JP2007105619A - Adsorbent comprising carbonized material and method for preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorbent comprising a carbonized material that performs an excellent capability of cleaning a fluid, can be made at a low production cost, and has a low maintenance cost. <P>SOLUTION: The adsorbent comprising a carbonized material is constituted of chips of carbonized wood having a specified particle size each remaining as an independent and unbonded particle with their surfaces covered with a coat layer of a solidified cement binder. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a carbide-based adsorbent and a method for producing the same, and in particular, by providing a coating layer made of a predetermined functional material on the surface of granular wood-based carbide, the fluid purification ability of the carbide is enhanced. The present invention relates to a carbide-based adsorbent and a method for producing the same.

  Conventionally, a filter material is formed by putting a powdery functional substance that exhibits adsorption ability for predetermined ions such as activated carbon into a predetermined container or binding with a binder, and such as air or water Adsorption, capture and purification of harmful substances contained by passing a fluid is performed.

  For example, Japanese Patent Application Laid-Open No. 11-226327 discloses an air cleaning and water purification filter plate in which granular activated carbon is sandwiched from both sides with polyester resin-treated cotton having high air permeability and molded with a plastic net. -116976 describes a deodorizing and dehumidifying agent in which granular charcoal is housed in a bag having high air permeability together with granular tourmaline.

  By using these carbides as a fluid filtration filter, harmful substances such as malodorous molecules contained in the fluid can be physically adsorbed and efficiently purified. However, such carbides are easily pulverized and powdered, producing carbon powder and causing dirt, and by continuing to adsorb substances, the adsorption capacity gradually decreases as the adsorption site approaches saturation. End up. This decrease in adsorption capacity can be recovered to some extent by high-temperature treatment or washing with a dedicated chemical, but it is not easy to perform on-site treatment, so it can be dealt with by changing the adsorbent for a specified period of time. There are many cases.

  On the other hand, JP-A-7-39553 and JP-A-2001-17859 disclose that the adsorbing ability for a predetermined harmful substance can be enhanced by adding a chemical component such as an alkaline substance to the surface of activated carbon or the resolution. Carbide-based adsorbents that enhance the fluid purification function and extend the effect duration have been proposed.

  However, these carbide-based adsorbents are not significantly improved in function due to alkalinization or the like, and also deteriorate in function after a predetermined period of time due to a decrease in the amount of chemical components and saturation of adsorption sites. On the other hand, since it takes a lot of labor and cost to carry out cleaning treatment or heat treatment on the carbide-based adsorbent for reuse, or to attach a chemical substance again, the replacement time is slightly more than that described above. In the end, there was a need for replacement after use for a predetermined period.

  As the adsorbent, activated carbon is frequently used from the viewpoint of high adsorbing ability, etc., but activated carbon is expensive to manufacture, and the introduction cost and the maintenance cost required for replacement are likely to increase. Moreover, when using activated carbon as an air filter, since activated carbon is a combustible substance, it also has the fault that it cannot be used near fire.

  In contrast, Japanese Patent Application Laid-Open No. 2001-519 proposes a deodorizing agent composed of lightweight aerated concrete (ALC) particles having a pH of 10 to 11.5. This is a non-flammable material that is less expensive to manufacture than general activated carbon, and has a chemical adsorption capacity and resolution by concrete in addition to physical adsorption capacity. It is characterized by being activated.

However, although the adsorption capacity of the deodorant composed of lightweight aerated concrete particles shows the same level as the adsorption capacity of coconut shell activated carbon, it does not greatly exceed this, and is sufficient when the odor strength is strong. In many cases, the deodorizing effect cannot be exhibited. Moreover, although it is said that it is low-cost compared with activated carbon, in addition to the process of mixing a foaming agent such as aluminum powder in the production process and the process of steam curing at high temperature and high pressure, a pulverization process to make particles of a predetermined size In other words, since the technique and labor for aligning the pore diameter and specific gravity within a predetermined range and aligning them with a predetermined size of strips are required, the manufacturing cost has not been sufficiently reduced. Furthermore, this deodorant is based on the premise that if the adsorption capacity is lowered after being used for a predetermined period, it will be replaced, and the maintenance cost will not be sufficiently reduced.
JP 11-226327 A JP 2003-116976 A JP 7-39553 A JP 2001-17859 A JP 2001-519 A

  The present invention is intended to solve the above-described problems, and can achieve excellent fluid purification performance while reducing the manufacturing cost and the maintenance cost of the carbide-based adsorbent. The challenge is to make it.

  Therefore, the present invention is that the strips of a predetermined particle size made of a wood-based carbide have a coating layer with a cement binder solidified on the surface, and maintain the granularity in a state where the individual strips are not bonded to each other. It was set as the characteristic carbide type adsorbent.

  In this way, a granular adsorbent that covers the surface of strips made of wood-based carbide, which is relatively inexpensive and easily available, with a predetermined thickness so that they are not bonded to each other with a relatively cheap and common cement-based binder; As a result, the manufacturing cost is low, and the filter can be used as a filter having various shapes by being placed in a breathable container having a predetermined shape, and also has excellent transportability. And since the coating layer made of cement binder exhibits substance permeability inside and outside the strip, the physical adsorption ability peculiar to carbide and the function peculiar to the coating layer made of alkaline cement binder exhibit a synergistic effect. It becomes.

  That is, by maintaining the granular shape without bonding the fine pieces, it is possible to cope with any shape while maximizing the adsorption surface area, and the physical adsorption ability of the carbide is exhibited to attract the target substance, thereby providing a cement binder. Since the functions such as the specific physical adsorption ability, chemical adsorption ability, and resolution can be fully exhibited, the fluid purification ability is extremely excellent.

  Moreover, in the conventional example, most of the target substances that have reduced the function by blocking the pores of the carbides are captured by the cement-based binder layer on the surface side, and most of them are added with water, resulting in alkali due to the cement component. It is rendered harmless by hydrolysis and removed by evaporation or the like. Accordingly, it is easy to restore the original purification ability and it becomes unnecessary to exchange over a long period of time, so that the maintenance cost is extremely low. Further, the surface of the combustible wood-based carbide is covered with a non-combustible cement-based binder, so that it is difficult to be powdered and extremely flame retardant as a whole, and can be used in the vicinity of fire.

  Further, in the above-described carbide-based adsorbent, if the wood-based carbide strip is made of flaky carbide obtained by firing a paper laminate, the raw material is inexpensive and carbonizes relatively easily. Therefore, the manufacturing cost is low, and the internal laminated structure has a large adsorption surface area of carbides and exhibits excellent physical adsorption ability.

Furthermore, in the above-mentioned carbide-based adsorbent, if the cement-based binder is mainly composed of Portland cement, the binder to be used is inexpensive and readily available and solidifies in a relatively short time. It has excellent strength and durability. Even if a relatively inexpensive specific surface area of less than 5000 cm ² / g is used as the Portland cement, the above-mentioned effects can be obtained while ensuring the form stability of the adsorbent, and therefore an expensive specific surface area of 5000 cm. There is no need to use ² / g or more, and the manufacturing cost can be further reduced.

  Furthermore, the above-mentioned carbide-based adsorbent is mixed by stirring and mixing 10 to 15 parts by volume of a cement-based binder and a predetermined amount of water to 100 parts by volume of wood carbide particles having a particle size of 1 mm to 7 mm. As a result, the binder layer on the surface of the strip becomes an extremely thin film or dot, and the material flowability inside and outside the carbide is excellent, so the synergy between the wood-based carbide and the cement-based binder coating layer The effect will be exhibited even better.

  In addition, if the particle size of the wood-based carbide particles in this carbide-based adsorbent is 4 mm to 7 mm, the carbide has an excellent balance between fluid permeability and adsorption surface area, and further excellent material adsorption ability. It becomes a system adsorbent.

  In addition, a predetermined amount of water is added in advance to the strip made of wood-based carbide to make the surface wet, and then a powdered cement binder is added and mixed with stirring at a predetermined ratio, and the cement surface is mixed with the water on the surface of the strip. As a state in which the binder adheres and the hydration reaction proceeds, by curing this for a predetermined period of time, the above-mentioned carbide-based adsorbent is produced by the method for producing a carbide-based adsorbent in which a cement-type binder is solidified. An adsorbent shall be manufactured. As a result, it is possible to obtain a carbide-based adsorbent having a coat layer and improved functionality at a low cost by a relatively simple process.

  On the other hand, the strips provided with the coating layer in the above-described carbide-based adsorbent are further bonded to each other with a cement-based binder and molded into a predetermined shape, and the carbide-based adsorption having a porosity of 25% or more. If it is set as the molding body of an agent, it can be used as a filter material as it is with excellent fluid permeability, and the function of the above-mentioned carbide-based adsorbent can be easily exhibited.

  The molded article of the carbide-based adsorbent is kneaded by adding 18 to 27 volume parts of a cement-based binder and a predetermined amount of water to 100 volume parts of the carbide-based adsorbent strip having the above-described coat layer. If it is molded into a predetermined shape and has a porosity of 27 to 37%, it will have an excellent balance between the strength of the molded body and fluid permeability. Alternatively, 27 to 37 parts by volume of a cement-based binder, 28 to 38 parts by volume of an aggregate having a particle size of 1 to 9 mm, and a predetermined amount of water are added to and kneaded with 100 parts by volume of a strip having a coating layer, and the desired shape is obtained. If it has a porosity of 25% or more, the strength and specific gravity can be increased, and it can be used as a fluid purification material that also serves as a structural material in addition to a fluid filter.

  Further, in the above-mentioned molded article of the carbide-based adsorbent, the strips having the coating layer are mixed with a large strip having a particle size of 4 mm to 7 mm and a small strip having a particle size of 1 mm to 2 mm in a predetermined ratio. If a small strip and a cement binder are interposed between adjacent large strips after molding, the strips can be bonded more firmly while securing a predetermined porosity with a small amount of binder. If the mixing ratio of the large and small strips is 2: 1 by volume, the balance between the porosity and the strength of the molded body is excellent.

  Further, the above-mentioned cement binder or the above-mentioned cement binder and the above-mentioned aggregate are mixed into the strip having the coating layer, and a kneaded mixture of a predetermined amount of water is put into the mold, and the longitudinal direction If the above-mentioned carbide-based adsorbent molded body is manufactured by a manufacturing method in which a vibration press is given for a predetermined time and molded, then immediately demolded and coated and cured for a predetermined period, it is relatively inexpensive. While using a general cementitious binder, a uniform porous body can be obtained with a simple process and at low cost with little unevenness, and has excellent fluid permeability and uniform strength.

  A relatively cheap and easy-to-obtain wood carbide strip surface is coated with a relatively inexpensive and common cement binder coat layer, or is further bonded with a cement binder to make it porous. The molded body of the present invention exhibits excellent fluid purification performance by synergistic effects of carbide-specific functions and cement-based binder functions while ensuring fluid permeability, and lowers manufacturing and maintenance costs. Can be realized.

  The best mode for carrying out the present invention will be described with reference to the drawings. In the present invention, the porosity refers to the porosity in the air, and the infiltration of the liquid into the sample is assumed only to infiltrate the void formed between the strips, and the infiltration into the inside of the strips is not assumed. In the case of a short time of about 5 minutes, the void volume is calculated by subtracting the true volume of the water level rise from the apparent volume by dimensional measurement, and the value is derived by dividing by the apparent volume. Further, the specific surface area refers to a specific surface area according to a specific surface area test: R5201 among physical test methods of JIS cement. Furthermore, the average particle diameter refers to the size expressed by the size of the sieve opening in the screening test, and the flake shape refers to the flake shape of the granular form.

  FIG. 1 shows a flowchart of a method for producing a carbide-based adsorbent according to the first embodiment of the present invention. The fine pieces to be used are wood-based carbides, which are obtained by preliminarily pulverizing the fine pieces into a particle size of 1 mm to 7 mm using a plurality of mesh size sieves. In addition, it is recommended to use a flaky carbide obtained by finely pulverizing and firing a paper laminate as the wood-based carbide. In other words, in addition to being able to recycle waste paper, which normally costs cost for disposal, it is relatively easy to carbonize, and the resulting carbide has excellent morphological stability due to the laminated structure and paper fiber structure, and has a large adsorption surface area and functions. It is because it is excellent in property.

If it demonstrates according to a flowchart, 100 volume part of this strip will be thrown into a mixer and will be stirred and mixed until it will be in a surface wet state, adding water suitably. Next, 10 to 15 parts by volume of a powdery cementitious binder is added thereto, and further stirred and mixed. For example, in the case of 10 liters having a particle diameter of 4 mm at normal humidity, the cement binder is about 1.25 liters. In addition, it is not necessary to use an expensive cement surface binder having a specific surface area of 5000 cm ² / g or more like a so-called early-strength cement, and a relatively inexpensive and easily available ordinary Portland cement having a specific surface area of about 3200 cm ² / g. Can be used.

  Then, this stirring and mixing is performed until the powdery cementitious binder is evenly adhered to and covered with the surface of the fine pieces wetted with water, and after the stirring and mixing, the bottom is placed in a mesh-like container and cured for a predetermined time. At that time, by blowing air from the container bottom side to dry the excess moisture, it is easy to maintain the granularity by avoiding the joining of the fine pieces. Moreover, if stirring and mixing are performed again after curing for a predetermined time, it becomes easier to avoid the bonding between the strips.

  In this way, the carbide-based adsorbent completed with a simple procedure using a cement-based binder that is relatively inexpensive and easily available is a cement-based binder with a thin or dot-like coating layer formed on the surface of a strip. Since the coating layer itself has flowability inside and outside the strip and has chemical adsorption ability and resolution in addition to physical adsorption ability, a synergistic effect with the function of carbide can be expected, and its fluid purification The enhancement of performance is realized. And by putting this in a breathable container of a predetermined shape, the porosity becomes high as a whole and it can be used in all shapes, and it can process a relatively large amount of fluid with excellent fluid permeability. It will exhibit an excellent function as a filter.

  And if the carbide | carbonized_material to be used can arrange | equalize a particle size in a predetermined range, since a cheap thing of a wood type can be used, it becomes possible to hold down manufacturing cost very cheaply. In addition, by covering with a cement-based binder having excellent shape stability after solidification, it is possible to avoid crushing and pulverization of the fine pieces made of carbides and to be extremely flame retardant. In addition, even if the target substance is stored / saturated after long-term use and the purification performance is reduced, an appropriate amount of water, such as odorous molecules, is sprayed on this. As the alkali hydrolysis proceeds, the adsorbate is decomposed and detoxified, and the decomposed product evaporates spontaneously, so it can be restored to its original performance, so there is no need for replacement over a long period of time. Cost can be kept very low.

FIG. 2 shows a flowchart relating to a method for manufacturing a molded article of a carbide-based adsorbent used as a fluid purification filter, which is a second embodiment of the present invention. Explaining in accordance with the flow chart, a carbide-based adsorbent composed of large pieces having a particle size of 4 mm to 7 mm and a carbide-based adsorbent composed of small pieces having a particle size of 1 mm to 2 mm, prepared by the above-described method for producing a carbide-based adsorbent. For example, 100 parts by volume of a mixture of 2: 1 in a volume ratio is weighed into a mixer, and 18 to 27 parts by volume of a cement-based binder is added thereto. The cement binder used may be an inexpensive one having a specific surface area of less than 5000 cm ² / g as described above, and ordinary Portland cement is sufficient.

  Next, while stirring and mixing with a mixer, an appropriate amount of water is added until it has an appropriate viscosity as a whole while taking into account the conditions such as humidity, and the mixture is thoroughly kneaded before being put into the mold. Then, a vibration press (using a general vibration device for cement molding) is carried out for a predetermined time from the vertical direction so that there is no unevenness, and after molding into a flat plate or block with a predetermined thickness, it is removed immediately. Then, the coating is cured for a predetermined period to obtain a molded article of a carbide-based adsorbent. Note that the carbide-based adsorbent strip having the coat layer that is initially put into the mixer may be the one before the coat layer is completely solidified, and the method for producing the carbide-based adsorbent according to the first embodiment described above. Even if it transfers to the manufacturing method of the molded object of this carbide type adsorbent directly from the middle of the curing process in or before the stage, it can produce similarly.

  In this way, the molded article of the carbide-based adsorbent manufactured by the manufacturing method of a relatively simple procedure is such that the strips having the adjacent coat layers are partially bonded with a small amount of cement-based binder, and the void connectivity is improved. Although it becomes highly porous and the adsorption surface area of the granular carbide adsorbent is slightly reduced by the bonded portion, it exhibits substantially the same action and effect, and has a porosity of 27 to 37% and fluid permeability. It can be used as a fluid purification filter as it is.

  FIG. 3 shows a flowchart relating to a method of manufacturing a molded article of a carbide-based adsorbent that can also serve as a structural material, according to a third embodiment of the present invention. If it demonstrates according to a flowchart, this Embodiment adds the process which throws in an aggregate in the process of the manufacturing method of 2nd Embodiment. That is, as described above, for example, 100 parts by volume of a mixture of large strips and small strips in a volume ratio of 2: 1 is weighed and put into a mixer, and then aggregates 28 to 38 having a particle diameter of 1 mm to 9 mm. Adding a volume part and 27-37 parts by volume of a cement-based binder, and thereafter molding into a predetermined shape and curing as described above to obtain a molded article of a carbide-based adsorbent having a porosity of 25% or more It was.

  Thus, although the ratio of the carbide which is a functional substance slightly decreases compared with the carbide molded body of the second embodiment by mixing the aggregate, the strength is increased and the specific gravity is increased, so the fluid purification filter It is suitable not only for use as a fluid purification material but also as a structural material such as a wall material and a flooring material. Even when used as a structural material, the porosity is relatively high at 25% or more, and in the same manner as described above, the surface of the carbide strip is in a state where the binder coat layer is point-bonded in a thin film or dot form. Since it covers, it maintains the adsorbability of carbides and is excellent in the flowability inside and outside the strip and can fully exhibit its original function. For example, by using it as an inner wall material, it effectively adsorbs harmful substances such as formaldehyde and other odorous molecules contained in indoor air, or absorbs moisture when the humidity is high in addition to air purification ability and moisture when it is low It is also possible to exert the humidity control ability to release the water.

  Hereinafter, the carbide-based adsorbent and the molded article of the carbide-based adsorbent of the present invention will be described in more detail with reference to examples. The fluid purifying ability of the air filter according to the present invention was tested and verified under the following conditions.

  Referring to FIG. 7, 150 g of the carbide-based adsorbent according to the manufacturing method of the first embodiment described above is put into a 25 cm × 25 cm square air-permeable bag (nonwoven fabric filter bag), and the inside is 4 etc. A filter 10A in the form of a cushion is prepared by inserting cross perforations as shown, and set so as to cover all the suction ports 13 having a diameter of 20 cm of the air cleaner 1A incorporating the ventilation fan 11 created by the present inventors. Then, this was sandwiched between the opening window 12a having a diameter of 20 cm on the bottom side and a lid 12 having a net, and fixed to a thickness of 2.2 cm. Then, the air cleaner 1A was disposed in close contact with the suction port 4b having a diameter of 20 cm provided on the back side of the test box 4 having a size of 60 cm × 34 cm × 60 cm so that the opening window 12a was aligned. Then, the front door 4a of the test box 4 is opened, the specimen 2 placed in a 30 cm × 24 cm × 2 cm tray is disposed, and the air inside the box is sucked and purified by the air cleaner 1A. Measured in seconds. When the front door 4a is closed, the odor hardly leaks to the outside, but the inflow of outside air from the door gap is possible with the suction of the air cleaner 1A.

Preparation of the carbide-based adsorbent is a fine piece of particle size 3 mm to 5 mm (trade name: Cerachip, product number: S5020, as a fine piece of wood-based carbide, finely pulverized and fired paper phenol laminates to make a wood-based carbide) 10 liters of Nippon CMK Co., Ltd.) is put into a mixer and mixed with stirring while adding an appropriate amount of water so that the surface becomes wet. As a cement binder, ordinary Portland cement (specific surface area 3300 cm ² / g, Taiheiyo Cement) 1.25 liters) was added and stirred and mixed until the cement powder was evenly adhered to the surface of the strip. And the mesh of the opening which does not let a 3 mm strip pass was moved to the drying container provided in the bottom face, and it air-cured and cured until the excess water | moisture content dried from the lower side, and created.

  With reference to the appearance comparison photograph of the finished carbide-based adsorbent (right) in FIG. 4 and the wood-based carbide strip (left) before the coating layer is provided, and the enlarged photograph of the carbide adsorbent in FIG. 5, Portland cement The carbide-based adsorbent thus produced has a slightly grayish color tone, whereas the carbide strips before being covered with black are black. Portland cement turns light gray after solidification, while the carbide adsorbent strip surface is not completely covered with gray Portland cement, and the surface is covered with a thin film-like part and covered with dots. It is presumed that the coating layer has a broken portion. In addition, the magnified photograph shows that the strips with the coating layer maintain a granular shape that is not bonded to each other to form flakes, and these are innumerable voids between adjacent adsorbent strips in an aggregated state. Is formed.

  The test was performed as Sample 2 1. 1. 100 ml of formalin (Japanese Pharmacopoeia, 36% formaldehyde aqueous solution) 2. 100 ml of buticello (generic name: butyl cellosolve (100%), manufactured by Daiso Chemical Co., Ltd.) Three types of ignited cigarettes (brand: Mild Seven (registered trademark), manufactured by Nippon Tobacco Inc.) were used, placed in a tray-like container, and placed as a specimen 2 at a substantially central position on the bottom surface of the test box 4. Tobacco measurement is performed by a person who blows the two cigarette smokes lit at the start of the measurement into the test box 4 to fill the smoke, and then puts them on the tray with the fires on. went.

  The measurement terminal 3a of the odor monitor device (trade name: handy odor monitor, product number: OMX-GR, manufactured by Shinei Co., Ltd.) was placed in the immediate vicinity of the air outlet 14 of the air cleaner 1A and measured for 15 minutes at a measurement interval of 10 seconds. As a control example, the odor intensity on the specimen side was measured at the same time with a measuring terminal 3b disposed approximately 30 cm above the specimen 2. 9 to 11 show graphs of the experimental results (the odor intensity level is indicated by points). The average wind speed by the air cleaner 1A was 0.38 m / sec on the suction side and 1.44 m / sec on the blowout side.

(Result) Formaldehyde: As shown in FIG. 9, the odor intensity on the specimen side recorded 200 points or more after 80 seconds, whereas the odor intensity on the outlet side after purification by the air cleaner 1A was continuously 20 seconds after 60 seconds. It became below the point. 2. Buticello: As shown in FIG. 10, the odor intensity on the specimen side showed 100 points or more after 90 seconds and was 150 points or more after 600 seconds, whereas the odor intensity on the blowout side was continuous after 90 seconds. Fell below 15 points. 3. Tobacco: As shown in FIG. 11, the odor intensity on the specimen side reached 440 points after 90 seconds and showed 40 to 430 points up to 600 seconds and then 60 to 290 points, whereas the odor on the blowing side The intensity was recorded at 5 to 70 points until 600 seconds, and continuously dropped below 5 points after 660 seconds when the fire was completely extinguished and no smoke was generated.

  As a result of this experiment, when the carbide-based adsorbent according to the present invention is used as an air filter in an air-permeable bag, humans are almost worried about 1 to 2 minutes after the operation of the air cleaner 1A (tobacco is extinguished). It can be said that the deodorizing function was sufficiently exerted because the odor intensity was at a level that would not be reached. Further, since the wind speed was 1.44 m / sec on the air outlet side of the air cleaner 1A, it can be seen that the filter 10A has excellent fluid permeability, and is considered as a material useful as an air filter. .

  Referring to FIG. 8, in the experimental apparatus used in Example 1, instead of the filter 10A containing the particulate carbide-based adsorbent, the molding of the carbide-based adsorbent shown in the second embodiment described above. 1. Using the 25 cm × 25 cm × 1.5 cm panel-like filter 10B manufactured by the body manufacturing method, under the same conditions as described above. Formalin, 2. Buticello, 3. Tobacco was tested.

  The fluid purification filter 10B is prepared by first preparing a carbide-based adsorbent according to the procedure described above. That is, as a fine piece of wood-based carbide, a fine piece (product name: Cerachip, product number: S5020, manufactured by Nippon CMK Co., Ltd.) having a particle diameter of 3 mm to 5 mm obtained by finely pulverizing and firing a paper phenol laminate. A mixer (250 liter capacity) measuring a small strip (product name: Cerachip, product number: S3005, manufactured by Nippon CMK Co., Ltd.) having a volume ratio of 2: 1 to 10 liters with a volume ratio of 1.5 mm to 2 mm. Product name: High-speed geared mortar mixer, model number: GM-6, manufactured by Takemura Tech Co., Ltd.), stirring and mixing while adding an appropriate amount of water to make the surface wet, and the above-mentioned ordinary Portland cement as a cement-based binder 1.25 liters was added and stirred and mixed until the cement powder was evenly adhered to the surface of the strip. And it moved to the container made into the net | network of the mesh which does not let the bottom piece 3 mm of a bottom face pass, and it ventilated and cured until the excess water | moisture content dried from the lower side, and created.

  Put the carbide-based adsorbent with a coating layer containing 2: 1 large strips and small strips into the mixer again, add 3 liters of ordinary Portland cement as described above, stir and mix, and then add an appropriate amount of water. Water was poured while being kneaded until it was injected and had an appropriate viscosity. The amount of water injected was 2 liters.

  Then, after sufficiently kneaded, it was put into a formwork (inside 30 cm × 30 cm, square) for producing a plate, and molded using a vibration press device created by the inventor. Specifically, a kneaded material sandwiched between an upper plate (30 cm × 30 cm) inserted into a mold and a lower plate (40 × 40 cm) receiving the same is air cylinder (product name: SCA2, tube diameter) from above. While pressing (351 kg) with 80 mm, manufactured by CKD), the vibration press is applied from above and below to the vibration motor (KM5-2PA (centrifugal force 0.49 KN), manufactured by Exen, one upper plate and two lower plates) Was carried out for 10 seconds and molded into a flat plate shape so as not to be uneven. With this vibration press, the original thickness of 2.2 cm became 1.5 cm. Immediately after the vibration press, the mold was removed, and after covering and curing, it was cut to 25 × 25 cm to obtain a filter 10B which is a molded body of a carbide-based adsorbent.

  With reference to the appearance photograph showing the state of the cross section of the filter 10B in FIG. 6 (A), the filter 10B made of a molded article of a carbide-based adsorbent is covered with all Portland cement surfaces. In contrast to the gray color of the carbide-based adsorbent of Example 1, the color tone of the carbide-based adsorbent of Example 1 is slightly closer to gray overall, but most of the portion exhibits a slightly grayish color tone of the black carbide. It is presumed that it is not completely covered with Portland cement for bonding the adsorbents. Moreover, it turns out that it is rich in a space | gap from the state of a cross section, and each space | gap is mutually connected. Furthermore, as shown in the external photograph of FIG. 6B in which the filter 10B is placed on the gas range and the water is boiled with kettle, even when heated with fire until the water boils, it burns or deforms. It is extremely flame retardant and has excellent fire resistance.

  This was mounted in the same manner as described above to obtain an air cleaner 1B, and the test was performed under the same conditions as described above (the tobacco deodorization test was completed in a test time of 660 seconds). 12 to 14 show graphs of the test results (the level of odor intensity is indicated by points). The porosity of the filter 10B was 35%, and the average wind speed by the air cleaner 1B was 0.55 m / sec on the suction side and 2.92 m / sec on the blowout side. For reference, the average wind speed when the volume ratio of large and small pieces is 1: 1 in wood-based carbide is 0.31 m / sec on the suction side and 2.18 m / sec on the blowout side. Yes, it is considered that the fluid permeability was improved by setting the volume ratio of the large strip to the small strip to 2: 1.

  (Result) Formalin: As shown in FIG. 12, the odor intensity on the specimen side recorded 50 points or more after 80 seconds, recorded 150 points or more at the maximum, and recorded almost 40 points or more after 500 seconds, The odor intensity on the outlet side after purification by the air cleaner 1B was continuously below 40 points. 2. Buticello: As shown in FIG. 13, the odor intensity on the specimen side recorded about 100 points to 400 points after 40 seconds, whereas the odor intensity on the blowout side continuously decreased below 100 points. 3. Tobacco: As shown in FIG. 14, the odor intensity on the specimen side had been recorded around 50 to 240 points after 110 seconds, whereas the odor intensity on the blowing side was continuously below 15 points after 120 seconds, After 460 seconds, 5 points or less were shown, and after 610 seconds, almost 0 points were shown.

  From this experimental result, the molded article of the carbide-based adsorbent according to the present invention has a significantly lower odor level compared to the control example even when used as a panel having a thickness of only 1.5 cm. It can be said that the odor function was fully exhibited. Moreover, since it had the wind speed of 2.92 m / sec in the blower outlet side of the air filter 1B, it turns out that it has the outstanding fluid permeability, and is considered to be a useful material as an air filter.

  As compared with the first embodiment, 1. Formalin and 2. Since the deodorizing effect of Buticello was somewhat inferior, when two fluid purification filters 10B were stacked for 30 mm in thickness for the same test, formalin recorded around 15 points after 80 seconds. However, Buticero did not exceed 10 points and continued to show 5 points or less continuously after 300 seconds. Therefore, it was found that the adsorption capacity of the filter 10B is improved by increasing the thickness. Although not shown in detail, the aggregated carbide-type adsorbent molded body of the third embodiment was also tested in the same manner, but its fluid permeability was slightly lower than that of the second embodiment. As a result, almost the same result was obtained and the significance could be confirmed. In addition, it was thought that it became useful especially in the usage method which also served as a structural material, since the gravity increased and the fastness was improved by adding the aggregate.

  Further, for comparison, the same filter is used as it is as a strip (product name: Cerachip, product number: S5020, manufactured by Nihon CMK Co., Ltd.) having a particle diameter of 3 mm to 5 mm before providing the coating layer with the cement binder in the first embodiment. When the deodorization test was carried out in the same manner after putting it in a bag and setting it in an air cleaner, the odor intensity was 20 points or less, but it did not fall below 5 points, and the tobacco odor was still at a level that can be felt by humans. From this, it can be seen that the present invention in which a cement-based binder coat layer is provided on carbide exhibits a deodorizing ability superior to that of carbide alone.

  From the results of Example 1 and Example 2 described above, the carbide-based adsorbent and the carbide molded body of the carbide-based adsorbent according to the present invention are excellent in enhancing the functions of the carbide while realizing cost reduction. It was confirmed that the fluid purification ability was demonstrated. From this extremely excellent deodorizing effect, it is thought that the deodorizing effect of the carbide itself is further enhanced, but this is influenced by the characteristics of the cement binder that is a negative ion material is assumed.

For example, odors and ketones, carboxylic acids (organic acids), esters, and the like, which are particularly unpleasant to humans as odor generating sources, include OH ^{− of} cement binders which are alkaline materials. The following reactions are considered to occur between

Aldehyde ketone: carbon of aldehyde and ketone, OH ^- is nucleophilic addition, given diol, they become water soluble anion. Carboxylic acids: Carboxylic acids leave protons under alkaline conditions and become water-soluble anions. For example, oxalic acid and valeric acid having an unpleasant odor become odorless by reacting with alkali. Esters: Esters contained in cosmetics and fruits are hydrolyzed under alkaline conditions to give water-soluble carboxylic acid anions and alcohols.

  Therefore, it is considered that not only the adsorption by the wood-based carbide but also that the odor-causing molecule is not brominated by touching the binder is involved in the deodorizing function. In addition, all the reactants mentioned above are deodorized by alkali hydrolysis as described above by adding water to the carbide-based adsorbent, and then the alcohol content is removed by evaporation. It is expected that it can be used over a long period of time, and the maintenance cost can be kept low. For example, in a semiconductor factory that uses Buticello, for example, activated carbon was used as the air filter for the air cleaner. Instead of the air cleaner 1A of Example 1, about 10 months have passed, but the air filter is replaced every month in the past. On the other hand, at present, there is no need for replacement, and the deodorizing ability superior to the case of using new activated carbon continues to be demonstrated.

  In the development of the carbide-based adsorbent according to the present invention and the carbide molded body of the carbide-based adsorbent, the inventors of the present invention have carried out with various raw materials, shapes, sizes and mixing ratios for the carbide strips used, Using various binders as the coating layer, the functions such as fluid permeability and fluid purifying ability when used as a filter were investigated. As a result, each configuration shown in the above solution is adopted because it is excellent in these viewpoints.

That is, by making the surface coating layer a cement-based binder, it is easy to ensure its physical adsorption capacity while maintaining the form of carbide, and the functions specific to the cement material work effectively. 10 to 15 parts by volume is due to the fact that the fluid purifying ability and the form maintaining ability suddenly decrease when the amount is less than 10 parts by volume, and the adsorbing ability suddenly decreases when the amount exceeds 15 parts by volume. Since it was sufficiently exhibited even with inexpensive ordinary Portland cement, it was not limited to an expensive specific surface area of 5000 cm ² / g or more.

  In addition, when the particle size of the carbide flakes is less than 1 mm, the porosity is insufficient and the fluid permeability is greatly reduced, and when it exceeds 7 mm, the total surface area in the void is insufficient and the adsorptive capacity is drastically reduced. Because. Furthermore, when the strip is molded in two sizes, a large strip with a particle size of 4 mm to 7 mm and a small strip with a particle size of 1 mm to 2 mm, using a mixture ratio of 2: 1, This is because the fluid permeability is excellent. Furthermore, when the cementitious binder for bonding the carbide-based adsorbents is less than 18 parts by volume, the binding force is suddenly reduced, and when it exceeds 27 parts by volume, the porosity is suddenly reduced and the adsorption capacity is large. This is due to the decline.

The flowchart which shows the manufacturing method of 1st embodiment of this invention. The flowchart which shows the manufacturing method of 2nd embodiment of this invention. The flowchart which shows the manufacturing method of 3rd embodiment of this invention. The external appearance comparison photograph with the carbide | carbonized_material type | system | group adsorption agent (right) created in Example 1 and the carbide | carbonized_material piece (left) before providing a coating layer. The enlarged photograph of the carbide type adsorbent of FIG. (A) is an appearance photograph showing the state of the cross section of the molded article of the carbide-based adsorbent prepared in Example 2, and (B) is an appearance photograph showing a state where the water of the kettle is boiled by placing the molded article on a gas range. 1 is a longitudinal sectional view showing a test apparatus in Example 1. FIG. FIG. 3 is a longitudinal sectional view showing a test apparatus in Example 2. The graph which shows the test result which used formalin as the specimen in the test apparatus of FIG. The graph which shows the test result which used the buticello in the test apparatus of FIG. The graph which shows the test result which used the tobacco for the test | inspection in the testing apparatus of FIG. The graph which shows the test result which used formalin as the specimen in the test apparatus of FIG. The graph which shows the test result which used buticello as a sample in the testing apparatus of FIG. The graph which shows the test result which used the tobacco for the test | inspection in the testing apparatus of FIG.

Explanation of symbols

  1A, 1B air cleaner, 2 samples, 3a, 3b measuring terminal, 10A, 10B filter

Claims (13)

  The strip having a predetermined particle diameter made of a wood-based carbide has a coating layer in which a cement-based binder is solidified on the surface, and maintains a granular shape in a state where the individual strips are not bonded to each other. Carbide-based adsorbent.   The carbide-based adsorbent according to claim 1, wherein the strip is a flaky carbide formed by firing a paper laminate.   The carbide-based adsorbent according to claim 1 or 2, wherein the cement-based binder is mainly composed of Portland cement. The Portland cement according to claim 3 has a specific surface area of less than 5000 cm ² / g, and is a carbide-based adsorbent.   The carbide-based adsorbent according to claim 1, 2, 3 or 4 adds 10 to 15 parts by volume of the cement-based binder and a predetermined amount of water to 100 parts by volume of the fine particles having a particle size of 1 to 7 mm. Carbide-based adsorbent characterized by being stirred and mixed.   6. The carbide-based adsorbent according to claim 5, wherein the strip has a particle size of 4 mm to 7 mm.   A predetermined amount of water is added to the strip in advance to obtain a wet surface, and then the cement-based binder in powder form is added at a predetermined ratio and mixed with stirring. The cement-based binder adheres to the water on the surface of the strip. The carbide-based adsorbent according to claim 1, 2, 3, 4, 5 or 6, wherein the coating layer is formed by solidifying by curing for a predetermined period of time. Manufacturing method.   The strips having the coat layer in the carbide-based adsorbent according to claim 1, 2, 3, 4, 5, or 6 are further partially bonded to each other with the cement-based binder and molded into a predetermined shape. A molded article of a carbide-based adsorbent characterized by having a porosity of 25% or more.   The molded article of the carbide-based adsorbent according to claim 8 is kneaded by adding 18 to 27 parts by volume of the cement-based binder and a predetermined amount of water to 100 parts by volume of the strip having the coat layer. A molded article of a carbide-based adsorbent, characterized in that it has a porosity of 27 to 37%.   The molded article of the carbide-based adsorbent according to claim 8 is an aggregate 28 to 38 having 27 to 37 parts by volume of the cement-based binder and a particle size of 1 to 9 mm with respect to 100 parts by volume of the strip having the coat layer. A molded article of a carbide-based adsorbent characterized by having a volume part and a predetermined amount of water added and kneaded to be molded into a predetermined shape and having a porosity of 25% or more.   The molded article of the carbide-based adsorbent according to claim 8, 9, and 10 is a predetermined ratio in which the fine pieces having the coat layer are large pieces having a particle diameter of 4 mm to 7 mm and small pieces having a particle diameter of 1 mm to 2 mm. A molded article of a carbide-based adsorbent, characterized in that the small strip and the cement binder are interposed between the large strips adjacent after molding.   The molded article of the carbide-based adsorbent according to claim 11, wherein a mixing ratio of the large strip and the thin strip is 2: 1 by volume ratio. The cement-type binder or the cement-type binder and the aggregate are mixed into the strip having the coat layer, and a kneaded mixture of a predetermined amount of water is added to the mold, and the vibration press is performed from the vertical direction. A method for producing a molded article of a carbide-based adsorbent according to claim 8, 9, 10, 11, or 12, wherein the mold is given for a predetermined time and then immediately demolded and coated and cured for a predetermined period.