JP2005306710A - Honeycomb structure and method for manufacturing the same, and canister using the honeycomb structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a honeycomb structure which maintains good adsorption performance and is not damaged for a long period of time when used for a sub-canister and can be more inexpensively manufactured, and to provide a method for manufacturing the same, and a canister. <P>SOLUTION: The honeycomb structure contains an active carbon and a clay-like material, has cells 52 to be sectioned and formed by a plurality of partition walls 53 on the inner side of an outer peripheral wall 51. The volumetric ratios of pores of 1 to 6 nm with respect to pores of a diameter 1 to 12 nm existing at the outer peripheral wall 51 and the partition walls 53 is 72 to 83%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a honeycomb structure using activated carbon and a clay-like substance having excellent characteristics as an adsorbent or a catalyst carrier, a method for manufacturing the honeycomb structure, and a canister used in an automobile fuel evaporation prevention apparatus using the honeycomb structure. It is about.

  When the car stops the engine, the vapor evaporated from the gasoline tank (hereinafter referred to as gasoline vapor) has been conventionally released into the atmosphere without being recovered. However, in recent years, in consideration of air pollution, a fuel evaporation prevention device equipped with a canister filled with granular activated carbon as an adsorbent for gasoline vapor has come to be installed in the middle of a discharge pipe into the atmosphere. This canister adsorbs gasoline vapor to the adsorbent and causes air to flow in the reverse direction during the next travel, thereby desorbing the gasoline vapor from the adsorbent and supplying it to the engine for reuse.

  In order to reduce the amount of leakage of gasoline vapor into the atmosphere, many proposals have been made for improving the adsorption performance of granular activated carbon or for the structure of a canister.

  On the other hand, in terms of regulations, automobile exhaust emission regulations have been set as LEV (Amendments to California 'Low-Emission Vehicle regulations) as of 2003 in California, USA, but the more stringent automobile exhaust emission regulations LEV2 will be enforced in 2004 It is. In this new automobile exhaust gas regulation LEV2, it is required to completely prevent leakage of gasoline vapor into the atmosphere, including when the vehicle is stopped, but a canister filled with granular activated carbon as an adsorbent. When a car equipped with is stopped for a long time, as the time passes, gasoline vapor diffuses in the canister, causing a problem that the amount of leakage into the atmosphere increases and exceeds the regulation value, and countermeasures are necessary It is supposed to be.

  In order to solve this problem, in Patent Document 1, another canister (hereinafter referred to as a sub-canister) is arranged in series after the canister, and the adsorbent of the sub-canister is an activated carbon honeycomb, thereby stopping for a long time. Even in such a case, an apparatus capable of suppressing the leakage amount of gasoline vapor has been proposed.

  In addition, various activated carbon honeycomb structures have been proposed in order to enhance the adsorption performance.

  For example, in Patent Document 2, the pore structure measured by mercury porosimetry is such that the pore volume with a diameter of 4 nm or more is 0.45 ml / g or more and the pore volume with a diameter of 600 nm or more is 0.20 to 0.35 ml / g. Thus, an activated carbon honeycomb structure with improved iodine adsorption performance and methylene blue decolorization performance has been proposed.

  In Patent Document 3, activated carbon powder, a solvent (methyl alcohol, ethyl alcohol, ethylene glycol monoethyl ether, acetone, diethyl ketone, ethyl acetate, acetonitrile, etc.), and a solid component at room temperature having a soluble component in the solvent of 50. There has been proposed an activated carbon honeycomb structure in which a kneaded body containing ~ 95% by mass of a phenol-aldehyde resin is molded, dried and cured, and then fired in an inert gas atmosphere.

  Moreover, in patent document 4, the shielding material containing a carbonaceous material is arrange | positioned around the activated carbon honeycomb molded object, the contact with surrounding oxygen is interrupted | blocked, and this activated carbon honeycomb molded object is baked at 400-1000 degreeC. A method for firing an activated carbon honeycomb structure has been proposed.

Further, Patent Document 5 proposes a method of using the activated carbon honeycomb structure in which the activated carbon honeycomb structure is sliced and stacked and mounted in the reaction system.
Japanese Patent Laid-Open No. 10-37812 Japanese Patent No. 3125808 JP 2002-301365 A JP-A-11-79724 JP-A-3-42036

  However, although Patent Document 1 proposes an activated carbon honeycomb structure as an effective adsorbent for gasoline vapor, the diameter and volume of pores existing in the interface and inside of the particles forming the activated carbon honeycomb structure are controlled. In addition, since the activated carbon honeycomb structure shown in the examples has a rectangular parallelepiped shape, when mounted on a sub-canister, the sub-canister is usually a cylindrical body, which causes a problem of space loss. was there.

Further, when the method for measuring the pore structure of the activated carbon honeycomb structure proposed in Patent Document 2, that is, the mercury intrusion method is used for measuring the diameter of the pores of the honeycomb structure proposed in the present invention, the diameter is 20 nm. Although it is suitable for the activated carbon honeycomb structure having the above pores, there is a problem that it is difficult to measure with the activated carbon honeycomb structure having pores having a diameter of less than 20 nm. (See “Porous Material Handbook” (IPC Co., Ltd.) p27)
In addition, the activated carbon honeycomb structure proposed in Patent Document 2 has improved iodine adsorption performance and methylene blue decolorization performance, which have a larger molecular diameter than butane, which is the main component of the fuel component, and has a smaller molecular diameter butane. Or, since it was not aimed at improving the adsorption / desorption performance of ethane, the pore structure contributing to this performance was not necessarily adjusted.

  In addition, in the activated carbon honeycomb structure proposed in Patent Document 3, a phenol / aldehyde resin is used for the production thereof, and the solvent is not water alone but methyl alcohol, ethyl alcohol, ethylene glycol monoethyl ether, acetone, diethyl ketone, acetic acid. Ethyl, acetonitrile, etc. are used, but the phenol-aldehyde resin itself is expensive, and the above-mentioned solvent must take an explosion-proof measure, and the activated carbon honeycomb structure also becomes expensive. there were.

  In addition, according to the method for manufacturing an activated carbon honeycomb structure proposed in Patent Document 4, since the shielding material is disposed around the activated carbon honeycomb molded body, contact with oxygen is blocked and the activated carbon honeycomb molded is flammable. Although the combustion of the body can be surely prevented, the firing temperature is as low as 400 to 1000 ° C., so it cannot be sufficiently sintered depending on the clay-like material used, and when the activated carbon honeycomb structure is attached to the sub-canister, the strength is increased. There was a problem of shortage.

  Furthermore, when the activated carbon honeycomb structure is sliced and used in the reaction system as proposed in Patent Document 5, if the vibration of the reaction system is weak, good adsorption performance can be obtained, but the sub-canister When mounted on the car, there is a problem that the activated carbon honeycomb structure overlaid interferes with and is damaged by strong vibration that the automobile receives while traveling. Moreover, the activated carbon honeycomb structure manufactured by this manufacturing method has a problem that the manufacturing cost is too high.

  In addition, the above Patent Documents 1 to 5 do not show any powdery activated carbon pore structure, which is a starting material of the activated carbon honeycomb structure, nor any suitable forming aid for obtaining the activated carbon honeycomb structure. There was also a problem that an activated carbon honeycomb structure with high desorption performance could not be obtained.

  The present invention provides a honeycomb structure that can maintain a good adsorption / desorption performance, and is not damaged for a long period of time when used in a sub-canister, and can be manufactured at a lower cost, its manufacturing method, and a canister. It is.

  The honeycomb structure of the present invention is a honeycomb structure including activated carbon and a clay-like substance, and includes a cell that is partitioned and formed by a plurality of partition walls inside the outer peripheral wall, and has a diameter that exists in the outer peripheral wall and the partition walls. The volume ratio of the pores having a diameter of 1 nm to 6 nm to the pores having a diameter of 1 nm to 12 nm is 72 to 83% when measured using a gas adsorption method.

Further, when the pores existing in the outer peripheral wall and the partition wall are measured using a gas adsorption method, the pore volume with a diameter of 2 nm is 140 mm ³ / g or more, the pore volume with a diameter of 3 nm is 120 mm ³ / g or more, and The pore volume with a diameter of 4 nm has a structure of 90 mm ³ / g or more.

  Further, the honeycomb structure has a hydrocarbon gas adsorption performance, and the hydrocarbon gas adsorption amount is 3.2 g / 100 ml or more.

Furthermore, when the pores existing in the outer peripheral wall and the partition wall are measured using a gas adsorption method, the pore volume with a diameter of 8 nm is 50 mm ³ / g or more, the pore volume with a diameter of 10 nm is 40 mm ³ / g or more, In addition, the pore volume of 12 nm in diameter is a structure of 30 mm ³ / g or more.

Furthermore, at least one of alumina (Al ₂ O ₃ ), silica (SiO ₂ ), calcia (CaO), magnesia (MgO), spinel (MgAl ₂ O ₄ ), and forsterite (Mg ₂ SiO ₄ ) is included. It is characterized by being added.

  In addition, the honeycomb structure has a hydrocarbon gas desorption performance and a desorption rate of 50% or more.

  Furthermore, the thickness of the outer peripheral wall is 0.5 mm or more, the thickness of the partition wall is 0.35 mm or less, and a reinforcing portion is formed in the vicinity of a portion where the outer peripheral wall and the partition wall are in contact with each other. .

  Furthermore, the cell is characterized in that the cross-sectional shape perpendicular to the axial direction is a hexagon.

  Furthermore, the weight ratio of the activated carbon and the clay-like substance is 60:40 to 30:70.

  Further, the activated carbon is a wood activated carbon.

  Furthermore, the clay-like substance is at least one of Kibushi clay, Sasame clay, ball clay, zeolite, bentonite, and hydrous magnesium silicate fiber.

  Furthermore, the total of inevitable impurities is 2% by mass or less in terms of oxide.

  Furthermore, the method for manufacturing a honeycomb structure of the present invention includes extruding a kneaded body containing activated carbon and a clay-like material, to which a cellulose derivative, an alcohol copolymer, and a polyethylene glycol acrylate are added as a forming aid. A step of molding, a step of drying the obtained molded body at a temperature of 40 to 70 ° C., and a step of sintering the molded body at a temperature of 600 to 1300 ° C. after drying. .

  The cellulose derivative is at least one selected from the group consisting of methyl cellulose, ethyl cellulose, propyl cellulose, ethyl methyl cellulose, propyl methyl cellulose, and crystalline cellulose, and the alcohol copolymer is selected from the group consisting of polyvinyl alcohol and polyethylene vinyl alcohol. And at least one polyethylene glycol-based acrylate is selected from the group consisting of polyethylene glycol monoacrylate, polyethylene glycol tetramethylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol tetramethylene glycol monomethacrylate To be one kind Further, the ratio of the cellulose derivative to be added, the alcohol polymer, and the polyethylene glycol acrylate is 2 to 6% by mass, 7 to 15% by mass, and 30 to 35% by mass with respect to the kneaded body, respectively. .

  Furthermore, the method for manufacturing a honeycomb structure of the present invention includes activated carbon and clay to which at least one selected from the group consisting of sorbitan monocaprylate composite ester, glycols, and cellulose derivatives and methylcellulose are added as a forming aid. A step of extruding a kneaded body containing a particulate substance, a step of drying the obtained molded body at a temperature of 40 to 70 ° C, a step of sintering the dried molded body at a temperature of 600 to 1300 ° C, It is characterized by having.

  The glycol is at least one selected from the group consisting of propylene glycol and ethylene glycol, and the cellulose derivative is at least one selected from ethyl cellulose, propyl cellulose, ethyl methyl cellulose, propyl methyl cellulose, and crystalline cellulose, and added The ratios of sorbitan monocaprylate composite ester, glycols, cellulose derivative and methylcellulose are 3 to 5% by mass, 1 to 3% by mass, 1 to 3% by mass, and 3 to 10% by mass with respect to the kneaded body, respectively. It is characterized by that.

  Furthermore, the method for manufacturing a honeycomb structured body of the present invention is characterized in that a shielding material containing a carbonaceous material is disposed around the molded body and sintered.

  Furthermore, the canister of the present invention is characterized in that the honeycomb structure is mounted.

  In the present invention, when the volume ratio of the pores having a diameter of 1 nm to 6 nm to the pores having a diameter of 1 nm to 12 nm existing in the outer peripheral wall and partition walls of the honeycomb structure is measured using a gas adsorption method, it is 72 to 83%. As a result, the balance between the adsorption performance and the desorption performance can be easily maintained.

Further, when the structure of the pores existing in the outer peripheral wall and the partition walls of the honeycomb structure was measured using a gas adsorption method, the pore volume with a diameter of 2 nm was 140 mm ³ / g or more, and the pores with a diameter of 3 nm Adopting a structure in which the volume is 120 mm ³ / g or more and the pore volume having a diameter of 4 nm is 90 mm ³ / g or more, good adsorption performance can be maintained for a long time.

  Furthermore, the honeycomb structure has a hydrocarbon gas adsorption performance, and can be used as an adsorbent for a canister by setting the adsorption amount of the hydrocarbon gas to 3.2 g / 100 ml or more.

Furthermore, when the structure of the pores existing in the outer peripheral wall and partition walls of the honeycomb structure is measured using a gas adsorption method, the pore volume having a diameter of 8 nm is 50 mm ³ / g or more and the pore volume having a diameter of 10 nm is reduced. With a pore volume of 120 mm ³ / g or more and a pore volume of 12 nm in diameter having a structure of 90 mm ³ / g or more, good desorption performance can be maintained for a long time.

In addition, at least one of alumina (Al ₂ O ₃ ), silica (SiO ₂ ), calcia (CaO), magnesia (MgO), spinel (MgAl ₂ O ₄ ), and forsterite (Mg ₂ SiO ₄ ) is added. As a result, the specific heat of the honeycomb structure is increased, and the desorption performance is improved.

  Further, the honeycomb structure has the ability to adsorb and desorb hydrocarbon gases, and can be used as an adsorbing and desorbing agent for canisters by setting the desorption rate to 50% or more.

  Furthermore, the thickness of the partition wall for partitioning the honeycomb structure is set to 0.35 mm or less, the thickness of the outer peripheral wall is set to 0.5 mm or more, and a reinforcing portion is formed in the vicinity of the portion where the outer peripheral wall and the partition wall are in contact with each other. As a result, the adsorption / desorption performance can be improved, the strength can be increased, and the reliability becomes higher.

  Furthermore, by making the cross-sectional shape of the cell perpendicular to the axial direction a hexagonal shape, the adsorption area of gasoline vapor can be increased as compared with the case where the cross-sectional shape is square, so that the adsorption / desorption performance is further improved.

  Furthermore, by setting the weight ratio of the activated carbon and the clay-like substance to 60:40 to 30:70, it is possible to combine strength and adsorption / desorption performance required for the honeycomb structure.

  Further, by using the activated carbon as a woody activated carbon, the specific surface area of the honeycomb structure can be increased, and the adsorption / desorption performance can be further improved.

  Furthermore, the plasticity required at the time of shaping | molding is obtained by making the said clay-like substance into at least 1 sort (s) selected from the group which consists of Kibushi clay, Sasame clay, ball clay, a zeolite, bentonite, and a hydrous magnesium silicate fiber. In addition, the strength as the honeycomb structure can be easily secured.

  Furthermore, since the segregation of inevitable impurities in the honeycomb structure can be reduced by setting the total of inevitable impurities to 2% by mass or less in terms of oxides, local strength reduction can be prevented.

  Still further, a step of extruding a kneaded body containing activated carbon and a clay-like material, to which a cellulose derivative, an alcohol copolymer and a polyethylene glycol acrylate are added as a molding aid, and an extruded molded body A method for manufacturing a honeycomb structure having a step of drying at a temperature of 40 to 70 ° C. and a step of sintering the molded body at a temperature of 600 to 1300 ° C. If so, a high-strength honeycomb structure can be obtained, and good adsorption performance can be obtained.

  The cellulose derivative is at least one selected from the group consisting of methyl cellulose, ethyl cellulose, propyl cellulose, ethyl methyl cellulose, ethyl methyl cellulose, propyl methyl cellulose, and crystalline cellulose, and the alcohol copolymer is a group consisting of polyvinyl alcohol and polyethylene vinyl alcohol. At least one selected from the group consisting of polyethylene glycol monoacrylate, polyethylene glycol tetramethylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol tetramethylene glycol monomethacrylate Was At least one kind, and the ratio of the cellulose derivative to be added, the alcohol polymer, and the polyethylene glycol acrylate is 2 to 6% by mass, 7 to 15% by mass, and 30 to 35% by mass with respect to the kneaded body, respectively. By doing so, the shape retention of the molded body and the workability of extrusion molding can be improved.

  Further, as a molding aid, a kneaded body containing activated carbon and a clay-like substance, to which at least one selected from the group consisting of sorbitan monocaprylate complex ester, glycols, and cellulose derivatives and methylcellulose is added is extruded. And a step of drying the extruded molded body at a temperature of 40 to 70 ° C. and a step of sintering the molded body at a temperature of 600 to 1300 ° C. In particular, when a horizontal type extruder is used, a high-strength honeycomb structure can be obtained and good adsorption performance can be obtained.

  Furthermore, at least one selected from the group consisting of propylene glycol and ethylene glycol as the glycol, and at least selected from the group consisting of cellulose derivatives such as ethyl cellulose, propyl cellulose, ethyl methyl cellulose, ethyl methyl cellulose, propyl methyl cellulose, and crystalline cellulose. The ratio of the sorbitan monocaprylate complex ester, glycols, cellulose derivative and methylcellulose to be added is 3 to 5% by mass, 1 to 3% by mass, and 1 to 3% by mass, respectively, with respect to the kneaded body. By setting it as 3-10 mass%, the shape-retaining property of a molded object and the workability | operativity of extrusion molding can be improved.

  Furthermore, by arranging and sintering a shielding material containing a carbonaceous material around the molded body, oxygen in the air atmosphere is used for combustion of the shielding material, and the surrounding of the molded body becomes an oxygen-free atmosphere. The molded body can be effectively prevented from burning and fired at a low cost.

  In addition, by attaching any of the above honeycomb structures to the canister, the reliability of the canister can be improved and the price of the canister can be reduced.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  The honeycomb structure of the present invention adsorbs and desorbs gas such as gasoline vapor, and is used, for example, in the fuel evaporation prevention device shown in FIG. 1, and connects the main canister 1, the sub-canister 2, and both. The main canister 1 is composed of a connecting passage 3, and the main canister 1 is, for example, a container having a diameter of 100 mm and a length of 127 mm filled with activated carbon 4 having a predetermined particle size distribution, and the sub canister 2 equipped with the honeycomb structure 5 of the present invention is connected. They are connected in series via the passage 3. In this fuel evaporation prevention device, the gasoline vapor generated in the gasoline tank 7 while the engine 6 is stopped is introduced in the order of the main canister 1 and the sub-canister 2 through the charge passage 8 and the connection passage 3. When this gasoline vapor passes through the main canister 1 and the sub-canister 2, a fuel component such as hydrocarbon (HC) is adsorbed on the activated carbon 4 or the honeycomb structure 5, The mixed air is released into the atmosphere. Further, when the engine 6 is driven, fuel components such as hydrocarbon (HC) adsorbed by the main canister 1 are desorbed by the negative pressure generated in the intake passage 11 provided with the throttle valve 10, and the purge passage 12, It is supplied to the engine 6 through the intake passage 11.

  As shown in FIG. 2, the honeycomb structure 5 has an outer periphery made of a clay-like substance such as activated carbon and knot clay, ball viscosity, ball clay, zeolite, bentonite, hydrous magnesium silicate fiber, halloysite clay, flint clay and the like. A wall 51 and a cell 52 defined by a plurality of partition walls 53 are provided inside the outer peripheral wall 51, and fuel such as hydrocarbon (HC) contained in gasoline vapor by the outer peripheral wall 51 and the partition walls 53 forming each cell 52. Adsorbs and desorbs components.

  This fuel component is mainly composed of various hydrocarbons (HC) such as butane, n-pentane, i-octane, n-pentene, cyclohexane and toluene.

  The activated carbon contributes to the adsorption and desorption of these fuel components, and the clay-like substance contributes to the maintenance of the shape of the honeycomb structure. By making the honeycomb structure containing activated carbon and the clay-like substance, a granular structure is obtained. Compared with the case where the sub-canister 2 is filled with activated carbon, the pressure loss generated inside the sub-canister 2 can be greatly reduced.

  Here, in the honeycomb structure 5 of the present invention, when the volume ratio of the pores having a diameter of 1 nm to 6 nm to the pores having a diameter of 1 nm to 12 nm existing in the outer peripheral wall 51 and the partition wall 53 is measured using a gas adsorption method, It is important to set it as 72 to 83%.

  The pores having a diameter of 1 to 6 nm mainly contribute to the adsorption of the fuel component, and the pores having a diameter larger than 6 nm and a diameter of 12 nm or less mainly contribute to the desorption of the fuel component. The volume ratio was set to 72 to 83% when less than 72%, the molecular diameter of various hydrocarbons (HC) such as butane, n-pentane, n-pentene, cyclohexane, toluene and i-octane was 0.43 to 0.43. This is because these fuel components cannot be adsorbed efficiently because of the wide range of 0.74 nm. On the other hand, if the volume ratio exceeds 83%, the adsorption performance is remarkably increased, but the desorption performance is lowered. Therefore, in order to maintain a balance between the adsorption performance and the desorption performance and to obtain a honeycomb structure having both performances, it is important to set the volume ratio to 72 to 83%.

In order to obtain the honeycomb structure 5 as described above, the pore structure of the powdered activated carbon used as a starting material is important, as will be described later. For example, when measured using a gas adsorption method, a volume of pores is 1000 mm ³ / g with a diameter 1Nm～12nm, the volume of pores having a diameter 1nm~6nm may be used powdered activated carbon structure is a 720~830mm ³ / g.

  Further, the honeycomb structure of the present invention does not exclude pores having a diameter of less than 1 nm or pores having a diameter of more than 12 nm, and there is no problem even if these pores are present.

  Furthermore, in order to maintain a balance between adsorption performance and desorption performance, the pore volume with a diameter of 1 nm to 12 nm is defined as a micropore (pore with a diameter of 0.8 nm to 2 nm) as defined by the International Genuine Applied Chemical Association (IUPAC). And 84 to 96% of the total volume of the mesopores (pores having a diameter of 2 nm to 50 nm).

Further, in the honeycomb structure 5 of the present invention, when the pores existing in the outer peripheral wall 51 and the partition wall 53 are measured using a gas adsorption method, the pore volume with a diameter of 2 nm is 140 mm ³ / g or more and the diameter is 3 nm. It is preferable to have a structure with a pore volume of 120 mm ³ / g or more and a pore volume with a diameter of 4 nm of 90 mm ³ / g or more, so that higher adsorption performance can be maintained over a long period of time.

  The main components of the fuel component are butane having a molecular diameter of 0.43 nm, n-pentane and n-pentene having a molecular diameter of 0.63 nm, cyclohexane having a molecular diameter of 0.67 nm, toluene having a molecular diameter of 0.69 nm, molecular diameter. I-octane of 0.74 nm or the like, and according to the molecular kinetic theory, the pore diameter of the honeycomb structure 5 is appropriate to be about 4 to 5 times the adsorption molecular diameter. As a result of diligent investigation of the pore structure, it was found that the adsorption capacity can be exhibited almost according to the size of the molecular diameter by defining the pore volume of each pore of diameter 2 nm, 3 nm and 4 nm as described above. It was.

  That is, although any of the above main components is adsorbed to each pore, the adsorption ratio of butane having a molecular diameter of 0.43 nm is high in the ratio of adsorption by the pore having a diameter of 2 nm, and n-pentane and n having a molecular diameter of 0.63 nm. -Adsorption of pentene, cyclohexane with a molecular diameter of 0.67 nm and toluene with a molecular diameter of 0.69 nm increases the ratio of adsorption by pores with a diameter of 3 nm. Further, the adsorption of i-octane having a molecular diameter of 0.74 nm increases the ratio of pores having a diameter of 4 nm.

  Examples of the gas adsorption method include a nitrogen adsorption method, a helium adsorption method, a fluorine adsorption method, and an argon adsorption method. The nitrogen adsorption method is preferable from the viewpoint of cost.

  In addition, if pores having an extremely large diameter are present, the adsorption performance of the honeycomb structure is deteriorated. Therefore, the pore diameter is preferably less than 600 nm.

  Here, in order to measure the pore diameter and pore volume, after putting powdered activated carbon obtained by pulverizing the honeycomb structure into a container, first, as a pretreatment, vacuum deaeration is performed, and the mixture is heated to 150 ° C. Remove foreign substances such as impurities and water adhering to the activated carbon. Thereafter, the entire container is cooled with liquid nitrogen to a liquid nitrogen temperature (77 K), and a known amount of nitrogen gas is injected into the container while changing the pressure. Then, using the capillary condensation phenomenon that occurs according to the Kelvin equation (a phenomenon in which nitrogen entering the smaller pores saturates and aggregates at a lower pressure), the relative pressure (= adsorption equilibrium pressure / saturated vapor pressure) is plotted on the horizontal axis. In addition, the pore diameter and the pore volume may be calculated from an adsorption isotherm in which the amount of nitrogen adsorbed on the activated carbon is plotted on the vertical axis. Regarding the volume ratio, the pore volume having a diameter of 1 nm to 12 nm may be measured, for example, every 1 nm in diameter, and the ratio may be calculated after counting the pore volume in each range of diameter 1 nm to 12 nm and diameter 1 nm to 6 nm. Moreover, what is necessary is just to calculate according to the above-mentioned method also about the measurement of the pore diameter and pore volume of the powder of the activated carbon which is a starting material.

  Also, it has adsorption performance of hydrocarbon gas, and the adsorption amount of hydrocarbon gas is preferably 3.2 g / 100 ml or more, and it can be used as an adsorbent for canisters because it can reduce leakage into the atmosphere. Can do. Furthermore, the adsorption amount of the hydrocarbon-based gas is more preferably 4.0 g / 100 ml or more.

In order to obtain the honeycomb structure 5 as described above, the pore structure of the powdered activated carbon used as a starting material is important. For example, when measured using a gas adsorption method, the pore volume having a diameter of 2 nm is used. Is 400 mm ³ / g or more, the pore volume of 3 nm in diameter is 300 mm ³ / g or more, and the powdery activated carbon having a structure in which the pore volume of 4 nm in diameter is 30 mm ³ / g or more may be used. .

Furthermore, when the pores existing in the outer peripheral wall 51 and the partition wall 53 are measured using a gas adsorption method, the pore volume with a diameter of 8 nm is 50 mm ³ / g or more, and the pore volume with a diameter of 10 nm is 40 mm ³ / g or more. In addition, it is preferable to have a structure with a pore volume of 12 mm in diameter and 30 mm ³ / g or more. By using such a pore structure, good desorption performance can be maintained for a long time.

  As described above, it is appropriate that the pore diameter of the honeycomb structure 5 is about 4 to 5 times the adsorbed molecular diameter. However, the applicant of the present application has studied improvement of the desorption performance of the honeycomb structure 5. As a result, it was found that desorption performance can be exhibited by defining the pore volume of each pore having a diameter of 8 nm, 10 nm, and 12 nm as described above.

  That is, when the fuel component is adsorbed in each pore and then desorbed, butane having a molecular diameter of 0.43 nm is mainly desorbed from a pore having a diameter of 8 nm, n-pentane having a molecular diameter of 0.63 nm, and n- The elimination of pentene, cyclohexane with a molecular diameter of 0.67 nm and toluene with a molecular diameter of 0.69 nm mainly contributes to pores with a diameter of 10 nm, and the elimination of i-octane with a molecular diameter of 0.74 nm contributes to pores with a diameter of 12 nm. In particular, the removal performance when used as a canister for gasoline can be made high.

The honeycomb structure 5 of the present invention includes alumina (Al ₂ O ₃ ), silica (SiO ₂ ), calcia (CaO), magnesia (MgO), spinel (MgAl ₂ O ₄ ), forsterite (Mg ₂ SiO _4). ) (Hereinafter referred to as an additive) is preferably added.

  The specific heat of these additives is 760 J / (kg · K) or higher and higher than the specific heat of activated carbon 400 J / (kg · K), so it easily absorbs and stores the heat of activated carbon. The decrease in the temperature of the activated carbon is suppressed by the heat previously stored in the agent, and the amount of gasoline vapor desorbed from the activated carbon can be increased. What is necessary is just to measure the specific heat of an additive and activated carbon based on JISR1611-1997, and it is more suitable that the said additive is further contained 20-50 mass% in a honeycomb structure.

  Furthermore, it has a hydrocarbon gas adsorption / desorption performance, and its desorption rate is preferably 50% or more, and can be more suitably used as an adsorption / desorption agent for canisters.

  In particular, the adsorption and desorption of hydrocarbon gases having a molecular diameter of 0.4 to 0.74 nm, such as propane, butane, ethane, propylene, butene, n-pentane, n-pentene, cyclohexane, toluene, i-octane, etc. It is suitable for separation.

  Here, the desorption rate is a characteristic value determined by a repeated adsorption / desorption test of hydrocarbon gas. Specifically, a cycle in which a hydrocarbon-based gas having a concentration of 50% is introduced from the axial direction of the honeycomb structure, adsorbed until saturation, and then nitrogen gas is also flowed from the axial direction to desorb, is defined as one cycle. The mass (W1) of the honeycomb structure after saturated adsorption of hydrocarbon gas at the 40th cycle and the mass (W2) of the honeycomb structure after desorption of hydrocarbon gas at the end of the 40th cycle were measured by the following formula: Find it.

Desorption rate (%) = (W1-W2) / W1 × 100
FIG. 3 shows a honeycomb structure 5 according to the present invention, in which partition walls 53 defining the honeycomb structure 5 are formed in the axial direction, the thickness thereof is 0.35 mm or less, and the outer peripheral wall 51 has a thickness. In addition to being 0.5 mm or more, it is preferable that the reinforcing portion 54 is formed in the vicinity of a portion where the outer peripheral wall 51 and the partition wall 53 are in contact with each other.

  In general, when the number of cells is constant, reducing the partition wall thickness and increasing the cell aperture ratio can reduce pressure loss and improve adsorption performance. There is a trade-off relationship that strength decreases. Here, the aperture ratio refers to the ratio of the area of the opened cells to the area of the cross section perpendicular to the axial direction of the honeycomb structure 5. When the honeycomb structure 5 is mounted on, for example, a sub-canister, in order to satisfy the trade-off relationship, the partition wall 53 defining the honeycomb structure 5 has a thickness of 0.35 mm or less, and the outer peripheral wall 51 has a thickness of 0. It is preferable that the reinforcing portion 54 is formed in the vicinity of the portion where the outer peripheral wall 51 and the partition wall 53 are in contact with each other, and the opening ratio of the cell 52 is preferably 50% or more.

  Further, if the outer peripheral wall 51 is thin, it may be damaged due to insufficient strength as a honeycomb structure depending on vibrations that the automobile receives on a rough road or the like, and the outer peripheral wall 51 has a thickness of 0.5 mm or more. As a result, the required strength can be maintained even when the vehicle is subjected to strong vibrations while the vehicle is running, and therefore, the vehicle is not damaged.

  In order to obtain the honeycomb structure 5 as described above, it is necessary to design a mold to be attached to the extruder in consideration of the shrinkage rate before the sintering and the size and arrangement of the reinforcing portion. More specifically, the thickness of the outer peripheral wall and the partition wall is determined by the width of the groove provided in the mold. For example, when firing conditions are set such that the shrinkage rate is 10%, What is necessary is just to set the width | variety of a groove | channel large 10% with respect to the thickness of a partition. In addition, since the cell opening ratio is defined as the ratio of the area of the open cell to the area of the cross section perpendicular to the axial direction of the honeycomb structure, the open cell and the reinforcing part as well as the thickness of the outer peripheral wall and the partition wall The shape of the mold may be set in consideration of the shrinkage rate.

  Further, the cross-sectional shape of the cell perpendicular to the axial direction is preferably a hexagon as shown in FIG. 4, and when the diameter of the outer peripheral wall of the honeycomb structure is constant, the cross-sectional shape of the cell perpendicular to the axial direction is six. This is because when the rectangular shape is used, the area in which the gasoline vapor passing through the cell contacts the partition wall can be increased and the gasoline vapor can be adsorbed in a short time compared to the case where the cell has a square cross-sectional shape.

  In addition, when the diameter of the outer peripheral wall of the honeycomb structure is constant, when the cross-sectional shape of the cell perpendicular to the axial direction is any of a triangle, a circle, and an ellipse, the partition wall is smaller than when the cross-sectional shape of the cell is a square. The area of the cross section can be increased and the strength can be increased.

  In addition, what is necessary is just to provide a groove | channel in the said metal mold | die so that it may become the same shape as the cross-sectional shape of a cell, in order to make the cross-sectional shape of a cell into the above shapes.

  Moreover, it is preferable that the weight ratio of the said activated carbon and a clay-like substance is 60: 40-30: 70. If the activated carbon exceeds 60 parts by weight (the clay-like substance is less than 30 parts by weight), the honeycomb structure may have insufficient strength when the honeycomb structure is large. This is because if the amount is less than 30 parts by weight (the amount of clay-like material exceeds 70 parts by weight), the amount of activated carbon in the honeycomb structure is reduced, and the usable time as an adsorbent may be reduced.

The activated carbon is preferably woody activated carbon. In the honeycomb structure using coconut husk activated carbon, the specific surface area contributing to the adsorption of the organic compound is as large as about 900 to 1300 m ² / g, and the adsorption performance is good, but the average fine particle contributing to the desorption of the organic compound such as gasoline vapor. The pore diameter is as small as about 1.75 nm and the desorption performance is inferior. Moreover, in the honeycomb structure using carbon black, the average pore diameter is as large as 3 nm and the desorption performance is good, but the specific surface area is as small as about 300 to 650 m ² / g and the adsorption performance is inferior. On the other hand, the wood activated carbon honeycomb structure according to the present invention has a specific surface area of 900 to 1300 m ² / g, diameters of 2 nm, 3 nm, and 4 nm of pore volumes of 140 mm ³ / g or more, 120 mm ³ / g or more, and 90 mm ^{3, respectively.} This is because the organic compound adsorption performance and desorption performance can be improved.

  In addition, the above clay-like substance is composed of Kibushi clay, Sasame clay, Ball clay, Zeolite, Bentonite, Hydrous magnesium silicate fiber, considering the ease of pore formation, cost, and availability of the compact. It is preferably at least one selected from the group.

When high strength is required for the honeycomb structure, at least one kind of clay-like material of Kibushi clay, Sasame clay, and ball clay containing 45 to 57% by mass of SiO ₂ and 26 to 37% by mass of Al ₂ O ₃ Is preferably used. The SiO ₂ contained in the clayey material 45-57 wt%, by the _Al 2 _{O 3} and 26-37 wt%, and the plasticity index 44 or more, which is defined as the difference between the liquid limit and plastic limit This is because the plasticity required for molding can be obtained and the strength of the honeycomb structure can be easily secured.

  Moreover, when high desorption performance is required for the honeycomb structure, it is more preferable that the honeycomb structure is at least one selected from the group consisting of zeolite, bentonite, and hydrous magnesium silicate fiber.

When zeolite is selected as the clay-like substance, among natural zeolite, synthetic zeolite, and artificial zeolite, artificial zeolite or synthetic zeolite having high fuel component adsorption performance is preferable. There are two factors that affect the adsorption performance of zeolite, the SiO ₂ / Al ₂ O ₃ molar ratio and the pore diameter. Zeolite _has a property of having a different adsorption characteristics by SiO 2 / _Al 2 _{O 3} molar ratio (5 to 800). If the molar ratio of SiO ₂ / Al ₂ O ₃ is reduced, it becomes hydrophilic and strongly adsorbs water and polar substances. Conversely, if the molar ratio is increased, it becomes hydrophobic and adsorbs organic molecules more selectively than water. Because of these characteristics, among the synthetic zeolites, high silica zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 10 or more is particularly suitable.

  In addition, as the hydrous magnesium silicate fiber, a natural clay-like fibrous mineral such as sepiolite, attapulgite or palygorskite can be used.

As inevitable impurities, Fe ₂ O ₃ is 1.4% by mass or less, K ₂ O is 1.8% by mass or less, Na ₂ O is 1.1% by mass or less, and loss on ignition (Ig. Loss) is 17% by mass. The following may be included.

In addition, the total of inevitable impurities is preferably 2% by mass or less in terms of oxide, segregation of inevitable impurities in the honeycomb structure can be reduced, and local strength reduction can be prevented. Here, as inevitable impurities, for example, ferromagnetic materials such as Fe, Co, Ni, Ca, Ti, Cr, Mn, Y, Zr, Nb, Sr, Fe ₂ O ₃ , Cr ₂ O ₃ , MnO, Examples thereof include weak magnetic substances such as NiO and CuO, and fluorescent X-ray analysis may be used to detect these inevitable impurities.

  Next, the manufacturing method of the honeycomb structure of the present invention will be described.

In order to obtain the honeycomb structure of the present invention, first, powdery activated carbon 9 to 18 g and clay-like materials 21 to 12 g such as Kibushi clay, Sasame clay, zeolite, bentonite, hydrous magnesium silicate fiber were prepared. In addition, various auxiliary agents suitable for longitudinal extrusion molding, methylcellulose 0.6 to 1.8 g, polyvinyl alcohol 2.1 to 4.5 g and polyethylene glycol monoacrylate 9.0 to 10.5 g and a predetermined amount of water. Add, and mix, stir and knead in a kneader (Needer). When high desorption performance is required for the honeycomb structure, alumina (Al ₂ O ₃ ), silica (SiO ₂ ), calcia (CaO), magnesia (MgO), spinel (MgAl ₂ O ₄ ), forsterite ( A total of 5 to 15 g of at least one of Mg ₂ SiO ₄ ) can also be added.

  Here, in order to make the total of inevitable impurities 2.0% by mass or less in terms of oxide, a predetermined amount of water is added to the powdered activated carbon and the clay-like substance, and a mixture is formed with an electromagnet or a permanent magnet. After removing inevitable impurities through a magnetic field, 0.6 to 1.8 g of methyl cellulose, 2.1 to 4.5 g of polyvinyl alcohol and 9.0 to 10.5 g of polyethylene glycol monoacrylate are added, and a kneader ( Mixing, stirring, and kneading may be performed using a Needer. The weight ratio of activated carbon and clay-like substance contained in the kneaded body is 60:40 to 30:70, and the ratio of methylcellulose, polyvinyl alcohol and polyethylene glycol monoacrylate to be added to the kneaded body is 2 to 6 masses, respectively. %, 7 to 15% by mass, and 30 to 35% by mass, and this range is preferable. If the addition amount is less than the lower limit of this range, the shape retention may be insufficient depending on the size of the molded body, and if it is more than the upper limit, the viscosity becomes too high and workability may be deteriorated. It is. From the viewpoint of both shape retention and workability of the molded article, the range of the amount of the molding aid added is preferably within the above range.

In the obtained honeycomb structure, the pore volume with a diameter of 2 nm is 140 mm ³ / g or more, the pore volume with a diameter of 3 nm is 120 mm ³ / g or more, and the pore volume with a diameter of 4 nm is 90 mm ³ / g or more. To measure the activated carbon, the pore volume with a diameter of 2 nm is 400 mm ³ / g or more, the pore volume with a diameter of 3 nm is 300 mm ³ / g or more, and the diameter is 4 nm when measured using a gas adsorption method. What is necessary is just to use the powdery thing whose pore volume is 30 mm < ³ > / g or more.

In order to obtain a structure in which the pore volume of 8 nm in diameter is 50 mm ³ / g or more, the pore volume of 10 nm in diameter is 40 mm ³ / g or more, and the pore volume of 12 nm in diameter is 30 mm ³ / g or more,
As the activated carbon, when measured by a gas adsorption method, the pore volume of 8 nm in diameter is 300 mm ³ / g or more, the pore volume of 10 nm in diameter is 250 mm ³ / g or more, and the pore volume of 12 nm in diameter is 200 mm ^3. / Powder or more in powder form may be used.

  The activated carbon may have an average particle diameter of 20 to 30 μm, and the clay-like substance may contain 90% by mass or more of particles having a particle diameter of 5 μm or less, and may not include particles having a particle diameter of 75 μm or more.

  By making the clay-like material having a particle size of 5 μm or less 90% by mass or more and removing the clay-like material having a particle size of 75 μm or more, the adhesive force generated between the particles of the clay-like material is increased, and the molded product is maintained. This is because the shape can be maintained.

  As various auxiliary agents suitable for longitudinal extrusion, at least one of ethyl cellulose, propyl cellulose, ethyl methyl cellulose, propyl methyl cellulose, and crystalline cellulose is used as a substitute for methyl cellulose, and polyethylene vinyl alcohol and polyethylene glycol mono are used as substitutes for polyvinyl alcohol. As a substitute for acrylate, at least one selected from the group consisting of polypropylene glycol monomethacrylate and polypropylene glycol tetramethylene glycol monomethacrylate may be used.

  Next, the obtained kneaded body is put into an extrusion molding machine equipped with a predetermined die in a honeycomb shape, and pressure is applied to obtain a honeycomb-shaped formed body. Here, there are two methods of extrusion molding, a piston method and an auger method.

  In the piston system, as shown in FIG. 5, a rod-shaped kneaded body 15 is supplied from the upper part of the extruder to a vertical jacket 14 having a mold 13 fixed to the lower part of the extruder, and a hydraulic piston 16 or the like is provided from the upper part. Since this is a vertical extrusion molding machine, deformation in the side surface direction of the molded body 21 is suppressed, and it is suitable for molding complex shapes and relatively large products.

  Further, when the supply of the kneaded body 15 is unstable, a claw-like defect or a cut-off defect may occur on the outer peripheral wall of the molded body 21, but a donut-shaped ring 22 is formed on the front surface of the mold 13. And adjusting the inner diameter thereof to stably supply the raw material and form the reinforcing portion 54 to prevent the above defects.

  In the auger system, a horizontal extruder as shown in FIG. 6 is often used. After the kneaded body 15 or the mixed raw material is introduced from the inlet 17, the pug screw 18 is rotated and pressurized to knead. It is pushed out into the vacuum chamber 19. After vacuuming in the vacuum chamber 19 and degassing, it is transferred, and further, the auger screw 20 is kneaded by pressurizing and rotating to form a molded body 21 from the mold 13 fixed to the tip of the extruder. Extruded. Even in this method, a donut-shaped ring (not shown) is arranged on the front surface of the mold 13 and the inner diameter thereof is adjusted to stably supply the raw material and to form the reinforcing portion 54. It is preferable to prevent defects in the shape.

  In addition, this method is superior to the piston method in that it can be continuously formed and is excellent in mass productivity.

  However, since the molded body is extruded in the lateral direction, if the kneaded body is too soft, there is a risk of deformation without maintaining its own weight, and the molding aid is a group consisting of sorbitan monocaprylate composite ester, propylene glycol, and crystalline cellulose. It is necessary to improve the shape retention of the molded body by changing to at least one selected from the above and methylcellulose. In particular, methylcellulose is effective in preventing the turning and cracking of the outer peripheral wall surface, which tends to occur during extrusion, and improving fluidity.

  The sorbitan monocaprylate complex ester to be added to the kneaded body is 0.9 to 1.5 g (3 to 5% by mass), propylene glycol is 0.3 to 0.9 g (1 to 3% by mass), crystals It is preferable that cellulose is 0.3 to 0.9 g (1 to 3% by mass) and methyl cellulose is 0.9 to 3 g (3 to 10% by mass), and the addition amount should be less than the lower limit of these molding aids. For example, depending on the size of the molded body, the shape retention may be insufficient. If the amount added is larger than the upper limit, the viscosity becomes too high, and the workability may deteriorate. From the viewpoint of shape retention and workability of the molded product, the above range is preferable as the range of the amount of the molding aid added.

  Further, as various auxiliary agents suitable for extrusion in the transverse direction, at least one selected from the group consisting of ethylene glycol as a substitute for propylene glycol and ethylcellulose, propylcellulose, ethylmethylcellulose, ethylmethylcellulose, propylmethylcellulose as a substitute for crystalline cellulose Seeds may be used.

  Next, since the extruded molded body contains a lot of moisture and the like, a drying step is necessary, and the temperature is important to be 40 to 70 ° C.

  The reason why the drying temperature is 40 to 70 ° C. is that if it is less than 40 ° C., it takes a long time to dry the molded body, which is inefficient. On the other hand, if the temperature exceeds 70 ° C., the molded body cracks. This is because it becomes easier. It is necessary to dry at 40-70 degreeC from both sides of productivity and crack prevention.

  In general, a bulk-shaped molded body is subjected to hot air drying using an electric heater, a gas heater, or the like from the outside of the molded body, or drying using a microwave in combination. The honeycomb-shaped formed body is partitioned and formed with a plurality of partition walls inside the outer peripheral wall. Since only the outer peripheral wall is dried first only by drying by external heating, the drying shrinkage rate of the outer peripheral wall and the partition wall A difference arises between the drying shrinkage rate and defects such as cracks occur. For this reason, it is preferable to dry with hot air inside the cell defined by the partition walls so that the outer peripheral wall and the partition walls are uniformly dried. In particular, drying by the following procedure is more preferable in that it can facilitate the volatilization and release action of the molding aid filling the pores.

  First, after passing hot air of 40 to 45 ° C. from one end to the inside of the cell for 30 to 40 seconds, hot air is passed from the other end at the same temperature and for the same time. Next, after performing natural drying for 1 to 2 hours at room temperature, after passing hot air of 45 to 70 ° C. from one end to the inside of the cell for 15 to 25 minutes, hot air is also supplied from the other end at the same temperature and the same time. Pass through.

  In addition, when methylcellulose is included in the molding aid, methylcellulose gelates and cures at a relatively low temperature of about 50 to 80 ° C. Therefore, it is poured into hot water of about 50 to 80 ° C to cure the surface. Thereafter, a method such as hot air drying is also suitable.

  The dried molded body is cut into a predetermined length. As a cutting method, there are a method of cutting using a piano wire or the like before or during drying, a method of cutting a dried one with a cutter blade, and the like.

  Next, it is important that the dried and cut shaped body is fired in a firing furnace such as an electric furnace, a gas furnace, a vacuum furnace, and the temperature is fired at 600 to 1300 ° C. If the temperature is lower than 600 ° C., the honeycomb structure is not sufficiently sintered, so that the strength is remarkably reduced. If the temperature exceeds 1300 ° C., the pores of the honeycomb structure are not sufficiently formed and the adsorption performance is lowered. Because. In order to obtain the strength and adsorption performance required for the honeycomb structure, it is necessary to fire at 600 to 1300 ° C.

  When at least one of Kibushi clay, Sasame clay, and ball clay is selected as the clay-like substance, it is preferably calcined at 1000 to 1300 ° C., among zeolite, bentonite, and hydrous magnesium silicate fiber. When at least one type is selected, firing at 600 to 1000 ° C. is preferable.

  Here, the firing atmosphere is preferably a non-oxidizing atmosphere, for example, a nitrogen atmosphere, an inert gas atmosphere, or a nitrogen gas atmosphere. A shielding material containing a quality material may be disposed around the molded body and sintered. By arranging a shielding material containing a carbonaceous material around the molded body, oxygen in the atmosphere is used for combustion of the carbonaceous material, and the atmosphere around the molded body becomes an oxygen-free atmosphere, and the combustion of the molded body is effective. This is because the molded body may be buried in a carbonaceous material. The above-mentioned carbonaceous material refers to activated carbon such as granular powder, coke, charcoal, anthracite, elementary ash, carbon black, etc., whose composition contains 80% or more of carbon and whose ignition temperature is 500 ° or more is durable. It is also excellent in properties. Moreover, the said shielding material can be used repeatedly many times until it incinerates.

  If the honeycomb structure of the present invention is manufactured using the manufacturing method as described above, it is possible to maintain good adsorption performance, and to obtain an inexpensive honeycomb structure without being damaged for a long time.

  As described above, the case where the honeycomb structure of the present invention is used for a canister has been described, but the honeycomb structure of the present invention is separated by adsorption of ozone, nitrogen, hydrogen, carbon monoxide, carbon dioxide, hydrogen chloride, hydrogen fluoride, etc. It can also be used for adsorption of rare gas such as radioactive krypton and xenon generated by boiling water reactor, occlusion of natural gas such as methane, methanol or ethanol adsorption refrigerator, electric double layer capacitor, water purifier and the like.

  Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

(Example 1)
Powdered wood activated carbon having a predetermined pore diameter and pore volume and a clay-like substance shown in Table 1 prepared at a weight ratio of 45:55, 35% by mass of additives shown in Table 1, and a predetermined amount of methylcellulose Polyvinyl alcohol, polyethylene glycol and water were added, and the mixture was mixed, stirred and kneaded with a kneader (Needer). However, the additive was not added to the sample in which a horizontal line was given in the column of additive in Table 1. Next, the obtained kneaded body is put into a vertical extruder equipped with a mold, and by applying a predetermined pressure, the cross-sectional shape of the cell perpendicular to the axial direction is square, Of 200 / (inch) ² was obtained.

  The molded body was dried by passing hot air at 55 ° C. into the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut compact was put into an electric furnace, and coke was placed around the compact, and then fired at a temperature shown in Table 1 for a holding time of 2 hours. A honeycomb structure having a volume ratio of pores having a diameter of 1 to 6 nm to pores having a diameter of 12 nm and pore volumes of pores having diameters of 2 nm, 3 nm, 4 nm, 8 nm, 10 nm, and 12 nm shown in Table 1 was obtained. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

  Here, the pore diameter and pore volume of the pores were measured by a nitrogen adsorption method. Specifically, using a high-precision fully automatic gas adsorption device (BELSORP 36) manufactured by Nippon Bell Co., Ltd., the powder obtained by pulverizing the honeycomb structure was put into a container, vacuum degassed, and heated to 150 ° C. Then, foreign matters such as impurities and water adhering to the pulverized powder were removed. Thereafter, the entire container was cooled with liquid nitrogen to a liquid nitrogen temperature (77 K), and a known amount of nitrogen gas was injected into the container while changing the pressure. Then, using the capillary condensation phenomenon that occurs according to the Kelvin equation (a phenomenon in which nitrogen entering the smaller pores saturates and aggregates at a lower pressure), the relative pressure (= adsorption equilibrium pressure / saturated vapor pressure) is plotted on the horizontal axis. The pore diameter and pore volume were calculated from an adsorption isotherm in which the amount of nitrogen adsorbed on the activated carbon was plotted on the vertical axis.

  For the evaluation of the adsorption performance of the obtained honeycomb structure, ASTM (United States Standard Test Standard) D5228-92 (Reapproved 2002) was used to measure the adsorption amount of butane which is the main component of gasoline vapor. If the butane adsorption amount is large, the gasoline vapor adsorption performance by the honeycomb structure is high, and if the butane adsorption amount is small, the gasoline vapor adsorption performance is low. Table 1 shows the measurement results of the butane adsorption amount.

Further, the desorption performance of the obtained honeycomb structure was evaluated by repeated adsorption and desorption tests of ethane. More specifically, a cycle in which 50% concentration of ethane is introduced from the axial direction of the honeycomb structure, adsorbed until saturation, and then desorbed by flowing nitrogen gas in the same axial direction, is regarded as one cycle. The mass of the honeycomb structure after ethane saturation adsorption at the cycle and after ethane desorption at the end of the 40th cycle was measured, and the desorption rate was calculated. A high desorption rate means that ethane and butane having the same molecular diameter as ethane have high desorption performance, that is, gasoline vapor desorption performance. The measurement results of the ethane desorption rate are shown in Table 1.

  From Table 1, the sample No. whose volume ratio is less than 72% is shown. Sample Nos. 1 and 2 have a butane adsorption amount as low as 2.2 g / 100 ml or less and a volume ratio exceeding 83%. No. 8 had a low ethane elimination rate of 40%. On the other hand, Sample No. of the present invention having a volume ratio of 72 to 83%. 3 to 7 and 9 to 11 show that the butane adsorption amount is 3.0 g / 100 ml or more and the ethane desorption rate is 45% or more, which is favorable.

Particularly, sample Nos. ^{3 to 7 having} a structure in which the pore volume of 2 nm in diameter is 140 mm ³ / g or more, the pore volume of 3 nm in diameter is 120 mm ³ / g or more, and the pore volume of 4 nm in diameter is 90 mm ³ / g or more. The butane adsorption amount is even higher at 3.2 g / 100 ml or more, and the adsorption performance is good.

In addition, the above sample No. 3-7 and no. 11 has a structure in which the pore volume of 8 nm in diameter is 50 mm ³ / g or more, the pore volume of 10 nm in diameter is 40 mm ³ / g or more, and the pore volume of 12 nm in diameter is 30 mm ³ / g or more. The separation rate is as high as 50% or more and good.

  Furthermore, Sample No. with additive added. Nos. 12 to 17 have a high ethane desorption rate of 60% or more, and sample No. 1 to 11 show that the desorption performance is superior.

(Example 2)
Powdered wood activated carbon and Kibushi clay are mixed at a weight ratio of 45:55, and a predetermined amount of methylcellulose, polyvinyl alcohol, polyethylene glycol and water are added and mixed, stirred and kneaded by a kneader (Needer). went. Next, the obtained kneaded body is put into a vertical extruder equipped with a mold, and a predetermined pressure is applied so that the reinforcing portion is located near the portion where the outer peripheral wall of the honeycomb structure and the partition wall are in contact with each other. A honeycomb-shaped formed body having the above and a honeycomb-shaped formed body having no reinforcing portion were produced. In any of the molded bodies, the cross-sectional shape of the cells perpendicular to the axial direction was square, and the number of cells was 200 / (inch) ² . The molded body was dried by passing hot air at 55 ° C. into the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut molded body was put into an electric furnace, coke was placed around the molded body, and then fired at a temperature of 1200 ° C. and a holding time of 2 hours. Got the body. The pore volumes of 2 nm, 3 nm, and 4 nm in diameter were measured by the method shown in Example 1, and were found to be 250 mm ³ / g, 210 mm ³ / g, and 150 mm ³ / g, respectively.

  As for the evaluation of the gasoline vapor adsorption performance of the obtained honeycomb structure, the butane adsorption amount was measured using ASTM (United States Standard Test Standard) D5228-92 (Reapproved 2002) in the same manner as in Example 1.

Further, regarding the strength of the honeycomb structure, a strength was applied to the honeycomb structure in a direction perpendicular to the axis and parallel to the partition walls to break the honeycomb structure (B-axis compression strength, hereinafter simply referred to as compression strength).

  As can be seen from Table 2, the sample No. Nos. 18 to 26 are sample Nos. Having no reinforcing portion. Compared with 27 to 35, a honeycomb structure having partition walls and outer peripheral walls having the same thickness has a high compressive strength and is good.

  Sample No. 30-32 or sample no. As can be seen from the compression strength of 33 to 35, the sample No. The compressive strength of 30 and 33 is as low as 1.1 MPa or less, whereas the sample No. The compressive strength of 31, 32, 34, and 35 is as high as 1.2 MPa or more, which is good.

  In addition, Sample No. with a partition wall thickness exceeding 0.35 mm. 27-29 butane adsorption amount is 3.5 g / 100 ml or less, whereas the partition wall thickness is 0.35 mm or less. Since 30 to 35 have a large effective area for adsorption, the butane adsorption amount is as large as 5.4 g / 100 ml or more, which is favorable.

(Example 3)
Powdered wood activated carbon and Kibushi clay are mixed at a weight ratio of 45:55, and a predetermined amount of methylcellulose, polyvinyl alcohol, polyethylene glycol and water are added and mixed, stirred and kneaded by a kneader (Needer). went. Next, the obtained kneaded body was put into a vertical extrusion molding machine equipped with a mold, and by applying a predetermined pressure, the number of cells was 200 / (inch) ² , A honeycomb-shaped formed body having a square cell cross-sectional shape perpendicular to the axial direction and a honeycomb-shaped formed body having a hexagonal shape were obtained. The molded body was dried by passing hot air of 55 ° C. into the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut formed body was put into an electric furnace, and coke was placed around the formed body, and then fired at a temperature of 1200 ° C. and a holding time of 2 hours to obtain a honeycomb structure. The pore volume of 2 nm, 3 nm, and 4 nm in diameter was measured by the method shown in Example 1. As a result, all honeycomb structures were 250 mm ³ / g, 210 mm ³ / g, and 150 mm ³ / g, respectively. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

  About the evaluation of the gasoline vapor adsorption performance of the obtained honeycomb structure, the butane adsorption amount was measured using ASTM (United States Standard Test Standard) D5228-92 (Reapproved 2002) as in Example 1.

As for the strength of the honeycomb structure, the B-axis compressive strength (hereinafter simply referred to as compressive strength) was measured in the same manner as in Example 2.

  As can be seen from Table 3, the sample No. 1 in which the cross-sectional shape of the cell perpendicular to the axial direction is square is shown. Compared to Sample No. 37, sample No. No. 36 has a good butane adsorption amount and a high compressive strength.

Example 4
Powdered activated carbon and clay-like substances prepared in the types and weight ratios shown in Table 4 are added with a predetermined amount of methylcellulose, polyvinyl alcohol, polyethylene glycol and water, mixed with a kneader (Needer), stirred, Kneading was performed. Next, the obtained kneaded body is put into a vertical extruder equipped with a mold, and by applying a predetermined pressure, the cross-sectional shape of the cell perpendicular to the axial direction is square, Of 200 / (inch) ² was obtained. The molded body was dried by passing hot air of 55 ° C. into the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut formed body was put into an electric furnace, and coke was placed around the formed body, and then fired at a temperature of 1200 ° C. and a holding time of 2 hours to obtain a honeycomb structure. Table 5 shows the results of measuring the pore volume of 2 nm, 3 nm, and 4 nm in diameter by the method shown in Example 1. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

  About the evaluation of the gasoline vapor adsorption performance of the obtained honeycomb structure, the butane adsorption amount was measured using ASTM (United States Standard Test Standard) D5228-92 (Reapproved 2002) as in Example 1.

Further, the compressive strength was also measured for the strength of the honeycomb structure in the same manner as in Example 2.

  As can be seen from Table 4, sample No. using wood activated carbon. Nos. 38 to 42 are sample Nos. Using coconut shell activated carbon. Compared with 43 to 47, the butane adsorption amount is large and good. Sample No. 38-42 or sample no. In 43 to 47, when the weight ratio of the activated carbon increases, the butane adsorption amount increases, but the compressive strength also decreases. Sample No. in which the weight ratio of activated carbon and Kibushi clay is 60:40 to 30:70. 39-41, no. 44-46 is preferred.

  In this example, Kibushi clay was used as the clay-like substance, but a honeycomb structure that is good even when using a clay mesh, ball clay, zeolite, bentonite, hydrous magnesium silicate fiber, or a mixture thereof. It goes without saying that can be obtained.

(Example 5)
Powdered woody activated carbon and Kibushi clay were added at a weight ratio of 60:40, and water was added and blended to reduce the inevitable impurities through a magnetic field whose strength was appropriately adjusted with an electromagnet. Next, 0.6 to 1.8 g of methyl cellulose, 2.1 to 4.5 g of polyvinyl alcohol, and 9.0 to 10.5 g of polyethylene glycol monoacrylate are added, and mixing, stirring, and kneading are performed using a kneader (Needer). Mixing, stirring, and kneading were performed with a machine (Needer). The obtained kneaded body is put into a vertical extruder equipped with a mold, and by applying a predetermined pressure, the cross-sectional shape of the cells perpendicular to the axial direction is square, and the number thereof is 200 pieces. A honeycomb-shaped formed body having / (inch) ² was obtained. The molded body was dried by passing hot air at 55 ° C. into the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut molded body was put into an electric furnace, coke was placed around the molded body, and then fired at a temperature of 1200 ° C. and a holding time of 2 hours to obtain a honeycomb structure. The pore volume of 2 nm, 3 nm, and 4 nm in diameter was measured by the method shown in Example 1. As a result, all honeycomb structures were 250 mm ³ / g, 210 mm ³ / g, and 150 mm ³ / g, respectively. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

Regarding the amount of inevitable impurities present in the obtained honeycomb structure, Table 5 shows numerical values measured by fluorescent X-ray analysis and converted into oxides. Further, segregation of inevitable impurities was observed with a scanning electron microscope at a magnification of 3000 times. Table 5 shows that no segregation was observed, and x that segregation was observed.

  Sample No. in which the total of inevitable impurities is 2% by mass or less in terms of oxide. 48 to 50 were good because no segregation was observed.

  Sample No. in which the total of inevitable impurities exceeds 2% by mass in terms of oxide. 51 and 52 may cause a partial reduction in strength, and mounting to a canister is inappropriate from the viewpoint of reliability.

(Example 6)
Powdered wood activated carbon and Kibushi clay are mixed at a weight ratio of 45:55, and a predetermined amount of methylcellulose, polyvinyl alcohol, polyethylene glycol and water are added and mixed, stirred and kneaded by a kneader (Needer). went. Next, the obtained kneaded body is put into a vertical extruder equipped with a mold, and by applying a predetermined pressure, the cross-sectional shape of the cell perpendicular to the axial direction is square, Of 200 / (inch) ² was obtained. The molded body was dried by passing hot air at a temperature shown in Table 6 inside the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut formed body was put into an electric furnace, and various shielding materials were arranged around the formed body, and then fired at a temperature shown in Table 6 for 2 hours to obtain a honeycomb structure. The pore volume of 2 nm, 3 nm, and 4 nm in diameter was measured by the method shown in Example 1. As a result, all honeycomb structures were 250 mm ³ / g, 210 mm ³ / g, and 150 mm ³ / g, respectively. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

  About the evaluation of the gasoline vapor adsorption performance of the obtained honeycomb structure, the butane adsorption amount was measured using ASTM (United States Standard Test Standard) D5228-92 (Reapproved 2002) as in Example 1.

In addition, the presence or absence of cracks in the honeycomb structure was also observed.

  As can be seen from Table 6, the sample No. No. 68 had cracks, whereas sample No. 68 of the present invention. 53-67, 69, 70, 72-76 are good without cracks. Sample No. baked above 1300 ° C. No. 71 had a small butane adsorption amount of 1.2 g / 100 ml because the pores were not sufficiently formed. 53-67, 69, 70, 72-76 had good sintering, and the butane adsorption amount was as high as 5.9 g / 100 ml or more.

(Example 7)
A predetermined amount of methylcellulose, polyvinyl alcohol, polyethylene glycol and water are added to powdery wood activated carbon and bentonite prepared at a mass ratio of 45:55, and mixed, stirred, and kneaded with a kneader (Needer). It was. Next, the obtained kneaded body is put into a vertical extruder equipped with a mold, and by applying a predetermined pressure, the cross-sectional shape of the cell perpendicular to the axial direction is square, Of 200 / (inch) ² was obtained. The molded body was dried by passing hot air at a temperature shown in Table 7 inside the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut molded body was put into an electric furnace, and various shielding materials were arranged around the molded body, and then fired at the temperature shown in Table 7 for 2 hours to obtain a honeycomb structure. The pore volume of 8 nm, 10 nm, and 12 nm in diameter was measured by the method shown in Example 1. As a result, all the honeycomb structures were 60 mm ³ / g, 50 mm ³ / g, and 40 mm ³ / g, respectively. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

  The desorption performance of the obtained honeycomb structure was evaluated by repeated adsorption and desorption tests of ethane. The evaluation method is the same as the method shown in Example 1.

In addition, the presence or absence of cracks in the honeycomb structure was also observed.

  As can be seen from Table 7, sample no. No. 92 had cracks, whereas sample No. 92 of the present invention. Nos. 77 to 91, 94, 95 and 96 to 100 have no cracks and are good. Sample No. baked at less than 600 ° C. No. 93 was insufficiently sintered, whereas Sample No. 77 to 91, 94, 95, 96 to 100 had good sintering, and the ethane desorption rate was as high as 50% or more.

(Example 8)
A predetermined amount of sorbitan monocaprylate composite ester, propylene glycol, crystalline cellulose, methylcellulose and water are added to a powdery wood activated carbon and Kibushi clay prepared at a weight ratio of 45:55, and a kneader (Needer) Were mixed, stirred and kneaded. Next, the obtained kneaded body is put into a horizontal extrusion molding machine equipped with a mold, and a predetermined pressure is applied, so that the cross-sectional shape of the cells perpendicular to the axial direction is square, and the number thereof is A honeycomb-shaped formed body of 200 / (inch) ² was obtained. The molded body was dried by passing hot air inside the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut formed body was put into an electric furnace, and various shielding materials were arranged around the formed body, and then fired at a temperature shown in Table 8 for 2 hours to obtain a honeycomb structure. The pore volume of 2 nm, 3 nm, and 4 nm in diameter was measured by the method shown in Example 1. As a result, all honeycomb structures were 250 mm ³ / g, 210 mm ³ / g, and 150 mm ³ / g, respectively. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

  About the evaluation of the gasoline vapor adsorption performance of the obtained honeycomb structure, the butane adsorption amount was measured using ASTM (United States Standard Test Standard) D5228-92 (Reapproved 2002) as in Example 1.

Further, the compressive strength was also measured for the strength of the honeycomb structure in the same manner as in Example 2. Furthermore, the presence or absence of cracks in the honeycomb structure was also observed.

  As can be seen from Table 8, sample no. No. 110 had cracks, whereas sample No. 110 of the present invention. 101-109, 111, 112, 114-120, 122-130 are good without cracks. Sample No. in which methylcellulose was not added was used. No. 121 could not obtain a molded product. Furthermore, sample No. 1 fired above 1300 ° C. No. 113 had a small butane adsorption amount of 1.7 g / 100 ml because the pores were not sufficiently formed. 101-109, 111, 112, 114-120, 122-130 had good sintering, and the butane adsorption amount was as high as 5.9 g / 100 ml or more.

Example 9
Add a specified amount of sorbitan monocaprylate composite ester, propylene glycol, crystalline cellulose, methylcellulose and water to a mixture of powdery wood activated carbon and zeolite at a mass ratio of 45:55, and mix with a kneader (Needer) , Stirring and kneading. Next, the obtained kneaded body is put into a horizontal extrusion molding machine equipped with a mold, and a predetermined pressure is applied, so that the cross-sectional shape of the cells perpendicular to the axial direction is square, and the number thereof is A honeycomb-shaped formed body of 200 / (inch) ² was obtained. The molded body was dried by passing hot air inside the cell of the obtained molded body, and then cut to a length of 5.5 mm with a cutter blade. The cut formed body was put into an electric furnace, and various shielding materials were arranged around the formed body, and then fired at a temperature shown in Table 9 for 2 hours to obtain a honeycomb structure. The pore volume of 8 nm, 10 nm, and 12 nm in diameter was measured by the method shown in Example 1. As a result, all the honeycomb structures were 60 mm ³ / g, 50 mm ³ / g, and 40 mm ³ / g, respectively. Moreover, the thickness of the partition walls of these honeycomb structures was 0.3 mm, the thickness of the outer peripheral wall was 0.75 mm, and the outer diameter was 30 mm.

  The desorption performance of the obtained honeycomb structure was evaluated by repeated adsorption and desorption tests of ethane. The evaluation method is the same as the method shown in Example 2.

Further, the compressive strength was also measured for the strength of the honeycomb structure in the same manner as in Example 2. Furthermore, the presence or absence of cracks in the honeycomb structure was also observed.

  As can be seen from Table 9, the sample no. No. 140 had cracks, whereas Sample No. 140 of the present invention. 131-139, 142, 143, 144-150, 152-160 are good without cracks. Sample No. baked at less than 600 ° C. No. 141 was insufficiently sintered and no sample No. methylcellulose was added. No. 151 could not obtain a molded body, whereas sample No. 151 of the present invention. 131-139, 142, 143, 144-150, 152-160 had good sintering, and the ethane desorption rate was as high as 50% or more.

It is the schematic which shows the fuel evaporation prevention apparatus using the honeycomb structure of this invention. 1 is a schematic view showing an embodiment of a honeycomb structure of the present invention. FIG. 5 is a part of a cross-sectional view perpendicular to the axial direction showing another embodiment of a honeycomb structure of the present invention. FIG. 5 is a part of a cross-sectional view perpendicular to the axial direction showing another embodiment of a honeycomb structure of the present invention. It is sectional drawing which shows the vertical type extrusion molding machine used for manufacture of the honeycomb structure of this invention. It is sectional drawing which shows the horizontal type extrusion molding machine used for manufacture of the honeycomb structure of this invention.

Explanation of symbols

1: Main canister 2: Sub-canister 3: Connection passage 4: Activated carbon 5: Honeycomb structure 6: Engine 7: Gasoline tank 8: Charge passage 9: Air passage 10: Throttle valve 11: Intake passage 12: Purge passage 13: Gold Mold 14: Jacket 15: Kneaded body 16: Hydraulic piston 17: Input port 18: Pag screw 19: Vacuum chamber 20: Auger screw 21: Molded body 22: Ring 51: Outer wall 52: Cell 53: Partition wall 54: Reinforcement part

Claims (18)

A honeycomb structure comprising activated carbon and a clay-like substance and having cells formed by partitioning a plurality of partition walls inside the outer peripheral wall, the diameter existing in the outer peripheral wall and the partition walls measured using a gas adsorption method A honeycomb structure having a volume ratio of pores having a diameter of 1 nm to 6 nm to pores having a diameter of 1 nm to 12 nm of 72 to 83%. With a structure in which the pore volume of 2 nm in diameter measured by the gas adsorption method is 140 mm ³ / g or more, the pore volume of 3 nm in diameter is 120 mm ³ / g or more, and the pore volume of 4 nm in diameter is 90 mm ³ / g or more. The honeycomb structure according to claim 1, wherein the honeycomb structure is provided. The honeycomb structure according to 1 or 2, wherein an adsorption amount of the hydrocarbon gas is 3.2 g / 100 ml or more. With a structure in which the pore volume of 8 nm in diameter measured by gas adsorption method is 50 mm ³ / g or more, the pore volume of 10 nm in diameter is 40 mm ³ / g or more, and the pore volume of 12 nm in diameter is 30 mm ³ / g or more. The honeycomb structure according to any one of claims 1 to 3, wherein the honeycomb structure is provided. At least one of alumina (Al ₂ O ₃ ), silica (SiO ₂ ), calcia (CaO), magnesia (MgO), spinel (MgAl ₂ O ₄ ), and forsterite (Mg ₂ SiO ₄ ) is added. The honeycomb structure according to claim 4, wherein: The honeycomb structure according to claim 4 or 5, wherein a desorption rate with respect to the hydrocarbon gas is 50% or more. The thickness of the outer peripheral wall is 0.5 mm or more, the thickness of the partition wall is 0.35 mm or less, and a reinforcing portion is formed in the vicinity of a portion where the outer peripheral wall and the partition wall are in contact with each other. The honeycomb structure according to any one of the above. The honeycomb structure according to any one of claims 1 to 7, wherein the cell has a hexagonal cross-sectional shape perpendicular to the axial direction. The honeycomb structure according to any one of claims 1 to 8, wherein a weight ratio of the activated carbon and the clay-like substance is 60:40 to 30:70. The honeycomb structure according to any one of claims 1 to 9, wherein the activated carbon is wood activated carbon. The honeycomb according to any one of claims 1 to 10, wherein the clay-like substance is at least one of Kibushi clay, Sasame clay, ball clay, zeolite, bentonite, and hydrous magnesium silicate fiber. Structure. The honeycomb structure according to any one of claims 1 to 11, wherein a total of inevitable impurities is 2% by mass or less in terms of oxide. The method for manufacturing a honeycomb structure according to any one of claims 1 to 12, wherein activated carbon and a clay-like substance, to which a cellulose derivative, an alcohol copolymer, and a polyethylene glycol acrylate are added as a forming aid, And a step of extruding the kneaded body containing the material, a step of drying the obtained molded body at a temperature of 40 to 70 ° C., and a step of sintering the dried molded body at a temperature of 600 to 1300 ° C. A method for manufacturing a honeycomb structured body. The cellulose derivative is at least one selected from the group consisting of methyl cellulose, ethyl cellulose, propyl cellulose, ethyl methyl cellulose, propyl methyl cellulose, crystalline cellulose, and at least the alcohol copolymer is selected from the group consisting of polyvinyl alcohol and polyethylene vinyl alcohol. At least one selected from the group consisting of polyethylene glycol acrylates, polyethylene glycol monoacrylate, polyethylene glycol tetramethylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol tetramethylene glycol monomethacrylate; And The ratio of the cellulose derivative to be added, the alcohol polymer and the polyethylene glycol acrylate is 2 to 6% by mass, 7 to 15% by mass, and 30 to 35% by mass with respect to the kneaded body, respectively. 14. A method for manufacturing a honeycomb structured body according to 13. The method for manufacturing a honeycomb structure according to any one of claims 1 to 12, wherein at least one selected from the group consisting of sorbitan monocaprylate composite ester, glycols, and cellulose derivatives as a forming aid and methylcellulose The step of extruding a kneaded body containing activated carbon and a clay-like substance to which is added, the step of drying the obtained molded body at a temperature of 40 to 70 ° C., and the molded body after drying at a temperature of 600 to 1300 And a step of sintering at 0 ° C. The glycol is at least one selected from the group consisting of propylene glycol and ethylene glycol, and the cellulose derivative is at least one selected from the group consisting of ethyl cellulose, propyl cellulose, ethyl methyl cellulose, propyl methyl cellulose, crystalline cellulose, The ratio of the sorbitan monocaprylate composite ester, glycols, cellulose derivative and methylcellulose to be added is 3 to 5% by mass, 1 to 3% by mass, 1 to 3% by mass, and 3 to 10% by mass with respect to the kneaded body, respectively. The method for manufacturing a honeycomb structured body according to claim 15, wherein the method is provided. The method for manufacturing a honeycomb structured body according to any one of claims 13 to 16, wherein a shielding material containing a carbonaceous material is disposed around the molded body and sintered. A canister comprising the honeycomb structure according to any one of claims 1 to 12 mounted as an adsorbent in a passage through which gasoline vapor flows.

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