JP2015024405A - Acidic gas adsorbent and remover and adsorption and removing filter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acidic gas adsorbent and remover in a gas phase capable of exhibiting a satisfactory removal performance in a temperature and humidity range in general life for long time, and to provide a filter using the same.SOLUTION: There is provided an acidic gas adsorbent and remover containing an active carbon to which one or more kind of compound selected from a group consisting of hydroxide, carbonate and hydrogen carbonate including alkali metals is added, and manganese oxide, having a BET specific surface area of the active carbon of 600 m/g or more, the BET specific surface area of manganese oxide of 100 m/g or more, a mixture ratio (weight ratio) of active carbon to which one or more kind of compound selected from a group consisting of hydroxide, carbonate and hydrogen carbonate including alkali metals is added and manganese oxide is active carbon to which one or more kind of compound selected from a group consisting of hydroxide, carbonate and hydrogen carbonate including alkali metals is added/manganese oxide=0.4 to 10.

Description

  The present invention relates to an acidic gas adsorption / removal agent excellent in adsorption / removal performance of acidic gas, particularly sulfur oxides such as sulfur dioxide and nitrogen oxides such as nitrogen dioxide, and an adsorption / removal filter using the same. More specifically, the present invention relates to an acid gas adsorbing / removing agent and an adsorbing / removing 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.

  However, in the drug-impregnated activated carbon disclosed in Patent Documents 1 and 2, the adsorption performance of acidic gases such as sulfur oxide and nitrogen oxide is insufficient, and the adsorption performance is limited, so over a long period of time, There is a problem that it is difficult to maintain the adsorption / removal performance of acidic gas such as sulfur oxide and nitrogen oxide.

  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 mainly of carbon, one or more alkali metals, and cerium, thorium, manganese, iron, copper, zinc, and tin. At least one selected from the group consisting of a nitrogen oxide adsorbent (for example, Patent Document 3) containing one or more kinds and having a surface layer made of a sulfur compound, or 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 Nitrogen oxide remover supported on at least one selected from the group consisting of titania-zirconia (for example, Patent Document 4) are disclosed.

  However, the nitrogen oxide adsorbent disclosed in Patent Document 3 is effective for removing nitrogen oxides 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 4 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 adsorbing / removing agent that can maintain acid gas adsorbing / removing performance such as sulfur oxide and nitrogen oxide over a long period of time.

JP-A-6-126162 JP-A-6-7634 Japanese Patent Publication No. 6-202 Japanese Patent Laid-Open No. 11-57399

  The present invention has been made against the background of the above-described prior art, and provides an acid gas adsorbing / removing agent and an adsorbing / removing filter using the acid gas adsorbing / removing agent capable of exhibiting sufficient removal performance over a long period of time in a temperature and humidity range in general life The task is to do.

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. It contains activated carbon and manganese oxide impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals, and the activated carbon has a BET specific surface area of 600 m ² / g or more. A manganese oxide having a BET specific surface area of 100 m ² / g or more, and activated carbon and manganese impregnated with at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals Activated carbon / manganese oxide in which at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing an alkali metal is mixed with oxides (weight ratio) = 0.4 to An acidic gas adsorption / removal agent characterized by being 10.
2. 2. The acidic gas adsorption / removal agent according to 1 above, wherein the manganese oxide contains at least α-type manganese oxide.
3. The acidic gas adsorption / removal agent according to 1 or 2, wherein the hydroxide containing the alkali metal is NaOH or KOH.
4). 4. The acidic gas adsorption / removal agent according to any one of 1 to ₃ , wherein the carbonate containing the alkali metal is Na ₂ CO ₃ or K ₂ CO ₃ .
5. 5. The acidic gas adsorption / removal agent according to any one of 1 to 4, wherein the hydrogen carbonate containing the alkali metal is NaHCO ₃ or KHCO ₃ .
6). 1 above, wherein the addition ratio of one or more compounds selected from the group consisting of the hydroxide, carbonate and bicarbonate containing an alkali metal is 0.03 to 30 parts by weight with respect to 100 parts by weight of activated carbon. The acid gas adsorption / removal agent according to any one of -5.
7). An acid gas adsorption / removal filter comprising a sheet-like or honeycomb-like molded body containing the acid gas adsorption / removal agent according to any one of 1 to 6 above.

  The acidic gas adsorbing / removing agent according to the present invention has an advantage that sufficient removal performance can be expressed over a long period of time in a temperature and humidity region in general life.

  Hereinafter, the present invention will be described in detail.

The acidic gas adsorbing / removing agent in the present invention contains activated carbon and manganese oxide impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals, and activated carbon The BET specific surface area of the manganese oxide is 600 m ² / g or more, the BET specific surface area of the manganese oxide is 100 m ² / g or more, and is selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals. The mixing ratio (weight ratio) of activated carbon and manganese oxide impregnated with one or more compounds is attached with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals. The present inventor has found that, by setting the activated carbon / manganese oxide to 0.4 to 10, sufficient removal performance can be expressed over a long period in the temperature and humidity range in general life. I put it out.
Although the removal mechanism of the gaseous sulfur oxide and nitrogen oxide, which are acid gases, is not clear, it is presumed as the following (1) to (3).

  First, (1) gaseous sulfur oxide to manganese oxide is nitrogen on activated carbon in which one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals are impregnated. Each 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, and activated carbon impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals If the mixing ratio is low, moisture is preferentially absorbed, so the mechanism (3) is hindered and sufficient acid gas adsorption / removal agent removal performance cannot be exhibited over a long period of time.

  The manganese oxide in the present invention preferably contains at least α-type manganese oxide. This is because by containing at least α-type manganese oxide, high removal performance at low temperatures can be realized.

The BET specific surface area of the manganese oxide in the present invention is 100 m ² / g or more. More preferably, it is 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 and heating, and then adding an aqueous potassium permanganate solution or the like, or oxygen gas, ozone water, or hydrogen peroxide solution to a solution containing a metal salt A method of adding an oxidizing agent such as the above to bring the metal into a highly oxidized state and then adding an alkali such as ammonia or ammonium salt such as ammonium carbonate to form a precipitate, and then filtering and drying the precipitate, or Add an oxidizing agent such as oxygen gas, ozone water, or hydrogen peroxide solution to the solution containing metal salt to bring the metal into a highly oxidized state, and then add an organic reducing agent such as sucrose, glucose, or polyvinyl alcohol. Then, the produced gel is filtered and dried, or an alkali such as ammonia or ammonium carbonate is added to the solution containing manganese salt to form a precipitate, and then the precipitate is filtered. Drying can be used baking process produced 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 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 600 m ² / g or more. More preferably, it is 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.

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 addition ratio of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals is 0.03 to 30 parts by weight with respect to 100 parts by weight of activated carbon. It is preferably 0.05 to 25 parts by weight. If the loading ratio of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals is less than 0.03 parts by weight, sufficient acid gas adsorption and removal performance over a long period of time Cannot be expressed. Further, when the addition ratio of one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals exceeds 30 parts by weight, hydroxides containing carbonates and carbonates attached This is because the activated carbon pores are blocked by one or more compounds selected from the group consisting of a salt and a hydrogen carbonate, resulting in a disadvantage that the acid gas adsorption / removal performance is lowered.

  In the present invention, the mixing ratio (weight ratio) of activated carbon and manganese oxide impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and hydrogen carbonates containing alkali metals is selected from alkali metals. Activated carbon / manganese oxide to which one or more compounds selected from the group consisting of hydroxides, carbonates and hydrogen carbonates contained are impregnated = 0.4-10. The mixing ratio (weight ratio) of activated carbon impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals and the manganese oxide is less than 0.4. For example, the generated sulfuric acid and nitrogen oxide cannot be immobilized on activated carbon, and sufficient acid gas adsorption / removal agent removal performance cannot be exhibited 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 agent for a long period of time is required. The removal performance cannot be expressed.

  The method for supporting one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals on activated carbon is not particularly limited, and conventionally known processing methods can be used. For example, spraying or impregnating, immersing and drying a solution containing one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals on activated carbon or an activated carbon-containing molded body Can be performed.

  About other components other than one or more compounds selected from the group consisting of manganese oxide, activated carbon, hydroxide containing alkali metal, carbonate and bicarbonate contained in the acidic gas adsorption / removal agent in the present invention 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 shape of the acidic gas adsorbing / removing agent in the present invention is not particularly limited, and may be in the form of powder or a granulated product thereof. When granulating, various binders such as inorganic compound binders such as bentonite, montmorillonite, sepiolite, silica sol, and organic compound binders such as polyvinyl alcohol can be used.

  The acidic gas adsorbing / removing agent in the present invention can also be used as a deodorizing filter after various processing. The production method of the deodorizing filter is not particularly limited, but a production method in which the acid gas adsorption / removal agent formed into a sheet is processed into a planar shape, a pleated shape, or a honeycomb shape is preferable. When using a pleated shape as a direct flow filter, or when using a honeycomb shape as a parallel flow filter, the contact area with the gas to be treated is increased to improve removal efficiency, and the deodorizing filter has a low pressure loss. Can be achieved simultaneously.

  The method for forming the acidic gas adsorption / removal agent into a sheet in the present invention is not particularly limited, and a conventionally known processing method can be used. For example, (a) a wet sheeting method obtained by dispersing acid gas adsorbing / removing agent particles in water together with sheet constituent fibers and dehydrating, (b) dispersing acid gas adsorbing / removing agent particles in the air together with sheet constituent fibers. (C) A method of filling a gas-acid gas adsorbing / removing agent between layers of two or more layers of nonwoven fabric or woven fabric, net-like material, film, membrane by thermal bonding, (d) emulsion A method of bonding and supporting an acid gas adsorbing / removing agent on a breathable material such as nonwoven fabric, woven fabric, foamed urethane, etc. using an adhesive or solvent-based adhesive, (e) thermoplasticity of a base material, hot melt adhesive, etc. A method of bonding and supporting an acid gas adsorbing / removing agent to a breathable material such as nonwoven fabric, woven fabric, and urethane foam, and (f) kneading the acid gas adsorbing / removing agent into a fiber or resin. A method in which mixing integrated Ri, it is possible to use an appropriate method depending on the application. Further, in the methods (a) to (f), it is not necessary to use a surfactant, a water-soluble polymer, etc., and the pore clogging of the porous body itself can be prevented, so that the processing method (b ), (C), (e) are preferably used.

  The acidic gas adsorbing / removing agent in the present invention can be widely used as a deodorizing filter 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)
About 100 mg of a remover sample was collected, vacuum-dried at 120 ° C. for 12 hours, and 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 determine the BET specific surface area [m ² / g] per weight.)

(Evaluation method of acid gas removal agent removal performance: sulfur dioxide removal)
200 mg of an acid gas adsorption / removal agent sample was packed in a glass column having an inner diameter of 15 mm, and air containing 100 ppm of sulfur dioxide gas at a temperature of 25 ° C. and a relative humidity of 50% was circulated at a flow rate of 2.0 L / min. 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 weight to obtain the dioxide dioxide per sample. The sulfur gas removal amount [mg / g] was calculated.

(Evaluation method of acid gas removal agent removal performance: nitrogen dioxide removal)
An acid gas adsorption / removal agent sample (300 mg) was packed in a glass column having an inner diameter of 26 mm, and air containing nitrogen dioxide gas (1.0 ppm) at a temperature of 25 ° C. and a relative humidity of 50% was circulated at a flow rate of 10 L / min. 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 weight to obtain the dioxide dioxide per sample. The nitrogen gas removal amount [mg / g] was calculated.

<Example 1>
19.8 g of manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 67.5 ml of ion exchange water, 6.8 ml of concentrated nitric acid (manufactured by Nacalai Tesque Co., Ltd.) was added, and 60 ° C. The mixture was stirred for a while while warming. Moreover, 13.3 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 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. The obtained manganese oxide was tableted to a density of 1.9 g / cm ³ and then pulverized and classified to 355 to 500 μm to obtain a granular sample.
Further, 3.0 g of potassium carbonate (manufactured by Nacalai Tesque) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the obtained manganese oxide and 3.0 g of coconut shell activated carbon subjected to potassium carbonate addition processing were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Example 2>
19.8 g of manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 67.5 ml of ion exchange water, 6.8 ml of concentrated nitric acid (manufactured by Nacalai Tesque Co., Ltd.) was added, and 60 ° C. The mixture was stirred for a while while warming. Moreover, 13.3 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 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. The obtained manganese oxide was tableted to a density of 1.9 g / cm ³ and then pulverized and classified to 355 to 500 μm to obtain a granular sample.
Further, 3.0 g of potassium carbonate (manufactured by Nacalai Tesque) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the obtained manganese oxide and 3.0 g of coconut shell activated carbon subjected to potassium carbonate addition processing were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Example 3>
3.0 g of potassium permanganate (manufactured by Nacalai Tesque) was dissolved in 50 ml of ion-exchanged water and stirred for a while. Then, after adding the sucrose solution which melt | dissolved 4.8g of sucrose (made by Wako Pure Chemical Industries Ltd.) in 20 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. The obtained manganese oxide was tableted to a density of 1.9 g / cm ³ and then pulverized and classified to 355 to 500 μm to obtain a granular sample.
Further, 3.0 g of potassium carbonate (manufactured by Nacalai Tesque) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the obtained manganese oxide and 3.0 g of coconut shell activated carbon subjected to potassium carbonate addition processing were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Example 4>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 1.0 g of the manganese oxide granulated sample obtained in Example 2 and 10 g of potassium carbonate-impregnated activated carbon were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 5>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 2.0 g of the manganese oxide granulated sample obtained in Example 2 and 4.0 g of potassium carbonate-impregnated activated carbon were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Example 6>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
And the granulated sample of manganese oxide obtained in Example 2 and 2.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Example 7>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
And the granulated sample of manganese oxide obtained in Example 2 and 2.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acid gas adsorbing / removing agent.

<Example 8>
0.1 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) is dissolved in 199.9 g of ion-exchanged water, 100 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) is added to the prepared potassium carbonate aqueous solution, and the mixture is stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (0.03 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 9>
0.2 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 199.8 g of ion-exchanged water, 100 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (0.05 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 10>
Dissolve 2.0 g of potassium carbonate (Nacalai Tesque Co., Ltd.) in 18 g of ion-exchanged water, add 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) to the prepared aqueous potassium carbonate solution, stir for 30 min, The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (5 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 11>
The same potassium carbonate aqueous solution as in Example 10, but the weight part of potassium carbonate relative to the activated carbon is different. Which is wrong?
Dissolve 2.5 g of potassium carbonate (Nacalai Tesque, Inc.) in 17.5 g of ion-exchanged water, add 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) to the prepared potassium carbonate aqueous solution, stir for 30 min, Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (7.5 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 12>
3.5 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 16.5 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (12.5 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 13>
4.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) is dissolved in 16 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) is added to the prepared potassium carbonate aqueous solution, and the mixture is stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (15 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

At the time of Comparative Example 6, the weight part of potassium carbonate relative to the activated carbon was 25 parts by weight in the following and 20 parts by weight in the table. Which is correct?
<Example 14>
Dissolve 6.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) in 14 g of ion-exchanged water, add 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) to the prepared potassium carbonate aqueous solution, and stir for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (20 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 15>
Please add to the ○○ g part so that the weight part of potassium carbonate with respect to the activated carbon is 30 parts by weight.
8.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 12 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (30 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 16>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 820 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 17>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1150 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 18>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1500 m ² / g) was added to the prepared potassium carbonate aqueous solution, and stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 19>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 2900 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Example 20>
60.0 g of manganese (II) nitrate hexahydrate (manufactured by Nacalai Tesque) was dissolved in 200 ml of ion-exchanged water and stirred for a while. Next, 20.0 g of potassium permanganate (manufactured by Nacalai Tesque) was dissolved in 100 ml of ion-exchanged 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. The obtained manganese oxide was tableted to a density of 1.9 g / cm ³ and then pulverized and classified to 355 to 500 μm to obtain a granular sample.
Further, 3.0 g of potassium carbonate (manufactured by Nacalai Tesque) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the obtained manganese oxide and 3.0 g of coconut shell activated carbon subjected to potassium carbonate addition processing were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Comparative Example 1>
19.8 g of manganese (II) sulfate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 67.5 ml of ion exchange water, 6.8 ml of concentrated nitric acid (manufactured by Nacalai Tesque Co., Ltd.) was added, and 60 ° C. The mixture was stirred for a while while warming. Moreover, 13.3 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. The obtained manganese oxide was tableted to a density of 1.9 g / cm ³ and then pulverized and classified to 355 to 500 μm to obtain a granular sample.
Further, 3.0 g of potassium carbonate (manufactured by Nacalai Tesque) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared potassium carbonate aqueous solution, and the mixture was stirred for 30 min. Thereafter, the solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the obtained manganese oxide and 3.0 g of coconut shell activated carbon subjected to potassium carbonate addition processing were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Comparative example 2>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
And the granulated sample 1.0g of manganese oxide obtained in Example 2 and 20g of potassium carbonate impregnated activated carbon were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Comparative Example 3>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 4.0 g of the manganese oxide granulated sample obtained in Example 2 and 1.0 g of potassium carbonate impregnated activated carbon were mixed uniformly to obtain an acid gas adsorption / removal agent.

<Comparative Example 4>
The manganese oxide granulated sample (3.0 g) obtained in Example 2 and coconut shell activated carbon (BET specific surface area: 1800 m ² / g) (3.0 g) were mixed uniformly to obtain an acid gas adsorption / removal agent. Obtained.

<Comparative Example 5>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) is dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 500 m ² / g) is added to the prepared potassium carbonate aqueous solution, and stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain potassium carbonate-impregnated activated carbon (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).
Then, 3.0 g of the granulated sample of manganese oxide obtained in Example 2 and 3.0 g of activated carbon impregnated with potassium carbonate were mixed uniformly to obtain an acidic gas adsorption / removal agent.

<Comparative Example 6>
After compressing and molding 6.0 g of the manganese oxide obtained in Example 2 to a density of 1.9 g / cm ³ , the mixture was pulverized and classified to 355 to 500 μm to obtain an acid gas adsorption / removal agent. . The acid gas adsorption / removal agent obtained had a BET specific surface area of 220 m ² / g.

<Comparative Example 7>
3.0 g of potassium carbonate (manufactured by Nacalai Tesque Co., Ltd.) was dissolved in 17 g of ion-exchanged water, 10 g of coconut shell activated carbon (BET specific surface area: 1800 m ² / g) was added to the prepared aqueous potassium carbonate solution, and the mixture was stirred for 30 min. The solution was filtered and dried at 120 ° C. for 6 hours to obtain an acid gas adsorption / removal agent (10 parts by weight of potassium carbonate with respect to 100 parts by weight of activated carbon).

The effects of the present invention will be described below with reference to Table 1. Examples 1-20 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 the activated carbon (Comparative Example 4), the BET specific surface area of the activated carbon is 600 m ² / g. It can be seen that the sulfur dioxide gas and nitrogen dioxide gas removal capacities are higher than those in the case of smaller than (Comparative Example 5). In addition, compared with the simple substance of manganese oxide containing α-type manganese oxide (Comparative Example 6) 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 agent and the adsorption / removal filter of the present invention can maintain the acidic gas adsorption / removal performance for a long period of time, they can be used in a wide range of fields and contribute to the industry.

Claims (7)

It contains activated carbon and manganese oxide impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals, and the activated carbon has a BET specific surface area of 600 m ² / g or more. A manganese oxide having a BET specific surface area of 100 m ² / g or more, and activated carbon and manganese impregnated with at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals Activated carbon / manganese oxide in which at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing an alkali metal is mixed with oxides (weight ratio) = 0.4 to An acidic gas adsorption / removal agent characterized by being 10.   The acidic gas adsorption / removal agent according to claim 1, wherein the manganese oxide contains at least α-type manganese oxide.   The acidic gas adsorption / removal agent according to claim 1 or 2, wherein the hydroxide containing an alkali metal is NaOH or KOH. Acid gas adsorption and removal agent according to any one of claims 1 to 3 carbonate is _Na 2 CO ₃ or _K 2 CO ₃ containing the alkali metal. The acid gas adsorption / removal agent according to any one of claims 1 to 4, wherein the hydrogen carbonate containing an alkali metal is NaHCO ₃ or KHCO ₃ .   The addition ratio of at least one compound selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals is 0.03 to 30 parts by weight with respect to 100 parts by weight of activated carbon. The acid gas adsorption / removal agent according to any one of 1 to 5.   An acidic gas adsorption / removal filter comprising a sheet-like or honeycomb-like molded body containing the acidic gas adsorption / removal agent according to claim 1.