JP2015134318A - Acidic gas adsorption and removal filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acidic gas adsorption and removal filter capable of exhibiting removal performance to be satisfied in a temperature and humidity range in a general life over a long time in terms of acidic gas adsorption and removal performance in a gas phase.SOLUTION: There is provided an acidic gas adsorption and removal filter which is a honeycomb structure filter, in which a mixture of one or more kinds of compounds selected from a group consisting of hydroxide containing an alkali metal, carbonate and hydrogen carbonate, active charcoal and manganese oxide is carried on a honeycomb carrier, with a ratio (weight ratio) of the total weight of the one or more kinds of compounds selected from a group consisting of hydroxide containing an alkali metal, carbonate and hydrogen carbonate and the active charcoal and the weight of manganese oxide, i.e., (total weight of one or more kinds of compounds selected from a group consisting of hydroxide containing an alkali metal, carbonate and hydrogen carbonate, and active charcoal)/(weight of manganese oxide)=0.4 to 10 and a BET specific surface area of the honeycomb structure filter of 50 to 310 m/cc.

Description

  The present invention relates to an acid gas adsorption / removal filter excellent in adsorption / removal performance of acid gas, particularly sulfur oxides such as sulfur dioxide and nitrogen oxides such as nitrogen dioxide. More specifically, the present invention relates to an acidic gas adsorption / removal filter that can exhibit removal performance over a long period of time in a temperature and humidity region in general life. The temperature / humidity region in general life referred to here is approximately −30 to 50 ° C. in the temperature range and approximately 20 to 95 RH% in the humidity range.

  In order to remove acidic gases in the atmosphere, particularly harmful gases such as sulfur oxides and nitrogen oxides, an adsorption removal method using the adsorption action of activated carbon is known. Moreover, when using activated carbon, the method of attaching a chemical | medical agent to activated carbon and providing chemical adsorption ability to activated carbon is also known.

  Examples of adding chemicals to activated carbon for the purpose of improving the performance of removing acidic gases such as sulfur oxides and nitrogen oxides include denitration agents (for example, Patent Document 1) in which alkaline chemicals, particularly potassium hydroxide, are added to activated carbon. An acid gas removing agent with an amino group-containing organic substance (for example, Patent Document 2) is disclosed.

  In addition, as a filter, a filter made of a corrugated structure having an inorganic or organic fiber base paper as a base material, activated carbon or zeolite as an adsorbing material, and potassium carbonate as a gas reaction material (for example, patent documents) 3) is disclosed.

  However, in the drug-impregnated activated carbon and the drug-added filter disclosed in Patent Documents 1 to 3, the adsorption performance of acidic gas such as sulfur oxide and nitrogen oxide is insufficient, and the adsorption performance is limited, There is a problem that it is difficult to maintain the adsorption and removal performance of acidic gases such as sulfur oxides and nitrogen oxides over a long period of time.

  Therefore, a technique is known in which a catalyst is supported on a porous body such as activated carbon or alumina, and the adsorbed acidic gas such as sulfur oxide or nitrogen oxide is decomposed or reacted to be removed.

  An example of supporting the catalyst on the porous carrier was selected from the group consisting of carbon as a main component, one or more alkali metals, and cerium, thorium, manganese, iron, copper, zinc, and tin. At least one element selected from the group consisting of a nitrogen oxide adsorbent (for example, Patent Document 4) containing one or more kinds and having a surface layer made of a sulfur compound, and platinum, palladium, rhodium and ruthenium And at least one element selected from the group consisting of manganese, nickel, cobalt and iron is alumina, silica, titania, zirconia, silica-alumina, alumina-zirconia, alumina-titania, silica-titania, silica-zirconia and titania A nitrogen oxide removing agent supported on at least one selected from the group consisting of zirconia (example: In Patent Document 5) are disclosed.

  However, the nitrogen oxide adsorbent disclosed in Patent Document 4 is effective for removing nitrogen oxide in the gas at a temperature in the range of 200 to 400 ° C., but is sufficient for a long period of time in the temperature and humidity range in general life. There is a problem that it is not possible to express the removal performance.

  Moreover, since the nitrogen oxide removing agent disclosed in Patent Document 5 uses platinum, palladium, rhodium and ruthenium, there is a problem that it is very expensive and disadvantageous in terms of cost.

  As described above, there is no acid gas adsorption / removal agent or acid gas adsorption / removal filter that can maintain acid gas adsorption / removal performance such as sulfur oxide and nitrogen oxide over a long period of time.

JP-A-6-126162 JP-A-6-7634 JP 2001-310109 A JP-A 63-287552 Japanese Patent Laid-Open No. 11-57399

  The present invention has been made against the background of the above-described prior art, and an object of the present invention is to provide an acid gas adsorption / removal filter that can exhibit sufficient removal performance over a long period of time in a temperature and humidity region in general life.

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 honeycomb structure filter comprising a honeycomb carrier carrying a mixture of at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals, activated carbon and manganese oxides, The ratio (weight ratio) of the total weight of one or more compounds selected from the group consisting of hydroxides, carbonates and hydrogen carbonates containing activated carbon and activated carbon to manganese oxides (weight ratio) The total weight of one or more compounds selected from the group consisting of a product, carbonate and bicarbonate and activated carbon) / (weight of manganese oxide) = 0.4-10, and the BET ratio of the honeycomb structure filter An acidic gas adsorption / removal filter having a surface area of 50 to 310 m ² / cc.
2. 2. The acidic gas adsorption / removal filter according to 1 above, wherein the hydroxide containing an alkali metal is NaOH or KOH.
3. _3. The acidic gas adsorption / removal filter according to 1 or 2 above, wherein the carbonate containing the alkali metal is Na ₂ CO ₃ or K ₂ CO ₃ .
4). 4. The acidic gas adsorption / removal filter according to any one of 1 to ₃ , wherein the hydrogen carbonate containing the alkali metal is NaHCO ₃ or KHCO ₃ .
5. The mixing ratio of at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals and activated carbon is 0.03 to 30 parts by weight with respect to 100 parts by weight of activated carbon. 5. The acidic gas adsorption / removal filter according to any one of 1 to 4 above.

  The acidic gas adsorption / removal filter according to the present invention has an advantage that sufficient removal performance can be exhibited over a long period in a temperature and humidity region in general life.

  Hereinafter, the present invention will be described in detail.

The acidic gas adsorption / removal filter in the present invention is a honeycomb carrier comprising a mixture of activated carbon and manganese oxide impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals. A honeycomb structure filter supported on the substrate, wherein the ratio of the total weight of the activated carbon and the weight of the manganese oxide to one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals (Weight ratio) is activated carbon / manganese oxide = 0.4-10 impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals, and honeycomb by the BET specific surface area of the structure filter to 50~310m ² / cc, it can express a sufficient removal performance over time at temperature and humidity area in the general life The present inventors have found that.

  Although it is not clear about the adsorption / removal mechanism of gaseous sulfur oxide, nitrogen oxide, etc., which are acidic gases, it is presumed as the following (1) to (3).

  First, (1) an activated carbon in which a gaseous sulfur oxide is added to manganese oxide and one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals are attached. Each nitrogen oxide is adsorbed.

  Thereafter, (2) the gaseous sulfur oxide is oxidized to a higher oxidation state sulfur oxide by the oxidation catalytic action of manganese oxide, and the nitrogen oxide is hydroxylated containing alkali metal on the activated carbon. It reacts with one or more compounds selected from the group consisting of products, carbonates and bicarbonates to be immobilized.

  (3) The generated highly oxidized sulfur oxide reacts with the moisture adsorbed on the manganese oxide, becomes sulfuric acid, moves to activated carbon, and is adsorbed and removed. Activated carbon acts as an acceptor for the generated sulfuric acid and nitrogen oxide. If the mixing ratio of the activated carbon is low, moisture is preferentially absorbed, so that the mechanism (3) is hindered for a long time. The removal performance of a sufficient acid gas adsorption / removal filter cannot be exhibited.

Examples of the hydroxide containing an alkali metal in the present invention include NaOH and KOH. Examples of the carbonate containing an alkali metal include Na ₂ CO ₃ and K ₂ CO _3. Examples of the bicarbonate include NaHCO ₃ and KHCO _3, and can be used alone or in combination of two or more.

  In the present invention, the mixing ratio of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals and activated carbon is 0.03 to 30 parts by weight with respect to 100 parts by weight of activated carbon. It is preferable that it is 0.05-25 weight part. If the mixing ratio of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals to the activated carbon is less than 0.03 parts by weight, sufficient acidic gas adsorption / The removal performance cannot be expressed. Further, when the mixing ratio of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals to activated carbon exceeds 30 parts by weight, hydroxides containing mixed alkali metals This is because the activated carbon pores are blocked by one or more compounds selected from the group consisting of carbonates and hydrogen carbonates, resulting in a disadvantage that the acid gas adsorption / removal performance decreases.

  In the present invention, the ratio (weight ratio) of the total weight of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals and activated carbon to the weight of manganese oxide is ( The total weight of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals and activated carbon) / (weight of manganese oxide) = 0.4-10. The ratio (weight ratio) of the total weight of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals and activated carbon to the weight of manganese oxide is less than 0.4. If so, the generated sulfuric acid and nitrogen oxides cannot be immobilized on the activated carbon, and sufficient removal performance of the acid gas adsorption / removal filter cannot be expressed over a long period of time. In addition, if it exceeds 10, the sulfur oxide removal performance by manganese oxide is significantly reduced, so the load of sulfur oxide and nitrogen oxide on the activated carbon increases, and a sufficient acid gas adsorption / removal filter for a long period of time is required. The removal performance cannot be expressed.

  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, activation is performed by a gas activation method in which a carbon raw material subjected to carbonization or infusibilization treatment is heat-treated at about 500 to 1000 ° C. in an activation gas such as water or carbon dioxide, or carbon subjected to carbonization or infusibilization treatment. A chemical activation method in which the raw material is mixed with an activator 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 preferably 600 m ² / g or more, and more preferably 700 m ² / g or more. If it is less than 600 m ² / g, the adsorption capacity of the acidic gas is small, and as a result, sufficient removal performance cannot be exhibited. Moreover, although the upper limit of the BET specific surface area of activated carbon is not specifically limited, it is preferable that it is 3000 m < ² > / g or less. If this range is exceeded, there is a disadvantage that the production becomes very difficult.

  The crystal form of the manganese oxide in the present invention is not particularly limited. Examples include α-type, γ-type, and ε-type, and these can be used alone or in combination of two or more.

The BET specific surface area of the manganese oxide in the present invention is preferably 100 m ² / g or more, and more preferably 150 m ² / g or more. This is because if the manganese oxide has a BET specific surface area of 100 m ² / g or more, high removal performance at low temperatures can be exhibited. The upper limit of the BET specific surface area of the manganese oxide is not particularly limited, but is preferably 500 m ² / g or less. If this range is exceeded, there is a disadvantage that the production becomes very difficult.

  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, oxygen gas, ozone water, or hydrogen peroxide solution to a solution containing a metal salt After adding an oxidizing agent, etc. to bring the metal into a highly oxidized state, adding an alkali such as ammonia or ammonium salt such as ammonium carbonate to form a precipitate, then filtering the precipitate and drying, metal, Add an oxidizing agent such as oxygen gas, ozone water, or hydrogen peroxide solution to the salt-containing solution to bring the metal into a highly oxidized state, and then add an organic reducing agent such as sucrose, glucose, or polyvinyl alcohol. , Method of filtering and drying the generated gel, adding alkali such as ammonia or ammonium carbonate to a solution containing manganese salt to form a precipitate, then filtering the precipitate, drying and baking It can be used granulation methods and the like. 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 removal performance cannot be achieved at low temperatures.

The BET specific surface area of the acidic gas adsorption / removal filter in the present invention is 50 to 310 m ² / cc. More preferably, it is 70-280 m < ² > / cc. If the BET specific surface area is less than 50 m ² / cc, the acid gas adsorption / removal performance of the acid gas adsorption / removal filter is not sufficient. If the BET specific surface area exceeds 310 m ² / cc, There are problems such as clogging of cells and the like, degradation of acid gas adsorption / removal performance, and high pressure loss of the filter.

  About other components other than one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals contained in the acid gas adsorption / removal filter in the present invention, activated carbon and manganese oxides Is not particularly limited, but preferably contains an oxide of zirconium, copper, cobalt, silver, alkali metal, or alkaline earth metal. More preferred is an oxide of zirconium, silver, alkali metal, or alkaline earth metal. By containing these elements, the acid gas adsorption / removal ability can be improved and sufficient removal performance can be expressed over a long period of time.

  The base material constituting the honeycomb carrier of the acid gas adsorption / removal filter in the present invention is not particularly limited, and conventionally known inorganic, organic fibers, ceramics, aluminum, and the like can be used.

The number of cells of the honeycomb carrier of the acidic gas adsorption / removal filter in the present invention is not limited, and a honeycomb structure having 50 to 1500 cells / inch ² can be used.

  The method for producing the acid gas adsorption / removal filter in the present invention is not particularly defined. The honeycomb carrier is an aqueous solution containing a mixture of one or more compounds selected from the group consisting of hydroxides, carbonates and hydrogen carbonates containing alkali metals, activated carbon, manganese oxides, and inorganic compound / organic compound binders. A general method of drying after contacting with the slurry can be used. The solid content ratio of the aqueous slurry is 10 to 50%, preferably 25 to 50%. When the solid content ratio is less than 10%, a mixture of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals on the support surface, activated carbon, and manganese oxides is sufficient. Since it is not carried, it is not preferable. On the other hand, if the solid content ratio exceeds 50%, the viscosity is increased, the fluidity of the aqueous slurry is lowered, and impregnation is not possible. The temperature at the time of drying is 60-200 degreeC normally, Preferably it is 100-150 degreeC. When the drying temperature exceeds 200 ° C., the organic compound binder is deteriorated, which is not preferable. In addition, if the drying temperature is less than 60 ° C., the drying time becomes longer, which increases the cost.

  One or more selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals contained in the layer supported on the surface of the honeycomb carrier used in the acidic gas adsorption / removal filter in the present invention The total amount of the compound, activated carbon, the mixture of manganese oxide, and the inorganic compound / organic compound binder component is 40 to 220 g / L, preferably 50 to 200 g / L. 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. Further, when the adhering amount is less than 40 g / L, the acid gas adsorption / removal performance is insufficient.

  The binder component contained in the acidic gas adsorption / removal filter in the present invention is not particularly limited, and organic compound binders such as polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, sodium alginate, dextrin, and inorganic such as bentonite, montmorillonite, sepiolite, silica sol, etc. A compound binder or the like can be used.

  The amount of the binder component contained in the layer supported on the surface of the honeycomb carrier used in the acidic gas adsorption / removal filter in the present invention is an organic compound binder with respect to the solid content in the layer supported on the carrier surface. Is preferably 0.5 to 10% by weight, and the inorganic compound binder is preferably 5 to 40% by weight. More preferably, the organic compound binder is 0.5 to 5.0% by weight, and the inorganic compound binder is 10 to 30% by weight. If the organic compound binder exceeds 10% by weight and the inorganic compound binder exceeds 40% by weight, the acidic gas adsorption / removal agent is coated with the binder, and the removal performance of the acidic gas adsorption / removal agent is lowered. Also, it is not preferable that the organic compound binder is less than 0.5% by weight and the inorganic compound binder is less than 5.0% by weight because the acidic gas adsorption / removal agent cannot be sufficiently supported on the surface of the carrier. .

  The acidic gas adsorption / removal filter in the present invention can be widely used for the purpose of reducing acidic gas indoors, in vehicles, wallpaper, furniture, interior materials, resin moldings, electrical equipment, and the like. In particular, it is preferably used for the purpose of removing acidic gas contained in the air. For example, it is preferable to fill a granular material in a container such as a breathable box, bag, or net, and leave it still or ventilate. Also, since the removal speed is fast and there is little problem of desorbing the acid gas once removed, it is more preferable to use it in a ventilated state, an air filter for purifying the air in the interior of a vehicle such as an automobile or a railway vehicle, health Used for air purifier filters, air conditioner filters, OA equipment intake / exhaust filters, building air condition filters, industrial clean room filters used in houses, pet-friendly condominiums, elderly entrance facilities, hospitals, offices, etc. It is more preferable.

  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.

(Measurement method of BET specific surface area of honeycomb filter)
A honeycomb filter sample was cut into a size of 5.0 × 5.0 × 5.0 mm, 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 range of relative pressure of 0.02 to 0.95. The sample was measured at 40 points while raising it to obtain an adsorption isotherm of the sample. (The results at a relative pressure of 0.02 to 0.15 were BET plotted to obtain the BET specific surface area [m ² / cc] per volume.)

(Method for evaluating acid gas adsorption / removal filter removal performance: sulfur dioxide removal)
Cut the acid gas adsorption / removal filter to 26φ and 20mm in height, set it in a glass column with an inner diameter of 26mm, and air with 100ppm sulfur dioxide gas at a temperature of 25 ° C and a relative humidity of 50% at a flow rate of 2.0L / min. Circulated. The temperature in the glass column was kept constant at 25 ° C. Glass column inlet and outlet concentrations were measured continuously with a photoacoustic gas monitor 1312 (manufactured by INNOVA) for 1 hour of sulfur dioxide gas concentration change from the start of measurement, and sulfur dioxide gas supply and removal rate were used to determine sulfur dioxide. The amount of gas removal was calculated. Then, the sulfur dioxide gas removal amount [mg] is calculated by integrating the sulfur dioxide gas removal amount and the time curve, and the sulfur dioxide gas removal amount [mg] is divided by the sample volume to obtain the dioxide dioxide per sample. The sulfur gas removal amount [mg / cc] was calculated.

(Method for evaluating acid gas adsorption / removal filter removal performance: nitrogen dioxide removal)
Cut the acid gas adsorption / removal filter to 26φ and 20mm height, set it in a glass column with an inner diameter of 26mm, and air at a temperature of 25 ° C and a relative humidity of 50% containing 1.0ppm of nitrogen dioxide gas at a flow rate of 10L / min. Circulated. The temperature in the glass column was kept constant at 25 ° C. The inlet of the glass column, the outlet concentration _{NO-NO 2 -NO x Analyzer Model} 42C (Thermo Fisher Scientific , Inc.), from the start of the measurement to the nitrogen dioxide gas removal rate reaches 40%, the change in the concentration of nitrogen dioxide gas It measured continuously and the nitrogen dioxide gas removal amount was computed from the nitrogen dioxide gas supply amount and the removal rate. Then, the nitrogen dioxide gas removal amount [mg] is calculated by integrating the nitrogen dioxide gas removal amount and the time curve, and this nitrogen dioxide gas removal amount [mg] is divided by the sample volume to obtain the dioxide dioxide per sample. The nitrogen gas removal amount [mg / cc] was calculated.

<Example 1>
198 g of manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 675 ml of ion-exchanged water, 68 ml of concentrated nitric acid (manufactured by Nacalai Tesque) was added, and the mixture was heated to 60 ° C. for a while. Stir. Further, 133 g of potassium permanganate (manufactured by Nacalai Tesque) was dissolved in 2250 ml of ion-exchanged water. 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 350 ° C. for 1.5 hours. As a result, manganese oxide containing α-type manganese oxide was obtained, and the BET specific surface area was 125 m ^2. / G.
30 g of the obtained α-type manganese oxide, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon) ), 2.1 g of polyvinylpyrrolidone was added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 98 g / L, and the BET specific surface area was 133 m ² / cc.

<Example 2>
198 g of manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 675 ml of ion-exchanged water, 68 ml of concentrated nitric acid (manufactured by Nacalai Tesque) was added, and the mixture was heated to 60 ° C. for a while. Stir. Further, 133 g of potassium permanganate (manufactured by Nacalai Tesque) was dissolved in 2250 ml of ion-exchanged water. 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 to obtain a manganese oxide containing α-type manganese oxide, and the BET specific surface area was 220 m ^2. / G.
30 g of the obtained α-type manganese oxide, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon) ), 2.1 g of polyvinylpyrrolidone was added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 100 g / L, and the BET specific surface area was 139 m ² / cc.

<Example 3>
180 g of potassium permanganate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 1500 ml of ion-exchanged water and stirred for a while. Then, after adding the sucrose solution which melt | dissolved 144 g of sucrose (made by Wako Pure Chemical Industries Ltd.) in 1000 ml ion-exchange water, it stirred for 1 hour. The obtained sol was filtered off and dried at 120 ° C. Then, when a baking treatment was performed at 250 ° C. for 1.5 hours, a manganese oxide containing α-type manganese oxide was obtained, and the BET specific surface area was 311 m ² / g.
30 g of the obtained α-type manganese oxide, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon) ), 2.1 g of polyvinylpyrrolidone was added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 98 g / L, and the BET specific surface area was 145 m ² / cc.

<Example 4>
Α-type manganese oxide obtained in Example 2 5.5 g, coconut shell activated carbon (BET specific surface area: 1800 m ² / g) 54.5 g, potassium carbonate (manufactured by Nacalai Tesque) 5.5 g (100 parts by weight of activated carbon) On the other hand, 10 parts by weight of potassium carbonate) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 99 g / L, and the BET specific surface area was 230 m ² / cc.

<Example 5>
20 g of α-type manganese oxide obtained in Example 2, 40 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 4.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 100 g / L, and the BET specific surface area was 180 m ² / cc.

<Example 6>
36 g of α-type manganese oxide obtained in Example 2, 24 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 2.4 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 97 g / L, and the BET specific surface area was 117 m ² / cc.

<Example 7>
Α-type manganese oxide 42.9 g obtained in Example 2, coconut shell activated carbon (BET specific surface area: 1800 m ² / g) 17.1 g, potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 1.7 g (100 parts by weight of activated carbon) On the other hand, 10 parts by weight of potassium carbonate) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 98 g / L, and the BET specific surface area was 92 m ² / cc.

<Example 8>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 0.9 mg of potassium carbonate (manufactured by Nacalai Tesque), carbonated with respect to 100 parts by weight of activated carbon Aqueous slurry was prepared by adding 0.03 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone in 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 99 g / L, and the BET specific surface area was 155 m ² / cc.

<Example 9>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 1.5 mg of potassium carbonate (manufactured by Nacalai Tesque), carbonated with respect to 100 parts by weight of activated carbon 0.05 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 100 g / L, and the BET specific surface area was 155 m ² / cc.

<Example 10>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 1.5 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 5 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 101 g / L, and the BET specific surface area was 147 m ² / cc.

<Example 11>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 2.25 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 7.5 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 99 g / L, and the BET specific surface area was 143 m ² / cc.

<Example 12>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.75 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) Aqueous slurry was prepared by adding 12.5 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone in 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 98 g / L, and the BET specific surface area was 135 m ² / cc.

<Example 13>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 4.5 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 15 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 100 g / L, and the BET specific surface area was 131 m ² / cc.

<Example 14>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 6.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 20 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 101 g / L, and the BET specific surface area was 124 m ² / cc.

<Example 15>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 9.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 30 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 98 g / L, and the BET specific surface area was 108 m ² / cc.

<Example 16>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 820 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 99 g / L, and the BET specific surface area was 71 m ² / cc.

<Example 17>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1150 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 101 g / L, and the BET specific surface area was 94 m ² / cc.

<Example 18>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1500 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 102 g / L, and the BET specific surface area was 118 m ² / cc.

<Example 19>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 2900 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 99 g / L, and the BET specific surface area was 215 m ² / cc.

<Example 20>
120 g of manganese (II) nitrate hexahydrate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 400 ml of ion exchange water and stirred for a while. Next, 40.0 g of potassium permanganate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 200 ml of ion exchange water and stirred for a while. Thereafter, an aqueous manganese nitrate solution was slowly added dropwise to the aqueous potassium permanganate solution with stirring and allowed to react for about 30 minutes. As a result, a white precipitate was obtained. Thereafter, the white precipitate was separated by filtration, washed with ion-exchanged water, dried at 120 ° C., and then subjected to a baking treatment at 300 ° C. for 1 hour, whereby manganese oxide was obtained. The obtained manganese oxide had a γ-type crystal form and a BET specific surface area of 152 m ² / g.
30 g of the obtained γ-type manganese oxide, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon) ), 2.1 g of polyvinylpyrrolidone was added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 100 g / L, and the BET specific surface area was 134 m ² / cc.

<Example 21>
Manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 151 g was dissolved in 980 ml of ion exchange water, 68 ml of sulfuric acid (manufactured by Nacalai Tesque Co., Ltd.) was added, and the mixture was stirred at 30 ° C. in a thermostatic bath for a while. Then, an oxygen gas containing 20 g / Nm ³ of ozone was passed through for 6 hours to carry out an oxidation reaction. As a result, a white precipitate was obtained. Thereafter, the white 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 180 m ² / g.
30 g of the obtained ε-type manganese oxide, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon) ), 2.1 g of polyvinylpyrrolidone was added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 102 g / L, and the BET specific surface area was 136 m ² / cc.

<Example 22>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 180 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 50 g / L, and the BET specific surface area was 82 m ² / cc.

<Example 23>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 118 g / L, and the BET specific surface area was 167 m ² / cc.

<Example 24>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 110 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 149 g / L, and the BET specific surface area was 208 m ² / cc.

<Example 25>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 100 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 176 g / L, and the BET specific surface area was 250 m ² / cc.

<Example 26>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium), 54 g of silica sol (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd .: solid content 30%, dry weight 16.2 g) are added to 100 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 105 g / L, and the BET specific surface area was 92 m ² / cc.

<Comparative Example 1>
198 g of manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 675 ml of ion-exchanged water, 68 ml of concentrated nitric acid (manufactured by Nacalai Tesque) was added, and the mixture was heated to 60 ° C. for a while. Stir. Further, 133 g of potassium permanganate (manufactured by Nacalai Tesque) was dissolved in 225 ml of ion-exchanged water. 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 550 ° C. for 1.5 hours to obtain a manganese oxide containing α-type manganese oxide, and the BET specific surface area was 88 m ^2. / G.
30 g of the obtained α-type manganese oxide, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon) ), 2.1 g of polyvinylpyrrolidone was added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 100 g / L, and the BET specific surface area was 104 m ² / cc.

<Comparative Example 2>
Α-type manganese oxide 2.9 g obtained in Example 2, coconut shell activated carbon (BET specific surface area: 1800 m ² / g) 57.1 g, potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 5.7 g (100 parts by weight of activated carbon) On the other hand, 10 parts by weight of potassium carbonate) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 99 g / L, and the BET specific surface area was 190 m ² / cc.

<Comparative Example 3>
48 g of α-type manganese oxide obtained in Example 2, 12 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 1.2 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 98 g / L, and the BET specific surface area was 59 m ² / cc.

<Comparative Example 4>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of attached filter was 100 g / L, and the BET specific surface area was 123 m ² / cc.

<Comparative Example 5>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 500 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 130 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 99 g / L, and the BET specific surface area was 40 m ² / cc.

<Comparative Example 6>
30 g of α-type manganese oxide obtained in Example 2, 30 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g), 3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) 10 parts by weight of potassium) and 2.1 g of polyvinylpyrrolidone were added to 230 g of 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 35 g / L, and the BET specific surface area was 58 m ² / cc.

<Comparative Example 7>
An aqueous slurry was prepared by adding 60 g of α-type manganese oxide obtained in Example 2 and 2.1 g of polyvinylpyrrolidone in 130 g of ion-exchanged water, stirring the mixture 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The total amount of the obtained filter was 35 g / L, and the BET specific surface area was 27 m ² / cc.

<Comparative Example 8>
Coconut shell activated carbon (BET specific surface area: 1800 m ² / g) 60 g, potassium carbonate (manufactured by Nacalai Tesque) 6.0 g (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon), 130 g of polyvinylpyrrolidone 2.1 g Was added to ion-exchanged water, stirred overnight, and fully 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. Excess slurry was blown off from the honeycomb by air blow, and then dried in a dryer (120 ° C.) for 3 hours to obtain an acid gas adsorption / removal filter. The obtained filter had a BET specific surface area of 198 m ² / cc.

The effects of the present invention will be described below with reference to Table 1. Examples 1-26 which are this invention, when the BET specific surface area of the manganese oxide containing (alpha) -type manganese oxide is smaller than 100 m < ² > / g (comparative example 1), the hydroxide containing an alkali metal, carbonate, and When the weight mixing ratio of activated carbon / manganese oxide impregnated with one or more compounds selected from the group consisting of bicarbonate is larger than 10 (Comparative Example 2), smaller than 0.4 (Comparative Example 3), When one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals are not attached to activated carbon (Comparative Example 4), and the amount of attachment is less than 40 g / L (Comparative example 5), it turns out that sulfur dioxide gas and nitrogen dioxide gas removal capacity are high compared with the case where the BET specific surface area of activated carbon is smaller than 600 m < ² > / g (comparative example 6). Moreover, compared with the simple substance of manganese oxide containing α-type manganese oxide (Comparative Example 7) and the activated carbon simple substance impregnated with an alkali metal salt (Comparative Example 7), the sulfur dioxide gas and nitrogen dioxide gas removal capacities are high. Recognize.

  Since the acidic gas adsorption / removal filter of the present invention can maintain the acidic gas adsorption / removal performance for a long period of time, it can be used in a wide range of fields and greatly contributes to the industry.

Claims (5)

A honeycomb structure filter comprising a honeycomb carrier carrying a mixture of at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals, activated carbon and manganese oxides, The ratio (weight ratio) of the total weight of one or more compounds selected from the group consisting of hydroxides, carbonates and hydrogen carbonates containing activated carbon and activated carbon to manganese oxides (weight ratio) The total weight of one or more compounds selected from the group consisting of a product, carbonate and bicarbonate and activated carbon) / (weight of manganese oxide) = 0.4-10, and the BET ratio of the honeycomb structure filter An acidic gas adsorption / removal filter having a surface area of 50 to 310 m ² / cc.   The acidic gas adsorption / removal filter according to claim 1, wherein the hydroxide containing an alkali metal is NaOH or KOH. The acid gas adsorption / removal filter according to claim 1 or 2, wherein the carbonate containing the alkali metal is Na ₂ CO ₃ or K ₂ CO ₃ . The acidic gas adsorption / removal filter according to any one of claims 1 to ₃ , wherein the hydrogen carbonate containing the alkali metal is NaHCO ₃ or KHCO ₃ .   The mixing ratio of at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals and activated carbon is 0.03 to 30 parts by weight with respect to 100 parts by weight of activated carbon. The acidic gas adsorption / removal filter according to claim 1.