ACTIVATED CARBON MOLDED ARTICLE

[Activated carbon molded body] 　The present invention is activated carbon molded body, obtained by the multi-point method based on JIS K 1474 BET was calculated from the specific surface area determined by the specific surface area per volume packing density 290m² /Ml-a 520m² In the/ml, outer surface area per volume of 1.4m² /L or more.

　The specific surface area per volume, and specific surface area as measured by JIS K 1474 BET multipoint found in packing density based product, obtained by the method described in the examples below. Also, the outer surface area per volume, determined by the method described in the examples below. The specific surface area per volume and the surface area per volume than a lower limit value of the numerical range specified in or outside the specified are satisfied or not, the activated carbon molded body, the desired effective adsorption amount of butane, butane having high efficiency and low residual amount can not be purged. The purge efficiency is low residual amounts of butane, meaning desorbing performance is excellent. Desorption performance is superior, even if the amount of fuel vapor is desorbed better purge air, as a result, residual amounts of butane are lowered, evaporation of the fuel at a low emission performance is realized. 　The specific surface area per volume, preferably 300m² /Ml-a 500m² /Ml, more preferably 330m² /Ml-a 470m² In the/ml, outer surface area per volume, preferably 1.41m² /L or more. The specific surface area per volume and the surface area per volume than a lower limit value of the numerical range or a specific outside specific is satisfied, the activated carbon molded body, which has a high efficiency and a low residual amount in addition to the desired effective adsorbing butane purged butane.

　The specific surface area per volume and the surface area per volume than a lower limit value of the numerical range or specific to certain outside is adjusted, for example, degree of activation of the activated carbon, or can be achieved by adjusting the ratio of the compounded material.

　Furthermore, the specific surface area per volume and the surface area per volume than a lower limit value of the numerical range or specific to certain outside is adjusted, the activated carbon molded body having a specified shape can be achieved. Accordingly, certain aspects of the present invention, the activated carbon molded body has a pillar structure, the columnar structure, having a hollow interior opening at the axial ends of the wall of the column and the column, and the other opening extends from one opening of the one or more compartments and a partition wall dividing the hollow 2.

　The columnar structures include, columnar structure, elliptical columnar structure, and substantially prismatic structure and the like. These column-axis orthogonal to the cross sectional shape of a column, or may comprise some rounded corners or irregular, macroscopic observation is circular, elliptic or polygonal shape if only. As the substantially prismatic structure, approximately triangular prism-like structure, substantially square prismatic structure, approximately five prismatic structure, substantially hexagonal-shaped structure and a substantially octagonal prismatic structures and the like that, when using a carbon canister body required tends to wear strength standpoint, the cross-section of rounded corner is preferably substantially prismatic structure. In view of the similar, elliptical columnar structure and preferred structure. The desired effective adsorption amount of butane, butane and higher purge efficiency is low residual amount can be obtained easily from the viewpoint, the columnar structure, more preferably a positive cylindrical structure.

　In the following, while referring to the accompanying drawings required by certain aspects of the described in detail.

　In a particular aspect of the invention, the bulkhead wall and connected to the post, the wall is not connected to each other. Specific examples of this aspect, the cross-section perpendicular to the axis of the pillars illustration, Figures 1 and 4 - 11 are shown. 　Also, in a particular aspect of the present invention, orthogonal to the column when the column cross section is observed, the partition, 1, 2 or 3 are present, both ends of each partition wall connected with the column. Specific examples of this aspect, the cross-section perpendicular to the axis of the pillars illustration, Figures 1 and 4 - 11 are shown. 　These particular shapes are not connected to each other by the activated carbon molded body having a partition, the partition is generated when the connection portion are connected to each other in the thickness of the activated carbon molded body of fuel evaporation due to contact efficiency is expressed not obtained, and the specific surface area per volume ratio per volume or a specific limit value or more easily adjusted externally of the numerical range.

　In Figure 1, 4 and 5 are, connected to each other by a partition 1, 2 or 3 are present, each partition wall at its ends is connected to the I-shaped column, III or II-shaped form. 　Figure 6 - 8 is, not connected to one another bulkhead 1, 2 or 3 are present, each partition wall at its ends is connected to the pillar shaped S, SS-SSS or shaped form. 　Figure 9 and 10 is, 2 or 3 are not connected to each other there is a partition, the partition is curved at both ends and each connected to the wall of the column. 　Fig. 11 is, the partition walls 3 are present, each partition wall at its ends is connected to the columns, each connected to form a triangular-like shape of the sides.

　In a particular aspect of the present invention, orthogonal to the column when the column cross section was observed, at least one or more of the partition wall 2, are connected to each other at positions other than the center of gravity of the column cross section. As a specific example of this aspect is, when observing the cross-section perpendicular to the axis of column, T-shaped partition wall 2 to form thereon, and H-shaped partition 3 to form include those.

　In a particular aspect of the present invention, orthogonal to the column when the column cross section was observed, at least one or more of the partitions 2, 2 or more on the peripheral wall of the column 1 are mutually connected. As a specific example of this aspect is, when observing the cross-section perpendicular to the column axis, V-shaped partition wall 2 to form one, two partition walls 3 formed therein-and-or A N, 2 or 3 to 1 is shaped like a triangular apex forms a closed partition such as those thereof.

　In a particular aspect of the present invention, orthogonal to the column when the column cross section is observed, the bulkhead, wall columns are connected to each other at a position on a triangular, quadrangular or pentagonal form. This aspect of the cross-section of the illustration, Figure 2, 3 and 12 as shown.

　In another aspect of the present invention specified, the activated carbon molded body, as the partition, the other opening 2 into two compartments extending from one opening to the hollow interior walls, the interior wall of the column wall and from one opening to the other opening extending to and connecting wall. 　In a particular aspect of the present invention, orthogonal to the column when the column cross section is observed, the inside circular wall, an oval shape, a triangular shape or a square shape is. 　In a particular aspect of the present invention, connected to the wall 2, 3 or 4 are present. 　Specific examples of these modes, a schematic illustration of a cross section perpendicular to the axis of column posts, 13 - 21 shown in FIG.

　The cross-section perpendicular to the axis of column 1 - 21 from the side of the activated carbon molded body as shown in Figure Figure is a diagrammatical beside, all of which are common, example 1 (fig. 22) side of the activated carbon molded body was manufactured according to the schematic illustration of the same.

　The desired effective adsorption amount of butane, butane and higher purge efficiency is low residual amount can be obtained easily from the viewpoint, the thickness of the partition wall, the partition wall thickness is preferably within a range of the center value of the -5% - + 5%, and more preferably within a range of -4% - + 4%, particularly preferably in the range of -3% - + 3%. The thickness of the wall thickness of the partition wall is closer to the center value, the thickness of the partition wall means and more uniform, it is preferred in the present invention.

　The desired effective adsorption amount of butane, butane and higher purge efficiency is low residual amount can be obtained easily from the viewpoint, the thickness of the column wall, the peripheral wall of the -5% - + 5% of the central value is within the range of the thickness of the column preferably, more preferably within a range of -4% - + 4%, particularly preferably in the range of -3% - + 3%. The wall thickness of the wall thickness of the center closer to the value of the column column, column wall thickness is more uniform mean, is preferred in the present invention.

　The desired effective adsorption amount of butane, butane and higher purge efficiency is low residual amount can be obtained easily from the viewpoint, the thickness of the partition wall to the thickness of the columns of the difference, the longest outside dimension less than the cross-section perpendicular to the axis of column was observed when 5% preferably, more preferably 3% or less, particularly preferably 0%. Here, a longest outside dimension and, in the case of the outer diameter of the cylindrical post or column corresponds, in the case of the major diameter of the elliptic section of the column or column corresponds, approximately square column is equivalent to a longest diagonal cross section or column. The smaller the difference, the thickness of the partition wall means and a more uniform thickness of a column, the present invention is preferred.

　The desired effective adsorption amount of butane, butane and higher purge efficiency is low residual amount can be obtained easily from the viewpoint, the columnar structure, the same having a cross sectional shape in the axial direction of the column. Such a shape may, for example, the activated carbon molded body produced by extrusion molding or the tableting obtained by molding.

　The desired effective adsorption amount of butane, butane and higher purge efficiency is low residual amount can be obtained easily from the viewpoint, the thickness of the partition wall and the wall thickness of each column, the longest dimension of the cross section perpendicular to the axis of the column when the column is in the range 5 - 35% preferably external observation, more preferably within a range of 7 - 25%, particularly preferably within a range of 10 - 20%.

　The partition wall thickness and the thickness of the column respectively, preferably within a range of 0.3 V 1.0 mm, more preferably within a range of 0.4 V 0.95 mm, particularly preferably within the range of 0.5 V 0.9mm. The partition wall thickness and the thickness of the column and within the range, a low residual amount of high hardness tends to butane.

　In a cross section perpendicular to the axis of column wall area with respect to the void area ratio of the column, preferably 20 - 50%, more preferably 25 - 45%, particularly preferably at 30 - 40%. The ratio within the above range, the amount of butane or high hardness tends to remain low.

　A longest outside dimension in cross section when viewed perpendicular to the axis of column column, preferably in the range of 3 mm - 9 mm, more preferably within a range of 4 a-7mm, especially preferably within the range of 4 d 6 mm. The longest outside dimension within the above range, while suppressing the flow resistance, low residual amounts of butane is apt to be obtained.

　The thickness of the partition wall and the wall of the column, their center value, the longest outside dimension, and a wall area of the cavity area ratio, obtained by the method described in the examples below. These values are, for example, activated carbon or activated carbon molded body produced by extrusion molding of a nozzle shape when manufacturing the mold shape can be adjusted by adjusting the tabled.

　The partition wall and the connecting part or the connecting part of the column partitioning walls, and the partition wall other than the connecting part of the column, but often present inside the wall surface of the activated carbon. This is, because undesirable deterioration in the efficiency of contact with evaporating fuel. Accordingly, the activated carbon is preferably present in reduced. In particular, the wall thickness of the partition walls is preferably made partially thin connection part or a column, it is, for example, activated carbon or activated carbon molded body produced by extrusion molding of a nozzle shape when manufacturing the mold shape can be achieved by adjusting the tabled.

　The activated carbon molded body obtained by the method of the present invention mean pore diameter is HK, preferably 2.1 nm a-2.6 nm, more preferably 2.1 nm Si 2.4 nm, especially preferably at 2.1 nm Si 2.2 nm. The average pore diameter is within the above range, the desired effective adsorption of butane can be easily obtained. The average pore diameter is adjusted to the range of, for example, activated carbon can be accomplished by adjusting the degree of activation. The average pore size is, for example obtained by a method described below.

　The activated carbon molded body conforming to ASTM D5228 found effective adsorption amounts of butane, preferably 8.0 g/dL-a 10 g/dL, more preferably 8.0 g/dL e 9.8g/dL, particularly preferably at 8.0 g/dL e 9.7g/dL. Within the scope of the effective amount of adsorbed butane, evaporating fuel is easily detached. The amount of butane to the range adjustment of the effective suction, for example, degree of activation of the activated carbon, or can be achieved by adjusting the ratio of the compounded material.

　The activated carbon molded body of the present invention conforms to ASTM D5228 is determined by residual amounts of butane, preferably less than 1.30 g/dL, more preferably less than 1.25 g/dL, particularly preferably less than 1.20 g/dL. The lower the amount of residual butane, attaching means and excellent performance, the present invention is preferred. The value is adjusted to the amount of remaining butane, for example, degree of activation of the activated carbon, or can be achieved by adjusting the ratio of the compounded material.

　The activated carbon molded body (hereinafter, also referred to MS hardness) the hardness of the inventive microphone lost length, preferably 60% or more, more preferably 70% or more, particularly preferably 75% or more. MS hardness, resistance to the measure of the weight load, measured by the method described in the examples later. The activated carbon molded body has a hardness of more than MS, activated carbon molded canister when using the wear strength can be easily obtained. The value of the hardness is adjusted to MS, for example, by adjusting the amount of binder can be achieved.

　The activated carbon molded body of the present invention is fine powder amount, preferably 0.12% or less, more preferably 0.10% or less, more preferably 0.07% or less, more preferably 0.05% or less, particularly preferably less than 0.025%. The amount of fine powder is less than the value, the activated carbon canister is used when reduced dust easily molded. The value of the amount of fine powder is adjusted to, for example, by adjusting the amount of binder can be achieved. The amount of the fine powder, obtained by the method described in the examples below.

　The activated carbon molded body obtained by the method of the present invention is pore volume BJH, preferably 0.480-a 0.555 ml/g, more preferably from 0.490 e 0.545 ml/g, particularly preferably in the 0.500 V 0.535 ml/g. The pore volume was determined by the method described above within the scope BJH, the desired effective capacity for adsorbing butane and tends. The range of adjustment is obtained by the method of pore volume BJH, for example, degree of activation of the activated carbon, or can be achieved by adjusting the ratio of the compounded material. The pore volume is, obtained by the method described in the examples below.

　The activated carbon molded body of the present invention is, in particular, based on the specific surface area as measured by JIS K 1474 BET multipoint found was calculated from the specific surface area per volume of packing density, and since the outer surface area per volume, in addition to good fuel evaporation, evaporation of fuel can be realized low emission performance. Furthermore, the activated carbon molded body of the present invention, the amount of fines can have low hardness and high MS. Therefore, the activated carbon molded body of the present invention, suited for use in a canister. Accordingly, the present invention, the activated carbon molded body of the present invention directed to a canister. In addition, the activated carbon molded body of the present invention, transpiration of various kinds, for example, a typical automobile gasoline not only normal fuel, such as gasoline containing alcohol can be applied.

[Method of manufacturing activated carbon molded body] 　The activated carbon molded body of the present invention is, for example, pulverulent or granular activated carbon, a slipping agent, an acid-soluble solid diluent is mixed, the resulting mixture was kneaded with a binder and water, molding the resulting mixture into a desired shape, and the resultant product is dried and then, at least a portion of diluent removed by washing the solid dissolved in the acid, further comprising drying the manufactured by the method.

"Powdered or granular activated carbon" 　The pulverulent or granular activated carbon, the activated carbon obtained by carbonizing a carbonaceous material as a raw material can be activated, for example 1 d 500 μm, preferably from 1 d 100 μm, more preferably 10 d 50 μm in average particle diameter so as to ground.

　As the carbonaceous material, carbonized and activated carbon is not particularly limited as long as the form, vegetable-based, mineral-based, synthetic material or the like and can be selected from a natural material. In particular, a plant-based carbonaceous material include, for example, wood, bamboo, wood charcoal, rice debris, such as shells and coconut fruit include, mineral-based carbonaceous material include, for example, coal and the like (for example, peat, lignite, coal, bituminous coal, anthracite coal and semi-like), and/or a petroleum petroleum pitch, coke and the like. Natural materials include, for example, starch, cellulose (cotton and hemp or natural fibers), resin (such as viscose rayon or regenerated fibers of rayon and) regeneration, and semi-synthetic resin (or semi-synthetic fibers such as acetate and tri-acetate) include such as, synthetic material may include, for example, the nylon 66 as the polyamide resin, such as vinylon polyvinyl alcohol-based resin, an acrylic-based resin (such as polyacrylonitrile resin), polyolefin resin (polyethylene and polypropylene), vinyl chloride resin, polyurethane resin, phenol resin, furan resin, epoxy resin and the like. These carbonaceous materials, alone or in combination of two or more kinds may be used.

　Among these carbonaceous material, the desired effective adsorption amount of butane, butane and higher purge efficiency is low residual amounts of activated carbon having a molded body is obtained from the viewpoint of easy, mineral-based carbonaceous material is preferably used, more preferably used for coal, anthracite or bituminous coal and/used is particularly preferred.

　The carbonaceous material is carbonized and activated condition is not particularly limited, the conventional conditions can be employed. Typically, the carbonaceous material is carbon, oxygen or air is cut off, for example 400 a-°C 800, preferably 500 a-°C 800, more preferably 550 a-°C 750 can be implemented. Furthermore, carbonized carbonaceous material is activated, typically, activated gas (e.g., steam or carbon dioxide gas) atmosphere, for example 700 a-°C 1200, preferably performed at 800 a-°C 1100.

　After the activated carbon obtained by activating, ASTM D5228 is measured on the basis of the adsorbing amount effective for butane, for example 10 d 20 g/dL, preferably 12.5 V 18g/dL, more preferably a 13 c 16 g/dL.

　The specific surface area of activated carbon obtained after activation BET, e.g. 250 a-1500m² /G, preferably from 350 a-1400m² /G, more preferably 500 a-1300m² A/g.

　The mean pore diameter of activated carbon obtained after activation, for example 0.1 V 100 nm, preferably 0.3-to 50 nm, more preferably 0.3 V 25 nm, more preferably 0.5-a 10 nm, particularly preferably 0.5 Si 5 nm is.

"Slip agent" 　Slip agents include, for example, bentonite-based compound, a compound selected from the group consisting of polyvinyl alcohol and cellulose compounds 1 or more can be used. The bentonite-based compounds include, for example, animal excreta absorber and calcium bentonite and the like. Cellulosic compounds include, for example, cellulose, and cellulose derivatives "cellulose ethers, e.g., methyl cellulose (hereinafter, also referred to MC) alkyl or the like; a carboxymethyl cellulose or a salt thereof; hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxyalkyl cellulose; or an alkyl such as hydroxypropylmethylcellulose" include etc., methylcellulose and/or carboxymethyl cellulose is preferably used. Polyvinyl alcohol compounds include, for example, polyvinyl alcohol and modified polyvinyl alcohol and the like of various kinds.

　The sliding agent is used in an amount, with respect to 100 parts by mass of a powdery or granular activated carbon, preferably 5 - 25 parts by mass, more preferably 5 - 20 parts by mass, particularly preferably 5 - 18 parts by mass.

"Acid-soluble solid diluent" 　Acid-soluble solid diluent, following acid cleaning process to remove at least a portion of elution, pores in the activated carbon molded body removed and the elution. Accordingly, the activated carbon molded body, formed by the pores of the granular activated carbon or powdered activated (hereinafter, also referred to "activation from fine holes") in addition to the, formed by dissolving and removing solid diluent (hereinafter, also referred to "remove eluted from pores") pores having. The pore formation can be controlled by removing the elution from the packing density, in the present invention, specific surface area as measured by JIS K 1474 BET multipoint was calculated from the specific surface area per volume is determined based on the packing density can be controlled. The activated carbon molded body may be removed from the elution of the pores, the practical hardness.

　Acid-soluble solid diluents include, inorganic compound, for example, a metal oxide such as magnesium oxide, magnesium carbonate and calcium carbonate or metal carbonate, metal hydroxide such as calcium hydroxide or the like; a basic polymer, e.g., N, dialkylamino C N -_{2 - 3} The alkyl (meth) acrylate monomer alone or a copolymer and the like. These solid diluent, alone or in combination of two or more kinds may be used. In the elution with acid, viscous polymer than tends, to form a solid diluent is preferred elution of low viscosity. Such solid diluents include, calcium carbonate.

　The average particle size of the solid diluent, desired pore size can be selected in accordance with the dissolving and removing from, for example 0.1-to 30 μm, preferably 0.1 d 20 μm, more preferably 0.2-a 15 μm, particularly preferably 0.2 al 10 μm is. The average particle size of powdery or granular activated carbon having an average particle diameter of the solid diluent ratio, e.g. 300-1-0 . 01/1, preferably 250/1 - 1/1, more preferably 100/1 - 10/1 is.

　The solid diluent is used in an amount, a desired pore size and proportions can be selected in accordance with the removed from the elution, to 100 parts by mass of a powdery or granular activated carbon, for example 10 - 150 parts by mass, usually 25 - 150 parts by mass, preferably 40 - 150 parts by mass, more preferably 50 - 130 parts by mass, particularly preferably 55 - 120 parts by mass.

　The pulverulent or granular activated carbon, a slipping agent, an acid-soluble solid diluent is mixed, a general method can be implemented. 　Then, the resulting mixture was kneaded with water and a binder.

"Binder" 　As the binder, in a short time without deterioration or elution of the adsorption and the desorption of fuel vapor in the atmosphere, to the acid insoluble is used. Furthermore, the kind and amount of the binder is determined by the hardness of the molded product of activated carbon, and a binder of pore blockage may occur in view of the active carbon, a binder type is selected, the amount of adjustment required. 　For the binder, a thermoplastic resin or a thermosetting resin may be. Examples thereof include, polyolefin resin "polyethylene, ethylene - vinyl acetate copolymer, ethylene - (meth) acrylic acid ester copolymer, an ethylene - (meth) acrylic acid copolymer or the like and", an acrylic resin, a polyester resin, an epoxy-based resin, and silicone-based resin and the like. These binders are, alone or in combination of two or more kinds may be used. The binder, such as a hot melt adhesive may be a heat-adhesive resin, aqueous (aqueous medium dissolved or dispersed form) or an oil (in the form dissolved in an organic solvent) may be. The binder, such as an acrylic resin emulsion, dispersion (particularly, emulsion or aqueous dispersion) often use form.

　The ratio of the binder, relative to 100 parts by mass of a powdery or granular activated carbon, in terms of solids, for example 5 - 35 mass parts, preferably 7 - 30 parts by mass, more preferably 9 - 25 parts by mass, particularly preferably 10 - 20 parts by mass.

　In order to adjust the density and the kneaded mixture, pulverulent or granular activated carbon and the mixture of solid lubricant and a diluent, a binder is kneaded, water may also be used. The amount of water, to 100 parts by mass of a powdery or granular activated carbon, e.g. 100 - 300 parts by mass, preferably 110 - 250 parts by mass, more preferably 120 - 200 parts by mass.

　The kneading, for example a mixer, a ribbon mixer, a static mixer, a ball mill, a kneader or the like can be carried out using a sample mill or a general method. The kneading temperature, from the viewpoint of reducing the moisture content, usually 0 V °C 50, preferably a 5 e 40 °C. The kneading time, from the viewpoint of preventing oxidative deterioration of production efficiency and binder, typically 1 - 60 minutes, preferably 5 - 30 minutes.

　Subsequently, the kneaded mixture was obtained, for example by extrusion or tabletting molding, molded into a desired shape. The kneaded material extruded, the extruded strands also includes cutting, after cutting the desired shape can be obtained. The shape desired, the activated carbon molded body, in particular, based on the specific surface area as measured by JIS K 1474 BET multipoint found was calculated from the specific surface area per volume of packing density, and an outer surface area per volume of the resulting shape, for example, the columnar structure, the columnar structure, having a hollow interior opening at the axial ends of the wall of the column and the column, the other opening extends from one opening of the one or more compartment 2 containing a partition wall dividing the hollow shape.

　Then, the obtained molded article after drying, the solid diluent is removed by washing with acid elution, further dried, the activated carbon molded body is obtained. As described above, the activated carbon molded body, in addition to the pores of the activated derived, eluted and removed from the pores.

　The drying method is not particularly limited either before acid cleaning, air, an inert gas (e.g. nitrogen) atmosphere or a mixture thereof, which may be dried using a dryer generally. From the viewpoint of production efficiency and preventing the degradation of the binder, the drying temperature is, typically 60 c 150 °C, preferably at 70 a-°C 140. The drying time, the drying temperature is dependent on the number, typically 0.1 - 36 hours, preferably 0.5 - 24 hours.

　Examples of solid diluent for dissolving and removing acid, hydrochloric acid and nitric acid such as carbonic acid, and acetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid and citric acid or organic acid. These acids may be used singly or in combination of two or more kinds may be. The safety, the ease of obtaining, from a cost standpoint, hydrochloric acid is preferred. 　The acid is usually used in the form of aqueous solution, the concentration is usually 0.5 V 3mol/L, preferably at 0.8 V 2.5mol/L. The amount of the acid aqueous solution is used, 100 g with respect to the molding, typically 0.5 V 2L, preferably at 0.8-a 1.5L. 　As the method for cleaning, drying and product is only in contact with an aqueous acid solution. The dried molded product after mixing with an aqueous acid solution, stirring or, boiling or heated by 50 d 90 °C or, cleaning efficiency can be improved. Also, ultrasonic washing machine may be used. 　The washing time, depends on the temperature, typically 0.1 - 48 hours, preferably from 0.5 - 24 hours. The washing times, preferably, is 1 - 5 times in boiling acid cleaning, acid cleaning is 1 - 10 times in warm.