JP4063316B2 - Deodorization method - Google Patents

Description

  The present invention includes, for example, deodorization of water-soluble malodorous gas generated by decay, fermentation, oxidation, etc. of organic matter in food processing factories, removal of unsaturated fatty acids, fertilizer / feed factories, barns, sewage, human waste treatment plants, asphalt regeneration plants In particular, the present invention relates to a method for detoxifying malodorous gases generated by decay, fermentation, oxidation, etc. of organic matter. More specifically, for example, ammonia-based malodors such as ammonia and trimethylamine, organic acids such as acetic acid and isovaleric acid, fatty acids, hydrocarbons generated in asphalt regeneration plants, etc. The present invention relates to a method for removing malodorous substances and harmful substances contained in the air for the purpose of reducing malodorous substances such as sulfur odor substances and oil mist.

  Conventionally, as a method for deodorizing exhaust gas discharged from various factories and treatment plants, the cleaning method, adsorption method, combustion method, catalytic combustion, etc., depending on the type, concentration, treatment amount, budget and final requirement standards of the target odor Various methods such as a method, an oxidation method, a neutralization method, a photocatalytic method, a biological deodorization method, and a masking method have been implemented.

  Of these various deodorizing methods, the cleaning method is low in construction cost and suitable for removing the ammonia odor, and is suitable for the treatment of malodorous gases having a low concentration and a large air volume. For this reason, the cleaning method is widely used in fertilizer / feed factories, foundries, sewage / human waste treatment plants, and the like. However, the cleaning method has a problem in that running costs are high for removing a large amount of waste water used for removing and cleaning ammonia dissolved in water.

  The adsorption method is a method employed in fertilizer / feed factories, sewage / human waste treatment plants, and the like. The adsorption method includes a method using activated carbon as an adsorbing material and a method using an ion exchange resin. Activated carbon is used for low-concentration mixed malodor gas, and the initial equipment cost is relatively low, but it is not very effective for basic malodor such as ammonia. On the other hand, when an ion exchange resin is used as an adsorbing material, an effect is recognized for a slightly high concentration of bad odor, but there is a drawback of lacking stability. Furthermore, the adsorption method requires frequent replacement of the adsorbent material.

  The neutralization method is easy to handle and is used in food factories, chemical factories, sewage and human waste treatment plants, and the like. However, the neutralization method has a low effect on ammonia and has a limited application range. Furthermore, the neutralization method requires a chemical for neutralization (neutralizing agent), and its running cost is high due to its replenishment.

  As described above, among the conventional deodorization methods, the cleaning method, the adsorption method, and the neutralization method have low construction costs and are easy to maintain and manage. Although chemicals are required, construction costs are relatively low, and maintenance is easy, the higher the raw odor concentration, the higher the cost of regeneration of the adsorbent and the cost of replenishing the neutralizing agent. Rebounds on running costs.

  Further, the catalytic combustion method has a very high malodor removal efficiency and is applied to high-concentration malodor. However, the catalytic combustion method is not applied to the livestock industry because of high equipment costs and running costs.

  The oxidation method is suitable for small-scale equipment, and is used in fertilizer and feed factories, food factories, petrochemical factories, sewage and human waste treatment plants, and the like. The oxidation method includes an ozone oxidation method and a chlorine oxidation method. All are effective against sulfur-containing malodor, but almost no effect is observed on basic malodor such as ammonia.

  In addition, the photocatalytic method is expensive for machinery, inferior in cost performance, and is not suitable for large-capacity processing. However, the deodorizing effect is low.

  The biological deodorization method uses the deodorizing effect of soil and the soil microorganisms that inhabit it, and is effective for almost all malodorous fields, and can be applied to almost all other than chemical factories. In addition, the biological deodorization method has an advantage that equipment costs and running costs are low. However, the biological deodorization method requires a large area in the facility, and complete deodorization is impossible, and the effect is not recognized when the malodor concentration is high.

  Furthermore, the masking method is not a removal of the original odor gas but a method of concealing a low-concentration malodor with another odor such as a perfume, and is not a fundamental solution and has limited applications.

  Thus, at present, there is still no definitive solution for removing malodors.

  A method of reactivating the catalyst by washing with water has also been proposed. For example, an oxidation catalyst layer in which a porous ceramic honeycomb body is impregnated with a catalyst metal is provided in a vertical cylinder, and a water spray nozzle is disposed above the catalyst layer, and a hot air supply nozzle is disposed below the catalyst layer. An exhaust gas treatment apparatus has been proposed in which an exhaust pipe is attached to the upper part, an exhaust gas supply pipe is attached to the lower part, and a drain pipe is attached to the bottom part (see Patent Document 1). In this exhaust gas treatment device, exhaust gas at 200 to 250 ° C. containing harmful substances such as carbon monoxide and hydrocarbons, carbon pitch, etc., discharged from an asphalt regeneration furnace, etc. is preheated and heated to 300 to 400 ° C. After being warmed, it is supplied into the cylinder from the exhaust gas supply pipe, is passed through the oxidation catalyst layer, is converted into a harmless substance such as carbon dioxide and hydrogen, and is exhausted from the exhaust pipe at the top of the cylinder. And when the catalyst layer is poisoned by exhaust gas treatment and the catalyst performance deteriorates, the washing water is sprayed from the water spray pipe to the catalyst layer to wash the dust adhering to the catalyst layer, and then the hot air supply nozzle From 500 to 700 ° C., hot air at 500 to 700 ° C. is supplied to incinerate and remove residual heating materials such as carbon and pitch attached to the catalyst layer to activate the catalyst, thereby extending the life of the catalyst. However, this exhaust gas treatment device is effective in detoxifying carbon monoxide, hydrocarbons, etc. discharged from asphalt regeneration furnaces, but other detoxification such as ammonia-based malodor and organic acid-based malodor ( Deodorization is not expected. Further, the sprayed water is used to stop the supply of exhaust gas and wash the catalyst, and serves only to reactivate the catalyst, and does not contribute to the detoxification of malodor. Furthermore, in this exhaust gas treatment device, it is necessary to raise the temperature of the exhaust gas to 300 to 400 ° C. by preheating prior to the detoxification treatment with the catalyst, and running costs such as fuel costs are high.

  In addition, as a deodorizing device for removing malodorous components such as hydrogen sulfide in human waste treatment facilities, a deodorizing tower is formed by forming a deodorizing gas outlet at the bottom and a deodorizing gas outlet at the top. At the bottom of the tower, a chemical circulation tank that stores the circulating liquid containing caustic soda is installed, and the chemical liquid circulated from the chemical circulation tank is sprinkled between the odor gas inlet and the deodorized gas outlet in the deodorization tower. A spray nozzle is provided, and a carbon ceramic filler layer having a columnar or prismatic shape with a diameter or length of 1 cm or more and a hole with a hole diameter of 100 mm or more is provided below the spray nozzle and flows into the deodorization tower. There has been proposed a deodorizing apparatus that removes malodorous components in odorous gas (see Patent Document 2). However, this deodorizing device detoxifies hydrogen sulfide generated in human waste treatment facilities and the like by reaction with caustic soda, and the carbon ceramic filler is merely a catalyst for promoting the reaction, and hydrogen sulfide. It is not expected to remove (deodorize) ammonia-based malodor or organic acid-based malodor.

Furthermore, Mg, SiO ₂ , Al ₂ O ₃ , and binder are mixed in the flue of the waste asphalt lump regeneration facility to eliminate odorous substances such as ammonia and methyl mercaptan in the exhaust gas from the waste asphalt lump regeneration facility. A ball (sphere), cylinder (cylinder), which is made of SiO ₂ containing Mg and semi-melt crystallized at 250 to 300 ° C., Al ₂ O ₃ , and has a myriad of 0.2 to 20 nm acicular micropores, There has been proposed a flue system for waste asphalt lump generation equipment provided with a catalytic reaction tower filled with soft ceramics formed into various shapes such as cones and supply means for supplying an appropriate amount of water to the ceramics ( (See Patent Document 3). According to this flue equipment, by contacting the exhaust gas containing malodorous substances with the ceramic needle-shaped micropores wetted with water, malodorous components are produced by the ion exchange reaction action, molecular classification effect and oxidation / reduction action. After being disintegrated and decomposed and further converted to an odorless substance, the odorless substance leaves the needle-shaped micropores and is released into the atmosphere through the chimney. Regarding the conversion / modification of the malodorous component into a harmless substance, the ceramic is generally composed of Mg as a nucleus, O (oxygen atom), Si (silicon), OH (hydroxyl), Al (aluminum), etc. the matrix are presumed to form a (three-dimensional lattice), when the water to the needle-like micropores are attached, Mg water molecules (H ₂ O), etc. are constituting the matrix, Si, elements such as Al Due to the catalytic action, the exhaust gas containing odor arrives where oxygen (O ₂ ) decomposes into oxygen ions and hydroxyl ions, and oxygen (O ₂ ) sticks to the needle-shaped micropores in the form of oxygen ions. malodorous substances as a source of rubber smell is oxidized or reduced, resulting in changes to H ₂ O and CO ₂ and electrons (e), a part of the H ₂ O exerts deodorization effect by decomposition Explained. However, this flue equipment is limited to detoxification of malodorous substances in the exhaust gas discharged from the waste asphalt lump processing equipment, and other than that, for example, acid gas discharged from the food industry, human waste processing equipment, etc. No consideration is given to application to detoxification treatment of exhaust gas containing various malodorous substances such as alkaline gas. Furthermore, the ceramic filled in the catalytic reaction tower is a relatively soft soft ceramic fired at a low temperature of 250 to 300 ° C., and its strength is not so great that it needs to be handled with care and has sufficient durability depending on the application. It may not be.

Also, in indoor spaces such as homes, offices and hospitals, bad odors such as cooking odor, food odor, tobacco odor, body odor, pet odor, toilet odor, nursing odor, toluene, xylene, formaldehyde, paradichlorobenzene, chloropyrifos, ethylbenzene As a gas phase reaction method for purifying air by continuously removing volatile harmful substances such as styrene and butyl phthalate over a long period of time, the peroxotitanate solution is heated and crystallized. A gas phase reaction method has been proposed in which water is intermittently applied to the surface of a photocatalyst while irradiating the photocatalyst produced using an anatase-type titanium oxide dispersion containing a peroxo group obtained by (See Patent Document 4). However, this gas phase reaction method can remove harmful substances such as malodor in the indoor space as described above, but contains a high concentration of malodorous components generated in, for example, food factories and human waste processing facilities. Detoxification of exhaust gas is difficult. Furthermore, in the case of such a treatment method using a photocatalyst, there is a problem that the mechanical device is expensive and inferior in cost performance as described above and is not suitable for large-capacity treatment. In this gas phase reaction method, water only regenerates the catalytic activity and does not participate in detoxifying malodorous components.
Japanese Utility Model Publication No. 3-54731 JP-A-9-882 JP 2001-232153 A JP 2002-301336 A

  The present invention has been made in view of the various problems of the conventional methods described above, and an object thereof is to provide a high-efficiency, low-cost deodorization method.

  In order to achieve the above object, the present inventors have made the best use of the structural effectiveness of ceramics in place of the existing catalytic method, and have acidic or basic malodorous and harmful components in the air (hereinafter referred to as the following). These are collectively referred to as “original odor substances.”) By providing an environment for primary modification and bringing the primary modified odor substances in the air into contact with the ceramic porous body, high efficiency and low cost We found a new deodorization method that can be deodorized with Furthermore, the present inventors have found a deodorizing method capable of deodorizing with higher efficiency by introducing an original odor substance in the air to an active point on the ceramic and employing water as a medium to be brought into contact with the ceramic.

  That is, in the deodorizing method according to the present invention, air containing malodorous components or harmful components is forced to pass through a deodorizing layer made of a ceramic porous body, thereby removing the malodorous components or harmful components and detoxifying them. A deodorizing method for discharging as air, wherein the ceramic porous body is a ceramic porous body having continuous through pores, and an acidic substance or a basic substance is supported thereon, and the acidic component in the air is the basic substance. It is characterized in that the basic component in the air is removed by passing through the ceramic porous body carrying the acidic substance.

  In the deodorizing method according to the present invention, the step of primary modification by a neutralization reaction in an acidic atmosphere in a basic atmosphere and the basic odor in an acidic atmosphere, and the primary modified odor, A basic substance or an acidic substance carried on the ceramic porous body according to the malodorous component or harmful component as a carrier, and further contacted with the ceramic porous body, and the malodorous component or harmful component contained in the air It is discharged as detoxified air.

Further, when cast iron slag is used as the ceramic porous body, a ceramic porous body having good continuous through pores is obtained, and MgO, MnO, FeO, CaO, SiO, Al ₂ O _{3 and the} like contained in the slag are obtained. The raw odor substance contained in the air is more efficiently removed by the action of the metal oxide.

  In addition, the ceramic porous body is granular, preferably spherical, filled into a case that can be ventilated to form a deodorizing layer, thereby reducing the airflow resistance. The chance of contact with the raw odor substance increases, and the removal efficiency of the raw odor substance is improved.

  Furthermore, the deodorizing efficiency is further improved by interposing moisture at the time of contact between the air containing the raw odor substance and the porous ceramic body. In other words, this deodorization method has the advantages of the conventional deodorization methods of adsorption method, neutralization method and cleaning method, and the original odor substance (ammonia, trimethylamine, acetic acid contained in the air) which is characteristic of ceramics. , Isovaleric acid, fatty acids, sulfur-containing odorous substances, oil mist, other malodorous and harmful ingredients), and an acidic atmosphere with an acidic or basic substance carried on a ceramic porous body Alternatively, water is used as a medium for primary modification of the original odor substance in a basic atmosphere and at the same time as a transfer medium for bringing the original odor substance into contact with the ceramic porous body. That is, in the present invention, water is not simply added to regenerate the catalytic activity as in the prior art, but the raw odor substance is generated by, for example, wind power constantly maintaining a wind speed of 0.5 m / s to 4.0 m / s. A new deodorizing system with high efficiency and low cost, which is unprecedented, is provided by forcibly flowing and moving water to a catalytic active point on a ceramic porous body.

  Further, a deodorizing apparatus for carrying out the above deodorizing method includes an apparatus main body having an intake port on one side and an exhaust port on the other side, and an inside of the apparatus main body between the intake port and the exhaust port. As air detoxified by supplying a plurality of deodorizing layers provided to partition into a plurality of spaces and air containing malodorous or harmful components into the device body and forcibly passing through the deodorizing layer. The deodorizing layer is a ceramic porous body having continuous through pores, and is made of a ceramic porous body carrying an acidic substance or a basic substance. In preferable embodiment of the said deodorizing apparatus, the water supply means for supplying water to the ceramic porous body of the said deodorizing layer is provided.

  According to the deodorizing method according to the present invention, it is possible to increase the raw odorous substance contained in the air at low cost simply by forcibly passing the air containing malodorous components or harmful components through the deodorizing layer made of the ceramic porous body. It can be efficiently removed and discharged as harmless air. Therefore, according to the present invention, it is possible to improve a working environment such as a factory, a surrounding living environment, an environment in a store such as a pet shop, and an indoor environment such as an office or a house.

  Moreover, by removing ammonia-based, organic acid-based and sulfur-containing malodorous substances in separate deodorizing layers in an oxidizing atmosphere and a reducing atmosphere, both basic and acidic raw odorous substances can be removed as a result.

  Furthermore, by interposing water when the air containing the raw odor substance is brought into contact with the ceramic porous body of the deodorizing layer, water provides more sites for primary modification of the raw odor substance and is harmless on the ceramic porous body. A highly efficient deodorizing action can be realized by increasing the frequency of contact with the activated activating point. That is, by using water as a medium, secondary modification following primary modification can be performed on the ceramic porous body at a high frequency, and a small amount of odor can be leaked into the air discharged from the deodorizing layer. , Can be lower. In addition, the use of water as a medium promotes the oxidation-reduction reaction. As a result, removal of all malodorous and harmful components such as ammonia, organic acid, sulfur-containing malodorous substances and fatty acids, that is, mixed malodor It is also effective for deodorization.

  Further, as a substance that promotes the detoxifying function, for example, a solid basic substance having a pH of 8.0 to 10.0 is used for an acidic odor, and a pH 3.0 to 5.0 is used for a basic odor. By using a solid acidic substance, a large amount of water is not required to create an acidic or basic atmosphere, and wastewater treatment costs can be kept low. In addition, since the water has a function of transferring the raw odor substance to the detoxifying active site on the ceramic porous body, it does not require a neutralizing agent to maintain the deodorizing ability, and can be treated at room temperature. It does not require light energy or heat energy to remove odorous substances and can be deodorized at low cost.

  In addition, by providing an oil mist removal step before the primary denaturation step, it is possible to efficiently adsorb and remove a large amount of unsaturated fatty acids and oil mist in the form of emulsion, and remove the oil mist and the like in advance. Thus, the subsequent removal efficiency of the raw odor substance in the deodorizing layer is also improved.

  The deodorization method according to the present invention is a continuous treatment method with almost no odorous substances and harmful substances mixed in the wastewater, so that the cost for wastewater treatment is equal to zero and the environmental load is small.

It is a schematic diagram (plane sectional drawing) of one Embodiment of the deodorizing apparatus used for implementation of the method of this invention. It is a plane sectional view of the deodorizing device used for the example. It is a plane sectional view of the other deodorizing apparatus used for the Example. It is a plane sectional view of the other deodorizing device used for the example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Deodorizing device, 2 Deodorizing device main body, 3 Deodorizing layer, 4 Ceramic porous body, 5 Water stop cock, 6 Sprinkling nozzle, 7 Drain outlet, 8 Drain pipe.

  The deodorization method according to the present invention forcibly passes air containing malodorous or harmful components (hereinafter sometimes referred to as “odor gas” or “raw gas”) through a deodorization layer made of a ceramic porous body. It is a deodorizing method for removing the malodorous component or harmful component. The malodorous or harmful components in the odor gas to be treated by the method of the present invention include ammonia, trimethylamine, acetic acid, isovaleric acid, fatty acids, sulfur-containing odorous substances, oil mist, other malodorous and harmful components, There is no particular limitation.

  An embodiment of a deodorizing apparatus for carrying out the deodorizing method of the present invention is shown in FIG. In addition, the form of the apparatus shown in FIG. 1 does not limit the deodorizing apparatus used for implementation of this invention.

  The deodorizing apparatus 1 shown in the figure forces odor gas (air containing odorous components and harmful components) to be processed from one side (right side in the figure) to the other side (left side in the figure) of the apparatus body 2. The raw odor substances such as malodorous components and harmful components contained in the odor gas are removed and exhausted from the apparatus main body 2 as detoxified air.

  The apparatus body 2 is a box made of a corrosion-resistant material such as stainless steel, provided with an intake port on one side thereof and an exhaust port on the other side thereof, and a plurality of deodorizing layers 3 are provided therein. The apparatus main body 2 between the intake side and the exhaust side is provided so as to be partitioned into a plurality of spaces. The deodorizing layer 3 is filled with a ceramic porous body 4 in a gas-permeable case whose both surfaces are covered with a metal mesh or the like. Further, in the space between the deodorizing layers 3, a watering nozzle 6 connected to a water supply means (not shown) is provided toward the deodorizing layer 3. In the figure, the reference numeral 5 indicates a water stop cock, and the reference numeral 7 indicates a drain outlet connected to the drain pipe 8. The drain pipe 8 may be connected to a water supply means to circulate and use water. Moreover, although the deodorizing apparatus 1 of the example is a horizontal type, it may be a saddle type or may be inclined.

  The deodorizing operation by the deodorizing apparatus 1 includes, for example, air (odor gas) containing various malodorous components and harmful components such as exhaust gas from a food processing factory, exhaust gas generated at a human waste treatment plant, and exhaust gas from an asphalt regeneration plant. Ceramics that are inhaled by the water supplied from the watering nozzle 6 when sucked by the suction means such as a sirocco fan, forcibly introduced into the apparatus main body 2 and passing through the ceramic porous body 4 of the deodorizing layer 3 By contacting the surface of the porous body 4, the pores or the pores, the raw odor substance in the air uses water as a medium, the acidic odor is in a basic atmosphere, and the basic odor is in an acidic atmosphere. Thus, the deodorized substances and harmful substances are removed from the air by being modified and contacting with the ceramic porous body, and the detoxified air is exhausted from the apparatus main body 2.

  The mechanism of deodorization in the present invention is considered as follows. That is, the odor gas to be treated first comes into contact with a basic substance or an acidic substance supported on the ceramic porous body, and the acidic odor is in a basic atmosphere of the basic substance, and the basic odor is In the acidic atmosphere with the acidic substance, it is quickly primary denatured by a neutralization reaction. Furthermore, in the present invention, the odor gas primarily modified as described above comes into contact with the catalytic metal contained in the ceramic porous body, or the basic material or acidic substance attached using the ceramic porous body as a carrier, The raw odor substance contained in the odor gas is removed.

  The ceramic porous body 4 constituting the deodorizing layer 3 is obtained by supporting a basic substance or an acidic substance on a ceramic porous body having continuous through pores.

  As the method for producing the ceramic porous body, for example, clay and foaming agent, which are ceramic raw materials, are mixed, mixed with water, kneaded, molded into a predetermined shape, and fired.

  More preferably, the ceramic porous body 4 contains a catalyst metal such as vanadium, iron, platinum, or nickel. These catalytic metals may be contained in the ceramic raw material, or the catalytic metal may be attached using the fired ceramic porous body as a carrier.

  Moreover, as a more preferable thing of the ceramic porous body 4 of this invention, after shape | molding and drying the composition which added the water | moisture content to the cast iron slag and the plastic clay, knead | mixed and dried, it is 900-1150 degreeC. Examples include foamed and fired at a temperature in the range. Preferably, the amorphous slag produced during the production of cast iron products is crushed and sieved to a particle size range of 0.25 to 2.0 mm and 50 to 80% by weight, and plastic clay is 20 to 50% by weight. A composition obtained by adding 12 to 25 parts by weight of water to 100 parts by weight of the mixture mixed and mixed and kneaded is molded into a desired shape, dried, and then foamed at a temperature in the range of 900 to 1150 ° C. , Fired.

  The ceramic porous body using the cast iron slag is disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-47075. More specifically, the amorphous slag produced during the manufacture of the ductile cast iron product is crushed and sieved, and the particles are sized to a particle size range of 0.25 to 2.0 mm. The slag particles are individually foamed and sintered with each other, and have continuous through-holes, by molding in a state and heating in a temperature range of 900 to 1150 ° C. It is a ceramic porous body.

The chemical component of the cast iron slag is the same as the glass composition disclosed in, for example, Japanese Patent Laid-Open No. 10-7433 (Patent No. 2899954), and is composed of 35 to 45% by weight of SiO ₂ and 10 to 10% of Al ₂ O ₃ . 15% by weight, 1% to 5% by weight of MgO, other components such as MnO, CaO, S and the like, and the weight ratio of (CaO + MgO) / SiO ₂ is 0.9 to 1.2, Al ₂ O ₃ / SiO ₂ The ratio of ₂ is 0.25 to 0.35. Specifically, for example, a SiO ₂ 40-41 wt%, the Al ₂ O ₃ 13 wt%, the MnO 1.5 to 2.5 wt%, the FeO 0.5 to 1.0 wt%, CaO 39 to 40% by weight, MgO 2% by weight, and S 0.4 to 1.0% by weight.

Cast iron slag as described above is mixed with plastic clay, kneaded with water, shaped so that individual slag particles are wrapped in plastic clay, and fired at a temperature range of 900-1150 ° C. A ceramic porous body used in the present invention having continuous through pores is obtained by foaming individual slag particles as individual pieces and sintering them individually. Parallel thereto, when the vitreous slag with a specific chemical composition as is heated above 700 ° C., with拆出of SiO ₂ -Al ₂ O ₃ -CaO such crystals takes place, and this The liquid phase with low viscosity is phase-separated, and the decomposition volatile component SO ₃ is present in the glass phase in a form combined with iron and manganese, and is accumulated due to a decrease in the viscosity of the glass phase due to an increase in temperature. It is considered that the gas component is foamed around 900 ° C. to form a foam.

  The larger the particle size of the slag, the higher the expansion ratio, and fine particles of less than 0.25 mm may not sufficiently foam. Moreover, the raw material which wraps each slag particle is plastic clay, such as Kibushi clay, Sasame clay, and bentonite, which sinters at around 900 ° C. where the slag particles foam and is suitable for a reaction system with slag. The plastic clay needs to be at least 20% by weight, but if it exceeds 50% by weight, the expansion ratio is greatly reduced, so the blending ratio of the clay is 20 to 50% by weight. This plastic clay also serves as a molding binder when molding a ceramic kneaded material.

  The amount of water added to the mixture of cast iron slag and plastic clay is 12 to 25 parts by weight, more preferably 13 to 15 parts by weight with respect to 100 parts by weight of the mixture. The molding method of the kneaded product is not particularly limited, and when molding into a granule, a method of extruding the kneaded product into a bar having an appropriate length from an extruder and shaping with a granulator such as a malmerizer, A method of granulating while stirring in an omni mixer can be employed.

  As a preferable firing condition of the ceramic porous body, a composition obtained by adding water to the cast iron slag and the plastic clay, mixing and kneading is formed into a desired shape, dried to a moisture content of 1% or less, and then at room temperature. Up to ˜700 ° C., sufficient uniform heating is performed according to the size and thickness of the molded body. This is an important temperature range of the foaming mechanism during which the crystallization of cast iron slag starts from a temperature exceeding 700 ° C. and phase separation and liquid phase is generated. This is because it is necessary to heat up the inside almost uniformly and to dehydrate the clay crystal water. Thereafter, in the temperature range of 700 to 1000 ° C., the slag particles are rapidly heated at a rate of temperature increase of 20 to 40 ° C./min to foam each slag particle at once. Thereafter, sintering is performed at a temperature of 1000 to 1150 ° C. More preferably, from 700 ° C. up to about 850 ° C. at which foaming starts, the heating rate is about 10 ° C./min. To achieve uniform surface and internal temperature, from 850 ° C. to 1000 ° C. During this period, it is preferable to increase the rate of temperature rise to rapidly reduce the viscosity, and to perform foaming and particle welding of the slag particles all at once. The temperature increase rate is appropriately adjusted according to the size and thickness of the ceramic molded body. In the temperature range of 1000 ° C. or higher, the strength of the molded body can be increased by increasing the heating temperature.

  In the deodorization method of the present invention, an acidic odor is primarily modified by a neutralization reaction in a basic atmosphere, and a basic odor is acidic in an acidic atmosphere.

In the present invention, a basic substance is supported on the ceramic porous body 4 so that an acidic raw odor substance such as acetic acid in the air passing through the ceramic porous body is primarily modified in a basic atmosphere. . For example, a solid basic substance having a pH of 8.0 to 10.0 is supported on the ceramic porous body 4 and used as the deodorizing layer 3. Preferred examples of the solid basic substance include active magnesia, which is particularly suitable for an odor component having an acetate group. Specifically, a ceramic porous body is impregnated with a slurry in which magnesium oxide is dispersed in an aqueous silica sol solution, dried at a temperature of 200 to 250 ° C., and supported on the ceramic porous body. As the silica sol, an aqueous lithium silicate solution is preferably used. The main component of the solid basic substance supported on the ceramic porous body is magnesia oxysulfide composed of 5MgO · MgSO ₄ · 8H ₂ O. Further, a slurry containing a small amount of charcoal and calcium sulfate (CaSO ₄ ) exhibiting a strong reducing action may be impregnated into the pores of the ceramic support. The MgO component reacts very well with acetic acid, and after producing magnesium acetate ions, it is considered that the raw odor substance is reduced and decomposed by sulfur ions (S ⁻ ) of CaS.

  In the present invention, the basic porous odor substance such as ammonia in the air passing through the ceramic porous body is primarily modified in an acidic atmosphere by supporting the acidic substance on the ceramic porous body 4. . For example, a material in which a solid acidic substance having a pH of 3.0 to 5.0 is supported on the ceramic porous body 4 is used as the deodorizing layer 3. Examples of the solid acidic substance include clay minerals having a two-dimensional layered structure such as acidic clay, montmorillonite, kaolinite, and halloysite. Furthermore, the clay mineral which consists of the said two-dimensional layer structure is heated to the temperature of the range of 300-600 degreeC, and after dehydrating interlayer water, what was acid-treated is used suitably. More specifically, the dehydrated clay mineral is dispersed in an aqueous solution of an inorganic acid such as sulfuric acid, nitric acid, phosphoric acid or the like adjusted to a hydrogen ion concentration (PH) of about 2 to 5, and the impregnating liquid contains the impregnating liquid. The ceramic porous body is immersed and impregnated, dried at 150 to 250 ° C., and acid-treated to pH 3.0 to 5.0.

  Further, the ceramic porous body 4 is more preferably one containing carbon having an adsorption function on the surface, pores or pore inner surfaces. As a specific example of such a porous ceramic body containing carbon and supporting a solid acidic substance, for example, a clay mineral composed of a two-dimensional layered structure such as acidic clay, montmorillonite, carolinite, halloysite, etc. is used at 300 to 600 ° C. After impregnating petroleum or vegetable oil into the pores dehydrated with interlayer water by heating to a temperature in the range of 600 to 700 ° C., or firing at a temperature in the range of 800 to 1000 ° C., the pores An activated carbon film is formed on the surface to obtain a clay mineral with improved hydrophobicity. This clay mineral containing activated carbon on the surface is dispersed in an aqueous solution of an inorganic acid such as sulfuric acid, nitric acid, phosphoric acid or the like adjusted to a hydrogen ion concentration (PH) of about 2 to 5 to obtain an impregnating solution. The porous ceramic is immersed and impregnated, dried at 150 to 250 ° C., and acid-treated to pH 3.0 to 5.0. This porous ceramic body carrying a solid acidic substance having carbon on its surface is composed of macropores and micropores, and is hydrophobic, but has a high affinity with organic compounds that are malodorous components and has a bad odor. Demonstrates rapid adsorption of components. The component adsorbed by the carbon film passes through the pores and moves to the active point on the surface of the porous ceramic as a base material, and is rendered harmless.

  Next, a method for supplying moisture to the ceramic porous body 4 of the deodorizing layer 3 will be described. In the deodorization method of the present invention, odor gas (air containing the original odor substance) may be brought into contact with the ceramic porous body 4 of the deodorization layer 3 in a dry state. However, if moisture is interposed at the time of contact, deodorization efficiency is improved. Further improvement. As a method of interposing moisture, there are a method of supplying water to the deodorizing layer 3 to wet the porous ceramic body 4 and a method of supplying odor to the deodorizing layer 3 in a humidified state, either of which may be used. When humidifying and supplying odor gas, the humidity shall be 50% or more, Preferably it is 50 to 70%. It is preferable to use tap water as the water supplied to the ceramic porous body 4. This is because tap water is generally contained in tap water, and it is considered that the redox reaction on the surface of the ceramic porous body 4 is promoted. Usually, the amount of chlorine contained in the tap water does not need to be adjusted and can be used regardless of the amount of chlorine. As a supply method, water may be directly supplied to the ceramic porous body 4 by drip water injection, or as shown in FIG. 1, it may be performed by a water spray nozzle 6 (spray nozzle). Furthermore, a micro mist nozzle can also be used for water dispersion. The supply amount of water is 1/3 volume as a standard with respect to 1 volume of the ceramic porous body per hour.

  As shown in FIG. 1, the deodorization method of the present invention includes a primary modification step using a solid basic substance or a solid acidic substance in which a plurality of deodorizing layers 3 are connected in series and water is appropriately interposed, and a ceramic porous body. Although the step of detoxifying the malodorous or harmful component by the contact may be repeated a plurality of times, it is not necessarily repeated a plurality of times. In addition, by providing both the treatment step with the ceramic porous body carrying the solid basic substance and the treatment step with the ceramic porous body carrying the solid acidic substance in series, the acidic and Both basic components can be removed from the air.

The ceramic porous body 4 of the deodorizing layer 3 may be in the form of a block, but in the granular form, the contact area with the original odor substance in the odor gas is larger, and the ceramic porous body 4 due to the air passing through it is larger. Due to this vibration, the contact frequency between the raw odor substance and the active point on the ceramic porous body 4 is increased, and the ventilation resistance is also reduced, so that the deodorizing efficiency is good. The ceramic porous body 4 preferably has a porosity of at least 50% or a specific surface area of 3 m ² / g or more from the viewpoint of ventilation resistance and deodorization efficiency. The smaller the pores and the larger the specific surface area, the larger the contact area with the raw odor substance in the air that passes through and the reaction point increases, but if the pores are too small, even if the porosity is large, the ventilation resistance increases, on the contrary. As a result, the deodorization efficiency is lowered. The size and shape of the granular ceramic porous body are not particularly limited, but the diameter or length is 2 mm to 20 mm, more preferably 3.5 mm to 15 mm, from the viewpoint of filling efficiency into the case, ventilation resistance, handling properties, and the like. The shape is not particularly limited, but a spherical shape is preferable from the viewpoint of filling efficiency, uniform filling, and the like.

  The supply rate of the odor gas to the deodorizing layer 3 is preferably in the range of 0.3 m / s to 4.0 m / s, more preferably 0.5 m / s to 2.5 m / s. When the supply speed is low, the processing efficiency is poor, and the penetration of the odor into the deep part of the ceramic porous body 4 is not realized, so that the deodorization efficiency is lowered. On the other hand, if the supply rate is too high, the detoxification reaction may be insufficient, or the ventilation resistance may increase and the processing efficiency may decrease. Moreover, the capacity | capacitance of the deodorizing layer 3, an aeration area, etc. can be suitably set with the processing amount required, the raw | natural odor substance density | concentration in odor gas, etc.

  In the treatment of exhaust gas containing an unsaturated fatty acid in the form of emulsion or oil mist, the deodorization efficiency is improved by removing the oil mist in advance before passing through the ceramic porous body 4. As the oil mist removing step, for example, a ceramic porous body that does not carry the acidic substance or basic substance, a gypsum-attached ceramic layer, or the like can be used, but is not limited thereto.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these.

1. Ceramic porous body A
(Manufacture of porous ceramics)
Clay and a foaming agent were mixed, added with water, kneaded, formed into a spherical shape having a diameter of 3.5 to 15 mm with a granulator (Malmerizer), and dried. This was fired to obtain a granular (spherical) ceramic porous body A (untreated ceramic porous body) containing a metal such as iron (Fe) or vanadium (V). The specific surface area of this ceramic porous body A was 1.7 m ² / g.

(Acid treatment)
The granular ceramic porous body A is immersed in a sulfuric acid aqueous solution containing acid clay and adjusted to a pH of about 2 to 5, impregnated, acid-treated to pH 3.0 to 5.0, dried, and iron (Fe) Thus, an acidic supported ceramic A having a pH of 4.65 containing vanadium (V), sulfur (S) and the like was obtained. The acidic supported ceramic A had a specific surface area of 47.0 m ² / g and a specific gravity of 0.59.

(Mg-based treatment)
The granular ceramic porous body A is impregnated with a magnesium sulfate aqueous solution containing magnesia (MgO), dried, and contains sulfur (S), magnesium (Mg), etc. in addition to iron (Fe), vanadium (V), etc. An Mg-based supported ceramic A was obtained.

Example 1
The original odor removal rate was examined when the aeration amount of mixed malodor of ammonia and trimethylamine whose concentration was adjusted by the malodor generator was changed.
An experimental deodorizing tower filled with 196.25 mL (10 cm layer height) of the above acidic support ceramics A in an experimental tower having an inner diameter of 5 cm and a height of 70 cm was aerated at 10 VVM, 20 VVM, 30 VVM, and 50 VVM, and 1 hour later. The inlet concentration and outlet concentration were measured using a gas tech detector tube manufactured by Gastec Co., Ltd., ammonia no. 3 L ((1) to 30 ppm; one suction time of about 1 minute), amine No. 180 L ((0.5) to 10 ppm; one suction time of about 1 minute) was measured according to a conventional method. Table 1 shows the odor removal rate.

  As shown in Table 1, ammonia and trimethylamine could be removed 100% when the airflow was 10 VVM and 20 VVM. In addition, the removal rate of ammonia was 78%, the removal rate of trimethylamine was 56% at an air flow rate of 30 VVM, and 33% and 13% at an air flow rate of 50 VVM, respectively.

(Example 2)
In the same manner as in Example 1, except that 100 mL of water was infiltrated into 196.25 mL (layer height: 10 cm) of acid-supported ceramics A packed in the experimental deodorization tower, The mixed odor of trimethylamine was aerated for 1 hour. Table 2 shows the odor removal rate.

  As shown in Table 2, when water is infiltrated into the acidic supported ceramic A, the mixed odor of ammonia and trimethylamine is measured with a gas-tech detector tube at any of the airflows of 10 VVM, 20 VVM, 30 VVM and 50 VVM. As long as this is done, all showed a removal rate of 100%, and the removal efficiency was improved as compared with Example 1 in which no water was interposed.

(Example 3)
In the same experimental deodorization tower as described above, 196.25 mL (layer height 10 cm) of Mg-based ceramics A was filled, and 100 mL of water was infiltrated at the start of the experiment, and the concentration-adjusted acetic acid odor was aerated for 1 hour. Inlet concentration and outlet concentration were measured using a gas tech detector tube manufactured by Gastec Co., Ltd., acetic acid no. Measurement was performed according to a conventional method using 81 L ((0.25) to 10.0 ppm; one suction time of about 1 minute). The results are shown in Table 3.

  In the same manner as in Example 2, the removal rate of acetic acid odor was 100% at 10 VVM, 20 VVM, 30 VVM, and 50 VVM as long as it was measured with a gas tech detector tube.

Example 4
The air flow rate to the experimental deodorizing tower filled with the acidic supported ceramic A of Example 2 and the experimental deodorizing tower filled with the Mg based ceramic of Example 3 was fixed at 50 VVM, once / day, on time 100 ml of water was replenished by automatic spraying, and continuous operation was carried out for 12 weeks. The concentration of the mixed raw odor was measured by a gas-tech detector tube at the inlet and outlet, respectively. Table 4 shows the measurement results for each week.

  As shown in Table 4, even in continuous aeration of ammonia, trimethylamine and acetic acid odor for 12 weeks, 100 mL of water is replenished at a fixed time every day, so that the acidic supported ceramic and the Mg supported ceramic porous body of the present invention are used in combination. By these deodorizing methods, 100% of these three kinds of bad odors could be removed.

(Example 5)
An experimental section in which an experimental tower having an inner diameter of 5 cm and a height of 70 cm is filled with a layer height of 10 cm each of the acid-based supported ceramic A and untreated ceramic (ceramic porous body A), and an experimental section in which the ceramic is not filled as a target. Deodorization experiments were conducted in a total of 3 experimental areas. Aeration was carried out for 4 minutes at an ammonia inlet concentration of 12.8 ppm, an aeration rate of 50 VVM, and a tap water spray rate of 200 mL / min, and 8 L of stored water below the deodorizing layer was subjected to analysis. The ammonium ion concentration was measured by the Nessler method, the nitrite ion was measured by the GR method, and the nitrate ion was measured by the Brucine method to obtain a nitrogen concentration value. Table 5 shows the measured concentration of each nitrogen state.

As shown in Table 5, in the experimental group of acidic supported ceramics A, the ammonium ion concentration in water was 1.1 ppm, the nitrite ion concentration was 0.01 ppm, the nitrate ion concentration was 0.3 ppm, in the experimental group of untreated ceramics. They were 6.4 ppm, 0.02 ppm, 0.3 ppm, respectively, and 26.8 ppm, 0.06 ppm, 0.3 ppm in the experimental section without ceramics filling, respectively.
In this experimental apparatus, the original odor was supplied from below the deodorizing layer, while water was sprinkled from above the deodorizing layer, so that the result was that some ammonia was dissolved in water in the space below the deodorizing layer. It was not a numerical value affecting the performance evaluation of the deodorizing layer itself.

2. Ceramic porous body B
(Manufacture of porous ceramics)
70 parts by weight of cast iron slag obtained by crushing the amorphous slag produced during the manufacture of the ductile cast iron product and 30 parts by weight of the clay are mixed. To 100 parts by weight of this mixture, 14 parts by weight of water was added and mixed and kneaded by a mixer. This kneaded product is extruded into a rod shape from an extruder, further formed into a spherical shape by a granulator (malmerizer), dried, fired at 1000 ° C., and a spherical ceramic porous body B having a diameter of 3.5 to 15 mm is obtained. Obtained. Table 6 shows the chemical composition of the cast iron slag used.

(Acid treatment)
The acid clay with the oils and fats attached by filtering the margarine was baked in a baking furnace to carbonize the oils and fats, and an acid clay with a carbon film formed on the surface, pores or inner surfaces of the fine pores was obtained. 1.4 kg of white clay containing carbon on the surface was dispersed in 20 L of sulfuric acid to obtain an impregnation solution. The spherical ceramic porous body B was added to this impregnating solution, and the mixture was stirred for 15 minutes with a mixer. The ceramic porous body B was supported with white clay containing carbon on the surface to obtain an acidic supported ceramic B.

(Mg-based treatment)
Mg (OH) ₂ was fired in a firing furnace and oxidized to obtain MgO. A slurry in which 2.8 kg of MgO was added to 20 L of an aqueous lithium silicate solution (lithium silicate 35, manufactured by Nissan Chemical Industries, Ltd.) was used as the impregnation solution. The spherical ceramic porous body B was added to this impregnating solution and stirred for 15 minutes with a mixer, and MgO and lithium silicate were supported on the ceramic porous body B to obtain an Mg-based supported ceramic B.

(Example 6: Deodorization test of acidic supported ceramic B)
Air (raw gas) containing ammonia or trimethylamine as a raw odor substance was forcibly passed through the column packed with the acidic support ceramic B, and the deodorizing effect according to wind speed was examined. The results are shown in Table 7.

(Example 7: Deodorization test of Mg-based supported ceramics B)
Air containing raw acetic acid (raw gas) as a raw odor substance is processed by forcibly passing through the column filled with the Mg-based ceramics B, and the deodorizing effect due to wind speed and presence / absence of moisture (dry and wet) is investigated. It was. The results are shown in Table 8.

(Example 8: Deodorization of complex odor in composting facility)
Mg-supported ceramics B (4 (Mg)) and acidic-supported ceramics B (4 (acidic)) were added to the deodorizing layer 3 having a ventilation area of 0.36 m ² (0.6 m × 0.6 m) and a thickness of 100 mm. The deodorizing apparatus 1A provided with the watering nozzle 6 in each of the two layers of the deodorizing layer 3 filled was used (see FIG. 2). The air containing the mixed odor (raw gas) discharged from the composting equipment of the composting facility while watering intermittently from the water spray nozzle 6 to each deodorizing layer 3 is converted into Mg-based ceramics B (4 (Mg)). , Acid-supported ceramics B (4 (acidic)) in this order at 1800 m ³ / h for deodorization treatment, and the gas concentration of the raw odor substance in the air before and after treatment is a gas detector tube (manufactured by Gastec Co., Ltd.) Measured with The results are shown in Table 9.

(Example 9: Deodorization of ammonia odor in composting facility)
Mg-supported ceramics B (4 (Mg)) and acidic-supported ceramics B (4 (acidic)) were added to the deodorizing layer 3 having a ventilation area of 0.36 m ² (0.6 m × 0.6 m) and a thickness of 100 mm. Two deodorizing apparatuses 1A (see FIG. 2) each having a watering nozzle 6 in each of the two layers of deodorizing layers 3 were connected in series and used. Air (raw gas) containing a large amount of ammonia discharged from the composting apparatus of the composting facility while intermittently sprinkling water from the water spray nozzle 6 to each deodorizing layer 3 is converted into Mg-based ceramics B (4 (Mg) ), Acidic supported ceramics B (4 (acidic)), Mg based supported ceramics B (4 (Mg)), and acidic supported ceramics B (4 (acidic)) in this order at 1800 m ³ / h, The ammonia concentration in the air before and after the treatment was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). The results are shown in Table 10.

(Example 10: Deodorization of asphalt regeneration factory)
The gas permeable area 0.36m ² (0.6m × 0.6m), with a thickness of 100mm deodorizing layer 3, Mg-based carrier ceramics B (4 (Mg)) with an acidic carrier based ceramics B and (4 (acidic)) Two deodorizing apparatuses 1A (see FIG. 2) each provided with a watering nozzle 6 for each of the two deodorized layers filled were connected in series and used. Air (raw gas) containing various malodorous components discharged from an asphalt regeneration plant while watering intermittently from the water spray nozzle 6 to each deodorizing layer 3 is converted into Mg-based ceramics B (4 (Mg)), acidic The support ceramic B (4 (acidic)), the Mg-based support ceramic B (4 (Mg)), and the acidic support ceramic B (4 (acidic)) are passed through in the order of 1800 m ³ / h, and the air before and after the treatment is processed. The concentration of various raw odor substances was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). The measurement was performed twice on the installation day of the deodorizing apparatus and on the 25th day of installation. The results are shown in Table 11.

(Example 11: Deodorization of composting facility)
Mg-supported ceramics B (4 (Mg)) and acidic-supported ceramics B (4 (acidic)) were added to the deodorizing layer 3 having a ventilation area of 0.36 m ² (0.6 m × 0.6 m) and a thickness of 100 mm. A first deodorizing apparatus 1A (see FIG. 2) having a watering nozzle 6 in each of the two deodorized layers 3 filled, a ventilation area of 1.44 m ² (1.2 m × 1.2 m), and a thickness of 100 mm A second deodorizing device 1A ′ (similar structure to the deodorizing device 1A shown in FIG. 2) having a water spray nozzle in each of the two deodorizing layers filled with Mg-based supported ceramic B and acidic-based supported ceramic B in the deodorized layer. And two large ones in series. The air (raw gas) containing a large amount of ammonia discharged from the high-speed composting device of the composting facility while watering intermittently from the sprinkling nozzle 6 to each deodorizing layer 3 is used as the Mg system of the first deodorizing device 1A. Supported ceramic B (4 (Mg)), acidic supported ceramic B (4 (Mg)), Mg supported ceramic B (4 (Mg)) of second deodorizing apparatus 1A ′, acidic supported ceramic B (4 ( Acidity)) was passed through in the order of 1800 m ³ / h, and the ammonia concentration in the air before and after the treatment was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). The results are shown in Table 12.

(Example 12: Deodorization of acetic acid odor in fishery food processing plant)
The gas permeable area 3.24m ² (1.8m × 1.8m), with a thickness of 100mm deodorizing layer 3, Mg-based carrier ceramics B (4 (Mg)) with an acidic carrier based ceramics B and (4 (acidic)) The deodorizing apparatus 1B (refer FIG. 3) provided with the watering nozzle 6 in each of the two layers of deodorizing layers 3 with which it filled was used. Air (raw gas) containing acetic acid discharged from the fishery food processing factory while being sprinkled intermittently from the watering nozzle 6 to each deodorizing layer 3 is converted into Mg-based ceramics B (4 (Mg)) and acidic-based materials. ceramics B (4 (acidic)) sequentially passed through at 18000m ³ / h of treated, the acetic acid concentration in the air before and after the treatment was measured by a gas detecting tube (Co. Gastec). The results are shown in Table 13.

(Example 13: Deodorization of indoor formaldehyde odor)
On the deodorizing layer 3 having a ventilation area of 0.09 m ² (0.3 m × 0.3 m) and a thickness of 100 mm, Mg-based supported ceramics B (4 (Mg)) and acidic-based supported ceramics B (4 (acidic)) A deodorizing apparatus (see FIG. 4) having two filled deodorizing layers was used. In a laboratory with a volume of 26.8 m ³ (W: 3640 mm x D: 2730 mm x H: 2700 mm), a concrete formwork plywood (900 mm x 900 mm) was placed and sealed as a formaldehyde source, The indoor formaldehyde concentration was adjusted to 15 ppm (high concentration) and 1.5 ppm (low concentration). The air in the laboratory is supplied from the intake side of the deodorizing apparatus 1C through a duct, and water is supplied to each deodorizing layer 3, while Mg-based ceramics B (4 (Mg)) and acidic-based ceramics B (4 (acidic) )) In order, and a circulation path was provided to return to the laboratory through the duct from the exhaust side, and the change in the formaldehyde concentration in the room was measured with a hortable gas monitor (manufactured by Thermo Electron, “Model INNOVA”). As a result, in the case of a high concentration (15 ppm), the formaldehyde concentration in the room decreased to 3 ppm in about one day after the start of the operation of the deodorizing apparatus. In the case of a low concentration (1.5 ppm), the indoor formaldehyde concentration decreased to 0.6 ppm after about 14 hours.

(Example 13: Deodorization of pet shop)
Mg-supported ceramic B (4 (Mg)) and acidic-supported ceramic B (4 (acidic)) were added to the deodorizing layer 3 having a ventilation area of 0.09 m ² (0.3 m × 0.3 m) and a thickness of 100 mm. A deodorizing apparatus 1C (see FIG. 4) having two filled deodorizing layers was used. The air in the pet shop's bird display room and dog display room is supplied from the intake side of the deodorizing device 1C through a duct, and water is supplied to each deodorizing layer 3 while supplying Mg-based ceramics B (4 (Mg)), acidic type A circulating path is provided in the order of supported ceramics B (4 (acidic)) and returned from the exhaust side to the exhibition room through the duct. The odor measuring instrument (stock) Measured with a handy type odor measuring device “e-nose mobile” manufactured by Futaba Electronics Co., Ltd.). As a result, the bird exhibition room where the odor intensity was about 1100 dropped to about 700 in 7.5 hours after the start of the operation of the deodorization apparatus, and the dog exhibition room where the odor intensity was 750 to 800 The odor intensity decreased to about 600 in 6 hours after the start of the operation of the deodorizing apparatus. The odor intensity in the pet shop store other than the exhibition room was about 500.

  According to the present invention, it is possible to remove the odorous substances and harmful substances from the air simply by passing the air containing the odorous substances and harmful substances through the deodorizing layer made of the ceramic porous body. It can contribute to prevention of environmental deterioration and environmental improvement. In addition, since the method of the present invention can improve the removal efficiency of the odorous substances and harmful substances by interposing moisture at the time of contact between the object to be treated and the ceramic porous body, only the odorous substances and harmful substances in the air can be obtained. In addition, it can be expected to remove harmful substances in the water and can be applied to water purification.

Claims (22)

A deodorizing method for removing the malodorous component or harmful component by forcing the air containing the malodorous component or harmful component through the deodorizing layer made of the ceramic porous body, and discharging it as detoxified air,
The ceramic porous body is a mixture of amorphous slag and plastic clay produced during the production of the ductile cast iron product mixed with water and mixed and kneaded. After forming into a desired shape and drying, 900-1150 An acidic substance or a basic substance is supported on a ceramic porous body having continuous through-holes fired at a temperature in the range of ° C.,
The acidic component in the air is removed by passing through the ceramic porous body supporting the basic substance, and the basic component in the air is removed by passing through the ceramic porous body supporting the acidic substance. The deodorizing method characterized by performing. The chemical component of the slag includes 35 to 45% by weight of SiO ₂ , 10 to 15% by weight of Al ₂ O ₃ , 1 to 5% by weight of MgO, and other components such as MnO, CaO, and S, and (CaO + MgO) / weight ratio of SiO ₂ is 0.9-1.2, deodorizing method according to claim 1, wherein the ratio of Al ₂ O ₃ / SiO ₂ is 0.25 to 0.35.   50-80% by weight of the ceramic porous body prepared by crushing the amorphous slag produced during the production of the cast iron product and adjusting to a particle size range of 0.25-2.0 mm, and plastic clay 20-20 A composition obtained by adding 12 to 25 parts by weight of water to 100 parts by weight of a mixture mixed at a ratio of 50% by weight and mixing and kneading is molded into a desired shape, dried, and then in the range of 900 to 1150 ° C. The deodorizing method according to claim 1 or 2, which is foamed and fired at a temperature.   The deodorizing method according to claim 1, wherein the ceramic porous body is granular.   The deodorizing method according to claim 4, wherein the ceramic porous body is spherical with a diameter of 2 mm to 20 mm.   The deodorizing method according to any one of claims 1 to 5, wherein the ceramic porous body carries a solid basic substance as the basic substance.   The deodorizing method according to claim 6, wherein the solid basic substance is active magnesia.   The deodorizing method according to claim 7, wherein the ceramic porous body is obtained by impregnating the ceramic porous body with magnesium sol together with silica sol and drying.   The deodorizing method according to claim 8, wherein an aqueous lithium silicate solution is used as the silica sol.   The deodorizing method according to any one of claims 1 to 5, wherein the ceramic porous body supports a solid acidic substance as the acidic substance.   The deodorizing method according to claim 10, wherein the solid acidic substance is obtained by dehydrating clay mineral interlayer water having a two-dimensional layered structure and then acid-treating it.   The deodorizing method according to claim 11, wherein the clay mineral contains carbon having an adsorption function on a surface thereof, a pore or an inner surface of a fine pore.   The deodorizing method according to claim 11 or 12, wherein the clay mineral is acid clay.   The deodorizing method according to any one of claims 11 to 13, wherein the ceramic porous body is obtained by impregnating the ceramic porous body with the clay mineral together with an inorganic acid and drying.   The deodorizing method according to claim 14, wherein the inorganic acid is sulfuric acid.   Both the step of removing the acidic component in the air with the ceramic porous body supporting the basic substance and the step of removing the basic component in the air with the ceramic porous body supporting the acidic substance The deodorizing method in any one of Claims 1-15 provided.   The deodorizing method of Claim 16 which performs the process of removing the said acidic component, and the process of removing the said basic component continuously.   The deodorizing method according to claim 17, wherein the step of removing the acidic component and the step of removing the basic component are repeated.   The moisture containing the ceramic porous body is interposed between the ceramic porous body and the air containing the malodorous component or harmful component when passing through the deodorizing layer made of the ceramic porous body. Deodorizing method as described.   The deodorizing method according to claim 19, wherein moisture is supplied to the porous ceramic body so as to be in a wet state, and air containing harmful components or malodorous components is passed through the wet ceramic porous body.   The deodorizing method according to any one of claims 1 to 20, wherein air containing the malodorous component or harmful component is forced to pass through the deodorizing layer at a speed of 0.5 m / s to 4.0 m / s.   The deodorizing method according to any one of claims 1 to 21, wherein an oil mist removing step is performed before the deodorizing step with the ceramic porous body.

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