Technical field
[0001]
　The present disclosure relates to a porous carbon material and a manufacturing method thereof that is solidified.
BACKGROUND
[0002]
　Porous carbon material and a manufacturing method thereof in which the plant-derived material as a raw material, for example, is known from Japanese Patent No. 4618308. The method disclosed in this patent publication, the value of specific surface area by the nitrogen BET method is 10 m 2 / g or more, volume of pores by BJH method and MP method 0.1 cm 3 at / g or more porous carbon material a manufacturing method, after carbonization at 800 ° C to 1400 ° C a plant-derived material is treated with acid or alkali, than Te, removes the silicon components in the plant-derived material after the carbonization.
CITATION
Patent Document
[0003]
Patent Document 1: Japanese Patent No. 4618308
Summary of the Invention
Problems that the Invention is to Solve
[0004]
　Although the manufacturing method for porous carbon material disclosed in the patent publication mentioned above is an excellent manufacturing method, as a plant-derived material (raw material), for example, one, it uses the powdered chaff, raw materials and porous it may become complicated transportation and handling of the carbon material, the value of the bulk density of the raw material is low, it may not perform the process of carbonization, the treatment with acid or alkali effectively. Further, the manufacturing apparatus related, there is a case where one of the processing amount at the time of production is limited.
[0005]
　Accordingly, an object of the present disclosure is to provide materials and porous transport and handling of the carbon material, the process of carbonization, the porous carbon material and a manufacturing method thereof easier treatment with acid or alkali.
Means for Solving the Problems
[0006]
　The porous carbon material which is solidified in the present disclosure in order to achieve the above object,
　a plant-derived material as a raw material,
　the bulk density of the solidified porous carbon material, 0.2 g / cm 3 to 0.4 g / cm 3 , preferably 0.3 g / cm 3 to 0.4 g / cm 3 is,
　the cumulative pore volume of pores size 0.05μm to 5μm based on mercury porosimetry value, the porous carbon material per gram 0.4cm which is solidified 3 to 1.2 cm 3 , preferably, 0.5 cm 3 to 1.0 cm 3 is.
[0007]
　Method for producing a solidified porous carbon material of the present disclosure in order to achieve the above object, solidified the plant-derived material, then, while solidified, carbon at 400 ° C to 1400 ° C However, then treated with an acid or alkali.
Effect of the invention
[0008]
　The porous carbon material of the present disclosure because it is solidified, it is possible to perform the transportation and handling of the porous carbon material more easily. Further, the method for producing the solidified porous carbon material of the present disclosure, solidified the plant-derived material, then, while solidified, and carbonized at 400 ° C to 1400 ° C, then since treatment with an acid or alkali can be carried out transport and handling of raw materials and the porous carbon material, the process of carbonization, the treatment with acid or alkali more easily. The effect described herein is not to be limited is merely illustrative, and there may be additional effects.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009]
[1] Figures 1A and 1B are graphs showing the measurement results of mercury porosimetry of porous carbon material which is solidified in Example 1.
[2] FIGS. 2A and 2B are graphs showing the measurement results of mercury porosimetry of various materials of Comparative Example 1.
3] Fig. 3A and 3B, the cumulative pore volume in the range of 0.05μm to 5μm obtained by mercury porosimetry of various materials solidified porous carbon material and Comparative Example 1 Example 1 is a graph showing the value.
[4] FIG. 4 is a schematic sectional view of a water purifier of Example 2.
[5] FIGS. 5A and 5B are schematic partial cross-sectional view and a schematic sectional view of the bottle in the second embodiment.
[6] FIGS. 6A and 6B are schematic plane cut away schematic partial cross-sectional view and a part of a modification of the bottle in the second embodiment.
DESCRIPTION OF THE INVENTION
[0010]
　Hereinafter, with reference to the drawings and describing the present disclosure based on examples, but the present disclosure is not intended to be limited to the embodiments, various numerical values and materials in the embodiments are illustrative. The description will be made in the following order.
1. It solidified porous carbon material and a manufacturing method thereof of the present disclosure, and General Description
2. Example 1 (solidified porous carbon material and the manufacturing method thereof of the present disclosure)
3. Example 2 (water purifier and its modification)
4. Otherwise
[0011]

　In the manufacturing method of the porous carbon material which is solidified in the present disclosure, the bulk density of the solidified porous carbon material, 0.2 g / cm 3 to 0.4 g / cm 3 , preferably 0.3 g / cm 3 to 0.4 g / cm 3 a pore size 0.05μm to 5μm based on mercury porosimetry the value of the cumulative pore volume in the range of, solidified porous carbon material per gram 0.4 cm 3 to 1.2 cm 3 , preferably, 0.5 cm 3 to 1.0 cm 3 to a form that is can.
[0012]
　Furthermore, in the porous carbon material or solidified porous carbon material obtained by the production method thereof are solidified in the present disclosure including the preferred embodiment described above, the following ranges pore size 10μm based on mercury porosimetry the value of the cumulative pore volume in the porous carbon material which is solidified per gram 0.7 cm 3 to 2.0 cm 3 , preferably, 0.7 cm 3 to 1.7 cm 3 can be in the form a .
[0013]
　Furthermore, in the porous carbon material or solidified porous carbon material obtained by the production method thereof are solidified in the present disclosure, including the various preferred forms described above, the pore volume based on the BJH method values solidified porous carbon material 1 cm 3 per 0.1 cm 3 can be not less than the form.
[0014]
　Furthermore, in the porous carbon material or solidified porous carbon material obtained by the production method thereof are solidified in the present disclosure, including the various preferred forms described above, the pore volume based on the MP method values solidified porous carbon material 1 cm 3 per 0.04 cm 3 to 0.1 cm 3 can be in the form a.
[0015]
　Furthermore, in the porous carbon material or solidified porous carbon material obtained by the production method thereof are solidified in the present disclosure, including the various preferred forms described above, the pore volume based on the BJH method values solidified porous carbon material per gram 0.3 cm 3 or more, and the value of pore volume based on the MP method, a porous carbon material which is solidified per gram 0.1 cm 3 or more It may be some form.
[0016]
　Furthermore, in the method for manufacturing the porous carbon material which is solidified in the present disclosure, including the various preferred forms described above, the bulk density of the plant-derived material which is solidified is 0.2 g / cm 3 to 1.4 g / cm 3 can be in the form a.
[0017]
　Furthermore, in the method for manufacturing the porous carbon material which is solidified in the present disclosure, including the various preferred forms described above, carbonized material in a state of being solidified (hereinafter, "porous carbon material precursor" the bulk density of the called if there is) and is 0.2 g / cm 3 to 0.8 g / cm 3 can be in the form a.
[0018]
　Furthermore, in the method for manufacturing the porous carbon material which is solidified in the present disclosure, including the various preferred forms described above, when the solidifying material of plant origin, be in a form using a starch or starch as a binder can. Alternatively, as a binder, without decomposition even subjected to any temperature from room temperature to 180 ° C when solidified the plant-derived material, when carbonizing the plant-derived material at 400 ° C to 1400 ° C from thus calcined material may be appropriately selected. The material and the binder of vegetable origin, it may be mixed using a suitable mixer.
[0019]
　Furthermore, in the porous carbon material which is solidified in the present disclosure including the preferred forms of the various described above, ignition value of remainder of solidified porous carbon material, 0.1 wt% or more, it can be in the form of 20 wt% or less, in the manufacturing method of the porous carbon material which is solidified in the present disclosure, including the various preferred forms described above, by treatment with acid or alkali, solid the reduction values ​​of the ignition residue of the porous carbon material, 0.1 wt% or more, 20 wt% or less, preferably, 0.1 mass% or more, 15 wt% or less, more preferably, 0.1 mass% or more, can be in the form of a 2 mass% or less. Ignition residues, JIS K1474: may be measured based on the 2014 "activated carbon test method".
[0020]
　Furthermore, in the porous carbon material which is solidified in the present disclosure, including the various preferred forms described above, residue on ignition bulk density of solidified porous carbon material, 1 × 10 -4 g / cm 3 to × 10 1 -1 g / cm 3 , preferably, 1 × 10 -2 g / cm 3 to × 10 1 -1 g / cm 3 can be in a form. In the method for producing a porous carbon material which is solidified in the present disclosure, including the various preferred forms described above, residue on ignition of carbonized material in a state of being solidified (porous carbon material precursor) min bulk density of 0.1 g / cm 3 or more, the residue on ignition bulk density of solidified porous carbon material, 1 × 10 -4 g / cm 3 to × 10 1 -1 g / cm 3 , preferably, 1 × 10 -2 g / cm 3 to × 10 1 -1 g / cm 3 can be in a form.
[0021]
　Furthermore, breaking hardness of the porous carbon material which is solidified in the present disclosure, including the various preferred forms described above is preferably 20N or more. Breaking hardness of solidified porous carbon material, Kiya type hardness meter can be obtained by (Corporation Fujiwara Seisakusho:: Item #. 043 019-C also applies to the following). Specifically, the disruption hardness of 10 samples were measured, except the top three samples, the lower three samples, may be derived destruction hardness than the mean value of the intermediate of 4 samples (rounded to the nearest).
[0022]
　Above the solidification of the present disclosure including the various preferred forms described porous carbon material or the manufacturing method thereof (hereinafter, these are generically, simply referred to as "the present disclosure"), the porous carbon material is a plant-derived material as a raw material. Here, as the plant-derived material, rice (rice), barley, wheat, rye, millet (millet), rice husks and straw, such as millet (millet), coffee beans, tea leaves (for example, leaves such as green tea and black tea), citrus (more specifically, squeezing sugar cane such debris) sugarcane acids, corn compound (more specifically, core corn acids), fruit peel (e.g., orange peel, grapefruit peel, such as mandarin orange peel skin and banana peel, etc.), or alternatively, reed, can be exemplified seaweed stem is not limited to, other, for example, vascular plants vegetation on land, ferns, bryophytes, algae , mention may be made of seaweed. Incidentally, these materials, as a raw material, may be used alone or may be used in admixture of plural kinds thereof. Furthermore, plant-derived materials (for convenience, referred to as "material -A") and, for example, coconut shell, husk seeds such as walnut shells; cedar and pine, sawdust such material wood of bamboo (for convenience, "Materials referred to as -B ") were mixed to be solidified. In this case, the mixing ratio of the material -A and material -B, on a mass basis, for
example, 0.1 ≦ (material -B) / (material -A) ≦ 10
is preferably set to such proportions by weight the present invention is not limited to. The shape and form of the plant-derived material is not particularly limited, for example, may be a chaff and straw itself, or may be dried products. Furthermore, it in food or drink processing, such as beer or liquor, fermentation, roasting process, also possible to use those which have been subjected to various processes of extraction treatment. In particular, from the viewpoint of achieving recycling of industrial waste, it is preferred to use straw or chaff after processing of threshing like. Straw and chaff of these post-processing, for example, agricultural cooperatives and producing an alcoholic beverage companies, food companies, from food processing company, a large amount, and can be easily obtained.
[0023]
　Also, before solidifying, the plant-derived material, it may be desired particle size by grinding if desired, may be classified. Plant-derived material may be washed beforehand. The porous carbon material precursor was coarsely pulverized may be a desired particle size, it may be classified. It solidification porous carbon material of the present disclosure may be desired particle size by grinding, may be classified, it is also possible to apply such a pulverized product or classified product in various products.
[0024]
　The method of manufacturing a solidified porous carbon material of the present disclosure (hereinafter, simply referred to as "method for producing the porous carbon material of the present disclosure"), as a method of solidifying a plant-derived material, the ring die method, and a method of molding into pellets in a flat die method, the molding machine of the screw type. There is also a method of solidifying a firewood shape and roll shape. After once solidified in these methods, it may be ground to an appropriate size. Further, in the present disclosure, the shape of the solidified porous carbon material (more specifically, the diameter 2mm to 15 mm, a length of 10mm to 60mm approximately cylindrical) pellets, firewood shape (more specifically the trade names Momigaraito shape represented by (R), 50mm diameter about the center hole 15mm approximately, the shape such as the length for example about 30cm), coiled (50mm diameter about the center hole 25mm about, width 20mm extent, can be exemplified ones) having a length of about 30 cm, it was ground particulate (diameter: may be a 0.5mm to 50 mm).
[0025]
　The method of manufacturing a porous carbon material of the present disclosure, after the acid treatment or alkali treatment, to be included the step of subjecting the activation treatment, was subjected to activation treatment, it may be subjected to acid treatment or alkali treatment. Further, in the method of manufacturing the porous carbon material of the present disclosure including such a preferred form, depending on the plant-derived material used, prior to carbonization plant-derived material which is solidified, low temperature (e.g., 400 ° C ~ 700 ° C) than the temperature for carbonization at a heating treatment to the plant-derived material in a state of blocking oxygen (pre-carbonizing treatment) may be performed. Thus, the results can be extracted tar components which would be generated in the course of carbonization can be reduced or eliminate tar components which would be generated in the course of carbonization. Incidentally, while blocking oxygen, for example, by an inert gas atmosphere such as nitrogen gas or argon gas, or alternatively, by a vacuum atmosphere, or alternatively, the plant-derived material as a kind of steamed state it can be achieved by. Further, in the method of manufacturing the porous carbon material of the present disclosure, in order depending on the plant-derived material to be used, in some cases, reducing the mineral components and water contained in the material of the plant-derived, Further, in order to prevent the generation of an odor in the course of carbonization, to the plant-derived material which is solidified it may be dipped in an acid or alkali, alcohol (e.g., methyl alcohol, ethyl alcohol, isopropyl alcohol) it may be immersed in. Also, when processing with an acid, such as hydrochloric acid, nitric acid, by treatment with an inorganic acid such as sulfuric acid, it is possible to remove the mineral components contained in the porous carbon material precursor. Incidentally, the method of manufacturing the porous carbon material of the present disclosure may then perform a pre-carbonization treatment. As is preferred the material is subjected to heat treatment in an inert gas, for example, a plant that generates a lot of wood vinegar (tar or light oil). Further, as is the preferred material is subjected to pretreatment with alcohol, for example, a seaweed rich in iodine and various minerals.
[0026]
　In the method for producing the porous carbon material of the present disclosure, will be carbonized plant-derived material at 400 ° C to 1400 ° C, wherein the carbonization generally organic substances (of the present disclosure in the solidified porous carbon material, which means that by heat-treating the material) of plant origin that are solidified into a carbonaceous material (see, for example, JIS M0104-1984). As an atmosphere for carbonization, can be cited atmosphere with block oxygen, specifically, a steamed state kind vacuum, such as nitrogen gas or argon gas an inert gas atmosphere, the plant-derived material mention may be made of the atmosphere. As heating rate up to the carbonization temperature, but are not limited to, an atmosphere of, 1 ° C / min or more, preferably 3 ° C / min or more, more preferably exemplified 5 ° C / min or more be able to. Further, the upper limit of the carbonization time, 10 hours, preferably 7 hours, more preferably be mentioned 5 hours, but the embodiment is not limited thereto. The lower limit of the carbonization time may be a time when the plant-derived material can be surely carbonized. It may be subjected to sterilization treatment in the finally obtained porous carbon material. Form of the furnace used for carbonization, configuration is not limited to the structure, can either be a continuous furnace, it is also possible to batch furnace and (batch furnace).
[0027]
　The method of manufacturing a porous carbon material of the present disclosure, as described above, if Hodokose activation treatment, pore size can be increased a small micropore than 2 nm. As a method for the activation treatment, it may be mentioned the gas activation method, a chemical activation method. Here, the gas activation method, oxygen and water vapor as an activator, carbon dioxide gas, using air or the like, under a gas atmosphere of, at 700 ° C to 1400 ° C, preferably at 700 ° C to 1000 ° C , more preferably at 800 ° C to 1000 ° C, several tens of minutes to several hours, by heating the porous carbon material, the volatile components and carbon molecules in the porous carbon material in a manner to develop the microstructure is there. Incidentally, more specifically, the heating temperature is based on a plant type from materials, gas type and concentration, etc., as appropriate, may be selected, is 950 ° C or less and more preferably 800 ° C or higher. The chemical activation method, instead of oxygen or water vapor used in the gas activation method, sodium hydroxide, potassium hydroxide, zinc chloride, iron chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, with sulfuric acid or the like it is activated, washed with hydrochloric acid, adjusting the pH with an aqueous alkaline solution, a method of drying.
[0028]
　Solidified porous carbon material of the present disclosure (hereinafter, simply if there is referred to as "porous carbon material of the present disclosure") to the surface of the may be performed chemical treatment or molecular modification. As chemical treatment, for example, a process of generating a carboxyl group on the surface by nitric acid treatment. Further, water vapor, oxygen, by performing the same processing as the activation treatment with an alkali or the like, on the surface of the porous carbon material of the present disclosure a hydroxyl group, a carboxyl group, a ketone group, an ester group, thereby generating a variety of functional groups It can also be. Furthermore, reactive hydroxyl groups and a porous carbon material of the present disclosure, a carboxy group, also be chemically reacting chemical species or protein having an amino group or the like, it is possible molecular modification.
[0029]
　In the method for producing the porous carbon material of the present disclosure, by acid treatment or alkali treatment, to remove the silicon component in the plant-derived material after the carbonization. Here, as the silicon components include silicon oxide or silicon dioxide, silicon oxide such as silicon oxide salts. Thus, by removing the silicon components in the plant-derived material after carbonization, it is possible to obtain a porous carbon material of the present disclosure having a high specific surface area. Sometimes, based on the dry etching method, it may be removed silicon component in the plant-derived material after the carbonization. By removing the silicon components, it is possible to reduce the ignition residue values. Solidified value of ignition residue of the porous carbon material of the present disclosure is as described above.
[0030]
　The porous carbon material of the present disclosure have many pores (pores). As pores, pore diameter "mesopores" of 2nm to 50nm is, pore size is more than 50nm "macropores" and the pore size are included is less than 2nm, "micropores". Specifically, it as mesopores, for example, contains a lot of pore diameters less than or equal to 20 nm, in particular, it contains many pore diameters less than or equal to 10 nm. Also, as a micro-pore, for example, a pore diameter of about 1.9nm pores, and pores of about 1.5 nm, contains many and pores of about 0.8 nm ~ 1 nm. In the porous carbon material of the present disclosure, the pore volume by the BJH method, per the porous carbon material 1 gram present disclosure, 0.3 cm 3 or more, preferably 0.5 cm 3 desirably not less than . Pore volume by MP method, per the porous carbon material 1 gram present disclosure, 0.1 cm 3 or more, preferably 0.2 cm 3 or more, more preferably 0.3 cm 3 is desirably higher.
[0031]
　In the porous carbon material of the present disclosure, the value of specific surface area by the nitrogen BET method (hereinafter, sometimes simply referred to as "value of specific surface area"), in order to obtain a more excellent functionality, the present disclosure porous carbon material per gram, 10 m 2 or more, preferably 50 m 2 or more, more preferably 100 m 2 or more, even more preferably 500 meters 2 is desirably higher. Alternatively, the porous carbon material 1cm of the present disclosure 3 per, 2 × 10 2 m 2 to 3 × 10 2 m 2 It is desirable that.
[0032]
　The nitrogen BET method, the adsorbent (here, the porous carbon material) the adsorption isotherm was measured by nitrogen adsorption and desorption as adsorbed molecules, the measured data on the BET formula represented by the formula (1) a method for on the basis of the analysis, it is possible to calculate the basis specific surface area and pore volume, etc. in this way. Specifically, when calculating the value of specific surface area by the nitrogen BET method, firstly, by nitrogen adsorption and desorption as adsorbed molecules on the porous carbon material, obtaining the adsorption isotherm. Then, from the adsorption isotherm obtained, based on the equation (1 ') obtained by modifying the formula (1) or the formula (1) [p / {V a (p 0 calculates -p)}], the equilibrium relative pressure (the p-/ the p- 0 to plot against). 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 )]) It is calculated. The expression from the slope s and intercept i thus obtained (2-1), based on the equation (2-2), V m is calculated, and C. Furthermore, V m from based specific surface area a in Equation (3) Sbet is calculated (Nippon Bel Co. Ltd. BELSORP-mini and BELSORP analysis software documentation, see Chapter 62, pages - 66 pages). Incidentally, the nitrogen BET method is a measurement method in accordance with JIS R 1626-1996 "Measurement method of the specific surface area by gas adsorption BET method for fine ceramics powder."
[0033]
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）
[0034]
　However,
V a : adsorption amount
V m : adsorption amount of monomolecular layer
p: pressure upon nitrogen equilibrium
p 0 : saturated vapor pressure of nitrogen
L: Avogadro's number
sigma: adsorption cross section of nitrogen
is.
[0035]
　Pore volume V by the nitrogen BET method p when calculating, for example, the adsorption data of the adsorption isotherm obtained by linear interpolation, obtaining the adsorption amount V at a relative pressure set by a pore volume calculation relative pressure. This adsorption amount V pore volume V based on the equation (4) p can be calculated (Nippon Bel Co. Ltd. BELSORP-mini and BELSORP analysis software documentation, see Chapter 62, pages - 65 pages). In addition, the pore volume based on the nitrogen BET method, hereinafter sometimes 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
[rho g : density of nitrogen
is.
[0038]
　The pore size of mesopores can, for example, based on the BJH method, can be calculated from the pore volume variation rate relative to the pore size as a distribution of pores. The BJH method is a method which is widely used as a pore distribution analysis method. If the pore distribution analysis on the basis of the BJH method, first, by nitrogen adsorption and desorption as adsorbed molecules on the porous carbon material, obtaining the desorption isotherm. Then, based on the desorption isotherm thus obtained, the pores are adsorbed molecules (e.g. nitrogen) thick adsorption layer when adsorbed molecules from the state filled is detachably stepwise by Is, and resulted in the hole It obtains an inner diameter (twice the core radius) of the pore radius r based on the equation (5) p , and calculates the pore volume based on the equation (6). The pore radius and pore diameter (2r from pore volume p pore volume variation rate relative) (dV p / dr p ) pore distribution curve is obtained by plotting the (Nippon Bel Co. Ltd. BELSORP-mini and BELSORP analysis software manual, see Section 85 pages - 88 pages).
[0039]
ｒ p＝ｔ＋ｒ k　　　　　　　　　　　　　　　　（５）
Ｖ pn＝Ｒ n・ｄＶ n－Ｒ n・ｄｔ n・ｃ・ΣＡ pj　　（６）
但し、
Ｒ n＝ｒ pn 2／（ｒ kn－１＋ｄｔ n） 2　　　　　　（７）
[0040]
　Here,
r p : pore radius
r k : pore radius r p of the pore inner wall to the core radius in the case where the adsorption layer is adsorbed thickness t at the pressure of the (inner diameter / 2)
V pn : nitrogen No. n-th pore volume when the detachable occurs in
dV n : amount of change in time
dt n : the thickness t of the adsorption layer when the n-th removable nitrogen occurs n the amount of change
r kn : at that time core radius
c: fixed value
r pn : pore radius when the n-th removable nitrogen has occurred
is. Further, .SIGMA.A pj represents an integrated value of the area of the wall surface of the pores from j = 1 to j = n-1.
[0041]
　The pore size of the micro pores, for example, based on the MP method, can be calculated from the pore volume variation rate relative to the pore size as a distribution of pores. When performing the pore distribution analysis by the MP method, firstly, by adsorbing nitrogen to the porous carbon material, obtaining the adsorption isotherm. Then, the adsorption isotherm (which t plotted) into the pore volume with respect to the thickness t of the adsorption layer. The curvature can be obtained pore distribution curve based on the (variation of pore volume with respect to the amount of change in the thickness t of the adsorption layer) (Nippon Bel Co. Ltd. BELSORP-mini and BELSORP analysis software documentation for this plot , 72nd page, second page 73, Section 82 pages).
[0042]
　Measurement of the pore by mercury porosimetry, JIS R1655: conforms to 2003 "moldings pore size distribution test method by mercury porosimetry of fine ceramics". Specifically, using POREMASTER 60GT (Quantachrome Corp.) was subjected to mercury porosimetry measurement. The pore measurement area was 3nm ~ 200μm. The measured interval pore volume by accumulating in the desired range, it is possible to calculate the cumulative pore volume. The bulk density, JIS K1474: can be determined based on the method of measuring the filling density is described in 2014 "activated carbon test method". Ignition residue bulk density can be determined by the product of the values ​​and ignition residue values ​​of bulk density. Ignition residue (residual ash) is, JIS K1474: 2014 can be measured based on the measurement method of the residue on ignition in the "activated carbon test method". The value of the ignition residue in solidified porous carbon material of the present disclosure (residual ash) is 20 mass% or less, preferably, it is desirable that 15 wt% or less. The value of the porous ignition residue in the carbon material precursor (residual ash) is 20 mass% or more, more preferably not more than 25 mass%.
[0043]
　Porous acid treatment or alkali treatment of a carbon material precursor, but as a specific treatment method, for example, a method of immersing the porous carbon material precursor in an aqueous solution of acid or alkali, a porous carbon material precursor with an acid or method may be mentioned are reacted in the gas phase and alkali. More specifically, in the case of acid treatment, the acid, e.g., hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, it may be mentioned a fluorine compound that shows acidity, such as sodium fluoride. When using a fluorine compound, enough. Elemental fluorine 4 times the amount of silicon element in the silicon components contained in the porous carbon material precursor, it is preferable that the concentration of the fluorine compound aqueous solution is at least 10 mass%. By hydrofluoric acid, the silicon component contained in the porous carbon material precursor (eg, silicon dioxide) when removing, silicon dioxide, and hydrofluoric acid as shown in chemical formula (A) or Formula (B) the reaction was, hexafluorosilicate (H 2 SiF 6 ) or silicon tetrafluoride (SiF 4 are removed as), it is possible to obtain a porous carbon material. Thereafter, washing may be performed dry.
[0044]
ＳｉＯ 2＋６ＨＦ　→　Ｈ 2ＳｉＦ 6＋２Ｈ 2Ｏ　　（Ａ）
ＳｉＯ 2＋４ＨＦ　→　ＳｉＦ 4＋２Ｈ 2Ｏ 　　　（Ｂ）
[0045]
　Further, when the alkali treatment to be processed by alkali (base), the alkali can be, for example, sodium hydroxide. When using an aqueous solution of alkali, pH of the aqueous solution may be at 11 or more. By aqueous sodium hydroxide, the silicon component contained in the porous carbon material precursor (eg, silicon dioxide) To remove, by heating the aqueous solution of sodium hydroxide, as silicon dioxide, represented by the chemical formula (C) the reaction was, sodium silicate (Na 2 SiO 3 are removed as), it is possible to obtain a porous carbon material. Also, when processing by reacting sodium hydroxide in a gas phase, by heating the solid sodium hydroxide, and reacted as shown in the chemical formula (C), sodium silicate (Na 2 SiO 3 are removed as) , it is possible to obtain a porous carbon material. Thereafter, washing may be performed dry.
[0046]
Sio 2 + 2NaOH → Na 2 see 3 + H 2 O (C)
[0047]
　The functional material may be attached to the porous carbon material of the present disclosure. Specifically, after the acid treatment or alkali treatment (Thereafter, when subjected to activation treatment, it was subjected to activation treatment), depositing a functional material solidified porous carbon material of the present disclosure it is sufficient to. As a functional material, for example, (specifically, for example, ethylene urea, phosphoric acid, copper nitrate) agent for adsorbing a substance present in the air more effectively can be exemplified, Alternatively, the functional material may be in the form of an optical catalytic properties. In the latter case, the functional material, for example, titanium oxide (TiO 2 may be composed of) or zinc oxide (ZnO). Incidentally, the use of ethylene urea, formaldehyde, to acetaldehyde can be effectively removed, by using phosphoric acid, it can be effectively remove ammonia, the use of copper nitrate, ammonia , it can be effectively deodorized hydrogen sulfide and the like. And, thereby, the porous carbon material is catalytic properties imparted by the photocatalytic effects, toxic substances decomposing agents permanently available, and can be applied as a hazardous substance removing material. Decomposition of harmful substances, in the removal, energy ray or an electromagnetic wave in the porous carbon material (e.g., ultraviolet light or sunlight, visible light, etc.) may be irradiated to. Can be mentioned harmful substances present in the air as harmful substances, specifically, various viruses, allergies cause material carcinogenic substances contained in tobacco smoke (e.g., benzopyrene) can be exemplified .
[0048]
　The type and structure of the functional material, structure, although also depending on the form, as a porous form of attachment to the carbon material of the functional material, the surface (including the pores) of the porous carbon material, deposited as particulates to have the state, the state adhering to the thin film, (if the surface of the porous carbon material was considered "sea" functional material corresponding to the "islands") Water islands are attached to the state can be mentioned. Incidentally, deposition and refers to the adhesion phenomenon between different materials. As a method for depositing a functional material solidified porous carbon material of the present disclosure, a method of depositing a functional material by immersing the porous carbon material on the surface of the porous carbon material in a solution containing a functional material , electroless plating on the surface of the porous carbon material (chemical plating method) or a method of precipitating the functional material by chemical reduction, by immersing the porous carbon material in a solution containing a precursor of the functional material, the method of precipitating the functional material on the surface of the porous carbon material by performing the heat treatment, by immersing the porous carbon material in a solution containing a precursor of the functional material, the porous carbon material by performing ultrasonic treatment the method of precipitating the functional material on the surface of, by immersing the functional porous carbon material in a solution containing a precursor of the material, precipitating the functional material on the surface of the porous carbon material by performing a sol-gel reaction how to It can be mentioned.
[0049]
　Solidified porous carbon material of the present disclosure is applied, for example, used in water purifier and water purifier cartridges, etc., used in the air purifier, the filter element (filter air cleaner filter and the water purifier) it can be exemplified, applications are not limited thereto. Alternatively, cosmetics, food, cigarette filters, can be applied to drug stain crowded so complex (porous carbon material with a impregnation agent) and the like.
[0050]
　For example, in the use in a water purifier, the solidified porous carbon material of the present disclosure may be used as a filter medium. It may also be used to adjust the pH by washing the solidified porous carbon material with acid or alkali. The solidified porous carbon material of the present disclosure, for example, the molecular weight 1 × 10 2 to 1 × 10 5 water with water containing substance, water containing dodecylbenzene sulfonate, water containing chlorothalonil, dichloroacetic boss , it is possible to perform water containing tetracycline, water containing soluble lead, water containing free chlorine, the removal of these various substances in water containing total organic halogen.
[0051]
　Water purification, air purification, widely when used for the purification of fluids, as used form of solidified porous carbon material of the present disclosure (Alternatively, the ground product in some cases), used in sheet form, foam use of adhered to a polyurethane foam, used in a state filled in the column or cartridge for use in a state of being accommodated in a bag having a water permeability, excipient into a desired shape using a binder (binder) such as use in the form state, it can be exemplified for use in powder. When removing material dispersed in the solution, can be used the surface hydrophilic treatment or hydrophobic treatment to. In the use of the sheet-like, can be mentioned woven or nonwoven fabric as a support member, a material constituting the supporting member, it can be mentioned cellulose, polypropylene, polyester. Then, it is possible to mention the form in which form the porous carbon material is sandwiched between the support member and the support member, the porous carbon material is kneaded to the support member.
[0052]
　In the water purifier, filter membrane (e.g., a hollow fiber membrane or a flat membrane having a hole of 0.4 .mu.m ~ 0.01 [mu] m) further having structure (the disclosure of solidified porous carbon material and the filtration membrane it can be a combination), it can be configured to further include a reverse osmosis membrane (RO) (combination of solidified porous carbon material and reverse osmosis membrane of the present disclosure), ceramic filter media it can be further having structure (the ceramic filter media having fine holes) (combination of solidified porous carbon material and the ceramic of the filter medium of the present disclosure), the configuration further having an ion-exchange resin ( It can also be a combination) of the solidified porous carbon material and the ion exchange resin of the present disclosure. In general, although minerals in the filtered water which has passed through the reverse osmosis membrane (RO) is hardly contained, after passing through a reverse osmosis membrane (RO), the solidified porous carbon material of the present disclosure by passing, it is possible to include minerals in the filtered water.
[0053]
　As the type of water purifier, continuous water purifier, batch water cleaner, it can be exemplified reverse osmosis water purifier, or alternatively, faucet type mounting the purifier body directly to the distal end portion of the faucet, stationary (also called top sink-type or desktop type), water purifier in faucet is integrated faucet integrated type, under sink type to be installed in the kitchen sink (built-in), purified water in a container such as a pot or pitcher vessel incorporating pot (pitcher), Central type directly attached to a water pipe after the water meter, portable, mention may be made of a straw-type. Water purifier, structures the same as the conventional water purifier may be structured. In water purifier, it solidified porous carbon material of the present disclosure, for example, placed in the cartridge can be used, may be provided water inflow and the water discharge portion in the cartridge. "Water" should be purified of interest in water purifier, JIS S3201: 2010 is not limited to specified in "3. Terms and Definitions", "water" in the "home water purifier Test Method".
[0054]
　Alternatively, as a member suitable for incorporating it solidified porous carbon material of the present disclosure, cap or lid, with straw member, spray member with the bottles (so-called PET bottle) and laminates containers, plastic containers, glass containers, may be mentioned cap or cover in glass bottles or the like. Here, arranged solidified porous carbon material of the present disclosure within the cap or lid, bottle or a laminate container, a plastic container, a glass container, a liquid or water of the glass bottle or the like (water or lotion and the like ) and, by drinking passed through a solidified porous carbon material of the present disclosure disposed inside the cap or lid, or the use it can be included minerals in the filtered water. Alternatively, store the filter medium composed of a porous carbon material which is solidified in the present disclosure in the bag having a water permeability, bottles (so-called PET bottle) and laminates containers, plastic containers, glass containers, glass bottles, pots in the liquid or water in various containers such as jugs (drinking water and makeup water, etc.), it is also possible to employ a configuration to inject the bag.
Example 1
[0055]
　Example 1 relates to solidified porous carbon material and its manufacturing method of the present disclosure.
[0056]
　Was solidified in Example 1 In the production method of (specifically, pelletized) porous carbon material, as a plant-derived material, using rice husk. Then, the rice husk is a material of plant origin, it solidified using pellets machine, specifically, the average diameter of 6 mm, average length is solidified substantially cylindrical pellets of 30mm It was to obtain a plant-derived material. At the time of solidification it does not use a binder. The bulk density of the solidified plant-derived materials, 0.2 g / cm 3 to 1.4 g / cm 3 , specifically, 0.70 g / cm 3 was. Then, in a state of being solidified and carbonized at 400 ° C to 1400 ° C. Specifically, by using a mantle heater under a nitrogen atmosphere and carbonized at 500 ° C, 3 hours. The resulting bulk density of the carbonized material in a state of being solidified (porous carbon material precursor) is 0.2 g / cm 3 to 0.8 g / cm 3 , in particular, 0. 50 g / Cm 3 was. Also, ignition residue of carbonized material in a state of being solidified is 42%, residue on ignition bulk density of 0.1 g / cm 3 or more, specifically 0.50 g / Cm 3 × 0.42 = 0.21 Guramu / Cm 3 was. In addition, measurement of the destruction hardness at Kiya hardness meter, was 73N. Thereafter, the carbonized material in a state of being solidified, 1 mol / liter, and immersed in an aqueous solution of sodium hydroxide at 80 ° C, 24 hours, followed by stirring. Then, washed until neutral, resulting solidified porous carbon material was filtered and dried 120 ° C, 24 hours.
[0057]
　Then, classified with a 20 mesh and 200 mesh sieve to obtain a sample shown in Table 1 below. Furthermore, with respect to solidified porous carbon material of Example 1A, activation treatment based on a gas activation method, specifically, Example 1C performs activation treatment with steam at 900 ° C, 2 hours It was obtained. Further, with respect to solidified porous carbon material of Example 1B, activation treatment based on a gas activation method, specifically, it performs activation processing using steam of 900 ° C, 2 hours and 3 hours, to give example 1D and example 1E. Obtained by treatment with acid or alkali, ignition value of remainder of solidified porous carbon material (Example 1A) is 0.1 mass% or more, 20 wt% or less, specifically, , was 9.3 mass%. Further, breaking hardness of Example 1A was 35N.
[0058]

Example 1A: 20 mesh on products (before steam-activated)
Example 1B: 20 mesh pass, 200 mesh on products (before steam-activated)
Example 1C: Example 1A steam-activated product
Example 1D: implementation example 1B of steam-activated product
example 1E: steam activation products of example 1B
[0059]
　Example 1F, Example 1G, Example 1H, Example 1 J, Example 1K, Example 1L, even in the preparation of Example 1M, as plant-derived material, using rice husk. Then, the rice husk is a material of plant origin, it solidified using pellets machine, specifically, the average diameter of 6 mm, average length is solidified substantially cylindrical pellets of 30mm It was to obtain a plant-derived material. At the time of solidification it does not use a binder. The bulk density of the solidified plant-derived materials, 0.2 g / cm 3 to 1.4 g / cm 3 , specifically, 0.70 g / cm 3 was. Then, in a state of being solidified and carbonized at 400 ° C to 1400 ° C. However, unlike the samples described above, specifically, by using a muffle furnace under a nitrogen gas atmosphere, and carbonization under the conditions of 800 ° C, 1 hour. The resulting bulk density of the carbonized material in a state of being solidified (porous carbon material precursor) is 0.2 g / cm 3 to 0.8 g / cm 3 , in particular, 0. 46 g / Cm 3 was. Also, ignition residue of carbonized material in a state of being solidified is 44%, residue on ignition bulk density of 0.1 g / cm 3 or more, specifically 0.46 g / Cm 3 × 0.44 = 0.20 Guramu / Cm 3 was. In addition, measurement of the destruction hardness at Kiya hardness meter, was 120N. Thereafter, the carbonized material in a state of being solidified, 1 mol / liter, and immersed in an aqueous solution of sodium hydroxide at 80 ° C, 24 hours, followed by stirring. Then, washed until neutral, resulting solidified porous carbon material was filtered and dried 120 ° C, 24 hours.
[0060]
　Then classified with a sieve, 3 mm on products, and to give 1mm on, 3 mm path articles (referred to as 1 ~ 3 mm product). Then, with respect to 3mm on products, activation treatment based on a gas activation method, specifically, 860 ° C, 2 hours of steam by performing the activation process using the porous which is solidified in Example 1F to obtain a carbon material. Furthermore, the solidified porous carbon material of Example 1F was washed with water, and dried at 120 ° C, to obtain a porous carbon material which is solidified in Example 1G. Further, with respect to 3mm on products, 860 ° C, by performing the activation treatment with steam for 2.5 hours, to obtain a porous carbon material which is solidified in Example 1H. Furthermore, the solidified porous carbon material of Example 1H washed with water, and dried at 120 ° C, to obtain a porous carbon material which is solidified in Example 1 J. Furthermore, with respect to 3mm on products, after the activation treatment with steam at 850 ° C, 3 hours, washed with water, and dried at 120 ° C, was solidified in Example 1K to obtain a porous carbon material. On the other hand, for 1 ~ 3 mm products, activation treatment based on a gas activation method, specifically, by performing the activation treatment with steam 860 ° C, 2 hours, was solidified in Example 1L porous to obtain a quality carbon material. Then, the solidified porous carbon material of Example 1L washed with water, and dried at 120 ° C, to obtain a porous carbon material which is solidified in Example 1M. Obtained in Example 1F, Example 1G, Example 1H, Example 1 J, the results of measuring the fracture hardness at Kiya hardness tester of Example 1K, below.

The scope of the claims
[Requested item 1]
　The plant-derived material as a raw material, a porous carbon material which is solidified,
　the bulk density of the solidified porous carbon material, 0.2 g / cm 3 to 0.4 g / cm 3 be ,
　the value of the cumulative pore volume of pores size 0.05μm to 5μm based on mercury porosimetry, a porous carbon material which is solidified per gram 0.4 cm 3 to 1.2 cm 3 is solidified is the porous carbon material.
[Requested item 2]
　The value of the cumulative pore volume of pores size 0.05μm to 5μm based on mercury porosimetry, a porous carbon material which is solidified per gram 0.5 cm 3 to 1.0 cm 3 to claim 1 which is It solidified porous carbon material according.
[Requested item 3]
　The value of the cumulative pore volume in the range of pore sizes 10μm based on mercury porosimetry, the porous carbon material per gram 0.7cm which is solidified 3 to 2.0 cm 3 solid according to claim 1 which is of porous carbon material.
[Requested item 4]
　The value of the pore volume based on the BJH method, solidified porous carbon material 1 cm 3 per 0.1 cm 3 porous carbon material which is solidified according to claim 1 is at least.
[Requested item 5]
　The value of the pore volume based on the MP method, the porous carbon material 1cm which is solidified 3 per 0.04 cm 3 to 0.1 cm 3 porous carbon material which is solidified according to claim 1 is.
[Requested item 6]
　The value of the pore volume based on the BJH method, solidified porous carbon material per gram 0.3 cm 3 or more, and the value of pore volume based on the MP method, the porous carbon material 1 which is solidified grams per 0.1 cm 3 porous carbon material which is solidified according to claim 1 is at least.
[Requested item 7]
　Ignition value of remainder of solidified porous carbon material, 0.1 wt% or more, a porous carbon material which is solidified according to claim 1 is 20 mass% or less.
[Requested item 8]
　Ignition residue bulk density of solidified porous carbon material, 1 × 10 -4 g / cm 3 to 1 × 10 -1 g / cm 3 a solidified porous according to claim 1, carbon material.
[Requested item 9]
　The porous carbon material which is solidified according to claim 1 fracture hardness is 20N or more.
[Requested item 10]
　The plant-derived material to solidify, then, in a state that solidified, and carbonized at 400 ° C to 1400 ° C, then treated with an acid or alkali, solidified process for the preparation of porous carbon material.
[Requested item 11]
　The bulk density of the solidified porous carbon material, 0.2 g / cm 3 to 0.4 g / cm 3 is,
　the cumulative pore in the range of pore sizes 0.05μm to 5μm based on mercury porosimetry the value of the volume, the porous carbon material per gram 0.4cm which is solidified 3 to 1.2 cm 3 manufacturing method of a porous carbon material which is solidified according to claim 10 which is.
[Requested item 12]
　The bulk density of the solidified plant-derived materials, 0.2 g / cm 3 to 1.4 g / cm 3 A method of manufacturing a solidified porous carbon material according to claim 10.
[Requested item 13]
　The bulk density of the carbonized material in the solidified state, 0.2 g / cm 3 to 0.8 g / cm 3 A method of manufacturing a solidified porous carbon material according to claim 10.
[Requested item 14]
　When solidified plant-derived material, method for manufacturing the porous carbon material which is solidified according to claim 10 using a starch or starch as a binder.
[Requested item 15]
　By treatment with acid or alkali, the ignition value of remainder of solidified porous carbon material, 0.1 wt% or more, which is solidified in claim 10, 20 mass% or less porosity method of manufacturing a quality carbon material.
[Requested item 16]
　Ignition residue bulk density of carbonized material solidified state 0.1 g / cm 3 or more,
　the residue on ignition bulk density of solidified porous carbon material, 1 × 10 - 4 g / cm 3 to × 10 1 -1 g / cm 3 a method of manufacturing a solidified porous carbon material according to claim 10.
Corrected claims (Convention Article 19)
[July 14, 2017 (14.07.2017) The International Bureau acceptance]
[1]
[Corrected] The plant-derived material as a raw material, a porous carbon material which is solidified,
　the bulk density of the solidified porous carbon material is preferably 0.2 g / cm 3 to 0.4 g / cm 3 a,
　the value of the cumulative pore volume of pores size 0.05μm to 5μm based on mercury porosimetry, the porous carbon material per gram 0.4cm which is solidified 3 to 1.2 cm 3 in
　There, the value of the pore volume based on the MP method, the porous carbon material 1cm which is solidified 3 per 0.04 cm 3 to 0.09 cm 3 solidified porous carbon material is.
[2]
　The value of the cumulative pore volume of pores size 0.05μm to 5μm based on mercury porosimetry, a porous carbon material which is solidified per gram 0.5 cm 3 to 1.0 cm 3 to claim 1 which is It solidified porous carbon material according.
[3]
　The value of the cumulative pore volume in the range of pore sizes 10μm based on mercury porosimetry, the porous carbon material per gram 0.7cm which is solidified 3 to 2.0 cm 3 solid according to claim 1 which is of porous carbon material.
[4]
　The value of the pore volume based on the BJH method, solidified porous carbon material 1 cm 3 per 0.1 cm 3 porous carbon material which is solidified according to claim 1 is at least.
[5]
[Delete]
[6]
[Delete]
[7]
　Ignition value of remainder of solidified porous carbon material, 0.1 wt% or more, a porous carbon material which is solidified according to claim 1 is 20 mass% or less.
[8]
　Ignition residue bulk density of solidified porous carbon material, 1 × 10 -4 g / cm 3 to 1 × 10 -1 g / cm 3 a solidified porous according to claim 1, carbon material.
[9]
　The porous carbon material which is solidified according to claim 1 fracture hardness is 20N or more.
[10]
And [corrected] solidification plant-derived material, then, while solidified, and carbonized at 400 ° C to 1400 ° C, then treated with an acid or alkali, which is solidified in the porous carbon material a manufacturing method,
　400 was carbonized at ° C to 1400 ° C, ignition value of residues of the material prior to treatment with acid or alkali is at least 20 mass%, solidified porous method of producing a carbon material.
[11]
　The bulk density of the solidified porous carbon material, 0.2 g / cm 3 to 0.4 g / cm 3 is,
　the cumulative pore in the range of pore sizes 0.05μm to 5μm based on mercury porosimetry the value of the volume, the porous carbon material per gram 0.4cm which is solidified 3 to 1.2 cm 3 manufacturing method of a porous carbon material which is solidified according to claim 10 which is.
[12]
　The bulk density of the solidified plant-derived materials, 0.2 g / cm 3 to 1.4 g / cm 3 A method of manufacturing a solidified porous carbon material according to claim 10.
[13]
　The bulk density of the carbonized material in the solidified state, 0.2 g / cm 3 to 0.8 g / cm 3 A method of manufacturing a solidified porous carbon material according to claim 10.
[14]
　When solidified plant-derived material, method for manufacturing the porous carbon material which is solidified according to claim 10 using a starch or starch as a binder.
[15]
　By treatment with acid or alkali, the ignition value of remainder of solidified porous carbon material, 0.1 wt% or more, which is solidified in claim 10, 20 mass% or less porosity method of manufacturing a quality carbon material.
[16]
　Ignition residue bulk density of carbonized material solidified state 0.1 g / cm 3 or more,
　the residue on ignition bulk density of solidified porous carbon material, 1 × 10 - 4 g / cm 3 to × 10 1 -1 g / cm 3 a method of manufacturing a solidified porous carbon material according to claim 10.