JP2006312164A - Gas adsorbent and its production method and filter for gas adsorption - Google Patents
Gas adsorbent and its production method and filter for gas adsorption Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 66
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 125000003277 amino group Chemical group 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 27
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- -1 alkali metal salts Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 claims description 3
- JTXUAHIMULPXKY-UHFFFAOYSA-N 3-trihydroxysilylpropan-1-amine Chemical compound NCCC[Si](O)(O)O JTXUAHIMULPXKY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical group [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract description 36
- 230000002378 acidificating effect Effects 0.000 abstract description 13
- 150000002894 organic compounds Chemical class 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 44
- 235000011118 potassium hydroxide Nutrition 0.000 description 34
- 238000003756 stirring Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000686 lactone group Chemical group 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 125000004151 quinonyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- Air-Conditioning For Vehicles (AREA)
- Filtering Materials (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、アセトアルデヒドなどの酸性ガスを吸着除去するために用いる酸性ガス吸着剤及び酸性ガス吸着用フィルターに関する。 The present invention relates to an acidic gas adsorbent and an acidic gas adsorption filter used for adsorbing and removing acidic gases such as acetaldehyde.
空気中のアセトアルデヒドなどの酸性ガスを除去するための吸着剤においては、活性炭などの吸着剤の物理的吸着作用を用いるのみでなく、吸着剤表面を化学処理することによって吸着性能を向上させることが従来から行なわれている。
そのような吸着性能を向上させる方法として、活性炭の表面をオゾンなどの酸化剤によって処理する方法（特許文献1参照）、アミノ基含有化合物などの塩基性化合物を担体に担持させる方法が知られている。
さらに、アミノ基含有化合物を担体に担持させるに際して、アミノ基含有有機ケイ素化合物を用い、そのシラノール基を担体表面の水酸基に結合させることによって担体表面にアミノ基含有有機ケイ素化合物を強固に添着し、塩基性アミノ基と酸性ガスとを化学的に反応させることによって吸着性能を向上させる方法も知られている（特許文献２〜５参照）。この方法によると、物理吸着より吸着性能が向上するが、担体表面の水酸基の量によりシラノール結合の量にも限度があるために、添着できるアミノ基含有有機ケイ素化合物の量が制限され、結果として、吸着性能の向上にも限界がある。
Adsorbents for removing acidic gases such as acetaldehyde in air not only use the physical adsorption action of adsorbents such as activated carbon, but also improve the adsorption performance by chemically treating the adsorbent surface. It has been performed conventionally.
As a method for improving such adsorption performance, a method of treating the surface of activated carbon with an oxidizing agent such as ozone (see Patent Document 1) and a method of supporting a basic compound such as an amino group-containing compound on a carrier are known. Yes.
Further, when the amino group-containing compound is supported on the carrier, the amino group-containing organosilicon compound is used, and the silanol group is bonded to the hydroxyl group on the carrier surface to firmly attach the amino group-containing organosilicon compound to the carrier surface. A method of improving adsorption performance by chemically reacting a basic amino group and an acidic gas is also known (see Patent Documents 2 to 5). According to this method, the adsorption performance is improved over physical adsorption, but the amount of silanol bonds is limited by the amount of hydroxyl groups on the surface of the carrier, which limits the amount of amino group-containing organosilicon compound that can be attached. There is also a limit to the improvement of adsorption performance.
本発明の課題は、上記の従来技術の問題点を解決することであって、アセトアルデヒドなどの酸性ガスを吸着除去するために用いるガス吸着剤の吸着性能を向上させることにある。さらに、本発明はそのような吸着性能の向上したガス吸着剤の製造方法、及びガス吸着用フィルターを提供することも課題とする。 An object of the present invention is to solve the above-described problems of the prior art, and to improve the adsorption performance of a gas adsorbent used for adsorbing and removing acidic gases such as acetaldehyde. Furthermore, another object of the present invention is to provide a method for producing such a gas adsorbent with improved adsorption performance, and a gas adsorption filter.
本発明者らは、上記課題を解決するために鋭意検討した結果、アミノ基含有有機ケイ素化合物を担体に添着させるに際して、予め担体をアルカリで処理することによって、アミノ基含有有機ケイ素化合物の添着量を増加させることができることを見出し本発明に至った。より詳細には、担体を予めアルカリ処理することによって、担体表面の水酸基を増加させ、その結果、担体表面のシラノール結合の数を増加させ、より多くのアミノ基含有有機ケイ素化合物を添着でき、ひいては酸性ガスの化学吸着量を向上できることに着想し本発明に至った。
すなわち、本発明は、以下の発明に関する。
（１）アルカリ処理された担体にアミノ基含有有機ケイ素化合物を反応させて得られるガス吸着剤。
（２）アルカリ処理はアルカリ金属の塩または水酸化物、アルカリ土類金属の水酸化物またはカルボン酸塩、アンモニア、脂肪族アミン、芳香族アミン、アミノ基含有高分子化合物の群からなる化合物のいずれか一種以上による処理である上記（１）のガス吸着剤。
（３）アルカリ金属の塩が炭酸カリウム、りん酸三カリウム、ケイ酸カリウム、炭酸水素ナトリウム、炭酸ナトリウム、亜硫酸ナトリウム、酢酸ナトリウムのいずれかである上記（２）のガス吸着剤。
（４）アルカリ金属の水酸化物が水酸化カリウム、水酸化ナトリウム、水酸化リチウムのいずれかである上記（２）のガス吸着剤。
（５）アルカリ土類金属の水酸化物が水酸化カルシウム、水酸化バリウムのいずれかである上記（２）のガス吸着剤。
（６）アルカリ土類金属のカルボン酸塩が酢酸カルシウムである上記（２）のガス吸着剤。
（７）脂肪族アミンがメチルアミン、ジメチルアミンのいずれかである上記（２）記載のガス吸着剤。
（８）芳香族アミンがアニリン、アミノベンゼンスルホン酸のいずれかである上記（２）記載のガス吸着剤。
（９）アミノ基含有高分子化合物がポリアリルアミン、ポリアリルアミン塩酸塩、ポリエチレンイミン、ポリアクリルアミド、キトサンのいずれかである上記（２）記載のガス吸着剤。
（１０）アミノ基含有有機ケイ素化合物が1個以上のアミノ基とケイ素に結合した水酸基またはアルコキシ基とを含む化合物である上記（１）〜（９）のいずれかに記載のガス吸着剤。
（１１）アミノ基とケイ素とが飽和炭化水素で結合したアミノ基含有有機ケイ素化合物ある上記（１０）記載のガス吸着剤。
（１２）ケイ素に結合したアルコキシ基がメトキシ基もしくはエトキシ基、イソプロポキシ基、ブトキシ基である上記（１０）記載のガス吸着剤。
（１３）アミノ基含有有機ケイ素化合物が３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリヒドロキシシラン、３−アミノプロピルトリエトキシシランのいずれか一種以上である上記（１０）または（１１）に記載のガス吸着剤。
（１４）担体が活性炭または無機酸化物である上記（１）〜（１３）のいずれかに記載のガス吸着剤。
（１５）無機酸化物がシリカ、アルミナ、チタニア、ジルコニア、モレキュラーシーブのいずれか一種以上である上記（１４）に記載のガス吸着剤。
（１６）担体をアルカリ処理した後、乾燥し、次いでアミノ基含有有機ケイ素化合物を含有する水溶液にアルカリ処理した担体を浸漬処理して乾燥することを特徴とするガス吸着剤の製造方法。
（１７）アルカリ処理はアルカリ溶液に担体を浸漬処理することを特徴とする上記（１６）記載のガス吸着剤の製造方法。
（１８）アルカリ溶液の濃度が８０重量％以下である上記（１７）に記載のガス吸着剤の製造方法。
（１９）上記（１）〜（１５）のいずれかに記載のガス吸着剤を支持体に担持させたガス吸着用フィルター。
（２０）上記（１）〜（１５）のいずれかに記載のガス吸着剤を不織布に挟持させてなるガス吸着用フィルター。
（２１）ガス吸着用フィルターが自動車室内清浄用のキャビンエアフィルターである上記（１９）または（２０）に記載のガス吸着用フィルター。
As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention, when attaching an amino group-containing organosilicon compound to a support, by treating the support with an alkali in advance, the amount of the amino group-containing organosilicon compound attached Has been found to be able to be increased, leading to the present invention. More specifically, by subjecting the support to an alkali treatment in advance, the number of hydroxyl groups on the surface of the support is increased, and as a result, the number of silanol bonds on the surface of the support can be increased, so that more amino group-containing organosilicon compounds can be attached. The inventor has arrived at the present invention based on the idea that the amount of chemical adsorption of acid gas can be improved.
That is, the present invention relates to the following inventions.
(1) A gas adsorbent obtained by reacting an alkali-treated carrier with an amino group-containing organosilicon compound.
(2) Alkali treatment is a compound comprising the group of alkali metal salts or hydroxides, alkaline earth metal hydroxides or carboxylates, ammonia, aliphatic amines, aromatic amines, and amino group-containing polymer compounds. The gas adsorbent according to the above (1), which is a treatment by any one or more kinds.
(3) The gas adsorbent according to (2) above, wherein the alkali metal salt is any one of potassium carbonate, tripotassium phosphate, potassium silicate, sodium bicarbonate, sodium carbonate, sodium sulfite, and sodium acetate.
(4) The gas adsorbent according to (2) above, wherein the alkali metal hydroxide is any one of potassium hydroxide, sodium hydroxide, and lithium hydroxide.
(5) The gas adsorbent according to (2) above, wherein the alkaline earth metal hydroxide is either calcium hydroxide or barium hydroxide.
(6) The gas adsorbent according to (2) above, wherein the alkaline earth metal carboxylate is calcium acetate.
(7) The gas adsorbent according to (2) above, wherein the aliphatic amine is either methylamine or dimethylamine.
(8) The gas adsorbent according to (2), wherein the aromatic amine is either aniline or aminobenzenesulfonic acid.
(9) The gas adsorbent according to (2) above, wherein the amino group-containing polymer compound is any of polyallylamine, polyallylamine hydrochloride, polyethyleneimine, polyacrylamide, and chitosan.
(10) The gas adsorbent according to any one of (1) to (9), wherein the amino group-containing organosilicon compound is a compound containing one or more amino groups and a hydroxyl group or alkoxy group bonded to silicon.
(11) The gas adsorbent according to the above (10), which is an amino group-containing organosilicon compound in which an amino group and silicon are bonded with a saturated hydrocarbon.
(12) The gas adsorbent according to the above (10), wherein the alkoxy group bonded to silicon is a methoxy group, an ethoxy group, an isopropoxy group, or a butoxy group.
(13) The above (10) or (11), wherein the amino group-containing organosilicon compound is at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltrihydroxysilane, and 3-aminopropyltriethoxysilane. Gas adsorbent.
(14) The gas adsorbent according to any one of (1) to (13), wherein the carrier is activated carbon or an inorganic oxide.
(15) The gas adsorbent according to (14), wherein the inorganic oxide is at least one of silica, alumina, titania, zirconia, and molecular sieve.
(16) A method for producing a gas adsorbent, comprising subjecting a carrier to alkali treatment and then drying, and then immersing and drying the alkali-treated carrier in an aqueous solution containing an amino group-containing organosilicon compound.
(17) The method for producing a gas adsorbent according to the above (16), wherein the alkali treatment comprises immersing the carrier in an alkaline solution.
(18) The method for producing a gas adsorbent according to the above (17), wherein the concentration of the alkali solution is 80% by weight or less.
(19) A gas adsorption filter in which the gas adsorbent according to any one of (1) to (15) is supported on a support.
(20) A gas adsorption filter obtained by sandwiching the gas adsorbent according to any one of (1) to (15) above in a nonwoven fabric.
(21) The gas adsorption filter according to the above (19) or (20), wherein the gas adsorption filter is a cabin air filter for automobile interior cleaning.
以上の本発明によれば、アセトアルデヒドなどの酸性ガスを吸着除去するために用いるガス吸着剤及びフィルターにおいて、酸性ガスの吸着量を顕著に増大することができた。 According to the present invention described above, in the gas adsorbent and filter used for adsorbing and removing acidic gas such as acetaldehyde, the amount of acidic gas adsorbed can be remarkably increased.
以下に、本発明を具体的に説明するが、本発明はそれに限定されるわけではない。
本発明のガス吸着剤及びフィルターは、酸性ガスを含有する空気、特に室内空気の清浄に用いることができる。とりわけ、本発明のガス吸着剤及びフィルターは、自動車の車内空気の清浄に用いるのに効果的である。
The present invention will be specifically described below, but the present invention is not limited thereto.
The gas adsorbent and filter of the present invention can be used for cleaning air containing acid gas, particularly indoor air. In particular, the gas adsorbent and the filter of the present invention are effective for use in cleaning the air inside the automobile.
空気汚染をする酸性物質としては、硫化水素、亜硫酸ガス、アルデヒド類、有機酸類などがあるが、本発明の吸着剤は特に、ホルムアルデヒド、アセトアルデヒドなどのアルデヒド類、酢酸などの有機酸類の除去に有効である。ホルムアルデヒドは主として新建材、アセトアルデヒド、酢酸は煙草が主たる発生源で、特に室内空気の汚染物質となっている。 Examples of acidic substances that pollute air include hydrogen sulfide, sulfurous acid gas, aldehydes, and organic acids. The adsorbent of the present invention is particularly effective for removing aldehydes such as formaldehyde and acetaldehyde, and organic acids such as acetic acid. It is. Formaldehyde is mainly a new building material, and acetaldehyde and acetic acid are the main sources of tobacco, especially indoor air pollutants.
本発明で用いるアミノ基含有有機ケイ素化合物は、1個以上のアミノ基とケイ素に結合した水酸基またはアルコキシ基とを含む化合物であることが好ましい。アミノ基は、酸性物質と化学反応して化学吸着作用をする。ケイ素に結合した水酸基またはアルコキシ基は、担体表面の水酸基と反応して、シラノール結合を生成する。
アミノ基含有有機ケイ素化合物は、アミノ基とケイ素とが飽和炭化水素で結合したものがさらに好ましく、また、ケイ素に結合したアルコキシ基はメトキシ基もしくはエトキシ基、イソプロポキシ基、ブトキシ基が好ましい。
好ましいアミノ基含有有機ケイ素化合物として、３−アミノプロピルトリヒドロキシシラン、３−アミノプロピルトリエトキシシシラン、３−アミノプロピルトリメトキシシランなどが挙げられるが、３−アミノプロピルトリメトキシシラン（ＡＰＴＭＳ）がもっとも好ましい。
The amino group-containing organosilicon compound used in the present invention is preferably a compound containing one or more amino groups and a hydroxyl group or alkoxy group bonded to silicon. The amino group chemically reacts with an acidic substance and has a chemisorption action. The hydroxyl group or alkoxy group bonded to silicon reacts with the hydroxyl group on the surface of the carrier to form a silanol bond.
The amino group-containing organosilicon compound is more preferably one in which an amino group and silicon are bonded with a saturated hydrocarbon, and the alkoxy group bonded to silicon is preferably a methoxy group, an ethoxy group, an isopropoxy group, or a butoxy group.
Preferred amino group-containing organosilicon compounds include 3-aminopropyltrihydroxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, etc., and 3-aminopropyltrimethoxysilane (APTMS) is preferred. Most preferred.
本発明で用いることができる担体は、活性炭、シリカ、アルミナ、チタニア、ジルコニア、モレキュラーシーブなどの無機酸化物である。活性炭がその中でも特に好ましい。 The carrier that can be used in the present invention is an inorganic oxide such as activated carbon, silica, alumina, titania, zirconia, or molecular sieve. Among them, activated carbon is particularly preferable.
担体を処理するアルカリとしては、炭酸カリウム、りん酸三カリウム、ケイ酸カリウム、炭酸水素ナトリウム、炭酸ナトリウム、亜硫酸ナトリウム、酢酸ナトリウムなどのアルカリ金属の塩、水酸化カリウム、水酸化ナトリウム、水酸化リチウムなどのアルカリ金属の水酸化物、水酸化カルシウム、水酸化バリウムなどのアルカリ土類金属の水酸化物、酢酸ナトリウム、酢酸カルシウムなどのアルカリ土類金属のカルボン酸塩、メチルアミン、ジメチルアミンなどの脂肪族アミン、アニリン、アミノベンゼンスルホン酸などの芳香族アミン、ポリアリルアミン、ポリアリルアミン塩酸塩、ポリエチレンイミン、ポリアクリルアミド、キトサンなどのアミノ基含有高分子化合物が挙げられるが、水酸化カリウム（ＫＯＨ）が特に好ましい。 Alkalis for treating the carrier include alkali metal salts such as potassium carbonate, tripotassium phosphate, potassium silicate, sodium hydrogen carbonate, sodium carbonate, sodium sulfite, sodium acetate, potassium hydroxide, sodium hydroxide, lithium hydroxide Alkali metal hydroxides, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, alkaline earth metal carboxylates such as sodium acetate, calcium acetate, methylamine, dimethylamine, etc. Amino group-containing polymer compounds such as aromatic amines such as aliphatic amine, aniline and aminobenzene sulfonic acid, polyallylamine, polyallylamine hydrochloride, polyethyleneimine, polyacrylamide and chitosan are exemplified, but potassium hydroxide (KOH) Is particularly preferred.
本発明の吸着剤のメカニズムをアミノ基含有有機化合物として３−アミノプロピルトリメトキシシラン（ＡＰＴＭＳ）、アルカリとしてＫＯＨ、処理対象酸性物質としてアセトアルデヒドを用いて説明する。
図１には、アミノ基含有有機ケイ素化合物とアセトアルデヒドとの反応メカニズムを図示した。アミノ基含有有機ケイ素化合物のアミノ基とアセトアルデヒドが反応してシッフ塩基を形成することによって、アセトアルデヒドが吸着剤に化学吸着する。
The mechanism of the adsorbent of the present invention will be described using 3-aminopropyltrimethoxysilane (APTMS) as the amino group-containing organic compound, KOH as the alkali, and acetaldehyde as the acidic substance to be treated.
FIG. 1 shows a reaction mechanism between an amino group-containing organosilicon compound and acetaldehyde. The acetaldehyde is chemically adsorbed on the adsorbent by the reaction of the amino group of the amino group-containing organosilicon compound with acetaldehyde to form a Schiff base.
アミノ基含有有機ケイ素化合物と担体表面の水酸基によるシラノール結合の生成メカニズムは図２に示した。従来技術においては、シリカ粒子などの担体物質が本来有している表面水酸基のみがシラノール結合に寄与する。 The generation mechanism of the silanol bond by the amino group-containing organosilicon compound and the hydroxyl group on the support surface is shown in FIG. In the prior art, only the surface hydroxyl groups inherent to carrier materials such as silica particles contribute to the silanol bond.
本発明では、担体を予めアルカリ処理することによって、担体の表面水酸基を増加させることが最大の特徴である。活性炭が担体である場合を図３を用いて説明する。
活性炭表面には、遊離の水酸基、カルボキシル基、ラクトン基、キノン基などが存在している。遊離の水酸基とカルボキシル基とはアミノ基含有有機ケイ素化合物とシラノール結合を形成することが可能であるが、ラクトン基、キノン基はシラノール結合を形成することができない。
本発明では活性炭を予めアルカリ処理することによって、図３に示すようにラクトン基やキノン基が加水分解され、シラノール結合を形成可能な水酸基が増えることになる。
The greatest feature of the present invention is to increase the surface hydroxyl groups of the support by subjecting the support to an alkali treatment in advance. A case where activated carbon is a carrier will be described with reference to FIG.
On the activated carbon surface, there are free hydroxyl group, carboxyl group, lactone group, quinone group and the like. A free hydroxyl group and a carboxyl group can form a silanol bond with an amino group-containing organosilicon compound, but a lactone group or a quinone group cannot form a silanol bond.
In the present invention, by subjecting activated carbon to alkali treatment in advance, as shown in FIG. 3, lactone groups and quinone groups are hydrolyzed, and the number of hydroxyl groups capable of forming silanol bonds increases.
本発明のガス吸着剤は、担体をアルカリ溶液に浸漬処理した後、乾燥し、次いでアミノ基含有有機化合物を含有する水溶液にアルカリ処理した担体を浸漬処理して乾燥することによって製造することができる。
アルカリ溶液の濃度は８０重量％以下が好ましく、さらに５重量％程度がより好ましい。アルカリ溶液の溶媒としては、水、あるいは水−アルコール類が用いられる。用いられるアルコール類としては、水に溶解するアルコール、例えば、メタノール、エタノール、１−プロパノール、２−プロパノールが好ましい。
アミノ基含有有機ケイ素化合物を含有する水溶液の濃度は、特に限定はしないが、１６重量％程度が好ましい。
担体をアルカリ溶液により浸漬処理するときは、アルカリ溶液に担体を加えて攪拌することが好ましい。また、アミノ基含有有機ケイ素化合物を含有する水溶液による浸漬処理に際しても攪拌子あるいは超音波による攪拌をすることが好ましい。
The gas adsorbent of the present invention can be produced by immersing the support in an alkaline solution and then drying, and then immersing and drying the alkali-treated support in an aqueous solution containing an amino group-containing organic compound. .
The concentration of the alkaline solution is preferably 80% by weight or less, and more preferably about 5% by weight. As the solvent for the alkaline solution, water or water-alcohols is used. As alcohols used, alcohols that are soluble in water, such as methanol, ethanol, 1-propanol, and 2-propanol, are preferable.
The concentration of the aqueous solution containing the amino group-containing organosilicon compound is not particularly limited, but is preferably about 16% by weight.
When the carrier is immersed in the alkaline solution, it is preferable to add the carrier to the alkaline solution and stir. In addition, it is preferable to stir with an agitator or ultrasonic waves in the immersion treatment with an aqueous solution containing an amino group-containing organosilicon compound.
以下には、実施例によって、本発明のガス吸着剤の最適製造条件などを説明する。
吸着能の評価方法
以下の実施例において、吸着能の評価は次のように行なった（図４参照）。
９リットルチャンバー（密閉容器）中に、所定量の吸着剤を載置する。該チャンバーに所定濃度（初濃度）のアセトアルデヒドを含有する空気を導入し、吸着剤載置箇所に通風できるようファンを始動し吸着を開始する。３０分後、チャンバー内のアセトアルデヒド濃度を測定する。
除去率＝（初濃度−３０分後濃度）／３０分後濃度
及び／あるいは
濃度変化の総量から計算した積算吸着容量
を用いて吸着能を評価する。
Hereinafter, the optimum production conditions of the gas adsorbent of the present invention will be described by way of examples.
Evaluation Method of Adsorption Capacity In the following examples, the evaluation of adsorption capacity was performed as follows (see FIG. 4).
A predetermined amount of adsorbent is placed in a 9-liter chamber (sealed container). Air containing acetaldehyde having a predetermined concentration (initial concentration) is introduced into the chamber, and the fan is started so that the adsorbent placement portion can be ventilated to start adsorption. After 30 minutes, the acetaldehyde concentration in the chamber is measured.
Removal rate = (initial concentration−concentration after 30 minutes) / concentration after 30 minutes and / or the integrated adsorption capacity calculated from the total amount of concentration change is used to evaluate the adsorption capacity.
吸着剤の製造方法
イソプロピルアルコール（ＩＰＡ）と水を３：２の割合で混合した溶液にＫＯＨを加える。ＫＯＨ濃度は３〜４５重量％に調製する。該ＫＯＨ溶液に活性炭を入れ攪拌する。攪拌後、濾過し、９０℃で２４時間乾燥した。
次いで、３−アミノプロピルトリメトキシシラン（ＡＰＴＭＳ）の０．２５〜６４重量％の水溶液を調製し、前記のＫＯＨ処理をした活性炭を加える。攪拌後、濾過、９０℃で２４時間乾燥して吸着剤を製造した。
また、ＫＯＨをＫ2ＣＯ3に変えて、同様に吸着剤を製造した。
Production method of adsorbent KOH is added to a solution in which isopropyl alcohol (IPA) and water are mixed at a ratio of 3: 2. The KOH concentration is adjusted to 3 to 45% by weight. Activated carbon is added to the KOH solution and stirred. After stirring, it was filtered and dried at 90 ° C. for 24 hours.
Next, an aqueous solution of 0.25 to 64% by weight of 3-aminopropyltrimethoxysilane (APTMS) is prepared, and the activated carbon subjected to the KOH treatment is added. After stirring, it was filtered and dried at 90 ° C. for 24 hours to produce an adsorbent.
Further, an adsorbent was produced in the same manner by changing KOH to K 2 CO 3 .
アルカリ溶液の影響
前記の製造方法において、アルカリ溶液の濃度を変えて吸着能を評価した。アルカリ溶液としてKOH溶液を用い、０．１重量％、１重量％、５重量％で、ＡＰＴＭＳ水溶液の濃度は１重量％に固定した。対照として、活性炭のみ、アルカリ処理をしないで１重量％濃度のＡＰＴＭＳ水溶液で処理した吸着剤を準備した。吸着剤０．２ｇを用いて、前記の評価方法で４回繰返し評価した結果を図５に示した。
図５の結果からアルカリ処理をしないときより、ＫＯＨ処理を行う方が吸着能が向上することが分かった。
Influence of Alkaline Solution In the above production method, the adsorption ability was evaluated by changing the concentration of the alkali solution. A KOH solution was used as the alkaline solution, and the concentration of the APTMS aqueous solution was fixed at 1 wt% at 0.1 wt%, 1 wt%, and 5 wt%. As a control, an adsorbent treated with only 1% by weight of an aqueous APTMS solution without using an alkali treatment was prepared. FIG. 5 shows the result of repeated evaluation four times by the above-described evaluation method using 0.2 g of the adsorbent.
From the result of FIG. 5, it was found that the adsorption ability is improved by performing the KOH treatment than when the alkali treatment is not performed.
製造条件の吸着能への影響の検討（１）
実施例１での結果を基に、最適製造条件を検討した。評価系は、前記の吸着能の評価方法の項で示したとおりであり、１．５ｃｍ径の円筒に０．１ｇの吸着剤を載置、つまり、５６５ｇ／ｍ２の吸着剤量で評価した。
ＫＯＨ濃度、ＫＯＨ処理時の攪拌時間、ＡＰＴＭＳ濃度、ＡＰＴＭＳ攪拌強度（攪拌子）のそれぞれの影響要因につき表１に示す水準により製造条件を変化させて影響要因の寄与度を分析した。その結果、アセトアルデヒド吸着容量に影響が大きいのはＡＰＴＭＳ濃度であることが分かった。また、図６には、要因効果の推定を図示した。この結果から、表１の水準では、ＫＯＨ濃度５重量％、ＡＰＴＭＳ濃度４重量％が最適であることが推定された。
Based on the results in Example 1, optimum production conditions were examined. The evaluation system was as shown in the above-mentioned method of evaluating the adsorption capacity, and 0.1 g of adsorbent was placed on a 1.5 cm diameter cylinder, that is, the adsorbent amount was evaluated at 565 g / m2.
With respect to the influence factors of the KOH concentration, the stirring time at the time of KOH treatment, the APTMS concentration, and the APTMS stirring strength (stirring bar), the production conditions were changed according to the levels shown in Table 1, and the contribution degree of the influence factors was analyzed. As a result, it was found that the APTMS concentration had a large influence on the acetaldehyde adsorption capacity. FIG. 6 illustrates the estimation of the factor effect. From these results, it was estimated that the KOH concentration of 5% by weight and the APTMS concentration of 4% by weight were optimal at the level shown in Table 1.
製造条件の吸着能への影響の検討（２）
実施例２によって実施例２の製造条件の中ではＫＯＨ濃度、ＡＰＴＭＳ濃度ともに高い方が吸着能が優れている傾向であることが分かったので、実施例３では、ＫＯＨ濃度、ＡＰＴＭＳ濃度をさらに高濃度側にして吸着能を試験した。評価系は実施例２と同様である。
表２は、ＫＯＨ濃度、ＫＯＨ処理時の攪拌時間、ＡＰＴＭＳ濃度、ＡＰＴＭＳ攪拌強度（攪拌子）のそれぞれの影響要因の水準を示す。その結果、アセトアルデヒド吸着容量に影響が大きいのはＫＯＨ濃度であることが分かった。
図７には、要因効果の推定を図示した。この結果から、ＫＯＨ濃度５重量％、ＡＰＴＭＳ濃度１６重量％が最適であることが分かった。
また、図７のＡ．ＫＯＨ濃度のグラフから、ＫＯＨ濃度８０重量％以下であれば、アルカリ処理による効果があると推定できる。
According to Example 2, it was found that the higher the KOH concentration and the APTMS concentration in the production conditions of Example 2, the better the adsorptive capacity. Therefore, in Example 3, the KOH concentration and the APTMS concentration were further increased. The adsorption ability was tested on the concentration side. The evaluation system is the same as in Example 2.
Table 2 shows the levels of the influence factors of the KOH concentration, the stirring time during the KOH treatment, the APTMS concentration, and the APTMS stirring strength (stirring bar). As a result, it was found that the KOH concentration had a large effect on the acetaldehyde adsorption capacity.
FIG. 7 illustrates the estimation of the factor effect. From these results, it was found that a KOH concentration of 5% by weight and an APTMS concentration of 16% by weight are optimal.
In addition, A. of FIG. From the graph of KOH concentration, if the KOH concentration is 80% by weight or less, it can be estimated that there is an effect of alkali treatment.
ＫＯＨ処理活性炭のＢＥＴ比表面積、細孔容積の評価
この実施例では、ＫＯＨ処理により、活性炭の比表面積及び細孔容積がどのように変化しているのかを調査し、活性炭の最適処理条件を検討した。
未処理の活性炭、１〜２５重量％濃度のＫＯＨ溶液により処理を行なった活性炭、及びそれらにＡＰＴＭＳ添着を行なった活性炭について、ＢＥＴ比表面積及び細孔容積を測定した。未処理の活性炭を基準とした比の結果を図８及び図９に示した。
図８及び図９より、ＫＯＨ処理によりいずれの活性炭も比表面積及び細孔容積が低下することが分かったが、5重量％濃度のＫＯＨ処理を行なった活性炭に対して4重量％濃度のＡＰＴＭＳ添着を行なったときには、比表面積及び細孔容積がわずかであるが増加するという結果が得られた（ＡＣ+５ｗｔ％ＫＯＨとＡＣ+５ｗｔ％ＫＯＨ＋４ｗｔ％ＡＰＴＭＳの対比）。
このことより、5重量％濃度のＫＯＨ処理を行う場合には活性炭の浸食作用は小さく、ＫＯＨ処理によりＡＰＴＭＳと結合するサイト（OH基）が多く出現し、それによってＡＰＴＭＳが効率よく添着できたものと推測できる。実施例２，３のKOH濃度は５重量％のとき、最も良いアセトアルデヒド吸着能を示したという結果と併せ考えると、5重量％濃度のＫＯＨ処理を行う場合、比表面積及び細孔容積が大きく、且つＡＰＴＭＳを効率よく添着でき、このことがアセトアルデヒド吸着能に優れていることと関連しているものと考えられる。
Evaluation of BET specific surface area and pore volume of KOH-treated activated carbon In this example, we investigated how the specific surface area and pore volume of activated carbon changed by KOH treatment, and examined the optimum treatment conditions for activated carbon. did.
BET specific surface area and pore volume were measured for untreated activated carbon, activated carbon treated with 1 to 25 wt% KOH solution, and activated carbon with APTMS attached thereto. The ratio results based on untreated activated carbon are shown in FIGS.
8 and 9, it was found that the specific surface area and pore volume of both activated carbons were reduced by KOH treatment, but 4% by weight of APTMS was added to the activated carbon that had been treated by 5% by weight of KOH. Results in a slight increase in specific surface area and pore volume (AC + 5 wt% KOH vs. AC + 5 wt% KOH + 4 wt% APTMS).
As a result, when 5% by weight KOH treatment is performed, the erosion action of activated carbon is small, and many sites (OH groups) that bind to APTMS appear due to KOH treatment, which allows APTMS to be attached efficiently. Can be guessed. When the KOH concentration of Examples 2 and 3 was combined with the result that the best acetaldehyde adsorption ability was shown when the KOH concentration was 5% by weight, the specific surface area and the pore volume were large when the 5% by weight concentration KOH treatment was performed. In addition, APTMS can be efficiently attached, which is considered to be related to the excellent acetaldehyde adsorption ability.
担体を予めアルカリ処理する本発明により、担体にアミノ基含有有機化合物をより多く添着することができ、その結果、吸着能が大幅に増大した。よって、吸着剤量を増やすことなく効率よくアセトアルデヒドなどのガスを吸着除去できた。 According to the present invention in which the carrier is alkali-treated in advance, a larger amount of an amino group-containing organic compound can be attached to the carrier, and as a result, the adsorptive capacity is greatly increased. Therefore, a gas such as acetaldehyde could be efficiently adsorbed and removed without increasing the amount of adsorbent.
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| JP2009113026A (en) * | 2007-10-16 | 2009-05-28 | Nicca Chemical Co Ltd | Gas adsorbent and gas adsorbing base stock |
| JP2010022952A (en) * | 2008-07-22 | 2010-02-04 | Toyobo Co Ltd | Agent and sheet for removing aldehyde |
| CN101811027A (en) * | 2009-02-20 | 2010-08-25 | 日华化学株式会社 | Gas adsorption agent and gas adsorption substrate |
| KR101403483B1 (en) | 2012-10-25 | 2014-06-11 | 한국화학연구원 | The dry absorbents for capturing acid gas and preparation methods thereof |
| KR101488237B1 (en) * | 2013-06-25 | 2015-01-30 | 경희대학교 산학협력단 | Preparation Process of Dry Adsorbent for Selective Capture of Gaseous Carbon Dioxide |
| CN104801279A (en) * | 2015-04-13 | 2015-07-29 | 运城学院 | Method for modifying activated carbon particles with sol-gel method |
| WO2017150729A1 (en) * | 2016-03-03 | 2017-09-08 | 合同会社ＩＰ Ｂｒｉｄｇｅ１号 | Porous capsule and method for producing same |
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| CN114772557A (en) * | 2022-04-06 | 2022-07-22 | 天津大学 | Method for simultaneously removing multiple impurities in aqueous hydrogen peroxide solution |
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