JP6349736B2 - Acid gas adsorption / removal filter - Google Patents
Acid gas adsorption / removal filter Download PDFInfo
- Publication number
- JP6349736B2 JP6349736B2 JP2014006635A JP2014006635A JP6349736B2 JP 6349736 B2 JP6349736 B2 JP 6349736B2 JP 2014006635 A JP2014006635 A JP 2014006635A JP 2014006635 A JP2014006635 A JP 2014006635A JP 6349736 B2 JP6349736 B2 JP 6349736B2
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- JP
- Japan
- Prior art keywords
- honeycomb
- activated carbon
- weight
- gas adsorption
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000001179 sorption measurement Methods 0.000 title claims description 92
- 239000002253 acid Substances 0.000 title claims description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 200
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 149
- 239000007789 gas Substances 0.000 claims description 119
- 229910052782 aluminium Inorganic materials 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052783 alkali metal Inorganic materials 0.000 claims description 34
- 150000001340 alkali metals Chemical class 0.000 claims description 34
- 230000002378 acidificating effect Effects 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 28
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 26
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 25
- 150000004679 hydroxides Chemical class 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
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- 230000008030 elimination Effects 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 description 139
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 86
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 56
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- 229910001868 water Inorganic materials 0.000 description 51
- 229910000027 potassium carbonate Inorganic materials 0.000 description 43
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- 239000011591 potassium Substances 0.000 description 22
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- 238000000034 method Methods 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 14
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 12
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 10
- 239000012286 potassium permanganate Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
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- 239000007864 aqueous solution Substances 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000002585 base Substances 0.000 description 3
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JIPBPJZISZCBJQ-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxycarbonyl]-3-(pyridin-4-ylmethyl)piperidine-3-carboxylic acid Chemical compound C1N(C(=O)OC(C)(C)C)CCCC1(C(O)=O)CC1=CC=NC=C1 JIPBPJZISZCBJQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1122—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Description
本発明は、酸性ガス、特に、二酸化硫黄などの硫黄酸化物や二酸化窒素などの窒素酸化物の吸着・除去性能に優れた酸性ガス吸着・除去フィルタに関する。さらに詳しくは、一般生活における温湿度領域において、長期にわたって除去性能を発現できる酸性ガス吸着・除去フィルタに関する。ここで言う、一般生活における温湿度領域とは、温度範囲でおおよそ−３０〜５０℃、湿度範囲でおおよそ２０〜９５ＲＨ％のことである。 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.
大気中の酸性ガス、特に、硫黄酸化物や窒素酸化物等の有害ガスを除去するために、活性炭の吸着作用を利用した吸着除去手法が知られている。また、活性炭を用いる際には、活性炭に薬剤を添着し、活性炭に化学吸着能を付与する手法も知られている。 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.
硫黄酸化物や窒素酸化物等の酸性ガス除去性能向上を目的として、活性炭に薬剤を添着した例としては、活性炭にアルカリ薬剤、特に水酸化カリウムを添着した脱硝剤（例えば、特許文献１）やアミノ基含有有機物を添着した酸性ガス除去剤（例えば、特許文献２）が開示されている。 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.
また、フィルタとしては、無機または有機繊維基紙を基材とし、吸着材として、活性炭、またはゼオライトを、ガス反応材として、炭酸カリウムをそれぞれ担持したコルゲート状構造体からなるフィルタ（例えば、特許文献３）が開示されている。 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.
しかしながら、特許文献１〜３に開示される薬剤添着活性炭や薬剤添着フィルタでは、硫黄酸化物や窒素酸化物等の酸性ガスの吸着性能が不十分であり、また吸着性能にも限界があるため、長期間にわたって、硫黄酸化物や窒素酸化物等の酸性ガス吸着・除去性能を維持することは困難であるという問題がある。 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.
そこで、活性炭やアルミナ等の多孔質体に触媒を担持し、吸着した硫黄酸化物や窒素酸化物等の酸性ガスを分解、または反応させて除去する手法が知られている。 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.
多孔質担体に触媒を担持した例としては、炭素を主成分とし、アルカリ金属の１種または２種以上と、セリウム、トリウム、マンガン、鉄、銅、亜鉛、および錫からなる群から選ばれた１種または２種以上とを含有し、硫黄化合物からなる表面層を有する窒素酸化物吸着剤（例えば、特許文献４）や白金、パラジウム、ロジウムおよびルテニウムからなる群から選ばれる少なくとも１種の元素と、マンガン、ニッケル、コバルトおよび鉄からなる群から選ばれる少なくとも１種の元素がアルミナ、シリカ、チタニア、ジルコニア、シリカ−アルミナ、アルミナ−ジルコニア、アルミナ−チタニア、シリカ−チタニア、シリカ−ジルコニアおよびチタニア−ジルコニアからなる群から選ばれる少なくとも１種に担持された窒素酸化物除去剤（例えば、特許文献５）が開示されている。 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.
しかしながら、特許文献４に開示される窒素酸化物吸着剤は２００〜４００℃の範囲内の温度ではガス中の窒素酸化物除去には効果は見られるが、一般生活における温湿度領域において長期にわたって十分な除去性能を発現できないという問題がある。 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.
また、特許文献５に開示される窒素酸化物除去剤は、白金、パラジウム、ロジウムおよびルテニウムを使用しているため、非常に高価であり、コスト的に不利であるという問題がある。 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.
上述のとおり、長期間にわたって硫黄酸化物や窒素酸化物等の酸性ガス吸着・除去性能を維持できる酸性ガス吸着・除去剤、酸性ガス吸着・除去フィルタは見当たらないのが現状である。 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.
本発明は上記従来技術の課題を背景になされたものであり、一般生活における温湿度領域で長期にわたって十分な除去性能を発現できる酸性ガス吸着・除去フィルタを提供することを課題とする。 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.
本発明者は上記課題を解決するため、鋭意研究した結果、遂に本発明を完成するに到った。すなわち本発明は、以下の通りである。
１．アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物、活性炭およびマンガン酸化物の混合物をハニカム担体に担持したハニカム構造体フィルタであって、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の合計重量とマンガン酸化物の重量の比率（重量比）が、（アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の合計重量）／（マンガン酸化物の重量）＝０．４〜１０であり、ハニカム構造体フィルタのＢＥＴ比表面積が５０〜３１０ｍ２／ｃｃであることを特徴とする酸性ガス吸着・除去フィルタ。
２．前記アルカリ金属を含む水酸化物がＮａＯＨまたはＫＯＨである上記１に記載の酸性ガス吸着・除去フィルタ。
３．前記アルカリ金属を含む炭酸塩がＮａ２ＣＯ３またはＫ２ＣＯ３である上記１または２に記載の酸性ガス吸着・除去フィルタ。
４．前記アルカリ金属を含む炭酸水素塩がＮａＨＣＯ３またはＫＨＣＯ３である上記１〜３のいずれかに記載の酸性ガス吸着・除去フィルタ。
５．前記アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の混合比率が、活性炭１００重量部に対して０．０３〜３０重量部である上記１〜４のいずれかに記載の酸性ガス吸着・除去フィルタ。
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.
本発明による酸性ガス吸着・除去フィルタは、一般生活における温湿度領域で長期にわたって十分な除去性能を発現することが可能であるという利点を有する。 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.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明における酸性ガス吸着・除去フィルタは、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物を添着した活性炭とマンガン酸化物の混合物をハニカム担体に担持したハニカム構造体フィルタであって、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の合計重量とマンガン酸化物の重量の比率（重量比）が、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物を添着した活性炭／マンガン酸化物＝０．４〜１０であり、ハニカム構造体フィルタのＢＥＴ比表面積が５０〜３１０ｍ２／ｃｃにすることにより、一般生活における温湿度領域で長期にわたって十分な除去性能を発現できることを本発明者は見出した。 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.
酸性ガスであるガス状硫黄酸化物や窒素酸化物等の吸着・除去メカニズムについては明確ではないが、次の（１）〜（３）のように推測される。 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).
まず、最初に（１）マンガン酸化物にガス状硫黄酸化物が、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物が添着された活性炭に窒素酸化物がそれぞれ吸着される。 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.
その後、（２）ガス状硫黄酸化物はマンガン酸化物の酸化触媒作用によりガス状硫黄酸化物がより高酸化状態の硫黄酸化物に酸化され、窒素酸化物は活性炭上のアルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と反応し、固定化される。 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.
そして、（３）生成した高酸化状態の硫黄酸化物はマンガン酸化物に吸着された水分と反応し、硫酸となり、活性炭に移行して、吸着除去される。活性炭は生成した硫酸、窒素酸化物の受容体として作用しており、もし、活性炭の混合比率が低ければ、水分が優先的に吸収されてしまうため、前記メカニズム（３）が阻害され、長期にわたって十分な酸性ガス吸着・除去フィルタの除去性能を発現することができない。 (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.
本発明におけるアルカリ金属を含む水酸化物としては、例えばＮａＯＨ、ＫＯＨなどが挙げられ、アルカリ金属を含む炭酸塩としては、例えばＮａ２ＣＯ３、Ｋ２ＣＯ３などが挙げられ、アルカリ金属を含む炭酸水素塩としては、例えばＮａＨＣＯ３、ＫＨＣＯ３などが挙げられ、単独または２種類以上組み合わせて使用することができる。 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.
本発明におけるアルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の混合比率が、活性炭１００重量部に対して０．０３〜３０重量部であることが好ましく、０．０５〜２５重量部であることがより好ましい。アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物の活性炭に対する混合比率が０．０３重量部未満であれば、長期にわたって十分な酸性ガス吸着・除去性能を発現することができない。また、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物の活性炭に対する混合比率が３０重量部を超えると、混合したアルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物により活性炭細孔が閉塞され、酸性ガス吸着・除去性能が低下するという不都合が生じるからである。 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.
本発明において、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の合計重量とマンガン酸化物の重量の比率（重量比）が、（アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の合計重量）／（マンガン酸化物の重量）＝０．４〜１０である。アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物と活性炭の合計重量とマンガン酸化物の重量の比率（重量比）が、０．４未満であれば、生成した硫酸や窒素酸化物を活性炭上で固定化することができず、長期にわたって十分な酸性ガス吸着・除去フィルタの除去性能を発現することができない。また、１０を超えると、マンガン酸化物による硫黄酸化物除去性能が大幅に低下するため、活性炭への硫黄酸化物、窒素酸化物の負荷が大きくなり、長期にわたって十分な酸性ガス吸着・除去フィルタの除去性能を発現することができない。 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.
本発明における活性炭種は、特に限定しない。例えば、黒鉛、鉱物系材料（褐炭、瀝青炭などの石炭系、石油または、石油ピッチなど）、植物系材料（木質、果実殻（ヤシ殻など）など）、高分子系材料（ポリアクリルニトリル、フェノール系材料、セルロース）などを原料とする活性炭が挙げられ、これらの原料を炭化、または不融化した後、賦活処理することによって得られる活性炭を使用することができる。 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.
本発明における活性炭作製時の炭化方法、不融化方法、賦活方法については、特に限定されず、従来公知の加工方法を用いることができる。例えば、賦活は、炭化、または不融化処理を施した炭素原料を水や二酸化炭素などの賦活ガス中で、５００〜１０００℃程度で熱処理するガス賦活法や炭化、または不融化処理を施した炭素原料をリン酸、塩化亜鉛、水酸化カリウムなどの賦活剤と混合し、３００〜８００℃程度で熱処理する化学賦活法などを用いることができる。 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.
本発明における活性炭のＢＥＴ比表面積は、６００ｍ２／ｇ以上であることが好ましく、７００ｍ２／ｇ以上であることがより好ましい。６００ｍ２／ｇ未満であれば、酸性ガスの吸着容量が小さく、結果として、十分な除去性能が発現できない。また、活性炭のＢＥＴ比表面積の上限は特に限定するものではないが、３０００ｍ２／ｇ以下であることが好ましい。この範囲を超えると、製造が非常に困難になるという不都合が生じるからである。 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 | capacitance of acidic gas is small, and as a result, sufficient removal performance cannot be expressed. 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.
本発明におけるマンガン酸化物の結晶形については、特に限定しない。例えば、α型、γ型、ε型が挙げられ、単独または２種類以上組み合わせて使用することができる。 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.
本発明におけるマンガン酸化物のＢＥＴ比表面積は、１００ｍ２／ｇ以上であることが好ましく、１５０ｍ２／ｇ以上がより好ましい。マンガン酸化物のＢＥＴ比表面積が１００ｍ２／ｇ以上であれば、低温での高い除去性能を発現することができるからである。また、マンガン酸化物のＢＥＴ比表面積の上限は特に限定するものではないが、５００ｍ２／ｇ以下であることが好ましい。この範囲を超えると、製造が非常に困難になるという不都合が生じるからである。 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.
本発明におけるマンガン酸化物の製造方法は、特に限定しない。金属塩を含有する溶液に濃硝酸等を添加して、加温後、過マンガン酸カリウム水溶液やオゾンガス等を添加する方法、金属塩を含有する溶液に酸素ガス、オゾン水、または過酸化水素水等の酸化剤を添加して、金属を高酸化状態にした後、アンモニア、炭酸アンモニウム等のアンモニウム塩等のアルカリを添加して沈殿を生成させた後、沈殿を濾別、乾燥させる方法、金属塩を含有する溶液に酸素ガス、オゾン水、または過酸化水素水等の酸化剤を添加して、金属を高酸化状態にした後、スクロース、グルコース、ポリビニルアルコール等の有機還元剤を添加して、生成したゲルを濾別、乾燥させる方法、マンガン塩を含有する溶液にアンモニア、炭酸アンモニウム等のアルカリを添加して沈殿を生成させた後、沈殿を濾別、乾燥、焼成して製造する方法等を用いることができる。使用する金属塩に関しては、特に定めないが、水酸化物、塩化物、硝酸塩、硫酸塩等の一般的な塩を使用することができる。溶解度の面から、硝酸塩、硫酸塩が好ましい。また、溶液の溶媒の種類に関しては、特に定めないが、一般的な有機溶剤、水等を使用することができる。環境への負荷を考慮すると、水が好ましい。乾燥、焼成温度に関しては、５００℃以下であることが好ましい。５００℃を超えると、マンガン酸化物の結晶化が進行し、結果として、低温で十分な除去性能が発現できない。 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.
本発明における酸性ガス吸着・除去フィルタのＢＥＴ比表面積は５０〜３１０ｍ２／ｃｃである。より好ましくは、７０〜２８０ｍ２／ｃｃである。ＢＥＴ比表面積が５０ｍ２／ｃｃ未満であれば、酸性ガス吸着・除去フィルタの酸性ガス吸着・除去性能が十分ではなく、３１０ｍ２／ｃｃを超えると、酸性ガス吸着・除去剤成分によるハニカム担体のセル目詰まり等が起こり、酸性ガス吸着・除去性能の低下やフィルタの圧力損失が高くなる等の問題がある。 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.
本発明における酸性ガス吸着・除去フィルタに含まれるアルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物、活性炭およびマンガン酸化物以外のその他の成分については特に限定しないが、ジルコニウム、銅、コバルト、銀、アルカリ金属、アルカリ土類金属の酸化物を含有することが好ましい。より好ましくは、ジルコニウム、銀、アルカリ金属、アルカリ土類金属の酸化物である。これらの元素を含有することにより、酸性ガス吸着・除去能を向上させ、長期にわたって十分な除去性能を発現することができる。 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.
本発明における酸性ガス吸着・除去フィルタのハニカム担体を構成する基材は、特に制限されず、従来公知の無機系、有機系繊維、セラミック、アルミ等を用いることができる。 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.
本発明における酸性ガス吸着・除去フィルタのハニカム担体のセル数については、制限されず、５０〜１５００セル／ｉｎｃｈ２を有するハニカム構造体を用いることができる。 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.
本発明における酸性ガス吸着・除去フィルタの製造方法については特に定めない。ハニカム担体を、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物、活性炭、マンガン酸化物の混合物と無機化合物系・有機化合物系バインダーを含む水性スラリーと接触させた後に乾燥するといった一般的な方法を用いることができる。前記水性スラリーの固形分比率は、１０〜５０％、好ましくは２５〜５０％である。固形分比率が１０％未満であると担体表面にアルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物、活性炭、マンガン酸化物の混合物が十分に担持されなくなるため好ましくない。また、固形分比率が５０％を越えると増粘して水性スラリーの流動性が低下して含浸できなくなるため好ましくない。乾燥する際の温度は、通常６０〜２００℃、好ましくは１００〜１５０℃である。乾燥温度が２００℃を越えると、有機化合物系バインダーが劣化するため好ましくない。また、乾燥温度が６０℃未満であると、乾燥時間が長くなるため、コストが高くなり、好ましくない。 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.
本発明における酸性ガス吸着・除去フィルタに用いられるハニカム担体の表面に担持されている層に含有されるアルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物、活性炭、マンガン酸化物の混合物および無機化合物系・有機化合物系バインダー成分の合計量は、４０〜２２０ｇ／Ｌ、好ましくは、５０〜２００ｇ／Ｌである。添着量が２２０ｇ／Ｌを越えると、ハニカム担体セルの目詰まり等が起こり、フィルタの圧力損失が高くなる等の問題がある。また、添着量が４０ｇ／Ｌ未満であると、酸性ガス吸着・除去性能が不十分である。 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.
本発明における酸性ガス吸着・除去フィルタに含まれるバインダー成分については特に限定されず、ポリビニルピロリドン、カルボキシメチルセルロース、メチルセルロース、アルギン酸ナトリウム、デキストリン等の有機化合物系バインダーやベントナイト、モンモリロナイト、セピオライト、シリカゾル等の無機化合物系バインダー等を用いることができる。 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.
本発明における酸性ガス吸着・除去フィルタに用いられるハニカム担体の表面に担持されている層に含有されるバインダー成分の量は、担体表面に担持される層中の固形分に対して有機化合物系バインダーでは０．５〜１０重量％、無機化合物系バインダーでは５〜４０重量％であることが好ましい。より好ましくは、有機化合物系バインダーでは０．５〜５．０重量％、無機化合物系バインダーでは１０〜３０重量％である。有機化合物系バインダー１０重量％、無機化合物系バインダーで４０重量％を超えると酸性ガス吸着・除去剤がバインダーにより被覆され、酸性ガス吸着・除去剤の除去性能が低下してしまうため、好ましくない。また、有機化合物系バインダーで０．５重量％未満、無機化合物系バインダーで５．０重量％未満であると、担体表面に十分に酸性ガス吸着・除去剤を担持することができないため、好ましくない。 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. .
本発明における酸性ガス吸着・除去フィルタは、屋内、乗り物内、壁紙、家具、内装材、樹脂成形体、電気機器等で、酸性ガスを低減する目的で広く用いることができる。特に空気中に含有される酸性ガスの除去目的で用いることが好ましく、例えば、粒状物を通気性の箱、袋、網等の容器に充填し、静置もしくは通気させて用いることが好ましい。また、除去速度が速く、一旦除去した酸性ガスが脱離する問題が少ないため、通風状態で用いることがより好ましく、自動車や鉄道車両等の車室内の空気を清浄化するためのエアフィルタ、健康住宅、ペット対応マンション、高齢者入所施設、病院、オフィス等で使用される空気清浄機用フィルタ、エアコン用フィルタ、ＯＡ機器の吸気・排気フィルタ、ビル空調用フィルタ、産業用クリーンルーム用フィルタに用いられることがより好ましい。 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.
以下、実施例によって本発明の作用効果をより具体的に示す。下記実施例は本発明方法を限定する性質のものではなく、前・後記の趣旨に沿って設計変更することはいずれも本発明の技術的範囲に含まれるものである。 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.
（ハニカムフィルタのＢＥＴ比表面積の測定方法）
ハニカムフィルタサンプルを５．０×５．０×５．０ｍｍのサイズにカットし、１２０℃で１２時間真空乾燥した後、秤量した。自動比表面積装置ジェミニ２３７５（マイクロメリティックス社製）を使用し、液体窒素の沸点（−１９５．８℃）における窒素ガスの吸着量を相対圧が０．０２〜０．９５の範囲で徐々に高めながら４０点測定し、前記サンプルの吸着等温線を作製した。（相対圧０．０２〜０．１５での結果をＢＥＴプロットし、体積当りのＢＥＴ比表面積［ｍ２／ｃｃ］を求めた。）
(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.)
（酸性ガス吸着・除去フィルタ除去性能の評価方法：二酸化硫黄除去）
酸性ガス吸着・除去フィルタを２６φ、高さ２０ｍｍにカットし、内径２６ｍｍのガラスカラム内にセットし、二酸化硫黄ガス１００ｐｐｍを含む温度２５℃、相対湿度５０％の空気を流量２．０Ｌ／ｍｉｎで流通した。ガラスカラム内の温度は２５℃一定とした。ガラスカラムの入口、出口濃度を光音響ガスモニター１３１２（ＩＮＮＯＶＡ社製）により、測定開始から１時間の二酸化硫黄ガスの濃度変化を連続的に測定し、二酸化硫黄ガス供給量と除去率から二酸化硫黄ガス除去量を算出した。そして、二酸化硫黄ガス除去量と時間の曲線を積分することにより、二酸化硫黄ガス除去量［ｍｇ］を算出し、この二酸化硫黄ガス除去量［ｍｇ］をサンプル体積で割ることにより、サンプル当りの二酸化硫黄ガス除去量［ｍｇ／ｃｃ］を算出した。
(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.
（酸性ガス吸着・除去フィルタ除去性能の評価方法：二酸化窒素除去）
酸性ガス吸着・除去フィルタを２６φ、高さ２０ｍｍにカットし、内径２６ｍｍのガラスカラム内にセットし、二酸化窒素ガス１．０ｐｐｍを含む温度２５℃、相対湿度５０％の空気を流量１０Ｌ／ｍｉｎで流通した。ガラスカラム内の温度は２５℃一定とした。ガラスカラムの入口、出口濃度をＮＯ−ＮＯ２−ＮＯｘ Ａｎａｌｙｚｅｒ Ｍｏｄｅｌ ４２Ｃ（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製）により、測定開始から二酸化窒素ガス除去率が４０％に到達するまで、二酸化窒素ガスの濃度変化を連続的に測定し、二酸化窒素ガス供給量と除去率から二酸化窒素ガス除去量を算出した。そして、二酸化窒素ガス除去量と時間の曲線を積分することにより、二酸化窒素ガス除去量［ｍｇ］を算出し、この二酸化窒素ガス除去量［ｍｇ］をサンプル体積で割ることにより、サンプル当りの二酸化窒素ガス除去量［ｍｇ／ｃｃ］を算出した。
(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 to 40% and 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.
＜実施例１＞
硫酸マンガン（II）一水和物（和光純薬工業株式会社製）１９８ｇを６７５ｍｌのイオン交換水に溶解させ、濃硝酸（ナカライテスク株式会社製）６８ｍｌを加え、６０℃に加温しながらしばらく撹拌した。また過マンガン酸カリウム１３３ｇ（ナカライテスク株式会社製）を２２５０ｍｌのイオン交換水に溶解した。その後、６０℃に加温・保持した硫酸マンガン温水溶液と過マンガン酸カリウム水溶液を混合したところ、白色の沈殿が得られた。その後、白色の沈殿を濾別し、１２０℃で乾燥させた後、３５０℃で１．５時間焼成処理を施したところα型酸化マンガンを含むマンガン酸化物が得られ、ＢＥＴ比表面積は１２５ｍ２／ｇであった。
得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９８ｇ／Ｌ、ＢＥＴ比表面積は１３３ｍ２／ｃｃであった。
<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.
＜実施例２＞
硫酸マンガン（II）一水和物（和光純薬工業株式会社製）１９８ｇを６７５ｍｌのイオン交換水に溶解させ、濃硝酸（ナカライテスク株式会社製）６８ｍｌを加え、６０℃に加温しながらしばらく撹拌した。また過マンガン酸カリウム１３３ｇ（ナカライテスク株式会社製）を２２５０ｍｌのイオン交換水に溶解した。その後、６０℃に加温・保持した硫酸マンガン温水溶液と過マンガン酸カリウム水溶液を混合したところ、白色の沈殿が得られた。その後、白色の沈殿を濾別し、１２０℃で乾燥させた後、２５０℃で１．５時間焼成処理を施したところα型酸化マンガンを含むマンガン酸化物が得られ、ＢＥＴ比表面積は２２０ｍ２／ｇであった。
得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１００ｇ／Ｌ、ＢＥＴ比表面積は１３９ｍ２／ｃｃであった。
<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.
＜実施例３＞
過マンガン酸カリウム（ナカライテスク株式会社製）１８０ｇを１５００ｍｌのイオン交換水に溶解させ、しばらく撹拌した。その後、スクロース（和光純薬工業株式会社製）１４４ｇを１０００ｍｌのイオン交換水に溶解したスクロース溶液を添加した後、１時間撹拌した。得られたゾルを濾別し、１２０℃で乾燥処理を行った。その後、２５０℃で１．５時間焼成処理を施したところα型酸化マンガンを含むマンガン酸化物が得られ、ＢＥＴ比表面積は３１１ｍ２／ｇであった。
得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９８ｇ／Ｌ、ＢＥＴ比表面積は１４５ｍ２／ｃｃであった。
<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.
＜実施例４＞
実施例２で得られたα型酸化マンガン５．５ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）５４．５ｇ、炭酸カリウム（ナカライテスク株式会社製）５．５ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９９ｇ／Ｌ、ＢＥＴ比表面積は２３０ｍ２／ｃｃであった。
<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.
＜実施例５＞
実施例２で得られたα型酸化マンガン２０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）４０ｇ、炭酸カリウム（ナカライテスク株式会社製）４．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１００ｇ／Ｌ、ＢＥＴ比表面積は１８０ｍ２／ｃｃであった。
<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.
＜実施例６＞
実施例２で得られたα型酸化マンガン３６ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）２４ｇ、炭酸カリウム（ナカライテスク株式会社製）２．４ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９７ｇ／Ｌ、ＢＥＴ比表面積は１１７ｍ２／ｃｃであった。
<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.
＜実施例７＞
実施例２で得られたα型酸化マンガン４２．９ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）１７．１ｇ、炭酸カリウム（ナカライテスク株式会社製）１．７ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９８ｇ／Ｌ、ＢＥＴ比表面積は９２ｍ２／ｃｃであった。
<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.
＜実施例８＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）０．９ｍｇ（活性炭１００重量部に対して、炭酸カリウム０．０３重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９９ｇ／Ｌ、ＢＥＴ比表面積は１５５ｍ２／ｃｃであった。
<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.
＜実施例９＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）１．５ｍｇ（活性炭１００重量部に対して、炭酸カリウム０．０５重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１００ｇ／Ｌ、ＢＥＴ比表面積は１５５ｍ２／ｃｃであった。
<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.
＜実施例１０＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）１．５ｇ（活性炭１００重量部に対して、炭酸カリウム５重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１０１ｇ／Ｌ、ＢＥＴ比表面積は１４７ｍ２／ｃｃであった。
<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.
＜実施例１１＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）２．２５ｇ（活性炭１００重量部に対して、炭酸カリウム７．５重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９９ｇ／Ｌ、ＢＥＴ比表面積は１４３ｍ２／ｃｃであった。
<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.
＜実施例１２＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．７５ｇ（活性炭１００重量部に対して、炭酸カリウム１２．５重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９８ｇ／Ｌ、ＢＥＴ比表面積は１３５ｍ２／ｃｃであった。
<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.
＜実施例１３＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）４．５ｇ（活性炭１００重量部に対して、炭酸カリウム１５重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１００ｇ／Ｌ、ＢＥＴ比表面積は１３１ｍ２／ｃｃであった。
<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.
＜実施例１４＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）６．０ｇ（活性炭１００重量部に対して、炭酸カリウム２０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１０１ｇ／Ｌ、ＢＥＴ比表面積は１２４ｍ２／ｃｃであった。
<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.
＜実施例１５＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）９．０ｇ（活性炭１００重量部に対して、炭酸カリウム３０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９８ｇ／Ｌ、ＢＥＴ比表面積は１０８ｍ２／ｃｃであった。
<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.
＜実施例１６＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：８２０ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９９ｇ／Ｌ、ＢＥＴ比表面積は７１ｍ２／ｃｃであった。
<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.
＜実施例１７＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１１５０ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１０１ｇ／Ｌ、ＢＥＴ比表面積は９４ｍ２／ｃｃであった。
<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.
＜実施例１８＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１５００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１０２ｇ／Ｌ、ＢＥＴ比表面積は１１８ｍ２／ｃｃであった。
<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.
＜実施例１９＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：２９００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９９ｇ／Ｌ、ＢＥＴ比表面積は２１５ｍ２／ｃｃであった。
<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.
＜実施例２０＞
硝酸マンガン（II）六水和物（ナカライテスク株式会社製）１２０ｇを４００ｍｌのイオン交換水に溶解し、しばらく撹拌した。次に、過マンガン酸カリウム（ナカライテスク株式会社製）４０．０ｇを２００ｍｌのイオン交換水に溶解し、しばらく撹拌した。その後、硝酸マンガン水溶液を過マンガン酸カリウム水溶液に撹拌下でゆっくり滴下し、約３０分間反応させたところ、白色の沈殿が得られた。その後、白色の沈殿を濾別、イオン交換水にて水洗し、１２０℃で乾燥させた後、３００℃で１時間焼成処理を施したところマンガン酸化物が得られた。得られたマンガン酸化物の結晶形はγ型、ＢＥＴ比表面積は１５２ｍ２／ｇであった。
得られたγ型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１００ｇ／Ｌ、ＢＥＴ比表面積は１３４ｍ２／ｃｃであった。
<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.
＜実施例２１＞
硫酸マンガン（II）一水和物（和光純薬工業株式会社製）１５１ｇを９８０ｍｌのイオン交換水に溶解させ、硫酸（ナカライテスク株式会社製）６８ｍｌを加え、３０℃に恒温槽内でしばらく撹拌した後、２０ｇ／Ｎｍ３のオゾンを含む酸素ガスを６時間通じ、酸化反応を行ったところ、白色の沈殿が得られた。その後、白色の沈殿を濾別し、１２０℃で１．５時間焼成処理を施したところε型酸化マンガンを含むマンガン酸化物が得られ、ＢＥＴ比表面積は１８０ｍ２／ｇであった。
得られたε型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１０２ｇ／Ｌ、ＢＥＴ比表面積は１３６ｍ２／ｃｃであった。
<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.
＜実施例２２＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１８０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は５０ｇ／Ｌ、ＢＥＴ比表面積は８２ｍ２／ｃｃであった。
<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.
＜実施例２３＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１１８ｇ／Ｌ、ＢＥＴ比表面積は１６７ｍ２／ｃｃであった。
<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.
＜実施例２４＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１１０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１４９ｇ／Ｌ、ＢＥＴ比表面積は２０８ｍ２／ｃｃであった。
<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.
＜実施例２５＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１００ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１７６ｇ／Ｌ、ＢＥＴ比表面積は２５０ｍ２／ｃｃであった。
<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.
＜実施例２６＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、シリカゾル（日産化学工業株式会社製スノーテックス３０：固形分率３０％、乾燥重量１６．２ｇ）５４ｇを１００ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１０５ｇ／Ｌ、ＢＥＴ比表面積は９２ｍ２／ｃｃであった。
<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.
＜比較例１＞
硫酸マンガン（II）一水和物（和光純薬工業株式会社製）１９８ｇを６７５ｍｌのイオン交換水に溶解させ、濃硝酸（ナカライテスク株式会社製）６８ｍｌを加え、６０℃に加温しながらしばらく撹拌した。また過マンガン酸カリウム１３３ｇ（ナカライテスク株式会社製）を２２５ｍｌのイオン交換水に溶解した。その後、６０℃に加温・保持した硫酸マンガン温水溶液と過マンガン酸カリウム水溶液を混合したところ、白色の沈殿が得られた。その後、白色の沈殿を濾別し、１２０℃で乾燥させた後、５５０℃で１．５時間焼成処理を施したところα型酸化マンガンを含むマンガン酸化物が得られ、ＢＥＴ比表面積は８８ｍ２／ｇであった。
得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１００ｇ／Ｌ、ＢＥＴ比表面積は１０４ｍ２／ｃｃであった。
<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.
＜比較例２＞
実施例２で得られたα型酸化マンガン２．９ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）５７．１ｇ、炭酸カリウム（ナカライテスク株式会社製）５．７ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９９ｇ／Ｌ、ＢＥＴ比表面積は１９０ｍ２／ｃｃであった。
<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.
＜比較例３＞
実施例２で得られたα型酸化マンガン４８ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）１２ｇ、炭酸カリウム（ナカライテスク株式会社製）１．２ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９８ｇ／Ｌ、ＢＥＴ比表面積は５９ｍ２／ｃｃであった。
<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.
＜比較例４＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は１００ｇ／Ｌ、ＢＥＴ比表面積は１２３ｍ２／ｃｃであった。
<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.
＜比較例５＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：５００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は９９ｇ／Ｌ、ＢＥＴ比表面積は４０ｍ２／ｃｃであった。
<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.
＜比較例６＞
実施例２で得られたα型酸化マンガン３０ｇ、ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）３０ｇ、炭酸カリウム（ナカライテスク株式会社製）３．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを２３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は３５ｇ／Ｌ、ＢＥＴ比表面積は５８ｍ２／ｃｃであった。
<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.
＜比較例７＞
実施例２で得られたα型酸化マンガン６０ｇ、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタの総添着量は３５ｇ／Ｌ、ＢＥＴ比表面積は２７ｍ２／ｃｃであった。
<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.
＜比較例８＞
ヤシ殻活性炭（ＢＥＴ比表面積：１８００ｍ２／ｇ）６０ｇ、炭酸カリウム（ナカライテスク株式会社製）６．０ｇ（活性炭１００重量部に対して、炭酸カリウム１０重量部）、ポリビニルピロリドン２．１ｇを１３０ｇのイオン交換水中に添加し、終夜撹拌し、十分に分散させることにより、水性スラリーを調整した。引き続いて、厚さ０．０２ｍｍのアルミ箔を基材としたハニカム（６００セル／ｉｎｃｈ２）を前記水性スラリーに浸漬し、水性スラリーがハニカム内部に十分に浸透したことを確認してから、ハニカムを引き上げた。エアーブローでハニカムから余分なスラリーを吹き落とした後、乾燥機内（１２０℃）で３時間乾燥させることで酸性ガス吸着・除去フィルタを得た。得られたフィルタのＢＥＴ比表面積は１９８ｍ２／ｃｃであった。
<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.
以下表１により本発明の効果を説明する。本発明である実施例１〜２１、２３〜２６から次のことが分かる。実施例は、α型酸化マンガンを含むマンガン酸化物のＢＥＴ比表面積が１００ｍ2／ｇよりも小さい場合（比較例１）、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物を添着した活性炭／マンガン酸化物の重量混合比率が１０より大きい場合（比較例２）、添着量が９８ｇ／Ｌよりも小さい場合（比較例６）、および、マンガン酸化物を含有しない場合（比較例８）と比較して、二酸化硫黄ガス除去容量が高いことが分かる。また、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物を添着した活性炭／マンガン酸化物の重量混合比率が、０．４より小さい場合（比較例３）、アルカリ金属を含む水酸化物、炭酸塩および炭酸水素塩からなる群より選ばれた１種以上の化合物が活性炭へ添着されていない場合（比較例４）、活性炭のＢＥＴ比表面積が６００ｍ2／ｇよりも小さい場合（比較例５）、添着量が９８ｇ／Ｌよりも小さい場合（比較例６）、および、α型酸化マンガンを含むマンガン酸化物単体（比較例７）と比較して、二酸化窒素ガス除去容量が高いことがわかる。
このように、比較例１，２，８は二酸化窒素ガス除去の性能は高いが、二酸化硫黄ガス除去の性能が実施例の最低値よりも低い。一方で、比較例３，４，５，７は二酸化硫黄除去の性能は高いが、二酸化窒素の性能が実施例の最低値よりも低い。
The effects of the present invention will be described below with reference to Table 1. The following can be understood from Examples 1 to 21, 23 to 26 according to the present invention . In the examples, when the BET specific surface area of the manganese oxide containing α-type manganese oxide is smaller than 100 m 2 / g (Comparative Example 1), it is selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals. When the weight mixing ratio of activated carbon / manganese oxide impregnated with one or more selected compounds is larger than 10 (Comparative Example 2), when the amount of adhering is smaller than 98 g / L (Comparative Example 6), and manganese It can be seen that the sulfur dioxide gas removal capacity is high compared to the case where no oxide is contained (Comparative Example 8). Also, when the weight mixing ratio of activated carbon / manganese oxide impregnated with one or more compounds selected from the group consisting of hydroxides, carbonates and bicarbonates containing alkali metals is less than 0.4 (comparison example 3), a hydroxide containing an alkali metal, if one or more compounds selected from the group consisting of carbonates and bicarbonates are not impregnated activated carbon (Comparative example 4), BET ratio of activated carbon When the surface area is smaller than 600 m 2 / g (Comparative Example 5 ), when the amount of adhesion is smaller than 98 g / L (Comparative Example 6), and manganese oxide alone containing α-type manganese oxide (Comparative Example 7) in comparison, it can be seen that two nitric oxide gas removal capacity is high.
As described above, Comparative Examples 1, 2, and 8 have high performance for removing nitrogen dioxide gas, but the performance for removing sulfur dioxide gas is lower than the minimum value of the examples. On the other hand, Comparative Examples 3, 4, 5, and 7 have high performance of removing sulfur dioxide, but the performance of nitrogen dioxide is lower than the lowest value of the examples.
本発明の酸性ガス吸着・除去フィルタは、長期にわたって酸性ガス吸着・除去性能を維持することができるため、広い分野で用いることができ、産業界に寄与すること大である。 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.
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| US20020177520A1 (en) * | 2001-03-30 | 2002-11-28 | Nichias Co., Ltd. | Chemical filter |
| JP5195127B2 (en) * | 2008-07-31 | 2013-05-08 | 東洋紡株式会社 | Deodorizing filter |
| JP6405718B2 (en) * | 2013-06-18 | 2018-10-17 | 東洋紡株式会社 | Acid gas adsorption / removal agent and adsorption / removal filter using the same |
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