Materials with functional materials attached and methods for manufacturing the same, water purifiers and methods for manufacturing the same, water purifier cartridges and methods for manufacturing the same, air purifiers and methods for manufacturing the same, filter members and methods for manufacturing the same, support members and methods for manufacturing the same, expanded polyurethane foams and methods for manufacturing the same, bottles and methods for manufacturing the same, containers and methods for manufacturing the same, members consisting of caps or lids and methods for manufacturing the same, materials consisting of solidified porous carbon material or pulverized products of the porous carbon material and a binder and methods for manufacturing the same, and porous carbon materials and methods for manufacturing the same.

Abstract

To provide a porous carbon material or a pulverized material of the porous carbon material hard to generate problems concerning transportation and handling of raw materials and a porous carbon material, carbonization treatment, and treatment with acid or alkali.SOLUTION: A porous carbon material pertaining to the present disclosure is a solidified porous carbon material, and is produced from a raw material of a plant-derived material, where the fracture hardness of the solidified porous carbon material is 20 N or higher, a value of an ignition residue of the solidified porous carbon material is 0.1 mass% or more and 20 mass% or less, and a value of a cumulative pore volume in a range of a pore size 0.05 μm to 5 μm based on a mercury press-in method is 0.4 cm3 to 1.2 cm3 per 1 gram of the solidified porous carbon material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a material having a functional material attached thereto and a method for manufacturing the same, a water purifier and a method for manufacturing the same, a water purifier cartridge and a method for manufacturing the same, an air purifier and a method for manufacturing the same, a filter member and a method for manufacturing the same, a support member and a method for manufacturing the same, a polyurethane foam and a method for manufacturing the same, a bottle and a method for manufacturing the same, a container and a method for manufacturing the same, a member made of a cap or lid and a method for manufacturing the same, a material made of a solidified porous carbon material or a pulverized product of the porous carbon material and a binder and a method for manufacturing the same, and a porous carbon material and a method for manufacturing the same. [Background technology]

[0002] A porous carbon material made from a plant-derived material and a method for producing the same are known, for example, from Japanese Patent No. 4618308. The method disclosed in this patent publication is for producing a porous carbon material having a specific surface area of ​​10 m or less by nitrogen BET method. 2 / g or more, and the pore volume by the BJH method and MP method is 0.1 cm 3 This method involves carbonizing a plant-derived material at 800°C to 1400°C, and then treating it with an acid or alkali to remove silicon components from the carbonized plant-derived material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 4618308 Summary of the Invention [Problem to be solved by the invention]

[0004] The manufacturing methods of porous carbon materials disclosed in the above patent publications are excellent manufacturing methods, but because they use, for example, powdered rice husks as plant-derived materials (raw materials), the transportation and handling of the raw materials and porous carbon materials may be complicated, and the raw materials may have low bulk densities, making it difficult to effectively perform carbonization treatments or acid or alkali treatments. Furthermore, due to the manufacturing equipment, the amount of material that can be processed at one time during production may be limited.

[0005] Therefore, an object of the present disclosure is to provide a porous carbon material and a method for producing the same that facilitates the transportation and handling of raw materials and porous carbon materials, carbonization treatment, and treatment with acid or alkali. [Means for solving the problem]

[0006] In order to achieve the above object, the solidified porous carbon material of the present disclosure is made from a plant-derived material as a raw material, and the bulk density of the solidified porous carbon material is 0.2 g / cm 3 to 0.4 grams / cm 3 , preferably 0.3 g / cm 3 to 0.4 grams / cm 3 and the breaking hardness is 20N or more.

[0007] To achieve the above object, the method for producing a solidified porous carbon material of the present disclosure includes solidifying a plant-derived material, carbonizing the solidified material at 400°C to 1400°C, and then treating the solidified material with an acid or alkali. [Effects of the Invention]

[0008] Since the porous carbon material of the present disclosure is solidified, the porous carbon material can be transported and handled more easily. Furthermore, in the method for producing a solidified porous carbon material of the present disclosure, a plant-derived material is solidified, and then, in the solidified state, it is carbonized at 400°C to 1400°C, and then treated with an acid or alkali. This makes it easier to transport and handle the raw material and the porous carbon material, to perform the carbonization treatment, and to treat with an acid or alkali. Note that the effects described in this specification are merely examples and are not limiting, and additional effects may also be present. [Brief explanation of the drawings]

[0009] [Figure 1] 1A and 1B are graphs showing the results of measurement of the solidified porous carbon material of Example 1 by mercury intrusion porosimetry. [Figure 2] 2A and 2B are graphs showing the results of measurements of various materials in Comparative Example 1 by mercury porosimetry. [Figure 3] 3A and 3B are graphs showing the cumulative pore volume values ​​in the range of 0.05 μm to 5 μm obtained by mercury intrusion porosimetry for the solidified porous carbon material of Example 1 and various materials of Comparative Example 1. [Figure 4] FIG. 4 is a schematic cross-sectional view of the water purifier of the second embodiment. [Figure 5] 5A and 5B are a schematic partial cross-sectional view and a schematic cross-sectional view of a bottle in Example 2. FIG. [Figure 6] 6A and 6B are a schematic partial cross-sectional view and a partially cutaway schematic surface of a modified bottle in Example 2. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure will be described below based on examples with reference to the drawings, but the present disclosure is not limited to the examples, and various numerical values ​​and materials in the examples are merely examples. The description will be made in the following order. 1. General Description of the Solidified Porous Carbon Material and Its Manufacturing Method of the Present Disclosure 2. Example 1 (Solidified Porous Carbon Material of the Present Disclosure and Its Manufacturing Method) 3. Example 2 (Water Purifier and Its Modification) 4.Other

[0011] <General Description of the Solidified Porous Carbon Material and Its Manufacturing Method According to the Present Disclosure> In the method for producing a solidified porous carbon material of the present disclosure, the bulk density of the solidified porous carbon material is 0.2 g / cm 3 to 0.4 grams / cm 3 , preferably 0.3 g / cm 3 to 0.4 grams / cm 3 The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of the solidified porous carbon material. 3 ~1.2cm 3 , preferably 0.5 cm 3 ~1.0cm 3 The present invention can be implemented in the following form.

[0012] Furthermore, in the solidified porous carbon material of the present disclosure including the above-described preferred embodiment or the solidified porous carbon material obtained by the manufacturing method thereof, the cumulative pore volume value in the pore size range of 10 μm or less as determined by mercury intrusion porosimetry is 0.7 cm per gram of the solidified porous carbon material. 3 ~2.0cm 3 , preferably 0.7 cm 3 ~1.7cm 3 The present invention can be implemented in the following form.

[0013] Furthermore, in the solidified porous carbon material of the present disclosure including the various preferred embodiments described above or the solidified porous carbon material obtained by the manufacturing method thereof, the value of the pore volume based on the BJH method is 3 0.1cm per 3 The above configuration can be adopted.

[0014] Furthermore, in the solidified porous carbon material of the present disclosure including the various preferred embodiments described above or the solidified porous carbon material obtained by the manufacturing method thereof, the value of the pore volume based on the MP method is 3 0.04cm per 3 ~0.1cm 3 The present invention can be implemented in the following form.

[0015] Furthermore, in the solidified porous carbon material of the present disclosure including the various preferred embodiments described above or the solidified porous carbon material obtained by the manufacturing method thereof, the value of the pore volume based on the BJH method is 0.3 cm per gram of the solidified porous carbon material. 3 The pore volume value based on the MP method is 0.1 cm per gram of solidified porous carbon material. 3 The above configuration can be adopted.

[0016] Furthermore, in the method for producing a solidified porous carbon material according to the present disclosure, including the various preferred embodiments described above, the bulk density of the solidified plant-derived material is 0.2 g / cm 3 to 1.4 grams / cm 3 The present invention can be implemented in the following form.

[0017] Furthermore, in the method for producing a solidified porous carbon material according to the present disclosure, including the various preferred embodiments described above, the bulk density of the material carbonized in a solidified state (hereinafter, sometimes referred to as a "porous carbon material precursor") is 0.2 g / cm 3 to 0.8 grams / cm 3 The present invention can be implemented in the following form.

[0018] Furthermore, in the method for producing a solidified porous carbon material according to the present disclosure, including the various preferred embodiments described above, starch or potato starch may be used as a binder when solidifying the plant-derived material. Alternatively, the binder may be appropriately selected from materials that do not decompose when exposed to temperatures ranging from room temperature to 180°C when solidifying the plant-derived material, but are burned when the plant-derived material is carbonized at temperatures ranging from 400°C to 1400°C. The plant-derived material and binder may be mixed using an appropriate mixer.

[0019] Furthermore, in the solidified porous carbon material of the present disclosure, including the various preferred embodiments described above, the ignition residue of the solidified porous carbon material can be 0.1 mass % or more and 20 mass % or less, and in the method for producing a solidified porous carbon material of the present disclosure, including the various preferred embodiments described above, the ignition residue of the solidified porous carbon material can be set to 0.1 mass % or more and 20 mass % or less, preferably 0.1 mass % or more and 15 mass % or less, and more preferably 0.1 mass % or more and 2 mass % or less by treating with an acid or alkali. Measurements can be made based on the "Activated Carbon Test Method" 14.

[0020] Furthermore, in the solidified porous carbon material of the present disclosure including the various preferred embodiments described above, the ignition residue bulk density of the solidified porous carbon material is 1×10 -4 grams / cm 3 〜1×10 -1 grams / cm 3 , preferably 1 x 10 -2 grams / cm 3 〜1×10 -1 grams / cm 3 In the method for producing a solidified porous carbon material according to the present disclosure, including the various preferred embodiments described above, the ignition residue bulk density of the carbonized material in a solidified state (porous carbon material precursor) can be 0.1 g / cm. 3The ignition residue bulk density of the solidified porous carbon material is 1×10 -4 grams / cm 3 〜1×10 -1 grams / cm 3 , preferably 1 x 10 -2 grams / cm 3 〜1×10 -1 grams / cm 3 The present invention can be implemented in the following form.

[0021] Furthermore, the breaking hardness of the solidified porous carbon material of the present disclosure, including the various preferred embodiments described above, is preferably 20 N or more. The breaking hardness of the solidified porous carbon material can be determined using a Kiya hardness tester (manufactured by Fujiwara Seisakusho Co., Ltd.: product number: 043019-C; the same applies hereinafter). Specifically, the breaking hardness of 10 samples is measured, the top 3 samples and the bottom 3 samples are removed, and the breaking hardness is calculated from the average value (rounded to the nearest integer) of the middle 4 samples.

[0022] In the solidified porous carbon material or the manufacturing method thereof according to the present disclosure, including the various preferred embodiments described above (hereinafter, these may be collectively referred to simply as "the present disclosure"), the porous carbon material is made from a plant-derived material. Examples of plant-derived materials include rice husks and straw from crops such as rice, barley, wheat, rye, barnyard millet, and foxtail millet, coffee beans, tea leaves (e.g., green tea leaves, black tea leaves, etc.), sugarcane (more specifically, sugarcane pomace), corn (more specifically, corn cobs), fruit peels (e.g., citrus peels such as orange peel, grapefruit peel, and mandarin peel, and banana peel), reeds, and wakame stems. However, the plant-derived materials are not limited to these, and other examples include terrestrial vascular plants, ferns, mosses, algae, and seaweed. These materials may be used alone or in combination as raw materials. Furthermore, plant-derived materials (for convenience, referred to as "material-A") may be mixed with materials such as seed shells, such as coconut shells and walnut shells, or woody sawdust, such as cedar, pine, and bamboo, (for convenience, referred to as "material-B"), and solidified. In this case, the mixing ratio of material-A to material-B is, for example, Preferably, the ratio is 0.1≦(material-B) / (material-A)≦10, but is not limited to this mass ratio. Furthermore, the shape and form of the plant-derived material are not particularly limited. For example, it may be rice husks or straw itself, or dried products. Furthermore, in the processing of food and beverages such as beer and alcoholic beverages, products that have undergone various processes such as fermentation, roasting, and extraction can also be used. In particular, from the perspective of recycling industrial waste, it is preferable to use straw and rice husks that have been processed, such as threshing. These processed straw and rice husks can be easily obtained in large quantities from, for example, agricultural cooperatives, alcoholic beverage manufacturers, food companies, and food processing companies.

[0023] Furthermore, before solidification, the plant-derived material may be pulverized to a desired particle size or may be classified as desired. The plant-derived material may be washed in advance. The porous carbon material precursor may be coarsely pulverized to a desired particle size or may be classified. The solidified porous carbon material of the present disclosure may be pulverized to a desired particle size or may be classified, and such pulverized or classified products may be applied to various products.

[0024] In the method for producing a solidified porous carbon material according to the present disclosure (hereinafter, sometimes simply referred to as "the method for producing a porous carbon material according to the present disclosure"), examples of a method for solidifying a plant-derived material include forming it into pellets using a ring die, flat die, or screw molding machine. Another method involves solidifying the material into a log-like or roll-like shape. After solidifying it using these methods, it may be crushed to an appropriate size. In addition, examples of the shape of the solidified porous carbon material according to the present disclosure include pellets (more specifically, cylindrical shapes with a diameter of about 2 mm to 15 mm and a length of about 10 mm to 60 mm), log-like shapes (more specifically, shapes represented by the trade name Momigalite (registered trademark), with a diameter of about 50 mm, a central hole of about 15 mm, and a length of, for example, about 30 cm), and coil shapes (with a diameter of about 50 mm, a central hole of about 25 mm, a width of about 20 mm, and a length of about 30 cm). These shapes may also be crushed into granules (diameter: 0.5 mm to 50 mm).

[0025] The method for producing a porous carbon material according to the present disclosure may include a step of performing an activation treatment after the acid or alkali treatment, or may perform the activation treatment followed by the acid or alkali treatment. Furthermore, in the method for producing a porous carbon material according to the present disclosure, including such a preferred embodiment, depending on the plant-derived material used, the solidified plant-derived material may be subjected to a heat treatment (pre-carbonization treatment) in an oxygen-blocked state at a temperature lower than the carbonization temperature (e.g., 400°C to 700°C) before carbonization. This allows extraction of tar components that would otherwise be produced during the carbonization process, thereby reducing or eliminating the tar components that would otherwise be produced during the carbonization process. The oxygen-blocked state can be achieved, for example, by creating an inert gas atmosphere such as nitrogen gas or argon gas, or by creating a vacuum atmosphere, or by subjecting the plant-derived material to a type of steam-baking state. Furthermore, in the method for producing a porous carbon material according to the present disclosure, depending on the plant-derived material used, in some cases, the solidified plant-derived material may be immersed in an acid or alkali, or in an alcohol (e.g., methyl alcohol, ethyl alcohol, or isopropyl alcohol) to reduce the mineral components and moisture contained in the plant-derived material and to prevent the generation of unpleasant odors during the carbonization process. When treating with an acid, for example, treatment with an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid can remove the mineral components contained in the porous carbon material precursor. In addition, in the method for producing a porous carbon material according to the present disclosure, a preliminary carbonization treatment may be performed thereafter. Examples of materials that are preferably subjected to heat treatment in an inert gas include plants that produce large amounts of wood vinegar (tar and light oils). Examples of materials that are preferably subjected to pretreatment with alcohol or the like include seaweeds that contain large amounts of iodine and various minerals.

[0026] In the method for producing a porous carbon material according to the present disclosure, a plant-derived material is carbonized at 400°C to 1400°C. Carbonization generally refers to converting an organic substance (in the case of the solidified porous carbon material according to the present disclosure, the solidified plant-derived material) into a carbonaceous substance through heat treatment (see, for example, JIS M0104-1984). The atmosphere used for carbonization may be an oxygen-free atmosphere, specifically a vacuum atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas, or an atmosphere in which the plant-derived material is steamed. The heating rate up to the carbonization temperature under such an atmosphere is not limited, but may be 1°C / min or higher, preferably 3°C / min or higher, and more preferably 5°C / min or higher. The upper limit of the carbonization time may be 10 hours, preferably 7 hours, and more preferably 5 hours, but is not limited thereto. The lower limit of the carbonization time should be set to a time sufficient to ensure that the plant-derived material is carbonized. The finally obtained porous carbon material may be subjected to a sterilization treatment. There are no limitations on the type, configuration, or structure of the furnace used for carbonization, and it can be a continuous furnace or a batch furnace.

[0027] In the method for producing a porous carbon material according to the present disclosure, as described above, activation treatment can increase the number of micropores with a pore size of less than 2 nm. Examples of activation treatment methods include gas activation and chemical activation. The gas activation method involves using oxygen, water vapor, carbon dioxide, air, or the like as an activator in a gas atmosphere, heating the porous carbon material at 700°C to 1400°C, preferably 700°C to 1000°C, and more preferably 800°C to 1000°C, for several tens of minutes to several hours, thereby developing a microstructure using volatile components and carbon molecules in the porous carbon material. More specifically, the heating temperature may be appropriately selected based on the type of plant-derived material, the type and concentration of gas, etc., but is more preferably 800°C to 950°C. Chemical activation is a method in which, instead of the oxygen or water vapor used in gas activation, sodium hydroxide, potassium hydroxide, zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, sulfuric acid, etc. are used to activate the material, followed by washing with hydrochloric acid, adjusting the pH with an alkaline aqueous solution, and drying.

[0028] The surface of the solidified porous carbon material of the present disclosure (hereinafter, sometimes simply referred to as the "porous carbon material of the present disclosure") may be subjected to a chemical treatment or molecular modification. Examples of chemical treatment include a treatment in which carboxy groups are generated on the surface by nitric acid treatment. Furthermore, various functional groups, such as hydroxyl groups, carboxyl groups, ketone groups, and ester groups, can also be generated on the surface of the porous carbon material of the present disclosure by performing a treatment similar to the activation treatment using water vapor, oxygen, alkali, or the like. Furthermore, molecular modification is also possible by chemically reacting the porous carbon material of the present disclosure with a chemical species or protein having a reactive hydroxyl group, carboxyl group, amino group, or the like.

[0029] In the method for producing a porous carbon material according to the present disclosure, silicon components are removed from the plant-derived material after carbonization by acid treatment or alkali treatment. Examples of silicon components include silicon oxides such as silicon dioxide, silicon oxide, and silicon oxide salts. By removing the silicon components from the plant-derived material after carbonization in this manner, the porous carbon material according to the present disclosure can be obtained, which has a high specific surface area. In some cases, the silicon components may be removed from the plant-derived material after carbonization by dry etching. Removing the silicon components can reduce the ignition residue. The ignition residue of the solidified porous carbon material according to the present disclosure is as described above.

[0030] The porous carbon material of the present disclosure has many pores. The pores include "mesopores" with a pore diameter of 2 nm to 50 nm, "macropores" with a pore diameter of more than 50 nm, and "micropores" with a pore diameter of less than 2 nm. Specifically, the mesopores include many pores with a pore diameter of, for example, 20 nm or less, and particularly many pores with a pore diameter of 10 nm or less. The micropores include many pores with a pore diameter of, for example, about 1.9 nm, about 1.5 nm, and about 0.8 nm to 1 nm. In the porous carbon material of the present disclosure, the pore volume measured by the BJH method is 0.3 cm per gram of the porous carbon material of the present disclosure. 3 More than 0.5cm, preferably 3 The pore volume measured by the MP method is preferably 0.1 cm or more per gram of the porous carbon material of the present disclosure. 3 More than 0.2cm, preferably 3 More than 0.3cm, preferably 0.3cm 3 It is desirable that this is the case.

[0031] In the porous carbon material of the present disclosure, the value of the specific surface area measured by the nitrogen BET method (hereinafter, sometimes simply referred to as the "value of specific surface area") is 10 m per gram of the porous carbon material of the present disclosure in order to obtain even better functionality. 2 More than 50m, preferably 2 More than 100m, preferably 2More than 500m, more preferably 2 Alternatively, the porous carbon material of the present disclosure may be 3 Win, 2 x 10 2 m 2 ~3×10 2 m 2 It is desirable that:

[0032] The nitrogen BET method is a method in which an adsorption isotherm is measured by adsorbing and desorbing nitrogen as an adsorbed molecule on an adsorbent (here, a porous carbon material), and the measured data is analyzed based on the BET equation expressed by equation (1). Based on this method, the specific surface area, pore volume, etc. can be calculated. Specifically, when calculating the value of the specific surface area using the nitrogen BET method, an adsorption isotherm is first obtained by adsorbing and desorbing nitrogen as an adsorbed molecule on a porous carbon material. Then, from the obtained adsorption isotherm, [p / {V a (p0-p)}] is calculated and plotted against the equilibrium relative pressure (p / p0). This plot is then considered as a straight line, and the slope s (= [(C-1) / (C V m )]) and intercept i(=[1 / (C V m Then, from the obtained slope s and intercept i, V is calculated based on equations (2-1) and (2-2). m and C are calculated. m From the above, the specific surface area a sBET (See pages 62 to 66 of the manual for BELSORP-mini and BELSORP analysis software manufactured by BEL Japan Co., Ltd.) This nitrogen BET method is a measurement method conforming to JIS R 1626-1996 "Method for measuring the specific surface area of ​​fine ceramic powders by the gas adsorption BET method."

[0033] V a =(V m ·C·p) / [(p0-p){1+(C-1)(p / p0)}] (1) [p / {V a (p0-p)}] =[(C-1) / (C·V m)](p / p0)+[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)

[0034] however, V a :Adsorption amount V m : Monolayer adsorption amount p: Nitrogen equilibrium pressure p0: saturated vapor pressure of nitrogen L: Avogadro's number σ: Nitrogen adsorption cross section is.

[0035] When calculating the pore volume Vp by the nitrogen BET method, for example, the adsorption data of the obtained adsorption isotherm is linearly interpolated to determine the adsorption amount V at the relative pressure set as the pore volume calculation relative pressure. The pore volume Vp can be calculated from this adsorption amount V based on formula (4) (see pages 62 to 65 of the manual for BELSORP-mini and BELSORP analysis software manufactured by BEL Japan Co., Ltd.). Hereinafter, the pore volume based on the nitrogen BET method may be simply referred to as "pore volume."

[0036] V p =(V / 22414)×(M g / ρ g ) (4)

[0037] however, V: Adsorption amount at relative pressure M g : Molecular weight of nitrogen ρ g : density of nitrogen is.

[0038] The pore size of mesopores can be calculated as a pore distribution from the rate of change in pore volume relative to the pore size, for example, based on the BJH method. The BJH method is a widely used method for analyzing pore distribution. When analyzing pore distribution based on the BJH method, first, a desorption isotherm is obtained by adsorbing and desorbing nitrogen as adsorbed molecules to a porous carbon material. Then, based on the obtained desorption isotherm, the thickness of the adsorbed layer when the adsorbed molecules (e.g., nitrogen) are gradually adsorbed and desorbed from the pores filled with adsorbed molecules, and the inner diameter of the pores (twice the core radius) generated at that time are calculated, and the pore radius r is calculated based on Equation (5). p The pore diameter (2r p ) to the pore volume change rate (dV p / dr p ) to obtain a pore size distribution curve (see pages 85 to 88 of the manual for BELSORP-mini and BELSORP analysis software manufactured by BEL Japan Co., Ltd.).

[0039] 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)

[0040] where: r p : pore radius r k : pore radius r p The core radius (inner diameter / 2) when an adsorption layer of thickness t is adsorbed on the inner wall of a pore at that pressure. V pn : Pore volume when the nth nitrogen absorption / desorption occurs dV n: Amount of change at that time dt n : Thickness of the adsorption layer when the nth nitrogen absorption / desorption occurs t n Amount of change in r kn : Core radius at that time c: fixed value r pn : Pore radius when the nth nitrogen absorption / desorption occurs Also, ΣA pj represents the integrated value of the wall area of ​​the pores from j=1 to j=n-1.

[0041] The pore size of the micropores can be calculated as a pore distribution from the rate of change in pore volume relative to the pore size, for example, based on the MP method. When analyzing the pore distribution using the MP method, first, an adsorption isotherm is obtained by adsorbing nitrogen onto a porous carbon material. This adsorption isotherm is then converted into a pore volume versus the thickness t of the adsorption layer (t-plot). A pore distribution curve can then be obtained based on the curvature of this plot (the amount of change in pore volume versus the amount of change in the thickness t of the adsorption layer) (see pages 72-73 and 82 of the manual for BELSORP-mini and BELSORP analysis software manufactured by BEL Japan Co., Ltd.).

[0042] The pore size measurement by mercury porosimetry conforms to JIS R1655:2003, "Method for testing pore size distribution of molded fine ceramics by mercury porosimetry." Specifically, mercury porosimetry measurements were performed using a POREMASTER 60GT (Quantachrome). The pore size measurement range was set to 3 nm to 200 μm. The cumulative pore volume can be calculated by accumulating the measured sectional pore volumes over a desired range. The bulk density can be determined based on the measurement method for packing density described in JIS K1474:2014, "Test methods for activated carbon." The ignition residue bulk density can be determined by multiplying the bulk density value by the ignition residue value. The ignition residue (residual ash) can be measured based on the measurement method for ignition residue described in JIS K1474:2014, "Test methods for activated carbon." The ignition residue (residual ash) value of the solidified porous carbon material of the present disclosure is desirably 20% by mass or less, preferably 15% by mass or less. Furthermore, it is desirable that the ignition residue (residual ash content) in the porous carbon material precursor is 20% by mass or more, and preferably 25% by mass or more.

[0043] The porous carbon material precursor is subjected to an acid treatment or alkali treatment. Specific treatment methods include, for example, immersing the porous carbon material precursor in an acid or alkali aqueous solution or reacting the porous carbon material precursor with an acid or alkali in the gas phase. More specifically, in the case of acid treatment, the acid may be an acidic fluorine compound such as hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, or sodium fluoride. When a fluorine compound is used, the amount of fluorine element relative to the amount of silicon element in the silicon component contained in the porous carbon material precursor is four times that of silicon element, and the concentration of the fluorine compound aqueous solution is preferably 10 mass% or more. When removing the silicon component (e.g., silicon dioxide) contained in the porous carbon material precursor with hydrofluoric acid, the silicon dioxide reacts with hydrofluoric acid as shown in chemical formula (A) or chemical formula (B) and is removed as hexafluorosilicic acid (HSiF) or silicon tetrafluoride (SiF), thereby obtaining a porous carbon material. This is followed by washing and drying.

[0044] SiO2+6HF → H2SiF6+2H2O (A) SiO2+4HF → SiF4+2H2O (B)

[0045] Furthermore, in the case of alkali treatment using an alkali (base), examples of the alkali include sodium hydroxide. When an alkali aqueous solution is used, the pH of the aqueous solution may be 11 or higher. When removing silicon components (e.g., silicon dioxide) contained in a porous carbon material precursor using a sodium hydroxide aqueous solution, the silicon dioxide reacts as shown in chemical formula (C) by heating the sodium hydroxide aqueous solution, and is removed as sodium silicate (Na2SiO3), thereby obtaining a porous carbon material. When treating by reacting sodium hydroxide in a gas phase, the sodium hydroxide solid reacts as shown in chemical formula (C) by heating, and is removed as sodium silicate (Na2SiO3), thereby obtaining a porous carbon material. After that, washing and drying can be performed.

[0046] SiO2+2NaOH → Na2SiO3+H2O (C)

[0047] A functional material may be attached to the porous carbon material of the present disclosure. Specifically, the functional material may be attached to the solidified porous carbon material of the present disclosure after acid or alkali treatment (or after the activation treatment, if any). Examples of the functional material include agents for more effectively adsorbing the above-mentioned airborne substances (specifically, ethylene urea, phosphoric acid, copper nitrate, etc.). Alternatively, the functional material may be in a form exhibiting photocatalytic properties. In the latter case, the functional material may be composed of, for example, titanium oxide (TiO) or zinc oxide (ZnO). The use of ethylene urea can effectively remove formaldehyde and acetaldehyde, the use of phosphoric acid can effectively remove ammonia, and the use of copper nitrate can effectively deodorize ammonia, hydrogen sulfide, and the like. This imparts catalytic properties to the porous carbon material, and the photocatalytic effect allows it to be used as a semi-permanently usable hazardous substance decomposer or hazardous substance remover. Harmful substances can be decomposed and removed by irradiating the porous carbon material with energy rays or electromagnetic waves (e.g., ultraviolet light, sunlight, visible light, etc.). Harmful substances include those present in the air, such as various viruses, allergy-causing substances, and carcinogenic substances contained in cigarette smoke (e.g., benzopyrene).

[0048] Although it depends on the type, composition, structure, and form of the functional material, the form of adhesion of the functional material to the porous carbon material can be exemplified by a state in which the functional material is attached to the surface (including the inside of the pores) of the porous carbon material as fine particles, a state in which the functional material is attached in the form of a thin film, or a state in which the functional material is attached in a sea-island form (when the surface of the porous carbon material is considered as a "sea," the functional material corresponds to the "islands"). Note that adhesion refers to the adhesion phenomenon between different types of materials. Methods for attaching a functional material to the solidified porous carbon material of the present disclosure include a method of immersing the porous carbon material in a solution containing the functional material to precipitate the functional material on the surface of the porous carbon material; a method of precipitating the functional material on the surface of the porous carbon material by electroless plating (chemical plating) or a chemical reduction reaction; a method of immersing the porous carbon material in a solution containing a precursor of the functional material and then subjecting it to heat treatment to precipitate the functional material on the surface of the porous carbon material; a method of immersing the porous carbon material in a solution containing a precursor of the functional material and then subjecting it to ultrasonic treatment to precipitate the functional material on the surface of the porous carbon material; and a method of immersing the porous carbon material in a solution containing a precursor of the functional material and then subjecting it to a sol-gel reaction to precipitate the functional material on the surface of the porous carbon material.

[0049] The solidified porous carbon material of the present disclosure can be used, for example, in water purifiers and water purifier cartridges, in air purifiers, and as filter members (air purifier filters and water purifier filters), but the application fields are not limited to these. It can also be used in cosmetics, food, and cigarette filters, and as composites impregnated with chemicals (porous carbon material with an adhesive), etc.

[0050] For example, when used in a water purifier, the solidified porous carbon material of the present disclosure may be used as a filter material. The solidified porous carbon material may be washed with an acid or alkali to adjust the pH before use. The solidified porous carbon material of the present disclosure can be used to obtain a porous carbon material having a molecular weight of, for example, 1×10 2 〜1×10 5This method can remove various substances from water containing the above substances, water containing dodecylbenzenesulfonate, water containing chlorothalonil, water containing dichlorovos, water containing tetracycline, water containing soluble lead, water containing free chlorine, and water containing total organic halogens.

[0051] When used for water purification, air purification, or generally fluid purification, the solidified porous carbon material (or, in some cases, a pulverized product) of the present disclosure may be used in the following forms: in sheet form, attached to polyurethane foam, packed in a column or cartridge, contained in a water-permeable bag, formed into a desired shape using a binder (binding agent), or in powder form. When removing a substance dispersed in a solution, the surface can be treated to be hydrophilic or hydrophobic before use. When used in sheet form, woven or nonwoven fabrics can be used as support members, and cellulose, polypropylene, or polyester can be used as materials constituting the support members. Furthermore, the porous carbon material may be sandwiched between support members or kneaded into the support members.

[0052] The water purifier may further include a filtration membrane (for example, a hollow fiber membrane or a flat membrane having 0.4 μm to 0.01 μm pores) (using the solidified porous carbon material of the present disclosure in combination with the filtration membrane), a reverse osmosis membrane (RO) (using the solidified porous carbon material of the present disclosure in combination with the reverse osmosis membrane), a ceramic filter medium (a ceramic filter medium having fine pores) (using the solidified porous carbon material of the present disclosure in combination with the ceramic filter medium), or an ion exchange resin (using the solidified porous carbon material of the present disclosure in combination with the ion exchange resin). Generally, filtrate that has passed through a reverse osmosis membrane (RO) contains almost no mineral components, but by passing the filtrate through a reverse osmosis membrane (RO) and then through the solidified porous carbon material of the present disclosure, mineral components can be added to the filtrate.

[0053] Examples of types of water purifiers include continuous water purifiers, batch water purifiers, and reverse osmosis membrane water purifiers. Alternatively, examples include faucet-mounted types in which the water purifier body is directly attached to the tip of a water faucet, freestanding types (also called top-sink or tabletop types), faucet-integrated types in which the water purifier is built into the faucet, under-sink types (built-in types) installed in a kitchen sink, pot types (pitcher types) in which the water purifier is built into a container such as a pot or pitcher, central types attached directly to the water piping downstream of the water meter, portable types, and straw types. The configuration and structure of the water purifier can be the same as those of conventional water purifiers. In a water purifier, the solidified porous carbon material of the present disclosure can be used, for example, housed in a cartridge, and the cartridge may be provided with a water inlet and a water outlet. The "water" to be purified by a water purifier is not limited to the "water" defined in "3. Terms and definitions" of JIS S3201:2010 "Test methods for household water purifiers."

[0054] Alternatively, examples of components suitable for incorporating the solidified porous carbon material of the present disclosure include caps or lids for bottles (so-called PET bottles) with caps or lids, straws, or sprayers, laminated containers, plastic containers, glass containers, glass bottles, etc. Here, by disposing the solidified porous carbon material of the present disclosure inside the cap or lid and passing liquid or water (drinking water, lotion, etc.) in the bottle, laminated container, plastic container, glass container, glass bottle, etc. through the solidified porous carbon material of the present disclosure disposed inside the cap or lid, or by drinking or using the filtered water, mineral components can be imparted to the filtered water. Alternatively, a filter medium made of the solidified porous carbon material of the present disclosure can be placed in a water-permeable bag, and the bag can be placed in liquid or water (drinking water, lotion, etc.) in various containers such as bottles (so-called PET bottles), laminated containers, plastic containers, glass containers, glass bottles, and kettle pitchers. [Example]

[0055] Example 1 relates to a solidified porous carbon material and a method for producing the same according to the present disclosure.

[0056] In the manufacturing method of the solidified (specifically, pelletized) porous carbon material of Example 1, rice husks were used as the plant-derived material. The rice husks, which are the plant-derived material, were solidified using a pellet machine, specifically to obtain a solidified plant-derived material in the form of approximately cylindrical pellets with an average diameter of 6 mm and an average length of 30 mm. Note that no binder was used during solidification. The bulk density of the solidified plant-derived material was 0.2 g / cm. 3 to 1.4 grams / cm 3 , specifically 0.70 g / cm 3 The solidified material was then carbonized at 400 to 1400°C. Specifically, it was carbonized at 500°C for 3 hours in a nitrogen atmosphere using a mantle heater. The resulting carbonized material in a solidified state (porous carbon material precursor) had a bulk density of 0.2 g / cm. 3 to 0.8 grams / cm 3 , specifically 0.50 g / cm 3 The ignition residue of the carbonized material in the solidified state was 42%, and the ignition residue bulk density was 0.1 g / cm. 3 More specifically, 0.50 grams / cm 3 x 0.42 = 0.21 g / cm 3 The fracture hardness was measured using a Kiya hardness tester and found to be 73 N. The solidified, carbonized material was then immersed in a 1 mol / L aqueous solution of sodium hydroxide at 80°C and stirred for 24 hours. It was then washed until neutral, and the resulting solidified porous carbon material was filtered and dried at 120°C for 24 hours.

[0057] The solidified porous carbon material of Example 1A was then classified using 20-mesh and 200-mesh sieves to obtain the samples shown in Table 1 below. Furthermore, the solidified porous carbon material of Example 1A was subjected to an activation treatment based on a gas activation method, specifically, an activation treatment using steam at 900°C for 2 hours, to obtain Example 1C. The solidified porous carbon material of Example 1B was subjected to an activation treatment based on a gas activation method, specifically, an activation treatment using steam at 900°C for 2 hours and 3 hours, to obtain Examples 1D and 1E. The ignition residue of the solidified porous carbon material (Example 1A) obtained by treatment with an acid or alkali was 0.1 mass% or more and 20 mass% or less, specifically, 9.3 mass%. Furthermore, the fracture hardness of Example 1A was 35 N.

[0058] Example 1A: 20 mesh-on product (before steam activation) Example 1B: 20 ​​mesh pass, 200 mesh on product (before steam activation) Example 1C: Steam activated product of Example 1A Example 1D: Steam activated product of Example 1B Example 1E: Steam activated product of Example 1B

[0059] In the production of Examples 1F, 1G, 1H, 1J, 1K, 1L, and 1M, rice husks were used as the plant-derived material. The rice husks, which are plant-derived material, were solidified using a pellet machine, specifically to obtain solidified plant-derived material in the form of approximately cylindrical pellets with an average diameter of 6 mm and an average length of 30 mm. Note that no binder was used during solidification. The bulk density of the solidified plant-derived material was 0.2 g / cm. 3 to 1.4 grams / cm 3 , specifically 0.70 g / cm 3 The solidified material was then carbonized at 400 to 1400°C. However, unlike the above-mentioned sample, the carbonization was carried out using a muffle furnace under a nitrogen gas atmosphere at 800°C for 1 hour. The bulk density of the obtained carbonized material in a solidified state (porous carbon material precursor) was 0.2 g / cm.3 to 0.8 grams / cm 3 , specifically 0.46 g / cm 3 The ignition residue of the carbonized material in the solidified state was 44%, and the ignition residue bulk density was 0.1 g / cm. 3 Specifically, 0.46 grams / cm 3 x 0.44 = 0.20 g / cm 3 The fracture hardness was measured using a Kiya hardness tester and found to be 120 N. The solidified, carbonized material was then immersed in a 1 mol / L aqueous solution of sodium hydroxide at 80°C and stirred for 24 hours. It was then washed until neutral, and the resulting solidified porous carbon material was filtered and dried at 120°C for 24 hours.

[0060] Next, the mixture was classified using a sieve to obtain a 3 mm on-size product, and 1 mm on-size and 3 mm pass-size products (referred to as 1 to 3 mm products). The 3 mm on-size product was subjected to an activation treatment based on a gas activation method, specifically, an activation treatment using steam at 860°C for 2 hours, to obtain the solidified porous carbon material of Example 1F. The solidified porous carbon material of Example 1F was washed with water and dried at 120°C to obtain the solidified porous carbon material of Example 1G. The 3 mm on-size product was subjected to an activation treatment using steam at 860°C for 2.5 hours to obtain the solidified porous carbon material of Example 1H. The solidified porous carbon material of Example 1H was washed with water and dried at 120°C to obtain the solidified porous carbon material of Example 1J. The 3 mm on-size product was subjected to an activation treatment using steam at 850°C for 3 hours, followed by washing with water and drying at 120°C to obtain the solidified porous carbon material of Example 1K. On the other hand, the 1-3 mm pieces were subjected to activation treatment based on a gas activation method, specifically, activation treatment using water vapor at 860°C for 2 hours, to obtain a solidified porous carbon material of Example 1L. The solidified porous carbon material of Example 1L was then washed with water and dried at 120°C to obtain a solidified porous carbon material of Example 1M. The fracture hardness of the obtained Examples 1F, 1G, 1H, 1J, and 1K was measured using a Kiya hardness tester, and the results are shown below.

[0061] Breaking Hardness Example 1F 81N Example 1G 77N Example 1H 66N Example 1J 75N Example 1K 73N

[0062] In the production of Examples 1N, 1P, 1Q, 1R, and 1S, rice husks were used as the plant-derived material. The rice husks, which are plant-derived material, were solidified using a pellet machine, specifically to obtain solidified plant-derived material in the form of approximately cylindrical pellets with an average diameter of 6 mm and an average length of 30 mm. Note that no binder was used during solidification. The bulk density of the solidified plant-derived material was 0.2 g / cm. 3 to 1.4 grams / cm 3 , specifically 0.67 g / cm 3 The solidified material was then carbonized at 400 to 1400°C. Specifically, the material was carbonized in a nitrogen gas atmosphere at 600°C for 0.5 hours using a rotary kiln. The bulk density of the resulting carbonized material in a solidified state (porous carbon material precursor) was 0.2 g / cm. 3 to 0.8 grams / cm 3 , specifically 0.55 g / cm 3 In addition, the ignition residue of the carbonized material in the solidified state was 40%, and the ignition residue bulk density was 0.1 g / cm 3 Specifically, 0.55 grams / cm 3 × 0.40 = 0.22 g / cm 3 It was.

[0063] Next, activation treatment based on a gas activation method, specifically, activation treatment using steam at 850°C for 3.5 hours (Example 1N), 4.0 hours (Example 1P), 4.75 hours (Example 1Q), 5.5 hours (Example 1R), and 5.75 hours (Example 1S), was performed, and then the material was immersed in a 4.0 mol / L potassium hydroxide aqueous solution at 50°C and stirred for 12 hours. Next, the material was washed with hydrochloric acid until it became neutral, and the resulting solidified porous carbon material was filtered and dried at 120°C for 24 hours. The five types of solidified porous carbon materials thus obtained were designated Example 1N, Example 1P, Example 1Q, Example 1R, and Example 1S.

[0064] For comparison, unconsolidated rice husks (i.e., rice husks in their original state) were carbonized using a mantle heater under a nitrogen atmosphere at 500 °C for 3 hours. The bulk density of the resulting unconsolidated material was 0.1 g / cm. 3 The ignition residue was 42%, and the ignition residue bulk density was 0.04 g / cm 3 The carbonized material in an unsolidified state was then immersed in a 1 mol / L aqueous sodium hydroxide solution at 80°C and stirred for 24 hours. Next, it was washed until neutral, and the obtained unsolidified porous carbon material was filtered and dried at 120°C for 24 hours. Then, it was classified using 20-mesh and 200-mesh sieves to obtain a sample of Comparative Example 1B shown in Table 2 below as a 20-mesh pass, 200-mesh on product. Note that almost no 20-mesh on product was obtained. Furthermore, unsolidified rice husks (i.e., rice husks in their original state) were carbonized in a self-combustion carbonization furnace. The bulk density of the obtained unsolidified material was 0.11 g / cm 3 The ignition residue was 36%, and the ignition residue bulk density was 0.04 g / cm 3 The sample was then immersed in a 1 mol / L aqueous sodium hydroxide solution at 80°C and stirred for 24 hours. The solution was then washed until neutral, and the resulting unsolidified porous carbon material was filtered and dried at 120°C for 24 hours. The sample was then classified using 20-mesh and 200-mesh sieves to obtain Comparative Example 1C (20-mesh pass, 200-mesh on) as shown in Table 2 below. The obtained Comparative Example 1C was further subjected to activation treatment using steam at 900°C for 2 hours and 3 hours, respectively, to obtain Comparative Examples 1D and 1E. In Comparative Examples 1F to 1J, commercially available materials were used. Reference Examples 1A to 1D are listed as reference examples because the raw materials used were not plant-derived. When the fracture hardness of Comparative Example 1B was measured, it broke immediately after the start of the test, making it impossible to measure.

[0065] Comparative Example 1B: 20 ​​mesh pass, 200 mesh on Comparative Example 1C: Unsolidified rice husks used as raw material Comparative Example 1D: Steam activated product of Comparative Example 1C Comparative Example 1E: Steam activated product of Comparative Example 1C Comparative Example 1F: Kuraray Coal GW (60 mesh or more, 30 mesh or less) manufactured by Kuraray Chemical Co., Ltd. Comparative Example 1G: Kuraray Coal GG (60 mesh or more, 30 mesh or less) manufactured by Kuraray Chemical Co., Ltd. Comparative Example 1H: Tsurumi Coal 4GS-S (coconut shell charcoal) Comparative Example 1J: SWKW (wood activated carbon) manufactured by Sanwa Co., Ltd. Reference Example 1A: UN 8-32 mesh (coal crusher) manufactured by Union Service Co., Ltd. Reference Example 1B: Union Service Co., Ltd. UP 4-6 mesh (coal pellets) Reference Example 1C: Activated carbon, crushed, 2 mm to 5 mm, manufactured by Wako Pure Chemical Industries, Ltd., vendor code 031-18061 (crushed peat) Reference Example 1D: Activated carbon, powder, neutral, manufactured by Wako Pure Chemical Industries, Ltd., vendor code 035-18101 (peat powder)

[0066] The measured values ​​of various physical properties of Examples 1A to 1E, Comparative Examples 1B to 1J, and Reference Examples 1A to 1D are shown in Table 3 below. In Table 3, "Mercury Porosimetry-A" indicates the cumulative pore volume per gram of solidified porous carbon material in the pore size range of 10 μm or less, as determined by mercury porosimetry, and "Mercury Porosimetry-B" indicates the cumulative pore volume per gram of solidified porous carbon material in the pore size range of 0.05 μm to 5 μm, as determined by mercury porosimetry. Furthermore, "Pore Volume-A" indicates the cumulative pore volume per gram of solidified porous carbon material in the pore size range of 10 μm or less, as determined by mercury porosimetry. 3 The "pore volume-B" indicates the cumulative pore volume per 1 cm of solidified porous carbon material having pore sizes in the range of 0.05 μm to 5 μm as determined by mercury intrusion porosimetry. 3 The cumulative pore volume per unit area is shown.

[0067] [Table 1]

[0068] <Table 3 (continued)> [Table 2]

[0069] <Table 3 (continued)> [Table 3]

[0070] <Table 3 (continued)> [Table 4]

[0071] From Table 3, in Examples 1A to 1E, the bulk density of the solidified porous carbon material was 0.2 g / cm 3 to 0.4 grams / cm 3 , preferably 0.3 g / cm 3 to 0.4 grams / cm 3 The cumulative pore volume value in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry ("Mercury intrusion porosimetry-B" value) is 0.4 cm per gram of solidified porous carbon material. 3 ~1.2cm 3 , preferably 0.5 cm 3 ~1.0cm 3 The cumulative pore volume value for pore sizes of 10 μm or less based on mercury intrusion porosimetry ("Mercury intrusion porosimetry-A" value) was 0.7 cm per gram of solidified porous carbon material. 3 ~2.0cm 3 , preferably 0.7 cm 3 ~1.7cm 3 Furthermore, the pore volume value based on the BJH method was 1 cm of the solidified porous carbon material. 3 0.1cm per 3 The pore volume value based on the MP method is calculated as follows: 30.04cm per 3 ~0.1cm 3 Moreover, the pore volume value based on the BJH method was 0.3 cm per gram of solidified porous carbon material. 3 The pore volume value based on the MP method is 0.1 cm per gram of solidified porous carbon material. 3 The bulk density of the ignition residue of the solidified porous carbon material was 1×10 -4 grams / cm 3 〜1×10 -1 grams / cm 3 , preferably 1 x 10 -2 grams / cm 3 〜1×10 -1 grams / cm 3 It was.

[0072] The results of the measurements by mercury intrusion porosimetry are shown in the graphs of Figures 1A, 1B, 2A, and 2B. The graph of Figure 1B is an enlarged view of the left-hand peak portion of the graph of Figure 1A, and the graph of Figure 2B is an enlarged view of the left-hand peak portion of the graph of Figure 2A. The horizontal axes of Figures 1A, 1B, 2A, and 2B represent pore diameter (unit: angstroms), and the vertical axes represent interval pore volume (unit: cm 3 The peaks on the right in the graphs of FIGS. 1A and 2A are due to gaps present between the solidified porous carbon materials. Graphs showing cumulative pore volume values ​​in the range of 0.05 μm to 5 μm obtained by mercury intrusion porosimetry are shown in FIGS. 3A and 3B. In FIGS. 1A, 1B, and 3A, "A" indicates the value for Example 1A, "B" indicates the value for Example 1B, "C" indicates the value for Example 1C, "D" indicates the value for Example 1D, and "E" indicates the value for Example 1E. In FIGS. 2A, 2B, and 3B, "b" indicates the value for Comparative Example 1B, "c" indicates the value for Comparative Example 1C, "d" indicates the value for Comparative Example 1D, "e" indicates the value for Comparative Example 1E, "f" indicates the value for Comparative Example 1F, and "g" indicates the value for Comparative Example 1G. In FIG. 3B, the value for Comparative Example 1F (f) and the value for Comparative Example 1G (g) overlap.

[0073] The porous carbon materials of Examples 1A to 1E are solidified, which makes it easier to transport and handle them than the unsolidified porous carbon materials (Comparative Examples 1B to 1E) and activated carbon made from coconut shell (Comparative Examples 1F to 1J). Furthermore, in the method for producing the porous carbon material of Example 1, a plant-derived material is solidified, then carbonized in the solidified state at 400°C to 1400°C, and then treated with an acid or alkali. This makes it easier to transport and handle the raw materials and porous carbon material, carbonize them, and treat them with an acid or alkali. Furthermore, because the solidified porous carbon materials of Examples 1A to 1E have the above-mentioned physical properties, they have larger surface areas per unit volume, larger micropores (pore volume values ​​based on the MP method), and larger mesopores (pore volume values ​​based on the BJH method) than the unsolidified porous carbon materials (Comparative Examples 1B to 1E). This increases the reaction surface and adsorption pores per unit volume, providing excellent advantages in terms of allowing more substances to react and adsorb in a limited space, such as in air purifier filters and water purifiers. Furthermore, compared to activated carbon made from coconut shell (Comparative Examples 1F to 1H), the proportions of mesopores and macropores are larger, which makes it easier for water, air, and solvents to diffuse inside the porous carbon material and increases the reaction rate, providing excellent advantages in applications requiring more reactions in a short period of time, such as air purifier filters, water purifier filters, and water purifier cartridges. Furthermore, since wood activated carbon (Comparative Example 1J) is produced from crushed sawdust, the product is in the form of a powder. When used as a filter for a water purifier or air purifier, the pressure loss becomes high, making it an unsuitable material for use as a filter for a water purifier or air purifier. [Example]

[0074] In Example 2, an example will be described in which the solidified porous carbon material described in Examples 1A to 1E is used as a filter medium in a water purifier.

[0075] A cross-sectional view of the water purifier of Example 2 is shown in Figure 4. The water purifier of Example 2 is a continuous water purifier, a faucet-mounted water purifier in which the water purifier main body is directly attached to the tip of a water faucet. The water purifier of Example 2 includes a water purifier main body 10, a first filling section 12 disposed inside the water purifier main body 10 and filled with the solidified porous carbon material 11 of Examples 1A to 1E, and a second filling section 14 filled with cotton 13. Tap water discharged from the water faucet passes through an inlet 15 provided in the water purifier main body 10, the porous carbon material 11, and the cotton 13, and is discharged from an outlet 16 provided in the water purifier main body 10.

[0076] Alternatively, as shown in a schematic partial cross-sectional view in FIG. 5A, a filter medium 40 (hereinafter simply referred to as "filter medium 40") made of the solidified porous carbon material described in Examples 1A to 1E can be incorporated into a bottle (so-called PET bottle) 20 with a cap member 30. Specifically, the filter medium 40 is disposed inside the cap member 30, and filters 31, 32 are disposed on the liquid inlet and liquid outlet sides of the cap member 30 to prevent the filter medium 40 from leaking. By passing liquid or water (drinking water, lotion, etc.) 21 in the bottle 20 through the filter medium 40 disposed inside the cap member 30 and drinking or using it, for example, the mineral content of the liquid (water) can be increased. The cap member 30 is usually closed with a lid (not shown).

[0077] Alternatively, as shown in the schematic cross-sectional view of FIG. 5B, a filter material 40 can be stored in a water-permeable bag 50, and the bag 50 can be placed in the liquid or water (drinking water, lotion, etc.) 21 in the bottle 20. Reference numeral 22 denotes a cap for closing the mouth of the bottle 20. Alternatively, as shown in the schematic cross-sectional view of FIG. 6A, the filter material 40 can be placed inside a straw member 60, and filters (not shown) can be placed on the liquid inlet and liquid outlet sides of the straw member to prevent the filter material 40 from leaking. Drinking the liquid or water (drinking water) 21 in the bottle 20 through the filter material 40 placed inside the straw member 60 increases the mineral content of the liquid (water). Alternatively, as shown in the schematic cut-away view of FIG. 6B, the filter material 40 can be placed inside a spray member 70, and filters (not shown) can be placed on the liquid inlet and liquid outlet sides of the spray member 70 to prevent the filter material 40 from leaking. 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 passes through the filter material 40 arranged inside the spray member 70 and is sprayed from the spray hole 72, thereby increasing the mineral components in the liquid (water).

[0078] Although the present disclosure has been described above based on preferred embodiments, the present disclosure is not limited to these embodiments and various modifications are possible. The solidified porous carbon material, raw materials (plant-derived materials), manufacturing methods, manufacturing conditions, etc. described in the embodiments are examples and can be modified as appropriate. The filter material described in Example 2 can also be a water purifier that combines a filter material made of the solidified porous carbon material described in Example 1 with a ceramic filter material (a ceramic filter material with fine holes), or a water purifier that combines a filter material with an ion exchange resin.

[0079] The present disclosure can also be configured as follows. [A01] Solidified porous carbon material A solidified porous carbon material made from a plant-derived material, The bulk density of the solidified porous carbon material is 0.2 g / cm 3 to 0.4 grams / cm 3 and The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. 3 ~1.2cm 3 A solidified porous carbon material. [A02] The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry is 0.5 cm per gram of solidified porous carbon material. 3 ~1.0cm 3 The solidified porous carbon material according to [A01], [A03] The cumulative pore volume in the pore size range of 10 μm or less based on mercury intrusion porosimetry is 0.7 cm per gram of solidified porous carbon material. 3 ~2.0cm 3 The solidified porous carbon material according to [A01] or [A02], [A04] The pore volume value based on the BJH method is calculated using the volume of 1 cm of solidified porous carbon material. 3 0.1cm per 3 The solidified porous carbon material according to any one of [A01] to [A03] above. [A05] The pore volume value based on the MP method is calculated using 1 cm of solidified porous carbon material. 3 0.04cm per 3 ~0.1cm 3 The solidified porous carbon material according to any one of [A01] to [A04], wherein [A06] The pore volume value based on the BJH method is 0.3 cm per gram of solidified porous carbon material. 3 The pore volume value based on the MP method is 0.1 cm per gram of solidified porous carbon material. 3 The solidified porous carbon material according to any one of [A01] to [A05] above. [A07] A solidified porous carbon material according to any one of [A01] to [A06], wherein the value of the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less. [A08] The bulk density of the ignition residue of the solidified porous carbon material is 1×10 -4 grams / cm 3 〜1×10 -1 grams / cm 3 The solidified porous carbon material according to any one of [A01] to [A07], wherein [A09] The solidified porous carbon material according to any one of [A01] to [A08], which has a breaking hardness of 20 N or more. [B01] Method for producing porous carbon material A method for producing a solidified porous carbon material, comprising solidifying a plant-derived material, carbonizing the solidified material at 400°C to 1400°C, and then treating the solidified material with an acid or alkali. [B02] The bulk density of the solidified porous carbon material is 0.2 g / cm 3 to 0.4 grams / cm 3 and The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. 3 ~1.2cm 3 The method for producing a solidified porous carbon material according to [B01], [B03] The bulk density of the solidified plant-derived material is 0.2 grams / cm 3 to 1.4 grams / cm 3 The method for producing a solidified porous carbon material according to [B01] or [B02], [B04] The bulk density of the carbonized material in the solidified state is 0.2 g / cm 3 to 0.8 grams / cm 3 The method for producing a solidified porous carbon material according to any one of [B01] to [B03], wherein [B05] A method for producing a solidified porous carbon material according to any one of [B01] to [B04], wherein starch or potato starch is used as a binder when solidifying the plant-derived material. [B06] A method for producing a solidified porous carbon material according to any one of [B01] to [B05], wherein the ignition residue of the solidified porous carbon material is set to 0.1 mass % or more and 20 mass % or less by treating with an acid or alkali. [B07] The bulk density of the ignition residue of the carbonized material in the solid state is 0.1 g / cm 3 That's all, The bulk density of the ignition residue of the solidified porous carbon material is 1×10 -4 grams / cm 3 〜1×10 -1 grams / cm 3 The method for producing a solidified porous carbon material according to any one of [B01] to [B06], wherein [B08] The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry is 0.5 cm per gram of solidified porous carbon material. 3 ~1.0cm 3 The method for producing a solidified porous carbon material according to any one of [B01] to [B07], wherein [B09] The cumulative pore volume in the pore size range of 10 μm or less based on mercury intrusion porosimetry is 0.7 cm per gram of solidified porous carbon material. 3 ~2.0cm 3 The method for producing a solidified porous carbon material according to any one of [B01] to [B08], wherein [B10] The pore volume value based on the BJH method is calculated using 1 cm of solidified porous carbon material. 3 0.1cm per 3 The method for producing a solidified porous carbon material according to any one of [B01] to [B09] above. [B11] The pore volume value based on the MP method is calculated as follows: 3 0.04cm per 3 ~0.1cm 3The method for producing a solidified porous carbon material according to any one of [B01] to [B10], wherein [B12] The pore volume value based on the BJH method is 0.3 cm per gram of solidified porous carbon material. 3 The pore volume value based on the MP method is 0.1 cm per gram of solidified porous carbon material. 3 The method for producing a solidified porous carbon material according to any one of [B01] to [B11] above. [B13] The method for producing a solidified porous carbon material according to any one of [B01] to [B12], wherein the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less. [B14] The bulk density of the ignition residue of the solidified porous carbon material is 1×10 -4 grams / cm 3 〜1×10 -1 grams / cm 3 The method for producing a solidified porous carbon material according to any one of [B01] to [B13], wherein [B15] The method for producing a solidified porous carbon material according to any one of [B01] to [B14], wherein the solidified porous carbon material has a breaking hardness of 20 N or more. [C01]《Water Purifier》 A water purifier comprising: a water purifier body; and a filling part disposed inside the water purifier body and filled with the porous carbon material 11 according to any one of [A01] to [A09]. [Explanation of symbols]

[0080] 10 Water purifier body, 11 Porous carbon material, 12 First filling part, 13 Cotton, 14 Second filling part, 15 Inlet, 16 Outlet, 20 Bottle, 21 Liquid or water, 22 Cap, 30 Cap member, 31, 32 Filter, 40 Filtering material, 50 Bag, 60 Straw member, 70 Spray member, 71 Push button, 72 Spray hole

Claims

1. A solidified porous carbon material, Porous carbon materials are made from plant-derived materials. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ That is, the material.

2. The pore volume value based on the BJH method is calculated for 1 cm of solidified porous carbon material. ３ 0.1cm per ３ The material according to claim 1 .

3. The ignition residue bulk density of the solidified porous carbon material is 1×10 －４ grams / cm ３ ~1×10 －１ grams / cm ３ 3. The material according to claim 1 or 2, wherein

4. A support member comprising a solidified porous carbon material, Porous carbon materials are made from plant-derived materials. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ A support member.

5. The support member according to claim 4 , wherein the support member sandwiches a porous carbon material.

6. 5. The support member according to claim 4, wherein the support member has a porous carbon material kneaded therein.

7. 7. A support member according to any one of claims 4 to 6, wherein the support member is made of a woven or nonwoven fabric.

8. 8. The support member according to claim 4, wherein the material constituting the support member is cellulose, polypropylene or polyester.

9. The pore volume value based on the BJH method is calculated for 1 cm of solidified porous carbon material. ３ 0.1cm per ３ The support member according to any one of claims 4 to 8, wherein:

10. The ignition residue bulk density of the solidified porous carbon material is 1×10 －４ grams / cm ３ ~1×10 －１ grams / cm ３ 10. The support member according to claim 4, wherein:

11. A material comprising a solidified porous carbon material and a binder, Porous carbon materials are made from plant-derived materials. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ A material comprising a porous carbon material and a binder.

12. The pore volume value based on the BJH method is calculated for 1 cm of solidified porous carbon material. ３ 0.1cm per ３ The material according to claim 11 .

13. The ignition residue bulk density of the solidified porous carbon material is 1×10 －４ grams / cm ３ ~1×10 －１ grams / cm ３ 13. The material according to claim 11 or 12, wherein

14. A water purifier comprising a solidified porous carbon material, Porous carbon materials are made from plant-derived materials. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ That is, a water purifier.

15. A water purifier cartridge comprising a solidified porous carbon material, Porous carbon materials are made from plant-derived materials. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ That is, a water purifier cartridge.

16. An air purifier comprising a solidified porous carbon material, Porous carbon materials are made from plant-derived materials. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ That is, an air purifier.

17. A filter element comprising a solidified porous carbon material, Porous carbon materials are made from plant-derived materials. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ That is, the filter element.

18. A method for producing a solidified porous carbon material, comprising: a solidification step of solidifying the plant-derived raw material; a carbonization step of carbonizing the plant-derived material at 400°C to 1400°C; a treatment step of treating the material carbonized in the carbonization step with an acid or alkali after the carbonization step. The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ A method for manufacturing the material.

19. A method for producing a pulverized product of a solidified porous carbon material, comprising: The solidified porous carbon material has a breaking hardness of 20 N or more when pressed with a pressure surface having a diameter of 5 mm, the ignition residue of the solidified porous carbon material is 0.1 mass % or more and 20 mass % or less; The cumulative pore volume in the pore size range of 0.05 μm to 5 μm based on mercury intrusion porosimetry was 0.4 cm per gram of solidified porous carbon material. ３ ~1.2cm ３ and pulverizing the solidified porous carbon material; A method for producing a pulverized product of a solidified porous carbon material.

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