JP6645549B2 - Air purification device, air purification filter, water purification device, and water purification cartridge - Google Patents

Description

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

  Activated carbon is often used in water purifiers for purifying water, for example, as disclosed in JP-A-2001-205253 and JP-A-06-106161. Further, the water purifier is often used, for example, by being directly attached to a water tap.

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

  Such a conventional water purifier has a problem that if the filtration flow rate is large, that is, if the flow rate of the water flowing through the water purifier is high, the water purification function may not be sufficiently exhibited. Further, for the purpose of increasing the specific surface area, a pulverized product of activated carbon is often used. However, there may be a problem that the pulverized activated carbon leaks from the water purifier together with purified water. Furthermore, there is a strong need for a contaminant remover, a carbon / polymer composite, and a contaminant removal sheet member that can more effectively remove contaminants. There is also a demand for controlling the hardness of water by passing through a filter medium. However, a technique that can achieve such a demand is not known as far as the present inventors have studied.

  Accordingly, a first object of the present invention is to provide a contaminant removing agent, a carbon / polymer composite, a contaminant removing sheet member, and a filter medium that can more effectively remove contaminants. A second object of the present invention is to provide a filter medium which can sufficiently exhibit a purifying function even when a filtration flow rate is large, and which hardly causes a problem of flowing out together with a purified fluid. Further, a third object of the present invention is to provide a filter medium capable of controlling the hardness of water.

The contaminant removing agent according to the first aspect of the present invention for achieving the first object has a specific surface area of 1 × 10 ² m ² / gram or more measured by a nitrogen BET method and a pore size measured by a 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. In addition, such a porous carbon material may be referred to as a “porous carbon material according to the first embodiment of the present invention” for convenience. Here, a porous carbon material having a particle size of 75 μm or more obtained by granulating a porous carbon material having a particle size of less than 75 μm, or a porous carbon material having a particle size of less than 75 μm and a particle size of 75 μm or more A porous carbon material having a particle size of 75 μm or more obtained by granulating a porous carbon material mixed with a porous carbon material is also included in the “porous carbon material having a particle size of 75 μm or more” of the present invention. Included. The same applies to the following description.

The pollutant remover according to the second aspect of the present invention for achieving the first object has a specific surface area of 1 × 10 ² m ² / gram or more measured by a nitrogen BET method and a delocalized 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 of 1.0 cm ³ / gram or more and a particle diameter of 75 μm or more determined by a functional method. . In addition, such a porous carbon material may be referred to as a “porous carbon material according to the second embodiment of the present invention” for convenience.

The contaminant removing agent according to the third aspect of the present invention for achieving the first object has a specific surface area of 1 × 10 ² m ² / gram or more measured by a nitrogen BET method and a delocalized density. In the pore diameter distribution determined by the functional theory, at least one peak is in the range of 3 nm to 20 nm, and the ratio of the total volume of the pores having the pore diameter in the range of 3 nm to 20 nm is entirely 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. In addition, such a porous carbon material may be referred to as a “porous carbon material according to the third embodiment of the present invention” for convenience.

The contaminant removing agent according to the fourth aspect of the present invention for achieving the first object has a specific surface area of 1 × 10 ² m ² / gram or more by a nitrogen BET method and a fine particle by a 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. Note that such a porous carbon material may be referred to as a “porous carbon material according to a fourth aspect of the present invention” for convenience.

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

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

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

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

  A contaminant removal sheet member according to a first aspect of the present invention for achieving the first object includes the porous carbon material according to the first aspect of the present invention and a support member.

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

  A contaminant removal sheet member according to a third aspect of the present invention for achieving the first object includes the porous carbon material according to the third aspect of the present invention, and a support member.

  A contaminant removal sheet member according to a fourth aspect of the present invention for achieving the first object includes the porous carbon material according to the fourth aspect of the present invention and a support member.

  A filter medium according to a first aspect of the present invention for achieving the second object includes the porous carbon material according to the first aspect of the present invention.

  A filter medium according to a second aspect of the present invention for achieving the second object comprises the porous carbon material according to the second aspect of the present invention.

  A filter medium according to a third aspect of the present invention for achieving the second object comprises the porous carbon material according to the third aspect of the present invention.

  A filter medium according to a fourth aspect of the present invention for achieving the second object comprises the porous carbon material according to the fourth aspect of the present invention.

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

A filter medium according to a sixth aspect of the present invention for achieving the third object has a specific surface area value of 1 × 10 ² m ² / gram or more measured 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 is 0.1 cm ³ / g or more, preferably 0.2 cm ³ / g or more, and sodium, magnesium, The porous carbon material is made from a plant and contains at least one component selected from the group consisting of potassium and calcium.

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

A filter medium according to an eighth aspect of the present invention for achieving the third object has a specific surface area value of 1 × 10 ² m ² / gram or more determined by a nitrogen BET method and a pore volume determined by a mercury intrusion method. Is not less than 1.0 cm ³ / gram and comprises a plant-based porous carbon material containing at least one component selected from the group consisting of sodium, magnesium, potassium and calcium.

The filter medium according to the ninth to fifteenth aspects of the present invention for achieving the first object,
Consisting of the porous carbon material according to the first aspect of the present invention, or
Consisting of the porous carbon material according to the second aspect of the present invention, or
Consisting of the porous carbon material according to the third aspect of the present invention, or
It is made of the porous carbon material according to the fourth aspect of the present invention.

The filter medium according to the ninth embodiment of the present invention continuously passes water containing 1 μg / liter of a substance having a molecular weight of 1 × 10 ^{2 to} 1 × 10 ⁵ at a space velocity of 1200 hr ⁻¹ for 48 hours. When the solution is applied, the time required for the removal rate of the substance to reach 80% is at least twice the time required for the removal rate of the substance to reach 80% when using coconut shell activated carbon. Here, Kuraray Coal GW manufactured by Kuraray Chemical Co., Ltd. is used as the coconut shell activated carbon.

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

The filter medium according to the eleventh aspect of the present invention is characterized in that, when water containing 6 micrograms / liter of chlorothalonil is continuously passed for 50 hours at a space velocity of 1200 h- ¹ , the removal rate of chlorothalonil is as follows. 60% or more.

The filter medium according to the twelfth aspect of the present invention, the 6 micrograms / liter containing water-dichloro boss, 25 hours at a space velocity 1200 hr ^-1, when performing liquid passing in succession, the removal of dichloro boss The rate is 60% or more.

The filter medium according to the thirteenth aspect of the present invention, the 6 micrograms / liter containing water soluble lead, 25 hours at a space velocity 1200 hr ^-1, when performing liquid passing in succession, soluble lead Is 30% or more.

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

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

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, the first to fourth aspects of the present invention In the contaminant removal sheet member according to the aspect or the filter media according to the first to fourth aspects, the ninth aspect to the fifteenth aspect of the present invention, the value of the specific surface area of the porous carbon material used Since the volume value and pore distribution of various pores are specified, contaminants can be removed with high efficiency, fluid can be purified at a high filtration flow rate, and high efficiency can be achieved. Can remove the desired substance. In addition, since the particle size of the porous carbon material is specified, the problem that the porous carbon material flows out accompanying the fluid is less likely to occur. 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 fourth aspect or the filter medium according to the first to fourth aspects of the present invention, in addition to the adsorption of the contaminants, for example,
HClO + C (porous carbon material) → CO (surface of porous carbon material)
⁺ H + + Cl ^-
Chlorine is removed based on such a chemical reaction. In the filter media according to the fifth to eighth aspects of the present invention, the value of the specific surface area, the value of the pore volume, and the pore distribution of the porous carbon material to be used are defined, In addition, since the raw material is specified, the hardness of the water that has passed through the filter medium can be controlled.

FIGS. 1A and 1B are graphs respectively showing the relationship between the test time of the filter medium of Example 1A, the filter medium of Comparative Example 1A and the filter medium of Comparative Example 1B, and the adsorption amount of methylene blue and black 5 per gram of the filter medium. It is. FIG. 2 shows the results obtained by filling the cartridges with the samples of Example 1B, Reference Example 1, Comparative Example 1C, and Comparative Example 1D, flowing an aqueous methylene blue solution into the cartridge, and measuring the methylene blue concentration of the water flowing out of the cartridge. FIG. FIG. 3 is a schematic sectional view of the water purifier of the first embodiment. FIG. 4 is a diagram illustrating a schematic cross-sectional structure of the contaminant removal sheet member according to the first embodiment. FIG. 5 is a graph showing the chlorine removal rates of the filter media made of the porous carbon material of Example 2 and the filter media of Comparative Examples 2A, 2B, and 2C. 6 (A), (B) and (C) show 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. FIG. 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 the 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 show examples 6a, 6a ', 6b, 6b', 6c, 6c ', 6d, and 6d', respectively. 4 is a graph showing an X-ray diffraction result of a sample. FIGS. 10A and 10B are graphs showing the measurement results of the pore volumes of the filter media of Example 6A, Example 6B, Example 6C, and Example 6D, and Comparative Example 6. FIG. 11 is a graph showing measurement results of the filter media of Examples 6A, 6B, 6C, and 6D, and the pore size distribution obtained by the delocalized density functional theory method of Comparative Example 6. is there. (A) and (B) of FIG. 12 are graphs showing the measurement results of the removal rates of sodium dodecylbenzenesulfonate of the samples of Example 7 and Comparative Example 7. FIGS. 13A and 13B are graphs showing the measurement results of the chlorothalonil removal rates of the samples of Example 7 and Comparative Example 7. FIG. FIG. 14 is a graph showing the measurement results of dichloroboss removal rates of the samples of Example 7 and Comparative Example 7. FIG. 15 is a graph showing the measurement results of the removal rates of soluble lead from the samples of Example 7 and Comparative Example 7. (A) and (B) of FIG. 16 are graphs showing the measurement results of the removal rates of free chlorine of the samples of Example 7 and Comparative Example 7. FIG. 17 is a graph showing the measurement results of the total organic halogen removal rates 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 according to an eighth embodiment. FIGS. 19A and 19B are a schematic partial cross-sectional view and a partially cutaway schematic view of a modification of the bottle in the eighth embodiment.

Hereinafter, the present invention will be described based on embodiments with reference to the drawings. However, the present invention is not limited to the embodiments, and various numerical values and materials in the embodiments are examples. The description will be made in the following order.
1. 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, the first to fourth aspects of the present invention 1. Contaminant removal sheet member according to the embodiment and filter media according to the first to fifteenth embodiments of the present invention; Example 1 (Pollutant remover 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, first aspect of the present invention -The contaminant removal sheet member according to the fourth aspect and the filter medium according to the first to fourth aspects of the present invention)
3. Example 2 (Modification of Example 1)
4. Example 3 (another modification of Example 1)
5. Example 4 (still another modification of Example 1)
6. Example 5 (still another modification of Example 1)
7. Example 6 (Filter media according to fifth to eighth aspects of the present invention)
8. Example 7 (Filter media according to ninth to fifteenth aspects of the present invention)
9. Example 8 (a modification of Examples 1 to 7) and others

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

The contaminant 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 aspect of the present invention. The porous carbon material constituting the filter medium according to the embodiment is not limited, but preferably has a pore volume of 1.5 cm ³ / gram or more measured by a mercury intrusion method. Further, the volume of the pores by the MP method is preferably 0.1 cm ³ / gram or more.

The contaminant removing agent 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 aspects, the ninth to fifteenth aspects of the present invention. The bulk density of the porous carbon material is preferably, but not limited to, 0.1 g / cm ^{3 to} 0.8 g / cm ³ . By defining the bulk density of the porous carbon material within the above range, there is no possibility that the flow of the fluid is hindered by the porous carbon material. That is, the pressure loss of the fluid caused by the porous carbon material can be suppressed.

  In the filter media according to the fifth to eighth aspects of the present invention including the preferred embodiments described above, the porous carbon material includes sodium (Na), magnesium (Mg), potassium (K), and A plant containing at least one component selected from the group consisting of calcium (Ca) is used as a raw material, and by using such a plant raw material, when used as a filter medium, a mineral component is converted from the porous carbon material into filtered water. As a result, the hardness of the filtered water can be controlled. In this case, 1 g of the filter medium is added to 50 ml of water (test water) having a hardness of 0.1 or less, and the hardness can be 5 or more after 6 hours. The porous carbon material preferably contains a total of 0.4% by mass or more of sodium (Na), magnesium (Mg), potassium (K), and calcium (Ca). Here, specific examples of plant raw materials include citrus peels such as orange peel, orange peel, and grapefruit peel, and banana peels.

  In addition, various functional foods including functional foods as a mineral adjusting material for the purpose of mineral replenishment from the porous carbon materials constituting the filter media according to the fifth to eighth aspects of the present invention. In addition, cosmetics, cosmetics and the like including cosmetics as a mineral adjusting material for the purpose of mineral supplementation can be constituted. In the functional food, in addition, for example, excipients, binders, disintegrants, lubricants, diluents, flavoring agents, preservatives, stabilizers, coloring agents, flavors, vitamins, coloring agents, Brighteners, sweeteners, bitters, sours, umami seasonings, fermented seasonings, antioxidants, enzymes, yeast extracts, and nutritional enhancers may be included. Examples of the form of the functional food include powder, solid, tablet, granule, granule, capsule, cream, sol, gel, and colloid. As cosmetics, for example, a lotion or a lotion-impregnated pack, a cleansing agent for removing dirt components such as sweat, oils and fats, and lipsticks can be exemplified, and as another component in cosmetics, a hydrophobic beauty component is included. Substances (for example, daidzein, genistein) can be mentioned, and examples of ingredients having a moisturizing effect and / or an antioxidant effect include active ingredients contained in a lotion 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 such a rule is based on JIS Z8801-1: 2006 “Test sieve-Part 1: Metal mesh sieve”. That is, a test is performed using a wire mesh having a nominal mesh size of 75 μm (so-called 200 mesh wire mesh). When the porous carbon material that does not pass through the wire mesh is 90% by mass or more, the particle size is defined to be 75 μm or more. I do. In the following description, such a porous carbon material is referred to as “200 mesh on product”, and a porous carbon material that has passed through a 200 mesh wire mesh is referred to as “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, the measurement includes primary particles and secondary particles in which a plurality of primary particles are aggregated.

  The measurement of pores by the mercury intrusion method complies with JIS R1655: 2003 “Method for testing pore diameter distribution of molded product by mercury intrusion method of fine ceramics”. Specifically, mercury porosimetry was measured using a mercury porosimeter (PASCAL440: manufactured by Thermo Electron). The pore measurement area was 15 μm to 2 nm.

  The pollutant remover of the present invention can be used, for example, for purifying water or air, and more generally for purifying fluids. Alternatively, the pollutant remover of the present invention can be used, for example, as a remover for removing harmful substances and wastes. The contaminant removing agent of the present invention may be used in the form of a sheet, used in a state packed in a column or a cartridge, used in a bag having water permeability, and used as a binder (binder). For example, use in a state where it is shaped into a desired shape by using the method, or use in a powder form can be exemplified. When used as a contaminant remover dispersed in a solution, the surface can be subjected to a hydrophilic treatment or a hydrophobic treatment before use. From the carbon / polymer composite and the contaminant removal sheet member of the present invention, for example, a filter, a mask, protective gloves and protective shoes of an air purification device can be formed.

  In the contaminant removal sheet member of the present invention including the above preferred embodiments, a woven fabric or a nonwoven fabric can be used as the support member, and cellulose, polypropylene, or polyester can be used as a material forming the support member. Examples of the form of the contaminant removal sheet member include a form in which the porous carbon material in the present invention is sandwiched between support members and a form in which the porous carbon material is kneaded into the support member. it can. Alternatively, as the form of the contaminant removal sheet member, the carbon / polymer composite of the present invention is sandwiched between support members, 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 purifying apparatus suitable for incorporating the filter medium of the present invention including the above-described preferred embodiments, specifically, a water purifier (hereinafter, sometimes referred to as “water purifier in the present invention”) includes a filtration membrane ( For example, a configuration (a combination of the filter medium and the filtration membrane of the present invention) further having a hollow fiber membrane or a flat membrane with a hole of 0.4 μm to 0.01 μm can be employed. Further, a configuration having both the filter medium of the present invention and the reverse osmosis membrane can be used, and a configuration further having a ceramic filter medium (a ceramic filter medium having fine holes) (the filter medium of the present invention and a ceramic filter medium) can be used. (A combination of a filter medium) and a structure further comprising 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. However, after passing through the reverse osmosis membrane (RO), the filtered water is passed through the filter medium of the present invention. Can contain a mineral component.

  Examples of the type of the water purifier in the present invention include a continuous water purifier, a batch type water purifier, and a reverse osmosis membrane water purifier, or a faucet direct connection type in which a water purifier body is directly attached to a tip of a water tap. , Stationary type (also called top sink type or tabletop type), integrated faucet with water purifier incorporated in the faucet, undersink type (built-in type) to be installed in the kitchen sink, containers such as pots and jugs A pot type (pitcher type) with a water purifier incorporated therein, a central type that is directly attached to the water pipe after the water meter, a portable type, and a straw type can be cited. The configuration and structure of the water purifier in the present invention can be the same configuration and structure as the 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 inlet and a water outlet. 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 or lid, a bottle with a straw member, a bottle with a spray member (so-called PET bottle), a laminated container, a plastic container, a glass container, a cap in a glass bottle, or the like Lids can be mentioned. Here, the filter medium of the present invention is arranged inside a cap or a lid, and liquid or water (drinking water, lotion, etc.) in a bottle, a laminate container, a plastic container, a glass container, a glass bottle, etc., is placed in the cap or the lid. Mineral components can be included in the filtered water by drinking or using the filter medium of the present invention disposed inside. Alternatively, the filter medium of the present invention is stored in a bag having water permeability, and the liquid or water in various containers such as a bottle (so-called PET bottle), a laminate container, a plastic container, a glass container, a glass bottle, a pot jug, 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), it is not particularly limited, but the ignition residue (residual ash content) in the porous carbon material is not particularly limited. ) Is desirably 15% by mass or less. Further, the content of the ignition residue (residual ash) in the porous carbon material precursor or the carbonaceous substance described below is desirably 20% by mass or more. Here, the residue on ignition (residual ash) refers to the mass% of the substance remaining 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 the thermogravimetry (TG) method.

  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 may be, for example, a plant-derived material at 400 ° C. to 1400 ° C. After carbonization, it can be obtained by treating with an acid or an 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”), carbonizing a plant-derived material at 400 ° C. to 1400 ° C. The material obtained by the above method, which is not subjected to the treatment with an acid or an alkali, is referred to as a “porous carbon material precursor” or a “carbonaceous substance”.

  In the method for producing a porous carbon material, a step of performing an activation treatment after the treatment with an acid or an alkali may be included, or a treatment with an acid or an alkali may be performed after the activation treatment. In addition, in the method for producing a porous carbon material including such a preferred form, although it depends on the plant-derived material to be used, before the plant-derived material is carbonized, the temperature for carbonization is lower than the temperature for carbonization. Alternatively, a heat treatment (preliminary carbonization treatment) may be applied to the plant-derived material at a low temperature (for example, 400 ° C. to 700 ° C.) with oxygen cut off. As a result, it is possible to extract the tar component that will be generated in the carbonization process, and as a result, it is possible to reduce or remove the tar component that will be generated in the carbonization process. The state in which oxygen is cut 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 a kind of steamed state. That can be achieved. Further, in the method for producing a porous carbon material, although it depends on the plant-derived material used, in some cases, in order to reduce mineral components and moisture contained in the plant-derived material, carbon In order to prevent the generation of offensive odor during the chemical conversion process, the plant-derived material may be immersed in acid or alkali, or may be immersed in alcohol (for example, methyl alcohol, ethyl alcohol, or isopropyl alcohol). In the method for producing a porous carbon material, a preliminary carbonization treatment may be performed thereafter. As a material that is preferably subjected to heat treatment in an inert gas, for example, a plant that generates a large amount of wood vinegar liquid (tar or light oil content) can be given. In addition, as a material that is preferably subjected to pretreatment with alcohol, for example, seaweeds rich in iodine and various minerals can be given.

  In the method for producing a porous carbon material, a plant-derived material is carbonized at 400 ° C. to 1400 ° C. Here, carbonization generally means an organic substance (porous carbon in the present invention). In the case of the porous carbon material constituting the filter material according to the fifth to eighth aspects of the present invention, it means that a plant-derived material is heat-treated to be converted into a carbonaceous substance. (See, for example, JIS M0104-1984). The atmosphere for carbonization may be an atmosphere in which oxygen is cut off. Specifically, a vacuum atmosphere, an inert gas atmosphere such as a nitrogen gas or an argon gas, or a plant-derived material is used as a kind of steamed state. Atmosphere. The heating rate up to the carbonization temperature is not limited, but under 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 may 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 at which the plant-derived material is surely carbonized. The plant-derived material may be pulverized to a desired particle size as required, or may be classified. The plant-derived material may be washed in advance. Alternatively, the obtained porous carbon material precursor or porous carbon material may be pulverized to a desired particle size as required, or may be classified. Alternatively, the porous carbon material after the activation treatment may be pulverized to a desired particle size as required, or may be classified. Further, a sterilization treatment may be applied to the finally obtained porous carbon material. The type, configuration and structure of the furnace used for carbonization are not limited, and the furnace may be a continuous furnace or a batch furnace.

  In the method for producing a porous carbon material, as described above, by performing the activation treatment, the number of micropores (described later) having a pore diameter smaller than 2 nm can be increased. Examples of the activation method include a gas activation method and a chemical activation method. Here, the gas activation method refers to the use of oxygen, water vapor, carbon dioxide gas, air, or the like as an activator under a gas atmosphere at 700 ° C. to 1400 ° C., preferably 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, a microstructure is developed by 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 uses 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, and cleans with hydrochloric acid. This is a method of adjusting the pH with an aqueous solution and drying.

  Chemical treatment or molecular modification may be performed on the surface of the porous carbon material in the present invention or on 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. Also, by performing the same treatment as the activation treatment with water vapor, oxygen, alkali, or the like, various functional groups such as a hydroxyl group, a carboxy group, a ketone group, and an ester group can be generated on the surface of the porous carbon material. Furthermore, molecular modification is also possible by chemically reacting a porous carbon material with a chemical species or protein having a hydroxyl group, a carboxy group, an amino group, or the like that can react.

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

  As the porous carbon material in the present invention, a plant-derived material can be used as a raw material. Here, as materials derived from plants, rice (rice), barley, wheat, rye, hay, millet, and other rice husks and straws, coffee beans, tea leaves (eg, leaves such as green tea and black tea), Sugar cane (more specifically, sugarcane scum), corn (more specifically, corn core), the above-mentioned fruit skin (for example, citrus skin such as mandarin or banana skin, etc.) ) Or reeds and stem wakame, but are not limited thereto, and include, for example, vascular plants, fern plants, bryophytes, algae and seaweed vegetated on land. . In addition, these materials may be used alone as a raw material, or may be used by mixing a plurality of types. The shape and form of the plant-derived material are not particularly limited, and may be, for example, chaff or straw itself, or may be a dried product. Furthermore, in the processing of foods and beverages such as beer and Western liquor, those subjected to various treatments such as a fermentation treatment, a roasting treatment, and an extraction treatment can also be used. In particular, from the viewpoint of recycling industrial waste, it is preferable to use straw or chaff after processing such as threshing. These processed straws and rice husks can be obtained in large quantities and easily from, for example, agricultural cooperatives, alcoholic beverage manufacturers, food companies, and food processing companies.

  The porous carbon material in the present invention includes non-metal elements such as magnesium (Mg), potassium (K), calcium (Ca), phosphorus (P), sulfur (S), and metal elements such as transition elements. It may be. The content of magnesium (Mg) is 0.01% by mass to 3% by mass, the content of potassium (K) is 0.01% by mass to 3% by mass, and the content of calcium (Ca) is 0.05% by mass. % To 3% by mass, the content of phosphorus (P) is 0.01% to 3% by mass, and the content of sulfur (S) is 0.01% to 3% by mass. The content of these elements is preferably small from the viewpoint of increasing the value of the specific surface area. The porous carbon material may contain elements other than the above-mentioned elements, and it goes without saying that the ranges of the contents 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, analysis of various elements is performed by, for example, energy dispersive X-ray. The analysis can be performed by an energy dispersing method (EDS) using an analyzer (for example, JED-2200F manufactured by JEOL Ltd.). 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 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 has many pores. The pores include “mesopores” having a pore size of 2 nm to 50 nm, “micropores” having a pore size smaller than 2 nm, and “macropores” having a pore size exceeding 50 nm. Further, in the porous carbon material according to the present invention, the volume of the pores 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 value of the specific surface area by the nitrogen BET method (hereinafter simply referred to as “specific surface area”) Is sometimes 4 × 10 ² m ² / gram or more in order to obtain more excellent functionality.

The nitrogen BET method is a method in which an adsorption isotherm is measured by adsorbing and desorbing nitrogen as an adsorbent on an adsorbent (here, a porous carbon material), and the measured data is converted into a BET equation represented by the equation (1). The specific surface area, the pore volume, and the like can be calculated based on this method. Specifically, when calculating the value of the specific surface area by the nitrogen BET method, first, 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 equation (1) or the equation (1 ′) obtained by modifying the equation (1), and calculating the equilibrium relative pressure. plotted against (p / p _0). Then, considers this plot a straight line, based on the least squares method, the inclination s (= [(C-1 ) / (C · V m)]) and the intercept i (= [1 / (C · V m)]) Is calculated. The expression from the slope s and intercept i thus obtained (2-1), based on the equation (2-2), calculates a V _m and C. Furthermore, the V _m, to calculate the basis specific surface area a _Sbet in equation (3) (Nippon Bel Co. Ltd. BELSORP-mini and BELSORP analysis software documentation, see Chapter 62, pages - 66 pages). The nitrogen BET method is a measurement method according to JIS R 1626-1996 "Method for measuring specific surface area of fine ceramics 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 monomolecular layer p: pressure p ₀ at the nitrogen equilibrium: saturated vapor pressure of nitrogen L: Avogadro's number sigma: an adsorption cross section of nitrogen.

When the pore volume _Vp is calculated by the nitrogen BET method, for example, the adsorption data of the obtained adsorption isotherm is linearly interpolated, and the adsorption amount V at the relative pressure set by the pore volume calculation relative pressure is obtained. From this adsorption volume V can be calculated pore volume V _p on the basis of the equation (4) (Nippon Bel Co. Ltd. BELSORP-mini and BELSORP analysis software documentation, see Chapter 62, pages - 65 pages). The pore volume based on the nitrogen BET method may be simply referred to as “pore volume” below.

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

However,
V: adsorption amount at relative pressure M _g : molecular weight of nitrogen ρ _g : density of nitrogen

The pore size of the mesopores can be calculated as a distribution of pores from the rate of change in pore volume with respect to the pore size, for example, based on the BJH method. The BJH method is a method widely used as a pore distribution analysis method. When the pore distribution analysis is performed based on the BJH method, first, nitrogen is adsorbed and desorbed on the porous carbon material as an adsorbed molecule to obtain a desorption isotherm. Then, based on the obtained desorption isotherm, the thickness of the adsorbing layer when the adsorbing molecules are gradually removed from the state where the pores are filled with the adsorbing 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, a pore distribution curve can be obtained by plotting a pore volume change rate (dV _p / dr _p ) with respect to the pore diameter (2r _p ) from the pore radius and the pore volume (BELSORP-mini manufactured by Nippon Bell Co., Ltd.). And BELSORP analysis software manuals, pages 85 to 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: when the adsorption layer having a thickness of t in the pressure on the inner wall of the pores in the pore radius r _p is adsorbed core radius (inside diameter / 2)
V _pn: pore volume when the n-th removable nitrogen occurs dV _n: variation in the time dt _n: variation in thickness t _n of the adsorption layer when the n-th removable nitrogen occurs Quantity r _kn : Core radius at that time c: Fixed value r _pn : Pore radius when the nth attachment / detachment of nitrogen occurs. ΣA _pj represents an integrated value of the area of the wall surface of the pore from j = 1 to j = n−1.

  The pore size of the micropores can be calculated as the distribution of pores from the rate of change in pore volume with respect to the pore size, for example, based on the MP method. When performing pore distribution analysis by the MP method, first, an adsorption isotherm is obtained by causing nitrogen to be adsorbed on the 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). Then, a pore distribution curve can be obtained based on the curvature of the plot (the amount of change in the pore volume with respect to the amount of change in the thickness t of the adsorption layer) (manual of BELSORP-mini and BELSORP analysis software manufactured by Bell Japan, Inc.). , Pages 72-73, page 82).

  JIS Z8831-2: 2010 "Pore size distribution and pore characteristics of powder (solid)-Part 2: Measurement method of mesopores and macropores by gas adsorption", and JIS Z8831-3: 2010 "Powder Analysis method for the delocalized density functional method (NLDFT method) specified in "Pore size distribution and pore characteristics of solids-Part 3: Measurement method of micropores by gas adsorption" The software attached to an automatic specific surface area / pore distribution measuring device “BELSORP-MAX” manufactured by Bell Japan Co., Ltd. is used. As a precondition, carbon black (CB) is assumed as a model having a cylinder shape, the distribution function of the pore distribution parameters is set to “no-assumption”, and the obtained distribution data is subjected to smoothing ten times.

The porous carbon material precursor is treated with an acid or an alkali. Specific treatment methods include, for example, a method of immersing the porous carbon material precursor in an aqueous solution of an acid or an alkali, and a method of treating the porous carbon material precursor with an acid. Alternatively, a method of reacting with an alkali in a gas phase can be used. More specifically, when treating with an acid, examples of the acid include an acidic fluorine compound such as hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, and sodium fluoride. When a fluorine compound is used, the fluorine element may be four times as much as the 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 combined with hydrofluoric acid as shown in the chemical formula (A) or (B). It reacts and is removed as hexafluorosilicic acid (H ₂ SiF ₆ ) or silicon tetrafluoride (SiF ₄ ) to obtain a porous carbon material. After that, washing and drying may be performed. In the case of treating with an acid, for example, by treating with an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid, etc., it is possible to remove the mineral components contained in the porous carbon material precursor.

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

When the treatment is performed with an alkali (base), for example, sodium hydroxide can be given as the alkali. When an aqueous solution of an alkali 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 by the aqueous solution of sodium hydroxide, heating the aqueous solution of sodium hydroxide causes the silicon dioxide to be removed as shown in the chemical formula (C). It reacts and is removed as sodium silicate (Na ₂ SiO ₃ ), and a porous carbon material can be obtained. When sodium hydroxide is reacted in the gas phase for treatment, the solid is reacted as shown by the chemical formula (C) by heating the solid, and removed as sodium silicate (Na ₂ SiO ₃ ). Thus, a porous carbon material can be obtained. After that, 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, the pores disclosed in JP-A-2010-106007 Is a porous carbon material having a three-dimensional regularity (a so-called porous carbon material having an inverse opal structure), specifically, a porous carbon material having an average diameter of 1 × 10 ⁻⁹ m to 1 × 10 ⁻⁵ m. Porous carbon material having spherical holes arranged in a three-dimensional manner and having a surface area of 3 × 10 ² m ² / gram or more, preferably the holes are arranged macroscopically in an arrangement state corresponding to a crystal structure. Alternatively, it is also possible to use a porous carbon material in which pores are arranged on the surface in a macroscopically arranged state corresponding to the (111) plane orientation in the face-centered cubic structure.

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

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

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

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

  In the production of the porous carbon material in Example 1, a 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, the rice husks are subjected to a heating treatment (preliminary carbonization treatment) in an inert gas. Specifically, the rice hulls were carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain carbides. In addition, by performing such a treatment, tar components that would be generated during the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was placed in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./min in a nitrogen stream (10 l / min). Then, it was carbonized at 800 ° C. for 1 hour to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. During the carbonization and cooling, nitrogen gas was kept flowing. Next, the porous carbon material precursor was subjected to an acid treatment by immersing it in a 46% by volume aqueous solution of hydrofluoric acid 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 1 is obtained by performing an activation treatment by heating at 900 ° C. in a steam stream (5 liters / minute) for 3 hours. I was able to. Then, the porous carbon material of Example 1 was pulverized, sieved, and a 60-mesh pass / 200-mesh-on portion was collected to obtain Example 1A.

  A filter medium used in a commercially available water purifier was sieved to collect a portion of 60 mesh pass / 200 mesh on, which was used as 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 the pore volume. As measurement conditions, the measurement equilibrium relative pressure (p / p ₀ ) was set to 0.01 to 0.99. Then, the specific surface area and the pore volume were calculated based on the BELSORP analysis software. The pore size distributions of the mesopores and the micropores were calculated based on the BJH method and the MP method using BELSORP analysis software by performing a nitrogen adsorption / desorption test using the above-described measuring device. Further, 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 Bell Japan 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 the pore volume of the filter media of Example 1A, Comparative Example 1A and Comparative Example 1B were measured, the results shown in Table 1 were obtained. In Table 1, "specific surface area" refers to the value of specific surface area by the nitrogen BET method, and the unit is m ² / g. The “MP method” and “BJH method” indicate the results of volume measurement of pores (micropores) by the MP method and the results of volume measurements of pores (mesopores to macropores) by the BJH method, respectively. 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, based on the delocalized density functional method (NLDFT method), 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) Table 2 shows the ratio (volume ratio) of the total volume of pores having pore diameters in the range of 3 nm to 20 nm with respect to the total volume. The results of the pore volume measurement based on the BJH method in Comparative Example 1A and the total volume (volume A) measurement results of all the pores based on the NLDFT method show large values. This is because the filter medium is not made of a porous carbon material but made of silica.

  For the measurement of the amount of adsorption, an aqueous solution of 0.03 mol / l of methylene blue and 0.5 mmol / l of black 5 was prepared, and 10 mg of the sample was added to each 40 ml of the aqueous solution. Then, the mixture was stirred at 100 rpm using a mixing rotor (stirring machine), and the stirring time was set to 0.5 minute, 1 minute, 3 minutes, 5 minutes, 15 minutes, 30 minutes, 60 minutes and 180 minutes, and then filtered. 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 methylene blue and black 5 adsorbed per gram of the filter medium was determined from the value of the calibration curve obtained from the absorbance per unit mass. Calculated.

  The results are shown in FIGS. 1A and 1B. The adsorption amount of methylene blue and black 5 of the filter medium of Example 1A is much larger than the adsorption amounts of the filter medium of Comparative Examples 1A and 1B. This is considered to be due to the influence of large volumes of mesopores and macropores not observed in the comparative example. In FIG. 1, the vertical axis represents the amount of adsorption (unit: milligram / gram), and the horizontal axis represents the test time (the time during which the filter medium was immersed in the test solution, the unit being minutes). Further, a triangle indicates data of Example 1A, a square indicates data of Comparative Example 1A, and a circle indicates data of Comparative Example 1B.

  In addition, the filter medium of Example 1 in another production lot was pulverized by hand using a mortar to obtain the filter medium of Example 1B. The filter medium of Example 1B is a 200 mesh-on product and has a particle size of 200 mesh. It is 0.50 mm to 0.85 mm. A 200 mesh pass filter medium obtained at the same time was used as Reference Example 1. When the specific surface area and the 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 Examples 1C and 1D.

  Further, 200 mg of each of the samples of Example 1B, Reference Example 1, Comparative Example 1C, and Comparative Example 1D were filled in a cartridge, and an aqueous methylene blue solution was flowed through the cartridge at a flow rate of 50 mL / min, and flowed out of the cartridge. The methylene blue concentration of the water was measured. The result is shown in FIG. Note that the vertical axis in FIG. 2 is the methylene blue adsorption rate (removal rate), which is a value normalized by assuming that the amount of adsorption (removal rate) of the filter medium of Reference Example 1 is 100%. The horizontal axis is the flow rate of the aqueous methylene blue solution. 2, the amount of methylene blue adsorbed by the filter media of Example 1B (indicated by a square) and Reference Example 1 (indicated by a diamond) is shown in Comparative Example 1C (indicated by a triangle) or Comparative Example 1D (indicated by a circle). ), It is much higher.

  FIG. 3 is a cross-sectional view of the water purifier of the first embodiment. The water purifier of the first embodiment is a continuous type water purifier, and is a faucet direct connection type water purifier in which a water purifier main body is directly attached to a tip of a water tap. The water purifier of Example 1 is disposed inside the water purifier main body 10, the water purifier main body 10, and is filled with the porous carbon material 11 of Example 1A or Example 1B or Reference Example 1; A second filling section 14 filled with cotton 13 is provided. Tap water discharged from the tap is discharged from an inflow port 15 provided in the water purifier main body 10, through a porous carbon material 11, cotton 13, and outflow port 16 provided in the water purifier main body 10. Is done.

  FIG. 4 is a schematic diagram illustrating a cross-sectional structure of the contaminant removal sheet member according to the first embodiment. 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 contaminant removal sheet member of Example 1 is a sheet-like porous carbon material, that is, carbon / carbon material, between a support member (nonwoven fabric 2) made of cellulose and the support member (nonwoven fabric 2). It has a structure in which the polymer composite 1 is sandwiched. The carbon / polymer composite 1 is made of the porous carbon material of Example 1A or Example 1B and Reference Example 1, and a binder, and the binder is made of, for example, carboxynitrocellulose. The contaminant removal sheet member is coated with the porous carbon material of Example 1A or Example 1B or Reference Example 1 on the support member, or the porous carbon material of Example 1 is kneaded into the support member. Can also be used.

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

  In the production of the porous carbon material in Example 2, a 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, the rice husks are subjected to a heating treatment (preliminary carbonization treatment) in an inert gas. Specifically, the rice hulls were carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain carbides. In addition, by performing such a treatment, tar components that would be generated during the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was placed in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./min in a nitrogen stream (10 l / min). Then, it was carbonized at 800 ° C. for 1 hour to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. During the carbonization and cooling, nitrogen gas was kept flowing. Next, the porous carbon material precursor was subjected to an acid treatment by immersing it in a 46% by volume aqueous solution of hydrofluoric acid 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 2 was activated by heating at 900 ° C. for 3 hours in a steam stream (3.5 L / min). Could be obtained.

When the specific surface area and the 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. In addition, samples of Example 2A and Example 2B having two kinds of particle size distributions were prepared. Table 3 shows the results of the particle size distribution measurement 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. Further, the same volume (2.0 cm ³⁾ the mass when filled with the sample to the first filling portion 12 (unit: grams) are shown in Table 1, when filled with the sample to the first filling portion 12 The filling ratio may be called “filling ratio”. Furthermore, based on the NLDFT method, fine pores having a pore diameter in the 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). Table 2 shows the volume ratio of the total volume of the holes. The measurement results of the mercury intrusion method are shown below. Furthermore, the ignition residue (i.e., the residue remaining when heating the sample dried at 120 ° C. for 12 hours to 800 ° C. with 300 ml / min of dry air based on the thermogravimetry (TG) method) The measurement results of the residual ash content are shown below. In addition, the measurement result of the ignition residue (residual ash) in the porous carbon material of Example 1 and Example 7, the measurement of the ignition residue (residual ash) in the porous carbon material precursor before performing 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

[Ignition residue]
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 chlorinated water having a concentration of 2.0 mg / l was flowed through the glass tube at a flow rate of 400 ml / min. And
Removal rate based on DPD absorption spectrophotometry (%)
= (Measured raw water value-measured passed water value) / measured raw water value x 100
FIG. 5 shows the measurement results of the chlorine removal rate obtained based on the above method. In addition, when the flow rate of 400 ml / min is converted into a space velocity (SV), it is as follows.

SV = 400 × 60 (milliliter / hour) / 2 cm ³ = 12000 hr ^-1

  From FIG. 5, the filter media made of the porous carbon materials of Example 2A and Example 2B have a significantly higher chlorine removal rate than Comparative Examples 2A, 2B, and 2C.

The third embodiment is also a modification of the first embodiment. In Example 3, evaluation regarding the removal rate of chlorine, the removal rate of 1,1,1-trichloroethane, and the removal rate of 2-chloro-4,6bisethylamino-1,3,5-triazine (CAT). The test was performed. 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 of Example 2A (200 mesh on product) was used. As Comparative Example 3, the same filter medium as in Comparative Example 2C was used.
Removal rate (%) = (measured value of raw water−measured value of passing water) / measured value of raw water × 100

  Using the filter media 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 mL, and chlorine water having a concentration of 2.0 mg / L and 0.3 mg / L of chlorine water were used. A 1,1,1-trichloroethane aqueous solution having a concentration of 0.003 milligrams / liter and a CAT aqueous solution having a concentration of 0.003 milligrams / liter were passed through the glass tube at a flow rate of 400 milliliters / minute. The removal rates of chlorine, 1,1,1-trichloroethane and CAT are shown in FIGS. 6 (A), (B) and (C). 6 (A), 6 (B) and 6 (C), it can be seen that the filter medium made of the porous carbon material of Example 3 has a significantly higher removal rate than Comparative Example 3. Was. In addition, when the flow rate of 400 ml / min is converted into a space velocity (SV), it is as follows.

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

  In eutrophic lakes and ponds, cyanobacteria (microcystis, etc.) may grow abnormally in summer, forming a thick layer of water with green powder. Is called Aoko. This cyanobacterium is known to generate toxins harmful to the human body, and among many toxins, the toxin called microcystin LR is particularly wary. When microcystin LR enters a living body, the liver is seriously damaged, and its toxicity has been reported in experiments using mice. Toxic blue water that produces microcystin LR occurs in lakes in Australia, Europe, the United States, and throughout Asia. Outbreaks of blue-green algae do not disappear throughout the year in the most affected Chinese lakes. Since lake water is used for drinking water and agricultural water, toxins produced by cyanobacteria in lakes and marshes have become a problem in securing drinking water for humans, and a solution to this problem is strongly desired.

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 treatment was a treatment of heating at 900 ° C. for 3 hours in a steam stream (2.5 L / min). Except for this point, it was obtained by the same method as that described in Example 1. When the specific surface area and the pore volume of the filter medium in Example 4 were measured, the results shown in Table 1 were obtained. Further, based on the NLDFT method, the pore diameter is set within a range of 3 nm to 20 nm with respect to the total volume of the pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m (volume A, total volume of all the pores). Table 2 shows the volume ratio of the total volume of the pores. Note that the filter medium in Example 4 is a 60 mesh pass / 200 mesh on product. 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 microcystine concentrations of the solution before and after the reaction were determined by a colorimetric method using an ultraviolet / visible spectrophotometer, and the removal rate was calculated. The results are shown in FIG. 7, and it was found that the filter medium made of the porous carbon material of Example 4 had a significantly higher removal rate than Comparative Example 4.

  In Example 5, the particle size dependence 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. Although the porous carbon material in Example 1 was used, a 200 mesh pass product was used as Reference Example 5. Further, as Comparative Example 5A, the granular activated carbon of Comparative Example 4 (60-mesh pass, 200 mesh-on product) was used, and as Comparative Example 5B, a 200-mesh pass product obtained by pulverizing the granular activated carbon of 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 the sample and 50 milliliters of the indole solution (3 × 10 ⁻⁴ mol / liter) were placed in a 50 milliliter screw tube. And the particle size dependency was evaluated based on the method of quantifying the amount of indole adsorbed after 1 hour. The results are shown in FIG. 8, and it was found that the filter media made of the porous carbon materials of Example 5 and Reference Example 5 did not have a particle size dependency as compared with Comparative Examples 5A and 5B.

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

Example 6 Example 6 relates to the filter media according to the fifth to eighth aspects of the present invention. The filter medium of Example 6 had a specific surface area value of 1 × 10 ² m ² / g or more according to the nitrogen BET method, a pore volume of 0.1 cm ³ / g or more according to the BJH method, and contained sodium, magnesium, potassium and The porous carbon material is made from a plant and contains 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 × 5 measured by the delocalized density functional method. × 10 ^-7 total pore volume of m is 0.1 cm ³ / g or more, preferably 0.2 cm ³ / g or more, sodium, magnesium, at least one member selected from the group consisting of potassium and calcium And a porous carbon material made from a plant containing the following components. Alternatively, the filter medium of Example 6 has a specific surface area value of 1 × 10 ² m ² / gram or more by a nitrogen BET method and a pore size distribution of 3 nm to 20 nm in a pore size distribution determined by a delocalized density functional method. A ratio 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, and sodium, magnesium, The porous carbon material is made from a plant and contains 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 a nitrogen BET method, a pore volume of 1.0 cm ³ / gram or more by a mercury intrusion method, and sodium, It is made of a plant-based porous carbon material 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 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 g of a filter medium is added to 50 ml of water (test water) having a hardness of 0.1 or less, and the hardness becomes 5 or more after 6 hours.

  More specifically, in Example 6, citrus peel such as mandarin peel (Example 6A), orange peel (Example 6B), grapefruit peel (Example 6C), and banana peel (Example 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 various plant raw 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. Next, after baking at 800 ° C. for 1 hour, the mixture was cooled to room temperature and pulverized using a mortar. The sample (carbonaceous substance, porous carbon material precursor) thus obtained is referred to as a sample of Example 6a, Example 6b, Example 6c, and Example 6d for convenience. Thereafter, each sample was immersed in concentrated hydrochloric acid for 24 hours, and then washed until the cleaning solution became neutral, thereby obtaining samples of Example 6a ', Example 6b', Example 6c ', and Example 6d'. Was. Next, the samples of Example 6a ', Example 6b', Example 6c ', and Example 6d' were subjected to an activation treatment in a steam stream at 900 ° C. for 1 hour, whereby Examples 6A and 6B were obtained. Thus, a filter medium comprising the porous carbon materials of Examples 6C and 6D was obtained.

Table 4 below shows the results of composition analysis of the samples of Example 6A, Example 6B, Example 6C, and Example 6D, and the sample of Comparative Example 6. X-ray diffraction of the samples of Examples 6a, 6b, 6c, and 6d, and the porous carbon materials of Examples 6a ', 6b', 6c ', and 6d'. The results are shown in FIGS. The filter media of Example 6A, Example 6B, Example 6C and Example 6D were all 200 mesh pass products. 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, based on the NLDFT method, the pore diameter is set within the range of 3 nm to 20 nm with respect to the total volume of the pores having a diameter of 1 × 10 ⁻⁹ m to 5 × 10 ⁻⁷ m (volume A, total volume of all the pores). Table 2 shows the volume ratio of the total volume of the pores. Further, FIG. 7 is a graph showing the filter media of Examples 6A, 6B, 6C, and 6D, and the measurement results of the pore size distribution obtained by the delocalized density functional theory method of Comparative Example 6. 11 is shown.

  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. From the X-ray diffraction results, the filter media of Example 6a ', Example 6b', Example 6c ', and Example 6d' show samples of Example 6a, Example 6b, Example 6c, and Example 6d. The observed crystalline peak derived from the mineral component was not observed. From this, it is considered that the mineral component is partially removed once by the acid treatment with concentrated hydrochloric acid, but the mineral component inside the filter medium is re-emerged 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 pure test water (hardness: <0.066) at a rate of 1 gram / gram. It was added at a rate of 50 ml, stirred for 6 hours, filtered, and the amount of various minerals contained in the filtrate was quantified by ICP-AES. Table 5 shows the amount of minerals 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) × 4.1
It was 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, extremely hard water: 180 or more) The classification of water according to the above is also given.

  From Table 5, in each sample of Example 6, the mineral elution characteristics 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. It was also found that the hardness of the filtrate obtained could be adjusted from soft water to medium hard water to hard water to very hard water depending on the plant material 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 1.88993 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 7cm ³ / gram Example 6B 0.0553 0.3038cm ³ / gram Example 6C 0.1566 0.7171cm ³ / gram Example 6D 0.2597 0.5044cm ³ / gram Comparative Example 6 0.0216 0.6935cm ³ / Gram

[Table 3]

[Table 4]

[Table 5]

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

  In Example 7, a porous carbon material was manufactured by the following method. Further, as Comparative Example 7, Kuraray Coal GW was used.

  In the production of the porous carbon material in Example 7, a 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, the rice husks are subjected to a heating treatment (preliminary carbonization treatment) in an inert gas. Specifically, the rice hulls were carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain carbides. In addition, by performing such a treatment, tar components that would be generated during the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide was placed in an alumina crucible and heated to 800 ° C. at a rate of 5 ° C./min in a nitrogen stream (10 l / min). Then, it was carbonized at 800 ° C. for 1 hour to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. During the carbonization and cooling, nitrogen gas was kept flowing. Next, the porous carbon material precursor was alkali-treated by immersing it overnight in a 10% by mass aqueous sodium hydroxide solution at 80 ° C., 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 activated by heating at 900 ° C. for 3 hours in a steam stream (2.5 L / min). Could be obtained.

  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 the 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. Further, 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 of 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) 0.9 milligrams of sodium dodecylbenzenesulfonate (B) 6.0 micrograms of chlorothalonil (C) 6.0 micrograms of dichloroboss (D) 6 micrograms of soluble lead (specifically, lead acetate) Conversion)
(E) 0.2 mg of sodium hypochlorite as free chlorine (in terms of chlorine)
(F) TOX concentration 130 ± 20 micrograms (chlorine conversion) as total organic halogen
Were prepared, and 2 cm ³ of each sample was passed at a flow rate of 40 ml / min. Then, the concentration before and after the passage of water was measured, and the removal rate was calculated. The 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 (in terms of chlorine)
Were prepared, and 2 cm ³ of each sample was passed through at a flow rate of 240 ml / min. Then, the concentration before and after the passage of water was measured, and the removal rate was calculated. The flow rate of 240 ml / min corresponds to the following space velocity (SV).

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

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

  The measurement results of the removal rate of sodium dodecylbenzenesulfonate (DBS) are shown in FIGS. 12A and 12B, and the measurement results of the removal rate of chlorothalonil (TPN) are shown in FIGS. 13A and 13B. FIG. 14 shows the measurement results of the removal rate of dichlorobos (DDVP), FIG. 15 shows the measurement results of the removal rate of soluble lead, and FIGS. 16A and 16B show the measurement results of the removal rate of free chlorine. FIG. 17 shows the measurement results of the removal rates of all organic halogens. In all cases, 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 h ⁻¹ . When performed, the time required for the removal rate of the substance to reach 80% is more than twice the time required for the removal rate of the substance to reach 80% when using coconut shell activated carbon.

Further, in the filter medium of Example 7, when water containing 0.9 mg / liter of dodecylbenzenesulfonate was continuously passed for 25 hours at a space velocity of 1200 h ^-1 , dodecyl benzene was added. The sulfonate removal rate is 10% or more.

Further, in the filter medium of Example 7, the 6 micrograms / liter containing water chlorothalonil, 50 hours at a space velocity 1200 hr ^-1, when performing liquid passing in succession, the removal rate of chlorothalonil 60% That is all.

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

In the filter medium of Example 7, when water containing 6 μg / L of soluble lead was continuously passed for 25 hours at a space velocity of 1200 h ⁻¹ , removal of the soluble lead was performed. The rate is 30% or more.

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 h- ¹ for 50 hours, the removal rate of free chlorine was reduced. Is 70% or more.

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

In addition, from the measurement result of the removal rate of sodium dodecylbenzenesulfonate (DBS), at SV = 1200 h < ^-1 >, the filter material of Example 7 had a filling rate of only about 27% of the activated carbon of Comparative Example 7, The removal rate was higher than that of the activated carbon of Comparative Example 7, and the removal rate was 100% in about 5 hours of passing water and 50% or more in about 27 hours of passing water. On the other hand, the removal rate of the activated carbon of Comparative Example 7 rapidly decreased shortly after passing water. This is probably because the activated carbon of Comparative Example 7 having only small pores has a low adsorption rate of DBS having a large molecular weight. From the results of the test, in Example 7, it was determined that the filter water of Example 7 was 150 ml using a stationary water purifier (hereinafter referred to as “stationary water purifier-A” for convenience). Assuming that water containing 2 mg / L of DBS was filtered at 25 L / day at a flow rate of 3.0 L / min, it was estimated that 100% of DBS could be removed for about 18 months. In addition, even when 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 mg / L of DBS is filtered at a flow rate of 1.8 L / min for 15 L / day, a stationary water purifier containing 15 mL 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”.

Further, from the measurement results of the chlorothalonil (TPN) removal rate, at SV = 1200 h ⁻¹ , the filter medium of Example 7 maintained the TPN removal rate higher than that of the activated carbon of Comparative Example 7, and the activated carbon of Comparative Example 7 did not. 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 that the filter medium of Example 7 having a higher adsorption rate is more advantageous than the activated carbon of Comparative Example 7, and TPN has a lower water solubility and thus has lower adsorptivity. Since it is high, it is considered that a high removal rate was maintained for a long time. From the test results, in Example 7, using the stationary water purifier-A, water containing 6.0 micrograms / liter of TPN was applied at a flow rate of 3.0 liters / min. Assuming that filtration is performed at 25 liters per day, it was estimated that TNP could be removed by 80% or more for about one year. On the other hand, at SV = 7200 h- ¹ , although the removal rate is lower than that at SV = 1200 h- ¹ , water containing 6.0 micrograms / liter of TPN is supplied at a flow rate of 1.8 liter / min. Assuming that filtration is performed at a rate of 15 liters per day, it is estimated that TNP can be removed by 50% or more using the stationary water purifier-B for about 7 months.

Also, from the measurement result of the removal rate of dichlorobos (DDVP), the removal rate of the filter medium of Example 7 was maintained higher than that of the activated carbon of Comparative Example 7 at SV = 1200 hr ⁻¹ , and the removal rate was about 32 hours. 80% or more. This is because the molecular weight of DDVP is slightly larger than 221. Therefore, it is considered that the filter medium of Example 7 having a higher adsorption rate was more advantageous than the activated carbon of Comparative Example 7. Since DDVP has a very high solubility in water of 10 g / liter and has a small equilibrium adsorption amount, the removal rate is 80% or more up to about 32 hours after passing water, but the removal rate decreases thereafter. Then, the removal rate became 50% in about 43 hours of passing water. For about 32 hours of passing water, the stationary water purifier-A was used to filter water containing 6.0 micrograms / liter of DDVP at a flow rate of 3.0 liters / minute for 25 liters per day. Assuming that it has been used for about 8 months, and about 43 hours of water passage correspond to about 10 months of use.

Also, from the measurement results of the removal rate of soluble lead, at SV = 1200 h ⁻¹ , the filter medium of Example 7 maintained a higher removal rate than the activated carbon of Comparative Example 7, and the removal rate was 50% in about 22 hours. That was all. In the activated carbon of Comparative Example 7, the removal rate was reduced to 50% or less in about 8 hours of passing water. This is considered to indicate that the filter medium of Example 7 has many active sites that readily adsorb lead. From the results of the test, using a stationary water purifier-A, 25 liters of water containing 6 micrograms / liter (in terms of lead) of soluble lead at a flow rate of 3.0 liters / minute per day was used. Assuming filtration, it was estimated that lead could be removed by more than 50% for about 5 months.

Further, the free chlorine removal rate measurement result of the SV = 1200 hr ^-1, the filter medium of Example 7, is maintained higher removal rate than Comparative Example 7, the water flow 48 hours after a 80% . 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. From the results of the test, using the stationary water purifier-A, 25 mg / day of water containing 0.2 mg / liter (in terms of chlorine) of free chlorine at a flow rate of 3.0 liter / min. Assuming filtration, it was estimated that 80% or more of free chlorine could be removed for about one year. On the other hand, even when SV = 7200 hr ⁻¹ , the removal rate was about 60% even after 48 hours of water flow. Then, from the test results, using the stationary water purifier-B, water containing 2.0 mg / liter (in terms of chlorine) of free chlorine at a flow rate of 1.8 liter / min, 15 liters / day, Assuming filtration, it was estimated that over 60% 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), at SV = 1200 h ^-1 , the filter medium of Example 7 showed that the activated carbon of Comparative Example 7 The removal rate was higher. Since the TOX component contains a substance having a higher molecular weight, the filter medium of Example 7 having a higher adsorption rate is considered to have a higher removal rate than the activated carbon of Comparative Example 7. From the results of the test, using the stationary water purifier-A, water containing all organic halogens having a TOX concentration of 130 micrograms (in terms of chlorine) / liter was fed at a flow rate of 3.0 liter / minute for 25 days / day. It was estimated that 50% or more could be removed for about 4 months, assuming liters of filtration.

  The eighth embodiment is a modification of the first to seventh embodiments. In Example 8, as illustrated in a schematic partial cross-sectional view of FIG. 18A, the filter medium described in Examples 1 to 7 is replaced with a bottle (so-called PET) having a cap member 30. (Bottle) 20. Specifically, the filter media 40 of Examples 1 to 7 are 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 media 40 does not flow out. Placed. Then, the liquid or water (drinking water, lotion, etc.) 21 in the bottle 20 is passed through the filter medium 40 disposed inside the cap member 30 and is drunk or used. Mineral components in (water) can be increased. Note that the cap member 30 is normally closed using a lid (not shown).

  Alternatively, as shown in a schematic sectional view of FIG. 18B, the filter medium 40 of the first to seventh embodiments is stored in a bag 50 having water permeability, and the liquid or water in the bottle 20 is stored. It is also possible to adopt a form in which the bag 50 is put into the (drinking water, lotion, etc.) 21. 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 media 40 of Examples 1 to 7 are arranged inside the straw member 60, and are not shown so that the filter media 40 does not flow out. The filters are arranged on the liquid inlet side and the liquid outlet side of the straw member. Then, the liquid or water (drinking water) 21 in the bottle 20 is passed through the filter medium 40 of Embodiments 1 to 7 disposed inside the straw member 60 and is drunk, so that the liquid (water) is Mineral components can be increased. Alternatively, as shown in FIG. 19B, a partially cut-out schematic surface is provided with the filter media 40 of Examples 1 to 7 inside the spray member 70 so that the filter media 40 does not flow out. , A filter (not shown) is disposed on the liquid inflow side and the liquid discharge side of the spray member 70. By pressing the push button 71 provided on the spray member 70, the liquid or water (drinking water, lotion, etc.) 21 in the bottle 20 is dispensed inside the spray member 70 according to the first to fifth embodiments. 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 described above, the present invention has been described based on the preferred embodiments, but the present invention is not limited to these embodiments, and various modifications are 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. Further, the porous carbon material constituting the filter medium of the present invention may be granulated and used.

  In the embodiment, 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, as other plants, for example, straw, reeds or stem wakame, vascular plants growing on land, ferns, bryophytes, algae, seaweed, and the like can be mentioned, and these may be used alone. However, a plurality of types may be mixed and used. Specifically, for example, a plant-derived material that is a raw material of the porous carbon material is rice straw (for example, from Kagoshima; Isehikari), and the porous carbon material is carbonized from the straw as a raw material to produce a carbonaceous material. (Porous carbon material precursor) and then subjected to an acid treatment. Alternatively, a plant-derived material, which is a raw material of the porous carbon material, is a rice reed, and the porous carbon material is carbonized from a rice reed as a raw material to produce a carbonaceous substance (porous carbon material precursor). And then subject to acid treatment. Similar results were obtained with a porous carbon material obtained by treating with an alkali (base) such as an aqueous sodium hydroxide solution instead of the aqueous hydrofluoric acid solution.

  Alternatively, a plant-derived material, which is a raw material of a porous carbon material, is referred to as stem wakame (from Sanriku, Iwate Prefecture), and the porous carbon material is carbonized from the stem wakame as a raw material to form a carbonaceous material (porous carbon material precursor). Can be obtained by converting the compound into a compound (I) and then subjecting it to an acid treatment. Specifically, first, for example, stem wakame is heated at a temperature of about 500 ° C. and carbonized. Before heating, for example, stem wakame as a raw material may be treated with alcohol. As a specific treatment method, a method of immersion in ethyl alcohol or the like is mentioned, thereby reducing water contained in the raw material, and other elements other than carbon contained in the finally obtained porous carbon material and , Mineral components can be eluted. Further, by the treatment with the alcohol, generation of gas at the time of carbonization can be suppressed. More specifically, the stem wakame is immersed in ethyl alcohol for 48 hours. In addition, it is preferable to perform an ultrasonic treatment in ethyl alcohol. Next, the stem wakame is carbonized by heating at 500 ° C. for 5 hours in a nitrogen stream to obtain a carbide. It should be noted that by performing such a treatment (preliminary carbonization treatment), tar components that would be generated during the next carbonization can be reduced or removed. Thereafter, 10 grams of this carbide is placed in an alumina crucible and heated to 1000 ° C. at a rate of 5 ° C./min in a nitrogen stream (10 l / min). Then, it is carbonized at 1000 ° C. for 5 hours to convert it into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. During the carbonization and cooling, the nitrogen gas is kept flowing. Next, the porous carbon material precursor is subjected to acid treatment by immersing it in a 46% by volume aqueous solution of hydrofluoric acid overnight, and then washed with water and ethyl alcohol until the pH becomes 7. Finally, by drying, a porous carbon material can be obtained.

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 ..The second filling portion, 15 ... inlet, 16 ... outlet, 20 ... bottle, 21 ... liquid or water, 22 ... cap, 30 ... cap member, 31, 32 filter, 40 filter medium, 50 bag, 60 straw member, 70 spray member, 71 push button, 72 spray hole

Claims (18)

Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / g or more, and the pore size distribution determined by the delocalized density functional method is in the range of 3 nm to 20 nm. Has at least one peak, and the proportion of the total volume of pores having pore diameters in the range of 3 nm to 20 nm is 0.3 or more of the total volume of all pores, and the particle size is 75 μm or more. Yes,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, lee husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A porous carbon material comprising at least one material selected from the group consisting of corns, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, diameter 1 × 10 determined by delocalized density functional theory ^-9 m to 5 × 10 ^-7 m total pore volume is 1.0 cm ^Three / G or more, the particle size is 75 μm or more,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, lee husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A porous carbon material comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, ferns, moss plants, algae and seaweed. Using a plant-derived material containing silicon as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, the volume of pores by the BJH method is 0.3 cm ^Three / G or more, the particle size is 75 μm or more, the content of the residue on ignition is 15% by mass or less,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A porous carbon material comprising at least one material selected from the group consisting of corns, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / g or more, and the pore size distribution determined by the delocalized density functional method is in the range of 3 nm to 20 nm. Has at least one peak, and the proportion of the total volume of pores having pore diameters in the range of 3 nm to 20 nm is 0.3 or more of the total volume of all pores, and the particle size is 75 μm or more. A filter for air cleaning filled with a certain porous carbon material,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, An air purifying filter comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, diameter 1 × 10 determined by delocalized density functional theory ^-9 m to 5 × 10 ^-7 m total pore volume is 1.0 cm ^Three / G or more, a filter for air cleaning filled with a porous carbon material having a particle size of 75 μm or more,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, An air purifying filter comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material containing silicon as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, the volume of pores by the BJH method is 0.3 cm ^Three / G or more, a particle size of 75 μm or more, and a content of an ignition residue of 15% by mass or less, which is a porous carbon material-filled air cleaning filter,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, An air purifying filter comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / g or more, and the pore size distribution determined by the delocalized density functional method is in the range of 3 nm to 20 nm. Has at least one peak, and the proportion of the total volume of pores having pore diameters in the range of 3 nm to 20 nm is 0.3 or more of the total volume of all pores, and the particle size is 75 μm or more. An air purification device including a column, a filter, or a cartridge filled with a certain porous carbon material,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, An air purification device comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae, and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, diameter 1 × 10 determined by delocalized density functional theory ^-9 m to 5 × 10 ^-7 m total pore volume is 1.0 cm ^Three / G or more, an air purification device provided with a column, filter or cartridge filled with a porous carbon material having a particle size of 75 μm or more,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, An air purification device comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material containing silicon as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, the volume of pores by the BJH method is 0.3 cm ^Three / G or more, a particle size of 75 μm or more, and a content of a residue of an ignition residue of 15% by mass or less.
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, An air purification device comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / g or more, and the pore size distribution determined by the delocalized density functional method is in the range of 3 nm to 20 nm. Has at least one peak, and the proportion of the total volume of pores having pore diameters in the range of 3 nm to 20 nm is 0.3 or more of the total volume of all pores, and the particle size is 75 μm or more. A water purification cartridge filled with a certain porous carbon material,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A water purification cartridge comprising at least one material selected from the group consisting of corns, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, diameter 1 × 10 determined by delocalized density functional theory ^-9 m to 5 × 10 ^-7 m total pore volume is 1.0 cm ^Three / G or more, a cartridge for water purification packed with a porous carbon material having a particle size of 75 μm or more,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A water purification cartridge comprising at least one material selected from the group consisting of corns, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material containing silicon as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, the volume of pores by the BJH method is 0.3 cm ^Three / G or more, a particle size of 75 μm or more, and a content of a residue on ignition of 15% by mass or less, a water purification cartridge filled with a porous carbon material,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A water purification cartridge comprising at least one material selected from the group consisting of corns, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / g or more, and the pore size distribution determined by the delocalized density functional method is in the range of 3 nm to 20 nm. Has at least one peak, and the proportion of the total volume of pores having pore diameters in the range of 3 nm to 20 nm is 0.3 or more of the total volume of all pores, and the particle size is 75 μm or more. A water purification device comprising a column or a cartridge filled with a certain porous carbon material,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A water purification device comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, diameter 1 × 10 determined by delocalized density functional theory ^-9 m to 5 × 10 ^-7 m total pore volume is 1.0 cm ^Three / G or more, a water purification device provided with a column or cartridge packed with a porous carbon material having a particle size of 75 μm or more,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A water purification device comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material containing silicon as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, the volume of pores by the BJH method is 0.3 cm ^Three / G or more, a particle size of 75 μm or more, and a content of a residue of an ignition residue of 15% by mass or less.
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A water purification device comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ² m ² / g or more, and the pore size distribution determined by the delocalized density functional method is in the range of 3 nm to 20 nm. Has at least one peak, and the proportion of the total volume of pores having pore diameters in the range of 3 nm to 20 nm is 0.3 or more of the total volume of all pores, and the particle size is 75 μm or more. A porous carbon material, and
Support members,
Equipped with a,
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A contaminant removal sheet member comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, ferns, moss plants, algae and seaweed. Using a plant-derived material as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, diameter 1 × 10 determined by delocalized density functional theory ^-9 m to 5 × 10 ^-7 m total pore volume is 1.0 cm ^Three / G or more, a porous carbon material having a particle size of 75 μm or more, and
Support members,
With
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A pollutant removal sheet member comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed. Using a plant-derived material containing silicon as a raw material, the value of the specific surface area by the nitrogen BET method is 1 × 10 ^Two m ^Two / G or more, the volume of pores by the BJH method is 0.3 cm ^Three / G or more, a particle size of 75 μm or more, and a content of a residue of the ignition residue of 15% by mass or less, and
Support members,
With
Plant-derived materials include rice husks or straws, barley husks or straws, wheat husks or straws, rye husks or straws, rice husks or straws, millet husks or straws, coffee beans, tea leaves, sugarcane, A pollutant removal sheet member comprising at least one material selected from the group consisting of corn, fruit bark reeds, stem wakame, vascular plants, fern plants, moss plants, algae and seaweed.