WO2016167172A1

WO2016167172A1 - Deodorizing purification filter

Info

Publication number: WO2016167172A1
Application number: PCT/JP2016/061369
Authority: WO
Inventors: 祐介西谷
Original assignee: 東洋紡株式会社
Priority date: 2015-04-14
Filing date: 2016-04-07
Publication date: 2016-10-20
Also published as: JPWO2016167172A1

Abstract

[Problem] To provide a deodorizing purification filter having sufficient removal performance for removing harmful gases or odorous components included in the exhaust gas of an electronic device such as a copy machine, a printer, a multifunctional OA machine, a computer, a projector, a POD printer, or the like. [Solution] The deodorizing purification filter includes a carrier which contains: a manganese oxide having a crystal form of ε and/or γ and having a BET specific surface area of 50-400 m²/g; and an active carbon having a BET specific surface area of 600-1500 m²/g, the filter being characterized in that the mixed weight ratio of the active carbon to the manganese oxide, i.e., active carbon/manganese oxide, is 0.2-5.0.

Description

Deodorizing filter

The present invention relates to a deodorizing and purifying filter for removing harmful gases and odorous components contained in exhaust gas from electronic devices such as copiers, printers, multi-function OA machines, computers, projectors, and POD printers.

In recent years, electronic devices such as copiers, printers, multifunction OA machines, computers, projectors, and POD printers have become increasingly integrated and miniaturized, and in order to prevent heat from being trapped inside the equipment, exhaust heat from fans, etc. is lacking. It has become impossible. The components used in printing, such as ink and toner, the plastics that make up the main body of electronic equipment, and the various components contained in rubber used in various joints are gasified to produce volatile organics. A compound (hereinafter referred to as “VOC”) is discharged into the room together with exhaust heat. Further, since a high voltage is used in a copying machine, a laser printer, etc., not only the VOC component but also harmful gas components such as ozone are discharged. *

Emission regulations have been implemented for harmful gas components such as VOC and ozone. For example, in Germany, an environmental label “BAM (Blue Angel Mark)” has been established, and environmental performance standards to be achieved for each electronic device are defined. In recent years, there has been a need to reduce the emission of odorous components emitted from copiers due to increasing awareness of environmental issues and comfort in living and office spaces. *

As a filter for removing harmful gases and odor components such as VOC and ozone, an activated carbon-supported honeycomb structure in which activated carbon is supported on a honeycomb carrier is well known (see, for example, Patent Documents 1 and 2). Generally, activated carbon can remove harmful gas components in exhaust gas, and therefore, using the activated carbon supporting honeycomb structure, it is possible to remove harmful gases and odor components contained in the exhaust gas of the electronic device. Conceivable. However, the activated carbon-supported honeycomb structure does not have sufficient ozone removal performance. *

Ozone decomposition catalysts such as manganese oxide are well known as removers having higher ozone removal performance than activated carbon (see, for example, Patent Document 3). Further, cryptomelane containing manganese oxide having an α-form crystal form (hereinafter sometimes referred to as “α-manganese oxide”) has a high ozone treatment performance and is described as being most suitable (for example, patent document) 4). However, although α-manganese oxide has high catalytic activity, its ozone removal performance is high. However, it reacts with harmful gases and odorous components emitted from electronic equipment to produce byproducts, which are unpleasant. There is a problem that it becomes a bad odor and is discharged outside the electronic device. *

As described above, a sufficient deodorization purification filter for removing harmful gas components and odor components contained in the exhaust gas of electronic devices such as copiers, printers, multi-function OA machines, computers, projectors, POD printers, etc. At present, no deodorizing and purifying filter having performance is found.

JP-A-1-293136 Japanese Patent Laid-Open No. 2-48015 Japanese Patent Laid-Open No. 61-11154 Special table 2003-527951 gazette

The present invention has been made against the background of the above-described prior art, and includes harmful gases and odor components contained in the exhaust gas of electronic devices such as copiers, printers, multi-function OA machines, computers, projectors, and POD printers. An object of the present invention is to provide a filter having sufficient removal performance with respect to a deodorizing and purifying filter for removing water.

As a result of intensive studies in order to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention is as follows. 1. A filter in which a carrier includes a manganese oxide having a BET specific surface area of 50 to 400 m ² / g and a crystal form of ε and / or γ form, and activated carbon having a BET specific surface area of 600 to 1500 m ² / g. A deodorizing and purifying filter, wherein a mixing weight ratio of the activated carbon and the manganese oxide is activated carbon / manganese oxide = 0.2 to 5.0. 2. 2. The deodorizing and purifying filter according to 1 above, wherein the carrier has a structure having a plurality of cells. 3. 3. The deodorizing and purifying filter as described in 1 or 2 above, wherein the carrier is a honeycomb carrier having a honeycomb shape. 4). 4. The manganese oxide according to any one of 1 to 3 above, wherein the manganese oxide is particles having an average particle diameter of 1.0 to 50 μm, and the activated carbon is particles having an average particle diameter of 1.0 to 50 μm. Deodorizing purification filter. 5. 5. An electronic device comprising the deodorizing and purifying filter according to any one of 1 to 4 above.

The deodorizing and purifying filter according to the present invention contains activated carbon and manganese oxide having a crystal form of ε-type and / or γ-type, and therefore can exhibit sufficient removal performance against harmful gases and odor components. Furthermore, it has the effect that generation | occurrence | production of the by-product by reaction with the exhaust gas from an electronic device can be suppressed, and the unpleasant odor resulting from a by-product can be reduced.

Hereinafter, the present invention will be described in detail. The deodorizing and purifying filter according to the present invention is a filter in which a carrier contains (supports) at least a manganese oxide having a crystal form of ε-form and / or γ-form and activated carbon. *

The present invention uses a manganese oxide having a crystal form of ε-form and / or γ-form, so that the ozone removal performance is high, and further, a by-product due to the reaction of manganese oxide with exhaust gas from electronic equipment. The present inventor has found that it is possible to suppress the generation of odor and reduce the generation of unpleasant odor caused by by-products. *

BET specific surface area of the manganese oxide in the present invention is 50 ~ 400m ² / g, preferably 100 ~ 300m ² / g. If the BET specific surface area of the manganese oxide is less than 50 m ² / g, sufficient ozone removal performance cannot be exhibited. Moreover, when the BET specific surface area of manganese oxide exceeds 400 m < ² > / g, the problem that manufacture will become very difficult will arise.

The manufacturing method of the manganese oxide in this invention is not specifically limited. A method of adding concentrated nitric acid or the like to a solution containing a metal salt, heating, and adding an aqueous potassium permanganate solution or ozone gas, or oxygen gas, ozone water, or peroxidation to a solution containing a metal salt A method of adding an oxidizing agent such as hydrogen water to bring the metal into a highly oxidized state, then adding an alkali such as ammonia or an ammonium salt such as ammonium carbonate to form a precipitate, and then filtering and drying the precipitate. Or, after adding an oxidizing agent such as oxygen gas, ozone water or hydrogen peroxide solution to a solution containing a metal salt to bring the metal into a highly oxidized state, an organic reducing agent such as sucrose, glucose or polyvinyl alcohol After adding gel and filtering the resulting gel and drying, or adding alkali such as ammonia or ammonium carbonate to a solution containing manganese salt to form a precipitate Precipitate is filtered off, dried, it is possible to use a method or the like for producing baked to. The metal salt to be used is not particularly defined, but general salts such as hydroxides, chlorides, nitrates and sulfates can be used. From the viewpoint of solubility, nitrates and sulfates are preferred. Further, the type of solvent of the solution is not particularly defined, but a general organic solvent, water, or the like can be used. Considering the environmental load, water is preferable. The drying and firing temperature is preferably 500 ° C. or lower. If it exceeds 500 ° C., crystallization of manganese oxide proceeds, and as a result, sufficient deodorizing performance cannot be exhibited. *

The average particle diameter of the manganese oxide in the present invention is preferably 1.0 to 50 μm, and more preferably 1.0 to 30 μm. If the average particle diameter is less than 1.0 μm, the manganese oxide tends to act as dust, and the handleability becomes poor. On the other hand, when the average particle diameter exceeds 50 μm, it becomes difficult to firmly support the carrier on the carrier, and the manganese oxide tends to fall off from the carrier. *

The activated carbon species in the present invention is not particularly limited. For example, graphite, mineral materials (coal such as lignite and bituminous coal, petroleum or petroleum pitch, etc.), plant materials (wood, fruit shells (coconut shell, etc.)), polymer materials (polyacrylonitrile, phenol, etc.) Activated carbon using a raw material such as a system material or cellulose), and activated carbon obtained by carbonizing or infusibilizing these raw materials and then performing an activation treatment can be used. *

The carbonization method, infusibilization method, and activation method at the time of producing activated carbon in the present invention are not particularly limited, and conventionally known processing methods can be used. For example, for activation, carbon raw material that has been carbonized or infusibilized is heat treated at about 500 to 1000 ° C. in an activated gas such as water or carbon dioxide, and carbon that has been carbonized or infusibilized. A chemical activation method in which the raw material is mixed with an activation agent such as phosphoric acid, zinc chloride, or potassium hydroxide and heat-treated at about 300 to 800 ° C. can be used. *

The BET specific surface area of the activated carbon in the present invention is 600 to 1500 m ² / g, and preferably 800 to 1400 m ² / g. When the BET specific surface area of the activated carbon is less than 600 m ² / g, the adsorption capacity is small, and as a result, sufficient deodorization performance cannot be expressed. Moreover, when the BET specific surface area of activated carbon exceeds 1500 m < ² > / g, the adsorption | suction performance of a noxious gas component and an odor component will fall.

The average particle diameter of the activated carbon in the present invention is preferably 1.0 to 50 μm, and more preferably 1.0 to 30 μm. If the average particle diameter is less than 1.0 μm, the manganese oxide tends to act as dust, and the handleability becomes poor. On the other hand, when the average particle diameter exceeds 50 μm, it becomes difficult to support the carrier firmly on the carrier, and the activated carbon easily falls off from the carrier. *

Although it does not specifically limit about other components other than activated carbon and manganese oxide contained in the deodorizing purification filter in this invention, Copper, cobalt, titanium, an alkali metal, an alkaline earth metal oxide, and an organic type deodorizer are contained. It is preferable. By containing these, deodorization performance can be improved. *

The mixing weight ratio of activated carbon and manganese oxide in the present invention is activated carbon / manganese oxide = 0.2 to 5.0. If the mixing ratio of activated carbon / manganese oxide is less than 0.2, since the mixing ratio of manganese oxide is high, the amount of by-products generated by reaction with manganese oxide increases. On the other hand, when the mixing ratio of activated carbon / manganese oxide exceeds 5.0, the mixing ratio of manganese oxide is low, so that the ozone removal performance is significantly lowered. *

The carrier of the deodorizing and purifying filter in the present invention preferably has a structure having a plurality of cells. For example, a honeycomb carrier can be used. Therefore, the following description will be made using a honeycomb carrier. The honeycomb carrier of the deodorizing purification filter in the present invention is not particularly limited, but is preferably a flame retardant or non-flammable carrier from the viewpoint of safety because it is installed in an electronic device. A honeycomb carrier having characteristics of high strength and low pressure loss is preferable. For example, inorganic fibers, ceramics, aluminum honeycomb carriers and the like can be used. *

The number of cells of the honeycomb carrier of the deodorizing purification filter in the present invention is not particularly limited, and those having 50 to 1500 cells / inch ² can be used.

The manufacturing method of the deodorizing purification filter in the present invention is not particularly defined. A general method of drying the honeycomb carrier after contacting it with an aqueous slurry containing a deodorizer (manganese oxide and activated carbon), an organic compound binder, and an inorganic compound can be used. The solid content ratio of the aqueous slurry is preferably 10 to 50%, more preferably 25 to 50%. When the solid content ratio is less than 10%, the deodorant is not sufficiently supported on the surface of the carrier. On the other hand, if the solid content ratio exceeds 50%, the viscosity is increased and the fluidity of the aqueous slurry is lowered, which makes impregnation impossible. The drying temperature is usually preferably 60 to 200 ° C, more preferably 100 to 150 ° C. When the drying temperature exceeds 200 ° C., the organic compound binder deteriorates. In addition, when the drying temperature is less than 60 ° C., the drying time becomes longer, so the cost becomes higher.

It does not specifically limit about the organic compound type binder component contained in the deodorizing purification filter in this invention, Polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, sodium alginate, dextrin etc. can be used. *

The amount of the organic compound binder component contained in the layer formed on the surface of the honeycomb carrier used in the deodorizing purification filter in the present invention is 0.5% by weight with respect to the solid content in the layer formed on the carrier surface. It is preferably ˜10% by weight, more preferably 0.5 to 5.0% by weight. When the amount of the organic compound binder exceeds 10% by weight, the deodorizing agent is coated with the binder, and the removal performance is deteriorated. Further, when the amount of the organic compound binder is less than 0.5% by weight, the deodorizer cannot be sufficiently supported on the surface of the carrier. *

The inorganic compound component contained in the layer formed on the surface of the honeycomb carrier used in the deodorizing purification filter of the present invention is not particularly limited, and bentonite, montmorillonite, sepiolite, silica sol, or the like can be used. *

Regarding the amount of the inorganic compound contained in the layer formed on the surface of the honeycomb carrier used for the deodorizing purification filter in the present invention, the weight ratio to the solid content in the layer formed on the carrier surface is 0.5 to 30. It is preferable that it is weight%. If the amount of the inorganic compound exceeds 30% by weight, sufficient voids cannot be formed in the layer formed on the surface of the honeycomb carrier, so that the deodorizing performance cannot be kept high. In addition, when the amount of the inorganic compound is less than 0.5% by weight, the organic binder component cannot be protected, so the organic binder component is deteriorated by ozone gas, and the deodorant is dropped off. *

The amount of activated carbon, manganese oxide, organic compound binder, and inorganic compound component contained in the layer formed on the surface of the honeycomb carrier used in the deodorizing purification filter of the present invention is preferably 40 to 220 g / L. 50 to 200 g / L is more preferable. When the adhering amount exceeds 220 g / L, there is a problem that the honeycomb carrier cell is clogged and the pressure loss of the filter is increased. Moreover, deodorizing performance will become inadequate that the amount of attachment is less than 40 g / L. *

The deodorizing and purifying filter in the present invention is a deodorizing and purifying filter for removing harmful gases and odorous components contained in the exhaust gas of electric devices such as copiers, printers, multifunctional OA machines, computers, projectors, and POD printers, etc. Can be used for Of course, it can also be used for a deodorizing filter or the like used in a refrigerator or a toilet deodorizer.

Hereinafter, the effects of the present invention will be described more specifically by way of examples. The following examples are not intended to limit the method of the present invention, and any design changes in accordance with the gist of the preceding and following descriptions are included in the technical scope of the present invention. *

[Method for Measuring BET Specific Surface Area of Activated Carbon and Manganese Oxide] A particle sample of activated carbon and manganese oxide was vacuum-dried at 120 ° C. for 12 hours, and then weighed. Using an automatic specific surface area device Gemini 2375 (manufactured by Micromeritics), the adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) is gradually increased in a relative pressure range of 0.02 to 0.95. The sample was measured at 40 points while raising it to obtain an adsorption isotherm of the sample. (Results at a relative pressure of 0.02 to 0.15 were BET plotted to determine the BET specific surface area [m ² / g] per weight.)

[Measurement method of ozone removal performance] A deodorizing and purifying filter is cut to 26φ and 20 mm in height, set in a glass column with an inner diameter of 26 mm, and air with a temperature of 25 ° C and a relative humidity of 50% containing ozone 1.0 ppm is flow rate 1 Circulated at 0.0 m / s. The temperature in the glass column was kept constant at 25 ° C. The inlet and outlet concentrations of the glass column were measured with an ozone measuring device (Model 1200, manufactured by Direc Co.), and the ozone removal rate [%] was calculated from the concentration change at the inlet and outlet of the glass column. *

[Toluene removal performance measurement method] A deodorizing and purifying filter is cut to 26φ and 20 mm in height, set in a glass column with an inner diameter of 26 mm, and air with a temperature of 25 ° C and a relative humidity of 50% containing 5.0 ppm of toluene gas is flowed. It was distributed at 1 m / s. The temperature in the glass column was kept constant at 25 ° C. The concentration at the inlet and outlet of the glass column was measured with a flame ionization type (FID type) VOC analyzer (manufactured by Shimadzu Corporation, VMS-1000F), and the toluene removal rate [%] from the change in the concentration at the inlet and outlet of the glass column Was calculated. *

[Method for Measuring Concentration of All Volatile Organic Compounds (TVOC) in Copier Exhaust Gas] A deodorizing and purifying filter was set in a copier, and 1000 sheets of color printing were performed. The exhaust gas from the copier at the time of printing is collected with a Tenax-TA collecting tube, and the total volatile organic compound (TVOC) concentration is measured with a thermal desorption GCMS (manufactured by Shimadzu Corporation, TD-20 / QP-2010Ultra). Was quantified in terms of toluene concentration. *

[Method for judging functional odor of copier exhaust gas] A deodorizing purification filter was set in the copier and 50 sheets of color printing were carried out. The exhaust gas from the copier at the time of printing is collected in a tedlar bag, the odor of the exhaust gas in the tedlar bag is sniffed by five panelists, and the sensory odor intensity is rated from 4 to 4 (A: Slightly weak odor, B: weak odor, C: slightly strong odor, D: strong odor). *

[Measuring method of average particle diameter] Using a scanning electron microscope (S-3500, manufactured by Hitachi, Ltd.), the diameter of the particle sample was measured at 100 points, and this was averaged to obtain the average particle diameter of the particle sample. Asked. *

<Example 1> Manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion-exchanged water, and an aqueous solution of sodium hydroxide (manufactured by Nacalai Tesque) was added and stirred for a while. Thereafter, oxygen gas containing ozone was passed for 5 hours to carry out an oxidation reaction. The obtained precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 350 ° C. for 1.5 hours. As a result, manganese oxide containing ε-type manganese oxide was obtained, and the BET specific surface area was 112 m. ² / g. 36.2 g of the obtained ε-type manganese oxide, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were added to ion-exchanged water and stirred overnight. The aqueous slurry was prepared by fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 78 g / L.

<Example 2> Manganese chloride (II) hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion-exchanged water and stirred for a while. Thereafter, an aqueous potassium permanganate solution was slowly added dropwise to the aqueous manganese chloride solution with stirring, and allowed to react for about 30 minutes. The obtained precipitate was filtered off, washed with ion-exchanged water and dried at 120 ° C. to obtain manganese oxide containing ε-type manganese oxide, and the BET specific surface area was 140 m ² / g. . 36.2 g of the obtained ε-type manganese oxide, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were added to ion-exchanged water and stirred overnight. The aqueous slurry was prepared by fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 80 g / L.

<Example 3> Manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion-exchanged water, an aqueous solution of sodium hydroxide (manufactured by Nacalai Tesque) was added and stirred for a while. Thereafter, oxygen gas containing ozone was passed for 5 hours to carry out an oxidation reaction. The obtained precipitate was filtered off and subjected to a baking treatment at 120 ° C. for 1.5 hours. As a result, a manganese oxide containing ε-type manganese oxide was obtained, and the BET specific surface area was 174 m ² / g. 36.2 g of the obtained ε-type manganese oxide, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were added to ion-exchanged water. The aqueous slurry was prepared by stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 78 g / L.

<Example 4> Ion exchange of 12.0 g of ε-type manganese oxide obtained in Example 1, 60.3 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 79 g / L.

<Example 5> Ion exchange of 18.1 g of ε-type manganese oxide obtained in Example 1, 54.3 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 80 g / L.

<Example 6> 41.4 g of ε-type manganese oxide obtained in Example 1, 31.0 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were ion-exchanged. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of the obtained filter was 77 g / L.

Example 7 Ion exchange of 55.7 g of ε-type manganese oxide obtained in Example 1, 16.7 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 78 g /.

Example 8 Ion exchange of 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 800 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 79 g / L.

<Example 9> 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1350 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite are ion-exchanged. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 81 g / L.

Example 10 Ion exchange of 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1500 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 82 g / L.

<Example 11> Manganese carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was baked in the air at 400 ° C for 5 hours. The obtained fired product was put into an aqueous nitric acid solution and stirred for 30 minutes for acid treatment. Then, when the obtained deposit was separated by filtration and dried at 120 ° C., manganese oxide containing γ-type manganese oxide was obtained, and the BET specific surface area was 115 m ² / g. 36.2 g of the obtained γ-type manganese oxide, coconut shell activated carbon (BET specific surface area: 1000 m ² / g) 36.2 g, polyvinylpyrrolidone 2.6 g, sepiolite 6.4 g were added to ion-exchanged water, and stirred overnight. The aqueous slurry was prepared by fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 80 g / L.

<Example 12> Manganese carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was baked in air at 350 ° C for 5 hours. The obtained fired product was put into an aqueous nitric acid solution and stirred for 30 minutes for acid treatment. Then, when the obtained deposit was separated by filtration and dried at 120 ° C., manganese oxide containing γ-type manganese oxide was obtained, and the BET specific surface area was 147 m ² / g. 36.2 g of the obtained γ-type manganese oxide, coconut shell activated carbon (BET specific surface area: 1000 m ² / g) 36.2 g, polyvinylpyrrolidone 2.6 g, sepiolite 6.4 g were added to ion-exchanged water, and stirred overnight. The aqueous slurry was prepared by fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 80 g / L.

<Example 13> Manganese nitrate (II) hexahydrate (manufactured by Nacalai Tesque) was dissolved in ion-exchanged water and stirred for a while. Thereafter, the aqueous manganese nitrate solution was slowly added dropwise to the aqueous potassium permanganate solution with stirring and allowed to react for about 30 minutes. The obtained precipitate was separated by filtration, washed with ion-exchanged water, and dried at 120 ° C. As a result, a manganese oxide containing γ-type manganese oxide was obtained, and the BET specific surface area was 198 m ² / g. . 36.2 g of the obtained γ-type manganese oxide, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were added to ion-exchanged water. The aqueous slurry was prepared by stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 82 g / L.

<Example 14> 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, sepiolite 6 An aqueous slurry was prepared by adding 0.4 g in ion-exchanged water, stirring overnight and thoroughly dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 54 g / L.

<Example 15> 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinyl pyrrolidone, sepiolite 6 An aqueous slurry was prepared by adding 0.4 g in ion-exchanged water, stirring overnight and thoroughly dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 100 g / L.

<Example 16> 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, sepiolite 6 An aqueous slurry was prepared by adding 0.4 g in ion-exchanged water, stirring overnight and thoroughly dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 125 g / L.

<Example 17> 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, sepiolite 6 An aqueous slurry was prepared by adding 0.4 g in ion-exchanged water, stirring overnight and thoroughly dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 152 g / L.

<Example 18> 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, silica sol (manufactured by Nissan Chemical Industries, Ltd.) Snowtex 30: solid content ratio 30%) 21.4 g was added to ion-exchanged water, stirred overnight, and sufficiently dispersed to prepare an aqueous slurry. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 82 g / L.

<Comparative example 1> Manganese sulfate (II) monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion exchange water, an aqueous solution of sodium hydroxide (manufactured by Nacalai Tesque) was added, and the mixture was stirred for a while. Thereafter, oxygen gas containing ozone was passed for 5 hours to carry out an oxidation reaction. The obtained precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 500 ° C. for 1.5 hours. As a result, manganese oxide containing ε-type manganese oxide was obtained, and the BET specific surface area was 35 m. ² / g. 36.2 g of the obtained ε-type manganese oxide, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were added to ion-exchanged water. The aqueous slurry was prepared by stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 80 g / L.

<Comparative example 2> Manganese sulfate (II) monohydrate (Wako Pure Chemical Industries, Ltd.) was dissolved in ion exchange water, and sulfuric acid (Nacalai Tesque, Inc.) was added. Then, manganese oxide was deposited on titanium as the anode by electrolysis at a current density of 0.5 A / dm ² using manganese as the anode and carbon as the cathode in the manganese sulfate and sulfuric acid solutions. Manganese oxide containing γ-type manganese oxide was obtained, and the BET specific surface area was 40 m ² / g. 36.2 g of the obtained γ-type manganese oxide, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were added to ion-exchanged water. The aqueous slurry was prepared by stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 79 g / L.

<Comparative Example 3> Ion-exchange 6.6 g of ε-type manganese oxide obtained in Example 1, 65.8 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 78 g / L.

Comparative Example 4 Ion exchange of 65.8 g of ε-type manganese oxide obtained in Example 1, 6.6 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 80 g / L.

<Comparative Example 5> Ion-exchange 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 500 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of the obtained filter was 35 g / L.

Comparative Example 6 Ion exchange of 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 500 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 79 g / L.

Comparative Example 7 Ion exchange of 36.2 g of ε-type manganese oxide obtained in Example 1, 36.2 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite. The aqueous slurry was prepared by adding in water, stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 81 g / L.

<Comparative Example 8> Manganese sulfate (II) monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion exchange water, concentrated nitric acid (manufactured by Nacalai Tesque Co., Ltd.) was added, and the mixture was heated to 60 ° C. Stir for a while. Thereafter, when a manganese sulfate warm aqueous solution heated and maintained at 60 ° C. and a potassium permanganate aqueous solution were mixed, a white precipitate was obtained. Thereafter, the white precipitate was filtered off, dried at 120 ° C., and then subjected to a baking treatment at 250 ° C. for 1.5 hours. As a result, manganese oxide containing α-type manganese oxide was obtained, and the BET specific surface area was 220 m. ² / g. 36.2 g of the obtained α-type manganese oxide, 36.2 g of coconut shell activated carbon (BET specific surface area: 1000 m ² / g), 6.4 g of sepiolite, 2.6 g of polyvinylpyrrolidone, and 6.4 g of sepiolite were added to ion-exchanged water. The aqueous slurry was prepared by stirring overnight and fully dispersing. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total supported amount of the obtained filter was 80 g / L.

<Comparative Example 9> 36.2 g of ε-type manganese oxide obtained in Example 1, 1.3 g of polyvinylpyrrolidone, and 3.2 g of sepiolite were added to ion-exchanged water, stirred overnight, and sufficiently dispersed to obtain an aqueous solution. The slurry was adjusted. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 42 g / L.

<Comparative Example 10> 36.2 g of γ-type manganese oxide obtained in Example 11, 1.3 g of polyvinylpyrrolidone, and 3.2 g of sepiolite were added to ion-exchanged water, stirred overnight, and sufficiently dispersed to obtain an aqueous solution. The slurry was adjusted. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of the obtained filter was 40 g / L.

<Comparative Example 11> Coconut shell activated carbon (BET specific surface area: 1000 m ² / g) 36.2 g, polyvinylpyrrolidone 1.3 g, and sepiolite 3.2 g are added to 130 g of ion-exchanged water, stirred overnight, and sufficiently dispersed. Thus, an aqueous slurry was prepared. Subsequently, a honeycomb (600 cells / inch ² ) based on an aluminum foil having a thickness of 0.02 mm was immersed in the aqueous slurry, and it was confirmed that the aqueous slurry sufficiently penetrated into the honeycomb. Raised. After excess slurry was blown off from the honeycomb by air blow, the deodorized purification filter was obtained by drying in a dryer (120 ° C.) for 3 hours. The total amount of attached filter was 41 g / L.

The effects of the present invention will be described below with reference to Table 1. In Examples 1 to 18 according to the present invention, when the BET specific surface area of the manganese oxide containing ε and γ type manganese oxide is smaller than 50 m ² / g (Comparative Examples 1 and 2), the weight of the activated carbon / manganese oxide When the mixing ratio is larger than 5.0 (Comparative Example 3), when smaller than 0.2 (Comparative Example 4), when the amount of adhesion is smaller than 40 g / L (Comparative Example 5), the BET specific surface area of the activated carbon is 600 m. Compared to the case where the oxide is less than ² / g (Comparative Example 6), the case where it is greater than 1500 m ² / g (Comparative Example 7), and the case where manganese oxide (α form) having a different crystal form is used (Comparative Example 8). Thus, the ozone and toluene removal performance is high, the volatile organic compound (VOC) generation concentration from the copying machine is low, and the odor determination result is also high. Further, compared with ε and γ-type manganese oxide alone (Comparative Examples 9 and 10) and activated carbon alone (Comparative Example 11), the ozone and toluene removal performance is high, and the volatile organic compound (VOC) from the copying machine. It can be seen that the generated concentration is low and the odor determination result is also high.

The deodorizing and purifying filter of the present invention has high removal performance of harmful gases and odor components. Therefore, it is used for deodorizing and purifying filters, refrigerators and toilet deodorizers for removing harmful gases and odorous components from the exhaust gas of electronic devices such as copiers, printers, multi-function OA machines, computers, projectors, and POD printers. It can be used in a wide range of deodorizing filters and the like, and can greatly contribute to the industry.

Claims

A filter in which a carrier includes a manganese oxide having a BET specific surface area of 50 to 400 m 2 / g and a crystal form of ε and / or γ form, and activated carbon having a BET specific surface area of 600 to 1500 m 2 / g. A deodorizing and purifying filter, wherein the mixing weight ratio of the activated carbon and the manganese oxide is activated carbon / manganese oxide = 0.2 to 5.0.
The deodorizing purification filter according to claim 1, wherein the carrier has a structure having a plurality of cells.
The deodorizing purification filter according to claim 1 or 2, wherein the carrier is a honeycomb carrier having a honeycomb shape.
4. The manganese oxide according to claim 1, wherein the manganese oxide is a particle having an average particle diameter of 1.0 to 50 μm, and the activated carbon is a particle having an average particle diameter of 1.0 to 50 μm. Deodorizing purification filter.
An electronic apparatus comprising the deodorizing and purifying filter according to claim 1.