flow is equivalent to using for about 10 months.

Further, from the measurement results of the removal rate of soluble lead, at SV = 1200 hr- ¹ , the filter medium of Example 7 maintains a higher removal rate than the activated carbon of Comparative Example 7, and the removal rate is 50% in about 22 hours of water flow. That was all. In addition, in the activated carbon of the comparative example 7, the removal rate has become 50% or less in about 8 hours of water flow. This is considered to indicate that the filter medium of Example 7 has many active sites that easily adsorb lead. And from the result of the test, using stationary water purifier-A, water containing soluble lead of 6 microgram / liter (lead conversion) at a flow rate of 3.0 liter / minute, 25 liters a day, Assuming filtration, it was estimated that 50% or more of lead could be removed for about 5 months.

Further, from the measurement result of the removal rate of free chlorine, at SV = 1200 hr- ¹ , the filter medium of Example 7 maintains a higher removal rate than Comparative Example 7, and is about 80% after 48 hours of water flow. . Since free chlorine is removed by a reduction reaction on the surface of the filter medium, it is presumed that the filter medium of Example 7 not only has a high intragranular diffusion rate, but also has many active sites on the surface where free chlorine can be easily reduced. And from the result of the test, using stationary water purifier-A, water containing 0.2 milligram / liter (chlorine conversion) of free chlorine at a flow rate of 3.0 liter / minute, 25 liters a day, Assuming filtration, it was estimated that 80% or more of free chlorine could be removed for about one year. On the other hand, even at SV = 7200 hr ⁻¹ , the removal rate is about 60% even after 48 hours of water flow. And from the result of the test, using stationary water purifier-B, water containing 2.0 milligrams / liter (in terms of chlorine) of free chlorine at a flow rate of 1.8 liters / minute, 15 liters a day, Assuming filtration, it was estimated that 60% or more of free chlorine could be removed for about one year.

In addition, from the measurement results of the removal rate of all organic halogens (including organic halogen compounds generated from humic substances), when SV = 1200 hours ⁻¹ , the filter medium of Example 7 was activated carbon of Comparative Example 7 up to 48 hours of water flow. The removal rate became higher. Since the TOX component contains a substance having a large molecular weight, it is considered that the filter medium of Example 7 having a higher adsorption rate has a higher removal rate than the activated carbon of Comparative Example 7. Based on the test results, using a stationary water purifier-A, water containing all organic halogens with a TOX concentration of 130 micrograms (chlorine conversion) / liter at a flow rate of 3.0 liters / min. Assuming filtration of liters, it was estimated that over 50% could be removed for about 4 months.

  The eighth embodiment is a modification of the first to seventh embodiments. In Example 8, as shown in FIG. 18A, which is a schematic partial cross-sectional view, the filter medium described in Examples 1 to 7 is used as a bottle with a cap member 30 (so-called pet). Bottle) 20. Specifically, the filter medium 40 of Examples 1 to 7 is arranged inside the cap member 30, and the filters 31 and 32 are placed on the liquid inflow side and the liquid discharge side of the cap member 30 so that the filter medium 40 does not flow out. Arranged. Then, the liquid or water (drinking water, skin lotion, etc.) 21 in the bottle 20 is allowed to pass through the filter medium 40 arranged in the cap member 30 or is used. The mineral component in (water) can be increased. The cap member 30 is normally closed using a lid (not shown).

  Alternatively, as shown in a schematic cross-sectional view of FIG. 18B, the filter medium 40 of Examples 1 to 7 is stored in a water-permeable bag 50, and the liquid or water in the bottle 20 is stored. A form in which the bag 50 is put into the (drinking water, lotion, etc.) 21 can also be adopted. Reference numeral 22 is a cap for closing the mouth of the bottle 20. Alternatively, as shown in a schematic cross-sectional view of FIG. 19A, the filter medium 40 according to the first to seventh embodiments is arranged inside the straw member 60 so that the filter medium 40 does not flow out. Filters are disposed on the liquid inflow side and the liquid discharge side of the straw member. Then, the liquid or water (drinking water) 21 in the bottle 20 is allowed to pass through the filter medium 40 of Examples 1 to 7 disposed inside the straw member 60, so that the liquid (water) The mineral component of can be increased. Alternatively, as shown in FIG. 19B, a schematic surface with a part cut away, the filter medium 40 of Examples 1 to 7 is arranged inside the spray member 70 so that the filter medium 40 does not flow out. The filter (not shown) is disposed on the liquid inflow side and the liquid discharge side of the spray member 70. Then, by pressing a push button 71 provided on the spray member 70, the liquid or water (drinking water, lotion, etc.) 21 in the bottle 20 is disposed in the spray member 70. The mineral component in the liquid (water) can be increased by passing through the filter medium 40 of Example 7 and spraying from the spray hole 72.

  As mentioned above, although this invention was demonstrated based on the preferable Example, this invention is not limited to these Examples, A various deformation | transformation is possible. As a filter medium, a water purifier in which the filter medium described in Example 1 and a ceramic filter medium (ceramic filter medium having fine holes) are combined, and the filter medium described in Example 1 and an ion exchange resin are combined. It can also be a water purifier. Moreover, you may granulate and use the porous carbon material which comprises the filter medium of this invention.

  In the examples, the case where rice husk is used as the raw material of the porous carbon material has been described, but other plants may be used as the raw material. Here, examples of other plants include pods, cocoons or stem wakame, vascular plants vegetated on land, fern plants, moss plants, algae and seaweeds, and these may be used alone. Further, a plurality of types may be mixed and used. Specifically, for example, plant-derived materials that are raw materials for porous carbon materials are rice straw (eg, from Kagoshima; Isehikari), and porous carbon materials are carbonized from raw straw as a carbonaceous material. It can be obtained by converting to (porous carbon material precursor) and then performing acid treatment. Alternatively, a plant-derived material, which is a raw material of the porous carbon material, is used as a rice bran, and a carbonaceous material (porous carbon material precursor) is obtained by carbonizing the porous carbon material as a raw material. And then acid treatment. Similar results were obtained with a porous carbon material obtained by treatment with an alkali (base) such as an aqueous sodium hydroxide solution instead of an aqueous hydrofluoric acid solution.

  Alternatively, the plant-derived material, which is the raw material of the porous carbon material, is used as stem wakame (from Sanriku, Iwate Prefecture), and the porous carbon material is carbonized from the stem wakame as raw material to produce a carbonaceous material (precursor of porous carbon material) Body) and then subjected to acid treatment. Specifically, first, for example, the stem wakame is heated at a temperature of about 500 ° C. and carbonized. In addition, you may process the stem wakame used as a raw material with alcohol before a heating, for example. As a specific treatment method, there is a method of immersing in ethyl alcohol or the like, thereby reducing moisture contained in the raw material, and other elements other than carbon contained in the porous carbon material finally obtained or , Mineral components can be eluted. Moreover, generation | occurrence | production of the gas at the time of carbonization can be suppressed by the process with this alcohol. More specifically, the stem wakame is soaked in ethyl alcohol for 48 hours. In addition, it is preferable to perform ultrasonic treatment in ethyl alcohol. Subsequently, this stem wakame is carbonized by heating in a nitrogen stream at 500 ° C. for 5 hours to obtain a carbide. In addition, by performing such a process (preliminary carbonization process), a tar component that will be generated in the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide is put in an alumina crucible and heated to 1000 ° C. at a rate of 5 ° C./minute in a nitrogen stream (10 liters / minute). And it carbonizes at 1000 degreeC for 5 hours, and after converting into a carbonaceous substance (porous carbon material precursor), it cools to room temperature. In addition, nitrogen gas is kept flowing during carbonization and cooling. Next, the porous carbon material precursor is subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed until it becomes pH 7 using water and ethyl alcohol. And the porous carbon material can be obtained by making it dry at the end.

DESCRIPTION OF SYMBOLS 1 ... Carbon / polymer composite, 2 ... Nonwoven fabric, 10 ... Water purifier main body, 11 ... Porous carbon material, 12 ... 1st filling part, 13 ... Cotton, 14 * ..Second filling part, 15 ... inlet, 16 ... outlet, 20 ... bottle, 21 ... liquid or water, 22 ... cap, 30 ... cap member, 31, 32 ... Filter, 40 ... Filter material, 50 ... Bag, 60 ... Straw member, 70 ... Spray member, 71 ... Push button, 72 ... Spray hole

Claims (16)

A porous carbon material having a specific surface area value by nitrogen BET method of 1 × 10 ² m ² / gram or more, a pore volume by BJH method of 0.3 cm ³ / gram or more, and a particle size of 75 μm or more was filled. An air purification device comprising a column, a filter or a cartridge,
An air purifier having a bulk density of the porous carbon material of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Volume of pores having a specific surface area of 1 × 10 ² m ² / gram or more determined by the nitrogen BET method and a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the delocalized density functional method An air purification device comprising a column, filter or cartridge filled with a porous carbon material having a total of 1.0 cm ³ / gram or more and a particle size of 75 μm or more,
An air purifier having a bulk density of the porous carbon material of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . The value of specific surface area by nitrogen BET method is 1 × 10 ² m ² / gram or more, and the pore size distribution obtained by delocalized density functional method has at least one peak in the range of 3 nm to 20 nm. The ratio of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm is 0.2 or more of the total volume of all pores, and a porous carbon material having a particle diameter of 75 μm or more is filled. An air purification device comprising a column, filter or cartridge,
An air purifier having a bulk density of the porous carbon material of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Filled with a porous carbon material having a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method, a pore volume of 1.0 cm ³ / gram or more by mercury intrusion method, and a particle size of 75 μm or more. An air purification device comprising a column, filter or cartridge,
An air purifier having a bulk density of the porous carbon material of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . A porous carbon material having a specific surface area value by nitrogen BET method of 1 × 10 ² m ² / gram or more, a pore volume by BJH method of 0.3 cm ³ / gram or more, and a particle size of 75 μm or more was filled. An air cleaning filter,
A filter for air cleaning in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Volume of pores having a specific surface area of 1 × 10 ² m ² / gram or more determined by the nitrogen BET method and a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the delocalized density functional method A filter for air purification filled with a porous carbon material having a total of 1.0 cm ³ / gram or more and a particle size of 75 μm or more,
A filter for air cleaning in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ . The value of specific surface area by nitrogen BET method is 1 × 10 ² m ² / gram or more, and the pore size distribution obtained by delocalized density functional method has at least one peak in the range of 3 nm to 20 nm. The ratio of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm is 0.2 or more of the total volume of all pores, and a porous carbon material having a particle diameter of 75 μm or more is filled. A filter for cleaning air,
A filter for air cleaning in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Filled with a porous carbon material having a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method, a pore volume of 1.0 cm ³ / gram or more by mercury intrusion method, and a particle size of 75 μm or more. A filter for cleaning air,
A filter for air cleaning in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ . A porous carbon material having a specific surface area value by nitrogen BET method of 1 × 10 ² m ² / gram or more, a pore volume by BJH method of 0.3 cm ³ / gram or more, and a particle size of 75 μm or more was filled. A water purification device comprising a column or cartridge,
A water purification apparatus in which the porous carbon material has a bulk density of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Volume of pores having a specific surface area of 1 × 10 ² m ² / gram or more determined by the nitrogen BET method and a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the delocalized density functional method A water purification apparatus comprising a column or cartridge filled with a porous carbon material having a total of 1.0 cm ³ / gram or more and a particle size of 75 μm or more,
A water purification apparatus in which the porous carbon material has a bulk density of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . The value of specific surface area by nitrogen BET method is 1 × 10 ² m ² / gram or more, and the pore size distribution obtained by delocalized density functional method has at least one peak in the range of 3 nm to 20 nm. The ratio of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm is 0.2 or more of the total volume of all pores, and a porous carbon material having a particle diameter of 75 μm or more is filled. A water purification device comprising a column or cartridge comprising:
A water purification apparatus in which the porous carbon material has a bulk density of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Filled with a porous carbon material having a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method, a pore volume of 1.0 cm ³ / gram or more by mercury intrusion method, and a particle size of 75 μm or more. A water purification device comprising a column or cartridge comprising:
A water purification apparatus in which the porous carbon material has a bulk density of 0.1 g / cm ^{3 to} 0.8 g / cm ³ . A porous carbon material having a specific surface area value by nitrogen BET method of 1 × 10 ² m ² / gram or more, a pore volume by BJH method of 0.3 cm ³ / gram or more, and a particle size of 75 μm or more was filled. A cartridge for water purification,
A cartridge for water purification in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Volume of pores having a specific surface area of 1 × 10 ² m ² / gram or more determined by the nitrogen BET method and a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m determined by the delocalized density functional method A cartridge for water purification filled with a porous carbon material having a total of 1.0 cm ³ / gram or more and a particle size of 75 μm or more,
A cartridge for water purification in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ . The value of specific surface area by nitrogen BET method is 1 × 10 ² m ² / gram or more, and the pore size distribution obtained by delocalized density functional method has at least one peak in the range of 3 nm to 20 nm. The ratio of the total volume of pores having a pore diameter in the range of 3 nm to 20 nm is 0.2 or more of the total volume of all pores, and a porous carbon material having a particle diameter of 75 μm or more is filled. Water purification cartridge,
A cartridge for water purification in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ . Filled with a porous carbon material having a specific surface area value of 1 × 10 ² m ² / gram or more by nitrogen BET method, a pore volume of 1.0 cm ³ / gram or more by mercury intrusion method, and a particle size of 75 μm or more. Water purification cartridge,
A cartridge for water purification in which the bulk density of the porous carbon material is 0.1 g / cm ^{3 to} 0.8 g / cm ³ .