JP5775038B2 - Method for producing activated carbon or cylindrical carbonaceous material containing activated carbon raw material - Google Patents

Description

The present invention relates to a method for manufacturing a carbonaceous material comprises activated carbon or activated carbon material.

  Patent Document 1 discloses a water purifier cartridge in which activated carbon, an ion removing member, and a hollow fiber membrane are stored at different positions. Activated carbon removes trace components such as free residual chlorine and organic substances contained in tap water. The ion removing member removes metal ions contained in tap water. The hollow fiber membrane removes turbid components such as iron rust contained in tap water.

JP 2008-194596 A JP 2009-23889 A

  In order to remove various components contained in tap water, it is necessary to provide the water purifier cartridge with a structure for storing hollow fiber membranes, activated carbon, and the like at different positions.

  Patent Document 2 discloses that pellet-shaped activated carbon that is packed in a random direction with respect to a cartridge of a deodorizing apparatus is formed into a short cylindrical shape. The reason why the through holes are formed in the pellet-shaped activated carbon is to increase the air volume in the deodorizing cartridge, and not to allow air to flow in and out of each cylindrical activated carbon.

The present invention is to provide a method for producing a novel tubular materials to solve the problems described above.

In the present invention, a mixture containing at least an activated carbon or activated carbon raw material having an average particle size of 0.2 to 200 μm, a first binder, and an organic binder washed away with water is kneaded and extruded into a cylindrical shape along the longitudinal direction. Forming a long cylindrical molded body with holes formed therein, washing the cylindrical molded body with water to remove the organic binder, drying the cylindrical molded body washed with water, and A long cylindrical carbonaceous body in which a binder remains and a hole is formed along the longitudinal direction, and a cylindrical carbonaceous body in which fluid can flow in and out of the cylindrical carbonaceous body is manufactured. It has an aspect.

That is, when the formed long cylindrical molded body is washed with water, the first binder remains, and the shape of the cylindrical carbonaceous body is maintained by the first binder. Further, by washing away the organic binder , the gap connecting the inside and outside of the cylindrical carbonaceous material is appropriately expanded, and the flow rate in the inside and outside directions is appropriately increased.
Here, in the case of a cylindrical carbonaceous material before activation including an activated carbon raw material having an average particle size of 0.2 to 200 μm and a binder that can flow in and out, it functions as a cylindrical activated carbon when activated.
Since a long cylindrical carbonaceous material containing activated carbon having an average particle size of 0.2 to 200 μm can flow fluid inward and outward, the fluid is circulated in and out of the cylindrical carbonaceous material and filtered. The function of activated carbon is demonstrated. For example, when this cylindrical carbonaceous material is applied to a filtration cartridge, it is not necessary to store the hollow fiber membrane and activated carbon in separate positions.

In the invention according to each claim, the average particle diameter is 50% particle diameter (D50, median diameter) defined in JIS K1474: 2007 (activated carbon test method) for particles of 50 μm or more, and for particles less than 50 μm. Is JIS Z5 89-1-2 (particle diameter) based on the particle size distribution in accordance with JIS K5600-9-3: 2006 (General coating test method-Part 9: Powder coating-Section 3: Measurement method of particle size distribution by laser diffraction) Expression of measurement results—Part 2: Average particle diameter from particle size distribution or calculation of average particle diameter and moment).
The activated carbon raw material includes a raw material before activation and a raw material before carbonization. That is, the activation includes activation treatment after carbonization treatment.
The fluid includes a liquid such as water and a gas such as air.
The cylindrical carbonaceous material may contain materials other than activated carbon, activated carbon raw material, and binder, such as an ion exchanger such as a metal treating agent.

  By the way, when the flow rate per unit length of the cylindrical carbonaceous material when a hydrodynamic pressure of 100 kPa is applied to the outer surface of the cylindrical carbonaceous material is 0.5 to 70 mL / min · 100 mm, Can be circulated in the inner and outer directions of the cylindrical carbonaceous material and filtered well.

According to the present invention, it is possible to provide a process for the preparation of novel tubular carbonaceous material having activated carbon performance in addition to Filtration capacity.

(A) is a perspective view illustrating the cylindrical carbonaceous body 1, (b) is a front view illustrating the cylindrical carbonaceous body 1, (c) is a front view illustrating the structure of the cylindrical activated carbon 10, (d) ) Is a front view illustrating the structure of the tubular carbonaceous body 20 before activation. The flowchart which shows the reference example of the manufacturing method of the cylindrical activated carbon 10 using a hydrophobic binder. The flowchart which shows the reference example of the manufacturing method of the cylindrical activated carbon 10 using the water-soluble binder. The flowchart which illustrates the manufacturing method of the cylindrical activated carbon 10 using the binder washed away with water and the binder which remains. (A) And (b) is a flowchart which shows the reference example of the manufacturing method of the cylindrical activated carbon 19 using the activated carbon raw material 21 , (c) is the flowchart which illustrates the manufacturing method of the cylindrical activated carbon 19 using the activated carbon raw material 21. (A) is a diagram illustrating a side surface of the filtration cartridge 30, (b) is a diagram illustrating an outlet side end of the filtration cartridge 30, and (c) is a diagram illustrating an inlet side end of the filtration cartridge 30; (D) is a figure which illustrates the principal part of the filtration cartridge 30. FIG.

  Embodiments of the present invention will be described below. Of course, the embodiments described below are merely illustrative of the present invention.

(1) Description of long cylindrical carbonaceous material:
First, with reference to FIG. 1, the cylindrical carbonaceous material which concerns on one Embodiment of this invention is demonstrated.
This cylindrical carbonaceous body 1 includes activated carbon 11 or activated carbon raw material 21 having an average particle diameter of 0.2 to 200 μm and a binder (12 or 22), and a hole (through hole 2) is formed along the longitudinal direction LD1. It is the long cylindrical carbonaceous body made, Comprising: The fluid can be distribute | circulated to the inside / outside direction RD1 of this cylindrical carbonaceous body. The inner / outer direction RD <b> 1 means a direction connecting the inner side surface 3 and the outer side surface 4 in the tubular carbonaceous body 1.

The cylindrical carbonaceous material 1 shown in FIG. 1 (a) is cylindrical. Here, let D be the average outer diameter of the cylindrical carbonaceous material 1. The cylindrical carbonaceous material may be non-cylindrical such as elliptical tubular or rectangular tubular other than cylindrical. The average outer diameter D is an arithmetic average of the measured value of the longest part and the measured value of the shortest part of the cylindrical carbonaceous material.
The cross-sectional shape of the cylindrical carbonaceous material 1 shown in FIG. 1 (a) is annular as shown in the front view of FIG. 1 (b). Here, the average inner diameter of the cylindrical carbonaceous body 1, that is, the average diameter of the holes (2) is defined as d. The cross-sectional shape of the hole (2) may be a non-circular shape such as an ellipse or a polygon other than a circular shape. In this case, the average inner diameter d is an arithmetic average of the measured value of the longest part and the measured value of the shortest part of the hole.

The average outer diameter D can be, for example, 0.3 to 3.0 mm, more preferably 0.4 to 2.5 mm, and still more preferably 0.5 to 2.0 mm. The average inner diameter d is, for example, 0.1 mm or more and (D−0.2) mm or less, more preferably 0.2 mm or more and (D−0.4) mm, and further preferably 0.3 mm or more and (D− 0.3) mm.
The ratio L / D of the length L of the cylindrical carbonaceous body 1 to the average outer diameter D can be, for example, 2 or more, more preferably 5 or more, and even more preferably 10 or more.

The tubular carbonaceous body 1 includes a tubular activated carbon 10 as shown in FIG. 1 (c) and a tubular carbonaceous body 20 before activation as shown in FIG. 1 (d).
The cylindrical activated carbon 10 is a long cylindrical activated carbon including an activated carbon 11 having an average particle diameter of 0.2 to 200 μm and a binder 12 and having through holes 2 formed along the longitudinal direction LD1. The fluid can flow in the inner and outer directions RD1 of the activated carbon. The cylindrical carbonaceous body 20 is a long cylindrical carbonaceous body including an activated carbon raw material 21 having an average particle size of 0.2 to 200 μm and a binder 22 and having through holes 2 formed along the longitudinal direction LD1. Thus, the fluid can flow in the inner and outer directions RD1 of the cylindrical carbonaceous body. In addition, in order for the fluid to flow in the inner and outer directions RD1, the fluid enters the cylindrical carbonaceous body from the outer surface 4 and exits from the inner surface 3 to the hole (2), and the fluid flows from the inner surface 3 to the cylindrical carbon. Both entering the mass and exiting from the outer surface 4 are included.

In the cylindrical activated carbon 10 shown in FIG. 1 (c), granular activated carbons 11 are spot-bonded with a binder 12, and there is a gap 5 between particles of the activated carbon 11. The fluid flows through the gap 5 in the inward / outward direction RD1. The activated carbon 11 only needs to be able to determine the average particle diameter, and may be pulverized, fibrous or the like.
In the cylindrical carbonaceous material 20 before activation shown in FIG. 1 (d), granular activated carbon raw materials 21 are spot-bonded with a binder 22, and there is a gap 5 between particles of the activated carbon raw material 21. The activated carbon raw material 21 only needs to be able to obtain an average particle diameter, and may be pulverized, fibrous, or the like. When the cylindrical carbonaceous body 20 is activated, it is a long cylindrical activated carbon that includes activated carbon and has holes formed along the longitudinal direction, and a fluid that allows fluid to flow in and out of the cylindrical activated carbon. Become activated carbon. When the binder 22 is an organic binder, the binder may be thermally decomposed and disappeared during the activation process including the carbonization process. When the binder 22 is a heat resistant inorganic binder, the binder may remain after the activation treatment.

  The activated carbon raw material 21 may be activated if activated carbon can be formed, and plant-based, coal-based, petroleum-based, synthetic resin-based, natural material-based, various organic ash, and the like can be used. As the plant-based carbonaceous material, fruit shells such as coconut shells and almond shells, wood, sawdust, bamboo, grass and the like can be used. As the coal-based carbonaceous material, peat, lignite, and charcoal, bituminous coal, anthracite, or the like can be used. Petroleum pitch or the like can be used as the petroleum-based carbonaceous material. As the synthetic resin-based carbonaceous material, phenol resin, epoxy resin, urea resin, polyamide resin, polyvinyl alcohol resin, polyacrylonitrile resin, polyolefin resin, and the like can be used. As the natural carbonaceous material, natural fibers such as cotton, regenerated fibers such as rayon, semi-synthetic fibers such as acetate, and the like can be used.

  As the pulverized activated carbon, activated carbon obtained by pulverizing an activated material of activated carbon material, activated carbon obtained by activating a pulverized material of activated carbon material, or the like can be used. The pulverized activated carbon includes powdered activated carbon smaller than 100 mesh (diameter 0.15 mm). As the granular activated carbon, coconut shell activated carbon, charcoal, bamboo charcoal, coal activated carbon, synthetic resin activated carbon, or the like can be used. The granular activated carbon may be activated carbon obtained by crushing an activated material and sieving to a predetermined particle size, or activated carbon obtained by activating a carbonaceous material having a predetermined particle size. The granular activated carbon includes powdered activated carbon. As the fibrous activated carbon, coal pitch, petroleum pitch, synthetic resin activated carbon, natural material activated carbon, or the like can be used.

The average particle diameter of the activated carbon 11 and the activated carbon raw material 21 is preferably 0.2 to 200 μm, more preferably 1 to 150 μm, and further preferably 2 to 130 μm. By setting the average particle size to the above lower limit or more, the fluid flowing in the cylindrical carbonaceous material in the inner and outer directions is increased to a preferable flow rate. Moreover, by setting the average particle size to be equal to or less than the above upper limit, a preferable filtration performance (for example, turbid component removal performance) such as a hollow fiber membrane can be obtained.
Activated carbon and activated carbon raw material may be one kind, but may be a combination of two or more kinds. When two or more kinds of activated carbons having different properties and / or particle size distributions are used, cylindrical activated carbon capable of treating each removed substance with a good balance can be obtained.

As the binders 12 and 22, a thermoplastic binder, a thermosetting binder, an inorganic binder, or the like can be used. The binder may be hydrophobic or hydrophilic (including water solubility).
Thermoplastic binders include polyolefins such as polyethylene (PE) and polypropylene (PP), polyesters such as polyethylene terephthalate, thermoplastic elastomers, resins obtained by hydrophilizing these resins, and resins obtained by adding additives such as modifiers to these resins. A mixture of these resins can be used. These resins are included in the thermoplastic resin. Specific examples of the hydrophobic thermoplastic binder include polyethylene powder manufactured by Mitsui Chemicals, Inc. (Miperon (registered trademark), polyethylene powder manufactured by Asahi Kasei Chemicals Corporation (Sunfine (registered trademark)), etc. Specific examples of the thermoplastic resin binder include polyolefin aqueous dispersion (Chemical (registered trademark)) manufactured by Mitsui Chemicals, Inc.

As the inorganic binder, p-alumina (Al ₂ O ₃ .nH ₂ O), phosphoric acid binder, silicon binder, titanium binder, and the like can be used. Clay-like minerals such as layered silicate minerals can also be used as the inorganic binder.
The water-soluble binder includes carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), an aluminum phosphate binder, and the like in addition to the above-described p-alumina. Water-soluble binders such as p-alumina, CMC, and PVA that are washed away with water function as a thickener when the cylindrical carbonaceous material is extruded.

  One type of binder may be used, but a combination of two or more types may be used. In addition, when a residual binder (first binder) showing persistence to water and a non-residual binder (second binder) washed away with water are used in combination, the tubular carbonaceous material washed with water is used. A residual binder remains, and the shape of the cylindrical carbonaceous material is maintained by the residual binder. Further, by washing away the non-residual binder, the gap that leads to the inside / outside direction RD1 of the cylindrical carbonaceous material is appropriately expanded, and the flow rate in the inside / outside direction RD1 is appropriately increased. The compounding ratio of the non-residual binder to 100 parts by weight of the residual binder can be, for example, 0.1 to 1000 parts by weight, more preferably 1 to 500 parts by weight, and still more preferably 3 to 300 parts by weight.

The compounding quantity of a binder can be 2-100 weight part with respect to 100 weight part of activated carbon or activated carbon raw material, for example, More preferably, it can be 3-50 weight part. When the blending amount of the binder is equal to or more than the lower limit, activated carbon or activated carbon raw material particles are bonded with each other with a preferable adhesive force in the cylindrical carbonaceous material. Moreover, when the compounding quantity of a binder shall be below the said upper limit, the surface which has the activity of activated carbon will remain in a preferable ratio, and cylindrical activated carbon will show the preferable adsorption activity. The blending ratio of the binder is preferably increased as the average particle size of the activated carbon or the activated carbon raw material decreases from the viewpoint of shape retention of the cylindrical carbonaceous material.
When water is added to and kneaded with activated carbon or activated carbon raw material and binder, the amount of water added is, for example, 25 to 300 parts by weight, more preferably 50 to 150 parts by weight with respect to 100 parts by weight of activated carbon or activated carbon raw material. be able to. When the amount of water added is equal to or higher than the lower limit, a kneaded product with good uniformity can be formed. When the amount of water added is not more than the above upper limit, the cylindrical shape of the cylindrical carbonaceous material can be kept good.

The structural component of the cylindrical carbonaceous body 1 may be only activated carbon or a combination of activated carbon raw material and binder, or an additive of about 0.1 to 60 parts by weight with respect to 100 parts by weight of activated carbon or activated carbon raw material may be added. good. As the additive, an ion exchanger such as a cation exchange resin, an anion exchange resin, a chelate resin, or a combination thereof can be used. The cation exchange resin or chelate resin functions as a metal treatment agent. When fibrous materials such as fibrous activated carbon and fibrous activated carbon raw material are added, the flexibility of the tubular carbonaceous body 1 increases, and the tubular carbonaceous body 1 becomes difficult to break.
When the average particle diameter of the additive can be determined, the average particle diameter of the additive is preferably 0.2 to 200 μm, more preferably 1 to 150 μm, and still more preferably 2 to 130 μm. By setting the average particle size to the above lower limit or more, the fluid flowing in the cylindrical carbonaceous material in the inner and outer directions is increased to a preferable flow rate. Moreover, preferable filtration performance is obtained by making an average particle diameter below the said upper limit.

The distribution performance of the cylindrical carbonaceous material 1 that allows fluid to flow in the inner and outer directions RD1 is, for example, the cylindrical carbonaceous material 1 when a fluid pressure of a predetermined pressure P is applied to the outer surface 4 of the cylindrical carbonaceous material 1. Can be quantified by the flow rate Q per unit length UL.
When water is circulated, for example, the flow rate per UL = 100 mm of the tubular carbonaceous material 1 when a hydrodynamic pressure of P = 100 kPa is applied to the outer surface 4 of the tubular carbonaceous material 1 is a quantitative value of the circulation performance. It can be. The flow rate Q is preferably 0.5 to 70 mL / min · 100 mm, more preferably 4 to 60 mL / min · 100 mm, and still more preferably 6 to 50 mL / min · 100 mm. By setting the flow rate Q to be equal to or higher than the lower limit, a fluid flowing in the cylindrical carbonaceous material in the inner and outer directions becomes a preferable flow rate. Moreover, preferable filtration performance is obtained by setting the flow rate Q to be equal to or less than the above upper limit. That is, by setting the flow rate Q within the above range, the fluid can be circulated in the inside / outside direction RD1 of the cylindrical carbonaceous body 1 and filtered well.
In order to increase the flow rate Q, the average particle diameter of the activated carbon or the activated carbon raw material is increased, the wall thickness {(D−d) / 2} of the cylindrical carbonaceous material is decreased, or it is washed away with water. What is necessary is just to increase the compounding ratio of a non-residual binder. In order to reduce the flow rate Q, the average particle diameter of the activated carbon or the activated carbon raw material is reduced, the thickness {(Dd) / 2} of the cylindrical carbonaceous material is increased, or the non-residue that is washed away with water. The mixing ratio of the conductive binder may be reduced.

  Since the long cylindrical activated carbon 10 including the activated carbon 11 having an average particle size of 0.2 to 200 μm can circulate fluid in the inner and outer directions RD1, the fluid is circulated in the inner and outer directions RD1 of the cylindrical activated carbon 10 and filtered. Sometimes the function of the activated carbon 11 is demonstrated. For example, when the cylindrical activated carbon 10 is applied to a filtration cartridge, it is not necessary to store the hollow fiber membrane and activated carbon in different positions, and the assembly operation of the filtration cartridge is facilitated.

(2) Description of manufacturing method of cylindrical activated carbon:
Next, an example of a method for producing cylindrical activated carbon will be described with reference to the flowcharts of FIGS.
The manufacturing method shown in FIG. 2 shows an example in which cylindrical activated carbon 10 is manufactured using a hydrophobic thermoplastic binder. In this example, since the water 13 is added in the middle, the hydrophobic binder 12 is previously attached to the activated carbon 11 having an average particle diameter of 0.2 to 200 μm.

In the heating and mixing step S1, a material containing activated carbon 11, a binder 12, and, if necessary, an additive 14 is heated and mixed in the absence of a liquid dispersion medium. When the softening temperature of the binder is indicated by the range T _{sl to} T _sh (° C.), the lower limit of the heating temperature may be T _sh . The softening temperature is the Vicat softening temperature specified in JIS K7206: 1999 (plastic-thermoplastic-Vicat softening temperature (VST) test method). When the softening temperature of the binder is unknown, a melting point higher than the softening temperature may be set as the lower limit of the heating temperature. When the ignition point of the binder is indicated by the minimum temperature _Til , the upper limit of the heating temperature may be less than _Til . In addition, since the ignition point of thermoplastic resins, such as polyethylene, is usually 350 degreeC or more, the preferable upper limit of heating mixing temperature is less than 350 degreeC. When the melting point of the binder is shown in the range T _{ml to} T _mh , a more preferable upper limit of the heating temperature may be T _ml + 70 ° C., and a preferable lower limit of the heating temperature may be T _mh . The same applies to the following heat treatment step S7.
For the heating and mixing, a kneader, a lab plast mill, a wheel type, a ball type, a blade type, a roll type or the like having a heating function such as preheating or direct heating can be used. The rotational speed of the mixing device may be any speed that reduces the temperature deviation of the mixture, and can be, for example, 2 to 200 rpm. The time for heating and mixing can be, for example, 10 to 120 minutes.

In crushing process S2, the block-shaped heating mixture solidified by cooling is crushed to a predetermined average particle size (for example, about 20 to 200 μm) with a crushing device. Prior to crushing, additive 15 may be added to the heated mixture. The crushing temperature is preferably less than the melting point of the binder 12, more preferably less than the softening temperature of the binder 12, and may be room temperature.
For crushing, crushing apparatuses such as a mixer, a blender, a mill, a jaw crusher, a gyratory crusher, a cone crusher, a hammer crusher, a ball mill, a roller mill, a high-speed rotating mill, and a jet mill can be used. The rotation speed of the crushing device can be set to, for example, 50 to 50000 rpm. The time for crushing can be, for example, 1 to 120 minutes.

In the mixing step S3, the crushed material obtained in the crushing step S2, water (liquid dispersion medium) 13, and a material containing the additive 16 as necessary are mixed by a mixing device. For mixing, mixer, blender, horizontal cylinder type, V type, double cone type, square solid type, S type, continuous V type, ball mill type, rocking type, cross rotary type, ribbon type, screw type, rotor type, A mixing device such as a pug mill type, a planetary type, a turbine type, a high-speed flow type, or a rotating disk type can be used. The rotational speed of the mixing device may be a speed that reduces the temperature deviation of the mixture, and can be set to 15 to 200 rpm, for example.
In addition, the various additives mentioned above can be used for the additives 14, 15, and 16, and the same kind may be sufficient and a different kind may be sufficient as them.

  In the kneading step S4, the mixture obtained in the mixing step S3 is kneaded with a kneading apparatus. “Kneading” means a dispersion operation in which the entire surface of the dispersoid is coated with a liquid dispersion medium. For kneading, a kneader such as a kneader can be used.

In the extrusion step S5, the kneaded product obtained in the kneading step S4 is extruded into a cylindrical shape by an extrusion device and cut into a predetermined length. It is preferable to attach a die having an annular extrusion port for extruding a material in a cylindrical shape matching the cross-sectional shape of the cylindrical carbonaceous body to the barrel head (downstream end) of the extrusion apparatus. Since the molded body extruded into a cylindrical shape is formed of an elongated soft material, it is often bent without being straight.
For extrusion, an extrusion apparatus such as a single screw extruder or a twin screw extruder can be used.

  In the shaping step S6, the long cylindrical molded body extruded in the extrusion step S5 is arranged into a predetermined shape (for example, a straight shape). Here, the straight line shape means a straight shape. For shaping, a device that rolls the cylindrical molded body on the mounting surface to bring it into a straight line, a device that puts the cylindrical molded body into a straight groove, and moves it closer to a straight line, or the like can be used.

  In the heat treatment step S7, the shaped cylindrical molded body is heat-treated at a temperature equal to or higher than the softening temperature of the binder. A heating device such as an oven can be used for the heat treatment. After cooling, the binder is solidified when cooled to below the softening temperature, and a long cylindrical activated carbon 10 is formed.

The manufacturing method shown in FIG. 3 shows an example of manufacturing cylindrical activated carbon 10 using a water-solubilized thermoplastic binder. In this example, the heating and mixing step S1 and the crushing step S2 described above are unnecessary. Steps S3 to S7 are the same as the steps shown in FIG.
In the mixing step S3 of the present manufacturing method, a raw material containing the activated carbon 11, the binder 12, the water 13, and the additive 14 as necessary is mixed by a mixing device. Thereafter, the mixture is kneaded by a kneading device in the kneading step S4, the kneaded product is extruded into a cylindrical shape by the extrusion device in the extrusion step S5 and cut into a predetermined length, and a long cylindrical molded body is predetermined in the shaping step S6. In the heat treatment step S7, the cylindrical molded body is heat-treated at a temperature higher than the softening temperature of the binder. After cooling, the binder is solidified when cooled to below the softening temperature, and a long cylindrical activated carbon 10 is formed.

The manufacturing method shown in FIG. 4 manufactures the cylindrical activated carbon 10 using the thermoplastic binder (1st binder) which shows persistence with respect to water, and a non-residual water-soluble binder (2nd binder). An example is shown. In this example, a water washing step S8 and a drying step S9 are added after the steps S3 to S7 shown in FIG. Non residual binder 12B, it is possible to use an organic binder over such like CMC or PVA, the binders are washed away with water. Steps S3 to S7 are the same as the steps shown in FIG.

  In the mixing step S3 of the present manufacturing method, the raw material containing the activated carbon 11, the residual binder 12A, the non-persistent binder 12B, the water 13, and the additive 14 as necessary is mixed by a mixing device. Thereafter, the cylindrical shaped body is heat-treated at the softening temperature of the residual binder 12A or higher in the heat treatment step S7 through the kneading step S4, the extrusion step S5, and the shaping step S6. After the heat treatment, when it is cooled to below the softening temperature, the residual binder 12A is solidified, and the shape of the long cylindrical molded body in which the through holes are formed along the longitudinal direction is maintained.

In the water washing step S8, the long cylindrical molded body is washed with water to remove the non-residual binder 12B. At this time, the residual binder 12A remains, and the shape of the cylindrical molded body is maintained by the residual binder 12A. Further, by washing away the non-residual binder 12B, the gap 5 connected to the inner and outer direction RD1 of the cylindrical activated carbon is appropriately expanded, and the flow rate to the inner and outer direction RD1 is appropriately increased.
In the final drying step S9, the cylindrical molded body washed with water is dried. The manufactured cylindrical activated carbon 10 is a long cylindrical activated carbon in which the residual binder 12A remains and the through hole 2 is formed along the longitudinal direction LD1, and the fluid flows in the inner and outer directions RD1 of the cylindrical activated carbon. It is possible.

  As described above, the present production example can provide a novel method for producing cylindrical activated carbon having the performance of activated carbon in addition to the filtration ability such as a hollow fiber membrane.

The manufacturing method shown in FIGS. 5A to 5C is a novel method in which the activated carbon raw material 21 is used to manufacture a cylindrical carbonaceous body 20 before activation, and the cylindrical activated carbon 19 is manufactured from the cylindrical carbonaceous body 20. An example of a manufacturing method is shown.
FIG. 5A shows an example in which a cylindrical carbonaceous material 20 is manufactured using a hydrophobic thermoplastic binder and a cylindrical activated carbon 19 is manufactured. The omitted steps S2 to S6 are the same as steps S2 to S6 shown in FIG.

  In the heating and mixing step S1 of this manufacturing method, a raw material containing the activated carbon raw material 21, the binder 22, and, if necessary, the additive 24 is heated and mixed in the absence of the liquid dispersion medium. Thereafter, the heated mixture is crushed to a predetermined average particle size in the crushing step S2, the raw material containing the crushed material, water, and additives as necessary is mixed in the mixing step S3, and the mixture is kneaded in the kneading step S4. In the extrusion step S5, the kneaded product is extruded into a cylindrical shape and cut into a predetermined length. In the shaping step S6, the long cylindrical molded body is adjusted to a predetermined shape. In the heat treatment step S7, the cylindrical molded body is softened with a binder. Heat treatment above temperature. After the heat treatment, when cooled to below the softening temperature, the binder is solidified and a long cylindrical carbonaceous material 20 is formed.

  In the activation step S10, the cylindrical carbonaceous material 20 is activated to form the cylindrical activated carbon 19. Activation is a reaction that develops micropores of the carbonaceous material and changes it to porous. Examples of the activation include gas activation for high-temperature treatment in the presence of water vapor, carbon dioxide, air, etc., chemical activation for chemical treatment with zinc chloride, sulfate, phosphoric acid, etc., activation using a combination of chemical and water vapor, etc. . Activation of the tubular carbonaceous body 20 includes activation treatment after carbonization treatment. The carbonization treatment can be, for example, a treatment for carbonizing the cylindrical carbonaceous material at 600 to 800 ° C. in an inert atmosphere such as nitrogen or argon. The activation treatment after the carbonization treatment is, for example, a treatment for activating the tubular carbonaceous body at 700 to 1100 ° C., more preferably 800 to 1000 ° C. in an atmosphere of an oxidizing gas such as water vapor or carbon dioxide. Can do. The carbonization treatment is preferable because the activity as activated carbon is increased, but the activation treatment can be performed by omitting the carbonization treatment.

  As described above, the cylinder in which the activated carbon raw material and the binder are included and the fluid is allowed to flow in the inner and outer directions before being activated, and the cylinder in which the activated carbon raw material is included and the fluid is allowed to flow in the inner and outer directions. The activated carbon 19 is formed. Therefore, the present production example can provide a novel cylindrical carbonaceous material having the performance of activated carbon in addition to the filtering ability such as a hollow fiber membrane.

  FIG. 5B shows an example in which a cylindrical carbonaceous body 20 is manufactured using a water-solubilized thermoplastic binder and a cylindrical activated carbon 19 is manufactured. In the mixing step S3 of the present manufacturing method, a raw material including the activated carbon raw material 21, the binder 22, water 23 and, if necessary, the additive 24 is mixed by a mixing device. Omitted steps S4 to S6 are the same as steps S4 to S6 shown in FIG. In the heat treatment step S7, the cylindrical shaped body is heat treated at a temperature equal to or higher than the softening temperature of the binder. After cooling to below the softening temperature, in the activation step S10, the cylindrical carbonaceous material 20 is activated to form the cylindrical activated carbon 19.

FIG.5 (c) manufactures the cylindrical carbonaceous body 20 using a residual thermoplastic binder (1st binder) and a non-residual water-soluble binder (2nd binder), and is cylindrical. The example which manufactures the activated carbon 19 is shown. Omitted steps S4 to S8 are the same as steps S4 to S8 shown in FIG.
In the mixing step S3 of the present manufacturing method, a raw material including the activated carbon raw material 21, the residual binder 22A, the non-residual binder 22B, water 23 and, if necessary, the additive 24 is mixed by a mixing device. Thereafter, the kneading step S4, through the extrusion step S5 and shaping step S6, heat treatment in the heat treatment step S7 the cylindrical molded body in the residual binder 22 A softening temperature above. After the heat treatment, when cooled to below the softening temperature, the shape of the long cylindrical molded body is maintained. In the water washing step S8, the long cylindrical molded body is washed with water to remove the non-residual binder 22B . In the drying step S9, the cylindrical molded body washed with water is dried. Tubular carbonaceous body 20 formed is a long tubular carbonaceous material through holes in the longitudinal direction remaining binder 22 A may remain is formed, the inner and outer direction of the tubular carbonaceous material It is supposed that the fluid can flow. In the activation step S10, the cylindrical carbonaceous material 20 is activated to form the cylindrical activated carbon 19.

(3) Description of filtration cartridge to which cylindrical activated carbon is applied:
The long cylindrical activated carbon formed by various methods can be used for the filtration cartridge 30 as shown to FIG. 6 (a)-(d), for example. In FIG. 6A, the upper half is viewed in cross section. The filtration cartridge 30 has a cylindrical activated carbon bundle 50 in which a plurality of cylindrical activated carbons 10 (a cylindrical activated carbon 19 is acceptable, the same applies hereinafter) bundled in the case 40.
The case 40 has a substantially cylindrical main body 41 and an inflow end 42 and an outflow end 43 provided on opposite sides of the main body 41 in the axial direction AD1. The inflow end 42 is formed with an inlet 42a for fluid before filtration. The outflow end 43 is formed with an outlet 43a for the filtered fluid. The case 40 can be formed of a synthetic resin such as a thermoplastic resin, a metal such as stainless steel, ceramics, activated carbon, or the like.

Each tubular activated carbon 10 constituting the tubular activated carbon bundle 50 has an open end 7 on the outflow end 43 side and a closed end 6 on the inflow end 42 side. The closed end 6 can be formed, for example, by heating and crushing the open end before the cylindrical activated carbon 10 is closed. Alternatively, the closed end 6 may be formed by closing the open end of the cylindrical activated carbon 10 before closing with a potting agent or the like. In the cylindrical activated carbon bundle 50, a plurality of cylindrical activated carbons 10 are bundled by combining the closed end 6 and the open end 7, and the open end 52 having the open end 7 is fixed to the case outflow end 43 by the potting agent 60. Yes. Accordingly, the closed end portion 51 of the cylindrical activated carbon bundle 50 is disposed in the flow path 44 on the inlet 42a side, and the outer surface 4 of each cylindrical activated carbon 10 is disposed in the inlet side flow path 44, and each cylindrical activated carbon is disposed. Ten holes (2) serve as a flow path 45 on the outlet 43a side.
Potting agents include urethane resin adhesives, epoxy resin adhesives, silicone resin adhesives, unsaturated polyester resin adhesives, phenolic resin adhesives, curable resin adhesives, hot melts, etc. A thermoplastic resin adhesive or the like can be used. For the hot melt, a polyolefin-based adhesive such as PE, an EVA resin (ethylene / vinyl acetate copolymer) -based adhesive, or the like can be used. Of course, the opening end 52 may be fixed to the case outflow end 43 by a fixing means other than the potting agent.

  The fluid that has flowed in from the inflow port 42a flows through the cylindrical activated carbon 10 from the flow channel 44 on the inflow port side inward and outward, enters the hole (2), and flows out from the outflow port 43a. Since a long cylindrical activated carbon containing activated carbon having an average particle size of 0.2 to 200 μm has a gap connecting inward and outward, a preferable filtration performance such as a hollow fiber membrane can be obtained. Moreover, since the cylindrical activated carbon is not a simple carbon material, the function of the activated carbon is exhibited when the fluid is circulated in the inside and outside of each cylindrical activated carbon and filtered. Therefore, it is not necessary for the present filtration cartridge 30 to store the hollow fiber membrane and the activated carbon at different positions.

  Although it is preferable that the closed end 6 of each cylindrical activated carbon is disposed in the inlet-side flow path 44 and the open end 7 is disposed in the outlet-side flow path 45, it is preferable because filtration ability can be obtained for a long time. The closed end 6 may be disposed in the outlet side channel 45 and the open end 7 may be disposed in the inlet side channel 44.

  The filtration cartridge 30 can be used for a liquid cartridge for processing a liquid such as water or a gas cartridge for processing a gas such as air. When the filtration cartridge 30 is used as a water purifier cartridge, the filtration function of the hollow fiber membrane that removes turbid components such as iron rust contained in tap water, and activated carbon that removes trace components such as free residual chlorine and organic substances contained in tap water Function. Further, when the filtration cartridge 30 is used as an air cleaning cartridge, a filtration function for removing suspended particles contained in the air and a function of activated carbon for removing odor components contained in the air are obtained.

  In addition, when two or more kinds of activated carbons and additives having different properties and / or particle size distributions are used as the raw material of the cylindrical activated carbon, cylindrical activated carbon capable of treating each removed substance with a good balance can be obtained. For example, a relatively large granular phenol activated carbon has pores around 0.7 nm that are excellent in adsorption of trihalomethane by suppressing activation. On the other hand, relatively small coconut shell activated carbon and fibrous activated carbon are activated and have a large surface area, and are excellent in removing residual chlorine. Therefore, when granulated activated carbon is formed using granular phenol activated carbon, coconut shell activated carbon or fibrous activated carbon, and if necessary, a metal treatment agent, coconut shell activated carbon alone, phenol activated carbon alone, metal treatment agent A combined removal capability that cannot be obtained alone can be obtained.

The following can also be considered as merits of the present technology described above.
For example, since the cross-sectional area of the cylindrical activated carbon can be set to the same cross-sectional area as that of the hollow fiber membrane, clogging that is likely to occur in a filtration cartridge using activated carbon having a small particle diameter can be suppressed. Therefore, it is possible to reduce the size and performance of the filtration cartridge. In addition, the downsizing reduces the length and radial restrictions of the cartridge storage portion, and allows the filtration cartridge to be shaped so as not to be held in a substantially cylindrical shape, thereby increasing the degree of freedom in design.
By forming the filtration cartridge by bundling the cylindrical activated carbon, the cylindrical activated carbon can be efficiently accommodated in the space in the case, and the pressure concentration generated when the granular activated carbon is closely packed is dispersed. be able to. Therefore, the flow rate can be increased and high filtration performance can be realized.

By forming cylindrical activated carbon including an antibacterial agent, it becomes possible to suppress odors generated by microorganisms during long-term water stoppage.
By performing the final treatment with cylindrical activated carbon, it is possible to suppress the resin odor and taste emitted from resin parts such as a membrane and a membrane case.
Moreover, cylindrical activated carbon can also be used for the removal of NOM (natural organic matter) that is a complex mixture derived from the remains of animals and plants and is ubiquitously present in the water environment.

(4) Example:
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited by the following examples.

[Example]
In the following examples, “activated carbon” is coconut shell activated carbon (GW48 / 100 manufactured by Kuraray Chemical Co., Ltd., having an average particle diameter of 8 μm or 20 μm using planetary ball mill FRITSCH type P-5), “Binder” is a polyolefin aqueous dispersion (manufactured by Mitsui Chemicals, trade name: Chemipearl (registered trademark) S100), and “second binder” is CMC (manufactured by ASONE Corporation). As a blender, Inoue Manufacturing Co., Ltd. PLM-15 was used. As the extrusion molding machine, a vacuum kneading extrusion molding machine was used. As the hot melt for measuring the flow rate and preparing the filtration module, a hot melt manufactured by Moresco Co., Ltd. (trade name: Morescommelt (registered trademark) ME-125) was used.

[Example 1]
100 parts by weight of activated carbon having an average particle size of 8 μm, 20 parts by weight of the first binder, 7 parts by weight of the second binder, and 98 parts by weight of water were placed in a blender and mixed at room temperature for 10 minutes at 500 rpm. The mixture was placed in an extruder, kneaded and extruded to a length of 100 mm. After shaping into a straight line and heat-treating at 120 ° C. for 2 hours, the first binder was solidified and washed with running water for 4 hours to remove the second binder. The obtained cylindrical carbonaceous material sample had an average value of a plurality of samples having an average outer diameter of 0.85 mm, an average inner diameter of 0.12 mm, a length of 98.9 mm, and a weight of 0.05 g.

[Example 2]
100 parts by weight of activated carbon having an average particle size of 20 μm, 15 parts by weight of the first binder, 5 parts by weight of the second binder, and 80 parts by weight of water were placed in a blender and mixed at 500 rpm for 10 minutes at room temperature. The mixture was placed in an extruder, kneaded and extruded to a length of 100 mm. After shaping into a straight line and heat-treating at 120 ° C. for 2 hours, the first binder was solidified and washed with running water for 4 hours to remove the second binder. The obtained cylindrical carbonaceous material sample had an average value of a plurality of average outer diameters of 1.0 mm, an average inner diameter of 0.3 mm, a length of 99.2 mm, and a weight of 0.07 g.

[Comparative Example 1]
As a hollow fiber membrane sample, a polysulfone hollow fiber membrane (manufactured by NOK Corporation, average outer diameter 0.4 mm, average inner diameter 0.3 mm) cut to a length of 100 mm was used.

[Measurement of flow rate]
One end of each of the cylindrical samples of Examples 1 and 2 and Comparative Example 1 was closed with hot melt, 100 kPa dynamic pressure was applied to the outer surface, and the flow rate of water coming out from the inner surface was measured.

[Preparation of filtration cartridge sample]
The cylindrical samples of Examples 1 and 2 and Comparative Example 1 were bundled with 500 pieces of one end closed with hot melt and packed into a column having an inner diameter of 80 mm, and the other end of the opened cylindrical sample was hot so as not to block the other end. A filter cartridge sample was prepared by fixing with a melt.

[Measurement of filtration capacity]
Pursuant to JIS S3201 “Household water purifier test method”, raw water adjusted to a turbidity of 2.0 degrees using a turbidity standard solution of 0.1 mg kaolin / mL was passed through the filtration cartridge sample at 2 L / min for 10 minutes. Water and the turbidity of the filtered water was measured.

[Evaluation of adsorption performance]
In accordance with JIS S3201 “Household water purifier test method”, an aqueous solution having a free residual chlorine concentration of 2.0 mg / L was passed through the filtration cartridge at 2 L / min for 10 minutes, and the free residual chlorine concentration was measured.

表１に示すように、実施例１，２の筒状炭素質体サンプルは、内外方向へ流体が流通可能とされていた。
また、実施例１，２の筒状炭素質体サンプルは、中空糸膜のように濾過性能を有していた。
さらに、実施例１，２の筒状炭素質体サンプルは、活性炭の吸着性能を有していた。
従って、本発明の筒状炭素質体は、濾過性能に加えて活性炭の性能を有することが確認された。 [Test results]
The test results are shown in Table 1.

As shown in Table 1, in the cylindrical carbonaceous material samples of Examples 1 and 2, fluid was allowed to flow inward and outward.
Moreover, the cylindrical carbonaceous material samples of Examples 1 and 2 had filtration performance like a hollow fiber membrane.
Furthermore, the cylindrical carbonaceous material samples of Examples 1 and 2 had an activated carbon adsorption performance.
Therefore, it was confirmed that the cylindrical carbonaceous material of the present invention has the performance of activated carbon in addition to the filtration performance.

(5) Specific examples:
Next, the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples.

[Concrete example]
In the following specific examples, “first binder”, “second binder”, “blender”, “extrusion machine” and “hot melt” are the same as those in the above examples, and “activated carbon raw material” is palm A shell shall be used.

[Specific Example 1]
100 parts by weight of the activated carbon raw material having an average particle size of 8 μm, 20 parts by weight of the first binder, 7 parts by weight of the second binder, and 98 parts by weight of water are placed in a blender and mixed at 500 rpm for 10 minutes at room temperature. The mixture is put into an extruder, kneaded, and extruded with an average outer diameter of 0.85 mm, an average inner diameter of 0.12 mm, and a length of 100 mm as targets. After shaping into a straight line and heat-treating at 120 ° C. for 2 hours, the first binder is solidified and washed with running water for 4 hours to remove the second binder. The obtained cylindrical carbonaceous material sample is carbonized at 700 ° C. for 10 minutes in the presence of nitrogen, and then activated at 900 ° C. for 15 minutes in the presence of water vapor to obtain a cylindrical activated carbon sample.

[Specific Example 2]
100 parts by weight of the activated carbon raw material having an average particle size of 20 μm, 15 parts by weight of the first binder, 5 parts by weight of the second binder, and 80 parts by weight of water are placed in a blender and mixed at 500 rpm for 10 minutes at room temperature. The mixture is put into an extruder, kneaded, and extruded with an average outer diameter of 1.0 mm, an average inner diameter of 0.3 mm, and a length of 100 mm as targets. After shaping into a straight line and heat-treating at 120 ° C. for 2 hours, the first binder is solidified and washed with running water for 4 hours to remove the second binder. The obtained cylindrical carbonaceous material sample is carbonized at 700 ° C. for 10 minutes in the presence of nitrogen, and then activated at 900 ° C. for 15 minutes in the presence of water vapor to obtain a cylindrical activated carbon sample.

[Flow rate]
One end of each of the cylindrical activated carbon samples of Examples 1 and 2 is closed with hot melt, and a water pressure of 100 kPa is applied to the outer surface to measure the flow rate of water coming out from the inner surface. The flow rate is estimated to be 0.5 to 70 mL / min · 100 mm.

[Preparation of filtration cartridge sample]
The cylindrical activated carbon samples of specific examples 1 and 2 were bundled with 500 pieces of one end closed with hot melt and packed into a column having an inner diameter of 80 mm, and the other end of the opened cylindrical activated carbon sample was hot melted so as not to block the other end. Secure and make filtration cartridge sample.

[Filtration capacity]
Pursuant to JIS S3201 “Household water purifier test method”, raw water adjusted to a turbidity of 2.0 degrees using a turbidity standard solution of 0.1 mg kaolin / mL was passed through the filtration cartridge sample at 2 L / min for 10 minutes. Water and measure the turbidity of the filtered water. The turbidity is estimated to decrease from 2.0 degrees.

[Adsorption performance]
According to JIS S3201 “Household water purifier test method”, an aqueous solution having a free residual chlorine concentration of 2.0 mg / L is passed through the filter cartridge sample at 2 L / min for 10 minutes, and the free residual chlorine concentration is measured. The free residual chlorine concentration is estimated to decrease from 2.0 mg / L.

  From the above, it is estimated that the cylindrical activated carbon obtained by activating the cylindrical carbonaceous material using the activated carbon raw material also has the performance of activated carbon in addition to the filtration performance.

(6) Conclusion:
As described above, according to the present invention, it is possible to provide a novel cylindrical material technology and the like according to various aspects. Needless to say, the above-described basic actions and effects can be obtained even with a technique that does not have the constituent elements according to the dependent claims but includes only the constituent elements according to the independent claims.
In addition, the configurations disclosed in the embodiments and modifications described above are mutually replaced, the combinations are changed, the known technology, and the configurations disclosed in the embodiments and modifications described above are mutually connected. It is possible to implement a configuration in which replacement or combination is changed. The present invention includes these configurations and the like.

DESCRIPTION OF SYMBOLS 1 ... Cylindrical carbonaceous body, 2 ... Through-hole, 3 ... Inner side surface, 4 ... Outer side surface, 5 ... Gap,
6 ... closed end, 7 ... open end,
10, 19 ... cylindrical activated carbon, 11 ... activated carbon, 12, 22 ... binder,
20 ... cylindrical carbonaceous material before activation, 21 ... activated carbon raw material,
30: Filtration cartridge,
40 ... Case, 41 ... Main body, 42 ... Inlet end (end on the inlet side), 42a ... Inlet,
43 ... Outflow end (end on the outlet side), 43a ... Outlet,
44 ... flow path on the inlet side, 45 ... flow path on the outlet side,
50 ... cylindrical activated carbon bundle, 51 ... closed end, 52 ... open end,
60 ... potting agent,
LD1 ... longitudinal direction, RD1 ... inward / outward direction, AD1 ... axial direction.

Claims (1)

A mixture containing at least an activated carbon or activated carbon raw material having an average particle diameter of 0.2 to 200 μm, a first binder, and an organic binder washed away with water is kneaded and extruded into a cylindrical shape to form holes along the longitudinal direction. Forming a long cylindrical molded body, washing the cylindrical molded body with water to remove the organic binder, drying the cylindrical molded body washed with water, and leaving the first binder remaining. It is a long cylindrical carbonaceous material having holes formed along the longitudinal direction, and a cylindrical carbonaceous material in which fluid can flow in and out of the cylindrical carbonaceous material is manufactured. A method for producing a cylindrical carbonaceous material.

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