JPH0439368B2 - - Google Patents
Info
- Publication number
- JPH0439368B2 JPH0439368B2 JP63266632A JP26663288A JPH0439368B2 JP H0439368 B2 JPH0439368 B2 JP H0439368B2 JP 63266632 A JP63266632 A JP 63266632A JP 26663288 A JP26663288 A JP 26663288A JP H0439368 B2 JPH0439368 B2 JP H0439368B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic amino
- acetaldehyde
- sepiolite
- acid
- amino acids
- 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.)
- Expired - Lifetime
Links
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 41
- -1 aromatic amino acid Chemical class 0.000 claims description 32
- 239000004113 Sepiolite Substances 0.000 claims description 28
- 229910052624 sepiolite Inorganic materials 0.000 claims description 28
- 235000019355 sepiolite Nutrition 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 13
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229960004909 aminosalicylic acid Drugs 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 6
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 claims 2
- 239000008187 granular material Substances 0.000 claims 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 64
- 150000001299 aldehydes Chemical class 0.000 description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- 239000007789 gas Substances 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000001877 deodorizing effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 235000019645 odor Nutrition 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006200 vaporizer Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- PUYFAZQODQZOFK-UHFFFAOYSA-N (2,4-dinitrophenyl)hydrazine;hydrochloride Chemical compound Cl.NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O PUYFAZQODQZOFK-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- KBOPZPXVLCULAV-UHFFFAOYSA-N mesalamine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 description 1
- 229960004963 mesalazine Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- HCKKSLZDSNNSTL-UHFFFAOYSA-M sodium;2-aminobenzoate Chemical compound [Na+].NC1=CC=CC=C1C([O-])=O HCKKSLZDSNNSTL-UHFFFAOYSA-M 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Description
［産業上の利用分野］
本発明は低級アルデヒド類の除去剤に関する。
詳しくは、ホルムアルデヒド、アセトアルデヒド
等の低級アルデヒド類を主に含有する臭気性ガス
の浄化に有効な除去剤に係る。
ホルムアルデヒド、アセトアルデヒド等の低級
アルデヒド類は、特異な刺激臭を持つ有害なガス
である。特にアセトアルデヒドは、悪臭８物質の
１つに挙げられており空気中に0.05ppmという非
常に低い濃度で存在していてもその臭気が感じら
れる。さらに5ppm程度の濃度になると目、喉へ
の刺激が強く、長時間接触すると炎症をおこし健
康上からも好ましくない。
これらの低級アルデヒド類の発生源としては、
低級アルデヒド類およびその誘導体の製造工場、
低級アルデヒド類を用いた樹脂例えばポリアセタ
ール樹脂の製造および成型工場、低級アルデヒド
類を用いた接着剤（フエノール系接着剤）の製造
および使用時、特に合板の製造工場、さらに生活
環境においては、煙草の煙、人体、し尿、冷蔵庫
内、自動車の排気ガスなどから発生している。
前記の工場においては、比較的高濃度の低級ア
ルデヒド類が発生するが、生活環境では数ppm以
下の比較的低い濃度で発生している。
［従来の技術］
従来このような低級アルデヒド類を除去する方
法としては、濃度の高い工場では白金族元素、銅
族元素、ランタノイド元素、アクチノイド元素を
アルミナ等の担体に担持した触媒を用いる方法が
知られている。また生活環境での除去は、活性炭
やシリカカゲルなどで吸着除去する方法がとられ
ている。
しかしながら、前者の触媒を用いて除去する方
法では、触媒が高価なうえ、接触酸化の起きる温
度が200℃以上という高温であり、取扱上でも不
便である。また後者の生活環境における活性炭や
シリカゲルなどで吸着除去する方法は、吸着剤の
細孔構造内に低級アルデヒド類を物理吸着させて
除去しようとするものである。この場合吸着剤の
種類によつては低級アルデヒド類を全く吸着でき
ないものもあり、また、吸着できるものでも吸着
剤の能力には限界があり、飽和吸着状態になると
低級アルデヒド類を吸着できず、逆に周囲の空気
中に放出され除去されない場合もある。さらに化
学薬品でアルデヒドと反応させて除去する方法が
ある。例えばフエニルヒドラジン、２，４−ジニ
トロフエニルヒドラジン等の塩は低級アルデヒド
類の捕集および定量に広く使われる物質であり、
特に２，４−ジニトロフエニルヒドラジンの塩酸
塩は、悪臭防止法にいうアセトアルデヒドの測定
に使用され、空気中のアセトアルデヒドを化学的
に除去するのに非常に有効であるがアルデヒドの
除去剤として使用するには、例えば塩酸水溶液と
しなければならず、一般の除去剤としての使用は
制約される。その他従来から低級アルデヒド類と
反応する物質として使用されてきた芳香族アミン
類等は、ガン誘因物質であるなど人体に対する影
響が懸念され、また生活空間で使用するには前記
物質の持つ臭気が、人体に対し嫌悪感を与えるこ
とが考えられることから好ましくない。
特開昭60−129054号公報には、アミノ酸やその
塩類を有効成分とした脱臭・消臭剤の開示があ
る。これは食品分野への応用を意図したもので、
その対象としている臭気も、アンモニア、トリメ
チルアミンなどの塩基性臭、あるいは、硫化水
素、メチルメルカプタンなどの硫化物系の臭気で
ある。その使用形態は、食品への添加を中心とし
有機溶剤、水などで稀釈して使用する。
［発明が解決しようとする課題］
本発明は、前記の事情に鑑みてなされたもの
で、低級アルデヒド類に対して迅速かつ優れた除
去効果を有し、無臭でしかも活性炭のように物理
吸着作用により比較的少量で飽和吸着状態に達す
る物でなく、しかも人体に悪影響を与えない低級
アルデヒド類の除去剤を提供することを目的とす
る。
［課題を解決するための手段］
本発明の低級アルデヒド類の除去剤は、芳香族
アミノ酸、および芳香族アミノ酸の塩類の少なく
とも一種を有効成分とする。
有効成分の芳香族アミノ酸、および芳香族アミ
ノ酸の塩類としては、ｏ−、ｍ−、ｐ−アミノ安
息香酸、ｐ−アミノサリチル酸、ｍ−アミノサリ
チル酸などの芳香族アミノ酸およびそれらのナト
リウム塩、カリウム塩などの金属塩類、または硫
酸塩、硝酸塩、塩酸塩などの無機塩類などが挙げ
られる。
芳香族アミノ酸、芳香族アミノ酸の塩類を低級
アルデヒド類の除去剤に使用するには、その粉末
のままで使用することができるが、その効果を高
めるため任意の濃度の水溶液または有機溶媒に溶
かした溶液にするか、または多孔性担体に担持さ
せて用いることができる。
多孔性担体としては、セピオライト、パリゴル
スカイト、活性炭、ゼオライト、活性炭素繊維、
セピオライト混合紙、シリカゲル、活性白土、ア
ルミナ、バーミキユライト、ケイソウ土等の無機
質多孔性担体のほか、パルプ、繊維、布、高分子
多孔体などの有機質多孔性担体などが使用でき
る。その形状は、シート状、ハニカム状、粉末
状、粒状、顆粒状、板状のいずれでもよい。
前記の多孔性担体は、それ自身低級アルデヒド
類を吸着する能力は小さいが、前記の芳香族アミ
ノ酸類を担持すると低級アルデヒド類の除去能力
が向上する。特にセピオライト、パリゴルスカイ
ト、活性炭、ゼオライトに芳香族アミノ酸類を担
持すると低級アルデヒド類の除去性が著しく向上
する。
芳香族アミノ酸、その塩類を前記多孔性担体に
担持する方法は特に問わないが、好ましくは芳香
族アミノ酸またはその塩類を、微粉砕して多孔性
担体の微粉末に混合して成形して担持するか、水
またはエタノール等の可溶性溶媒に溶解し、その
溶液を多孔性担体に含浸させた後溶媒を蒸散させ
て担持してもよい。
またこの低級アルデヒド類の除去剤を工業的に
製造する方法としては、例えば芳香族アミノ酸お
よびその塩類と多孔性担体とを、ヘンシエルミキ
サー、ニーダ、土練機、デイスパーミル等の混合
機を用いて混合する。乾燥後、ヘンシエルミキサ
ー、ハンマーミルなどの粉砕機で粉砕して、粉末
もしくは、顆粒状の除去剤とすることができる。
またこの除去剤は、用途に適した形状に成形す
ることもできる。例えば前記の粉末に水を加えて
練りこんだ状態のものを、押出し機で押出し、そ
のまま乾燥したもの、または一定間隔に切断して
円筒状の錠剤に成形したり、またはマルメライザ
ーで球状にしたり、ハニカム形状に押出し成形し
てもよい。
さらに前記の除去剤に強度を付与するためにポ
リビニールアルコール、CMCなどの有機系粘結
剤、シリカゲル、ケイソウ土等の無機系粘結剤を
添加して成形してもよい。
多孔性担体へ芳香族アミノ酸およびその塩類を
担持する量は、例えば担体に対し11.0〜90重量％
の範囲が好ましい。担持量が1.0重量％未満であ
ると低級アルデヒド類の除去効果が小さく、90重
量％を超えると担体への分散性が悪くなり低級ア
ルデヒド類の除去性も悪くなり経済的で無い。な
かでも５〜80重量％担持するのがより好ましい。
［発明の作用および効果］
本発明は低級アルデヒド類の除去剤の有効成分
として芳香族アミノ酸、およびその塩類を用い
る。この芳香族アミノ酸およびその塩類は、低級
アルデヒド類を除去することができる。そして、
その水溶液や多孔性担体に担持させて除去剤とす
ることができる。特に、多孔性担体に担持させる
と極めて効率よく低級アルデヒド類を除去するこ
とができる。多孔性担体に担持させると芳香族ア
ミノ酸と低級アルデヒド類とが接触する面積を広
げることになり吸着能を高めることができると考
えられるが、その作用のみではない。
この作用機構については、明確に分かつていな
いが多孔性担体などに芳香族アミノ酸類を担持さ
せると分子レベルの共役系が変化し、カルボキシ
ル基、アミノ基の電子が局在化してそこにアルデ
ヒドがくるとアミノ基とアルデヒド基との反応が
促進されると考えられる。また多孔性担体の種類
によつても、その除去性能を異にすることからし
て接触面積の増加に基づくものだけではない。
また、臭気性ガスの数成分を吸着させる場合に
おいても芳香族アミノ酸類を担持した多孔性担体
は、その吸着性能を低下させることなくアルデヒ
ド以外のガスを除去することができる。例えば、
活性炭では炭化水素類、硫化物類の臭気性ガス状
物質を、セピオライトの場合では、アンモニア、
イソ吉草酸、酪酸、トリメチルアミン、ピリジン
等の臭気性ガス状物質をよく吸着する。
［実施例］
以下実施例により具体的に説明する。
実施例 １
ｏ−、ｍ−、ｐ−アミノ安息香酸、およびｐ−
アミノサリチル酸のそれぞれ１ｇを各ビーカーに
秤量し、これら各ビーカーそれぞれにセピオライ
ト９ｇを加えてよくかきまぜた。さらにこれら各
ビーカーにエチルアルコールを20ml加えて、超音
波洗浄器を用いて約５分間撹拌混合した。次に各
ビーカーの口を塩化ビニリデンフイルムで閉じ70
℃で約30分間加熱した。その後、塩化ビニリデン
フイルムを取り除き、各々100℃で加熱乾燥し、
乳鉢で粉砕して４種類の粉末状の低級アルデヒド
除去剤No.１、２、３、４を作製した。
さらに、ｏ−アミノ安息香酸ナトリウム１ｇを
ビーカーに秤量し、これにセピオライト９ｇを加
えて良くかきまぜた。次に脱イオン水40mlを加え
て、超音波洗浄器で約５分間撹拌混合した。次い
でビーカーの口を塩化ビニリデンフイルムで閉じ
70℃で約30分間加熱した。その後、塩化ビニリデ
ンフイルムを取除き、100℃で加熱乾燥し、乳鉢
で粉砕して粉末の低級アルデヒド除去剤No.５を作
製した。
得られた前記５種類の各低級アルデヒド除去剤
の評価は、５容量のガス非透過性の袋に除去剤
と一定量のアセトアルデヒドを空気とともに封入
して所定時間後の残留アルデヒド量を測定して比
較した。低級アルデヒド除去剤（No.１〜５）をそ
れぞれ0.2ｇ（芳香族アミノ酸の含有量は20mgで
ある）秤量し、５容量のガス非透過性の袋に入
れた。この袋にアセトアルデヒド液１mlを水９ml
で希釈したアセトアルデヒド水溶液10μをドラ
イヤーで気化させて５の空気と共に導入して密
封し、室温で４時間放置した後、袋中のアセトア
ルデヒドの濃度をガスクロマトグラフで測定し
た。ガスクロマトグラフの測定条件を第１表に示
す。なお、アセトアルデヒドの濃度は、39.9ppm
のアセトアルデヒドのボンベ標準ガスを用いてま
ず検量線を求めこの検量線から求めた。
アセトアルデヒドの残留濃度、除去率、低級ア
ルデヒド除去剤のアルデヒド吸着量を第２表に示
[Industrial Field of Application] The present invention relates to a lower aldehyde remover.
Specifically, the present invention relates to a removing agent effective for purifying odorous gases mainly containing lower aldehydes such as formaldehyde and acetaldehyde. Lower aldehydes such as formaldehyde and acetaldehyde are harmful gases with a unique pungent odor. In particular, acetaldehyde is listed as one of the eight malodorous substances, and its odor can be felt even when it is present in the air at a very low concentration of 0.05 ppm. Furthermore, at concentrations of about 5 ppm, it is highly irritating to the eyes and throat, and prolonged contact can cause inflammation, which is not desirable from a health standpoint. The sources of these lower aldehydes are:
Manufacturing plant for lower aldehydes and their derivatives,
When manufacturing and molding resins such as polyacetal resin using lower aldehydes, when manufacturing and using adhesives (phenolic adhesives) using lower aldehydes, especially at plywood manufacturing factories, and in the living environment, cigarettes are It is generated from smoke, the human body, human waste, inside refrigerators, and automobile exhaust gas. In the factories mentioned above, lower aldehydes are generated at relatively high concentrations, but in the living environment they are generated at relatively low concentrations of several ppm or less. [Prior art] Conventionally, in factories where the concentration of lower aldehydes is high, a method using a catalyst in which platinum group elements, copper group elements, lanthanide elements, or actinide elements are supported on a carrier such as alumina has been used. Are known. For removal in the living environment, methods of adsorption and removal using activated carbon, silica gel, etc. are used. However, in the former method of removal using a catalyst, the catalyst is expensive and the temperature at which catalytic oxidation occurs is as high as 200°C or higher, making it inconvenient to handle. The latter method of adsorption removal using activated carbon, silica gel, etc. in the living environment attempts to remove lower aldehydes by physically adsorbing them within the pore structure of the adsorbent. In this case, depending on the type of adsorbent, there are some that cannot adsorb lower aldehydes at all, and even those that can adsorb the adsorbent have a limited ability, and when it reaches a saturated adsorption state, it cannot adsorb lower aldehydes. Conversely, it may be released into the surrounding air and not be removed. Another method is to remove it by reacting it with aldehyde using chemicals. For example, salts such as phenylhydrazine and 2,4-dinitrophenylhydrazine are substances widely used for collecting and quantifying lower aldehydes.
In particular, 2,4-dinitrophenylhydrazine hydrochloride is used in the measurement of acetaldehyde in the offensive odor control method, and is very effective in chemically removing acetaldehyde from the air, but it is also used as an aldehyde remover. To do this, for example, an aqueous solution of hydrochloric acid must be used, which limits its use as a general removing agent. Other aromatic amines, which have traditionally been used as substances that react with lower aldehydes, have concerns about their effects on the human body, such as being cancer-inducing substances, and the odor of these substances makes them unsuitable for use in living spaces. It is undesirable because it may cause disgust to the human body. JP-A-60-129054 discloses a deodorizing agent containing amino acids and their salts as active ingredients. This is intended for application in the food field.
The targeted odors are basic odors such as ammonia and trimethylamine, and sulfide odors such as hydrogen sulfide and methyl mercaptan. It is mainly used as an addition to food, diluting it with organic solvents, water, etc. [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and has a rapid and excellent removal effect on lower aldehydes, is odorless, and has a physical adsorption effect similar to activated carbon. The object of the present invention is to provide a lower aldehyde remover that does not reach a saturated adsorption state in a relatively small amount and does not have any adverse effects on the human body. [Means for Solving the Problems] The lower aldehyde remover of the present invention contains at least one of an aromatic amino acid and a salt of an aromatic amino acid as an active ingredient. Examples of aromatic amino acids and salts of aromatic amino acids as active ingredients include aromatic amino acids such as o-, m-, p-aminobenzoic acid, p-aminosalicylic acid, m-aminosalicylic acid, and their sodium salts and potassium salts. and inorganic salts such as sulfates, nitrates, and hydrochlorides. To use aromatic amino acids and salts of aromatic amino acids as a lower aldehyde remover, they can be used in their powder form, but to enhance their effectiveness, they can be dissolved in an aqueous solution or organic solvent of any concentration. It can be used as a solution or supported on a porous carrier. Porous carriers include sepiolite, palygorskite, activated carbon, zeolite, activated carbon fiber,
In addition to inorganic porous carriers such as sepiolite mixed paper, silica gel, activated clay, alumina, vermiculite, and diatomaceous earth, organic porous carriers such as pulp, fiber, cloth, and porous polymer materials can be used. Its shape may be sheet-like, honeycomb-like, powder-like, granular, granular, or plate-like. The porous carrier itself has a low ability to adsorb lower aldehydes, but when it supports the aromatic amino acids, the ability to remove lower aldehydes is improved. In particular, when aromatic amino acids are supported on sepiolite, palygorskite, activated carbon, or zeolite, the ability to remove lower aldehydes is significantly improved. The method of supporting the aromatic amino acid or its salts on the porous carrier is not particularly limited, but preferably the aromatic amino acid or its salts are finely pulverized, mixed with fine powder of the porous carrier, and then molded and supported. Alternatively, it may be supported by dissolving it in a soluble solvent such as water or ethanol, impregnating the porous carrier with the solution, and then evaporating the solvent. In addition, as a method for industrially producing this lower aldehyde remover, for example, aromatic amino acids and their salts are mixed with a porous carrier using a mixer such as a Henschel mixer, kneader, kneader, dispersion mill, etc. Mix. After drying, it can be pulverized with a pulverizer such as a Henschel mixer or a hammer mill to obtain a powder or granular removal agent. The remover can also be shaped into a shape suitable for the intended use. For example, the above powder can be kneaded with water, extruded using an extruder, and dried as is, or cut into regular intervals and formed into cylindrical tablets, or made into spheres using a marmerizer. , it may be extruded into a honeycomb shape. Furthermore, in order to impart strength to the removing agent, an organic binder such as polyvinyl alcohol or CMC, or an inorganic binder such as silica gel or diatomaceous earth may be added and molded. The amount of aromatic amino acids and their salts supported on the porous carrier is, for example, 11.0 to 90% by weight based on the carrier.
A range of is preferred. If the supported amount is less than 1.0% by weight, the effect of removing lower aldehydes will be small, and if it exceeds 90% by weight, the dispersibility in the carrier will be poor and the ability to remove lower aldehydes will also be poor, making it uneconomical. Among these, it is more preferable to carry 5 to 80% by weight. [Operations and Effects of the Invention] The present invention uses aromatic amino acids and salts thereof as active ingredients of a lower aldehyde remover. This aromatic amino acid and its salts can remove lower aldehydes. and,
It can be used as a removal agent by being supported on an aqueous solution or a porous carrier. In particular, when supported on a porous carrier, lower aldehydes can be removed extremely efficiently. It is thought that when supported on a porous carrier, the area of contact between the aromatic amino acid and the lower aldehyde is expanded and the adsorption capacity can be increased, but this is not the only effect. The mechanism of this action is not clearly understood, but when aromatic amino acids are supported on a porous carrier, the conjugation system at the molecular level changes, and the electrons of carboxyl and amino groups are localized, and aldehydes are formed there. It is thought that the reaction between the amino group and the aldehyde group is promoted. Moreover, since the removal performance differs depending on the type of porous carrier, it is not only based on an increase in the contact area. Furthermore, even when adsorbing several components of odorous gases, the porous carrier supporting aromatic amino acids can remove gases other than aldehydes without reducing its adsorption performance. for example,
Activated carbon removes odorous gaseous substances such as hydrocarbons and sulfides, while sepiolite removes ammonia,
Good adsorption of odorous gaseous substances such as isovaleric acid, butyric acid, trimethylamine, and pyridine. [Example] The following is a concrete explanation using Examples. Example 1 o-, m-, p-aminobenzoic acid, and p-
1 g of aminosalicylic acid was weighed into each beaker, and 9 g of sepiolite was added to each of these beakers and stirred well. Furthermore, 20 ml of ethyl alcohol was added to each of these beakers, and the mixture was stirred and mixed for about 5 minutes using an ultrasonic cleaner. Next, close the mouth of each beaker with vinylidene chloride film70
℃ for approximately 30 minutes. After that, the vinylidene chloride film was removed and each was heated and dried at 100℃.
Four types of powdered lower aldehyde removers No. 1, 2, 3, and 4 were prepared by pulverizing in a mortar. Further, 1 g of sodium o-aminobenzoate was weighed into a beaker, 9 g of sepiolite was added thereto, and the mixture was stirred well. Next, 40 ml of deionized water was added and mixed with stirring using an ultrasonic cleaner for about 5 minutes. Then close the beaker with vinylidene chloride film.
Heated at 70°C for about 30 minutes. Thereafter, the vinylidene chloride film was removed, dried by heating at 100°C, and ground in a mortar to produce powdered lower aldehyde removing agent No. 5. The obtained five types of lower aldehyde removers were evaluated by sealing the remover and a certain amount of acetaldehyde together with air in a 5-volume gas-impermeable bag, and measuring the amount of residual aldehyde after a predetermined period of time. compared. 0.2 g (aromatic amino acid content is 20 mg) of each of the lower aldehyde removers (Nos. 1 to 5) was weighed and placed in a 5-volume gas-impermeable bag. In this bag, add 1ml of acetaldehyde solution and 9ml of water.
After vaporizing 10μ of the acetaldehyde aqueous solution diluted with a dryer and introducing it together with air from step 5, sealing the bag and leaving it at room temperature for 4 hours, the concentration of acetaldehyde in the bag was measured using a gas chromatograph. Table 1 shows the measurement conditions of the gas chromatograph. The concentration of acetaldehyde is 39.9ppm.
First, a calibration curve was obtained using a cylinder standard gas of acetaldehyde, and the calculation was made from this calibration curve. Table 2 shows the residual concentration of acetaldehyde, the removal rate, and the amount of aldehyde adsorbed by the lower aldehyde remover.
【表】【table】
【表】
す。除去率は次の式により求めた。
除去率＝｛（ブランク濃度）−（除去剤を用いたもの
の残留濃度）｝／（ブランク濃度）
ブランク濃度は除去剤を使用しないで同様の処
理をおこなつた場合の残留濃度であり146.0ppm
である。
比較例として芳香族アミノ酸を用いず多孔性担
体のセピオライトのみのものC1、ヤシガラ活性
炭のみのものC2をNo.１〜５と同様にアセトアル
デヒドの除去試験をおこなつた。その結果を第２
表に示した。
No.１〜４の芳香族アミノ酸はアセトアルデヒド
の除去率が90％以上あり、吸着量も多く６mg／ｇ
以上あり、比較例のC1〜C2の50％前後および３
mg／ｇ前後に比べて優れている。No.５のナトリウ
ム塩の場合の除去率はやや低く71.9％であるが、
それでも比較例の1.5倍程度の除去率を示した。
実施例 ２
この例は多孔性担体の種類を代えたもので多孔【represent. The removal rate was calculated using the following formula. Removal rate = {(Blank concentration) - (Residual concentration using remover)} / (Blank concentration) Blank concentration is the residual concentration when the same treatment is performed without using remover, which is 146.0 ppm
It is. As comparative examples, an acetaldehyde removal test was conducted on C1 using only sepiolite as a porous carrier without using aromatic amino acids, and C2 using only coconut shell activated carbon in the same manner as Nos. 1 to 5. The result is the second
Shown in the table. Aromatic amino acids No. 1 to 4 have an acetaldehyde removal rate of over 90% and a large adsorption amount of 6 mg/g.
There are about 50% of C1 to C2 of the comparative example and 3
This is superior compared to around mg/g. The removal rate for No. 5 sodium salt is slightly lower at 71.9%, but
Even so, the removal rate was about 1.5 times that of the comparative example. Example 2 This example uses a different type of porous carrier.
【表】
性担体として、パリゴルスカイト、ヤシガラ活性
炭、ゼオライト13Xをそれぞれ９ｇずつビーカー
に秤量し、ｏ−アミノ安息香酸を１ｇずつ加えて
撹拌混合した。これにエチルアルコールを20ml加
え、超音波洗浄器を用いて約５分間撹拌混合し、
次いでビーカーの口を塩化ビニリデンフイルムで
閉じ70℃で30分間加熱した。その後実施例１と同
様に溶媒の除去および粉砕をおこなつて、除去剤
No.６〜８を作製した。
除去剤No.６〜８をそれぞれ0.2ｇ（この内アミ
ノ酸の重量は20mgである）秤量し、５容量のガ
ス非透過性の袋にいれた。以下実施例１と同様に
アルデヒドの除去性能試験をおこなつた。結果を
第３表に示す。この場合のブランクの濃度は
255ppmである。比較例は本例で用いた多孔性担
体のみを袋にいれC3〜５とした。
この結果多孔性担体のみのC3〜５よりｏ−ア
ミノ安息香酸を担持した多孔性担体（No.６〜８）
は、除去性能が優れている。特にパリゴルスカイ
トにｏ−アミノ安息香酸を担持したNo.６[Table] As sexual carriers, 9 g each of palygorskite, coconut shell activated carbon, and zeolite 13X were weighed into a beaker, and 1 g each of o-aminobenzoic acid was added and mixed with stirring. Add 20ml of ethyl alcohol to this, stir and mix using an ultrasonic cleaner for about 5 minutes,
Next, the mouth of the beaker was closed with vinylidene chloride film and heated at 70°C for 30 minutes. Thereafter, the solvent was removed and pulverized in the same manner as in Example 1, and the removal agent was
Nos. 6 to 8 were produced. Removers Nos. 6 to 8 were each weighed in an amount of 0.2 g (of which the amino acid weight was 20 mg), and placed in a 5-volume gas-impermeable bag. Thereafter, an aldehyde removal performance test was conducted in the same manner as in Example 1. The results are shown in Table 3. The density of the blank in this case is
It is 255ppm. In comparative examples, only the porous carrier used in this example was placed in a bag and designated as C3 to C5. As a result, porous carriers (Nos. 6 to 8) that supported o-aminobenzoic acid from C3 to 5 of porous carriers only.
has excellent removal performance. Especially No.6 with o-aminobenzoic acid supported on palygorskite.
【表】
は除去率が94％、吸着量10.9mg／ｇと高い値を示
した。
実施例 ３
予め乳鉢で粉砕したｏ−アミノ安息香酸と350
メツシユのふるいを通過した多孔性担体のセピオ
ライトを第４表に示す混合比でよく混合した。こ
れらの混合物を各々ビーカーにいれ、各々セピオ
ライトの３倍量のエチルアルコールを加えた。次
に、ビーカーの口を塩化ビニリデンフイルムで閉
じ、乾燥器で70℃で30分加熱した。その後、塩化
ビニリデンフイルムをとりはずして100℃で乾燥
させ、除去剤No.９〜21を作製した。
なおこの除去剤は、アルデヒドの除去試験の前
に再度粉砕して使用した。比較例としてセピオラ
イトのみのものをC6とした。
これらの各除去剤を0.2ｇ秤り取り、５容量
のガス非透過性の袋にいれた。以下実施例１と同
様の方法でアセトアルデヒドと空気を袋にいれ
た。４時間放置した後、ガスクロマトグラフを用
いて袋内のアセトアルデヒドの濃度を測定し除去[Table] showed a high removal rate of 94% and adsorption amount of 10.9 mg/g. Example 3 O-aminobenzoic acid pre-ground in a mortar and 350
The porous carrier sepiolite that had passed through the mesh sieve was thoroughly mixed at the mixing ratio shown in Table 4. Each of these mixtures was placed in a beaker, and ethyl alcohol in an amount three times that of sepiolite was added to each beaker. Next, the mouth of the beaker was closed with vinylidene chloride film, and the beaker was heated at 70°C for 30 minutes in a dryer. Thereafter, the vinylidene chloride film was removed and dried at 100°C to prepare removers Nos. 9 to 21. Note that this removing agent was used after being ground again before the aldehyde removal test. As a comparative example, a sample containing only sepiolite was designated as C6. 0.2 g of each of these removers was weighed out and placed in a 5-volume gas-impermeable bag. Thereafter, acetaldehyde and air were placed in a bag in the same manner as in Example 1. After leaving it for 4 hours, measure the concentration of acetaldehyde in the bag using a gas chromatograph and remove it.
【表】【table】
【表】
率および吸着量を求めた。結果を第５表に示す。
なおガスクロマトグラフの測定条件は、実施例１
と同一とした。ブランクは同様な条件で除去剤を
使用しないもので、アセトアルデヒドの濃度は
178ppmであつた。
この結果ｏ−アミノ安息香酸の担持量が0.1重
量％以下のNo.９では除去率が比較例のC6より低
い。また担持量が95重量％であるNo.21でも除去率
が比較例のC6より低く芳香族アミノ酸の担持量
は1.0〜90重量％の範囲が有効であることを示し
ている。特にNo.12〜19の芳香族アミノ酸の担持量
が５〜80重量％の範囲が低級アルデヒド類の除去
率が90％以上を示しより有効である。
実施例 ４
ｏ−アミノ安息香酸１ｇをビーカーに秤量し、
セピオライト９ｇを加えてよくかきまぜた。次に
エチルアルコール20mlを加え密封して超音波洗浄
器を用いて約５分間撹拌し、さらに乾燥器で70℃
で約30分間加熱した後開封し、100℃で乾燥して
除去剤No.22を作製した。
この低級アルデヒド類の除去剤を第１図に示す
繰返し試験装置の脱臭カラム１に充填し、アセト
アルデヒドを含む空気をカラム中に通過させて低
級アルデヒド類の除去性能の低下する状況を調べ
た。この試験装置は、25容量の容器２に循環ポ
ンプ７と臭気物質気化器３を途中に配備した送気
パイプ５と、循環ポンプ６と流量計と脱臭カラム
１とを途中に配備した送気パイプ４とを備え、該
容器２と脱臭カラム１とは恒温槽内で一定温度に
保たれている。そして容器２内の低級アルデヒド
類を含む空気は循環ポンプ６を介して絶えず脱臭
カラム１に送られ循環し平衡吸着状態を保つてい
る。脱臭カラム１中の除去剤は３ｇである。試験
条件は、ガス流量：50／min、圧力損失：18mm
H2O、温度：25±１℃、脱臭カラム：30×30×
240mm、充填長さ：８mmで容器２内の空気を循環
した。
まず、アセトアルデヒドを約10倍に稀釈した水
溶液を臭気物質気化器３から入れ、20分間空気を
循環したのち再度アセトアルデヒド水溶液を臭気
物質気化器３から注入するという繰返し試験を10
回おこなつた。このとき注入量は、１〜８回目ま
では20μ、９、10回目は40μとした。また、
アセトアルデヒドの濃度は注入後、０、１、３、
５、10、15、20分後にガスクロマトグラフにより
測定した。ガスクロマトグラフの測定条件は、実
施例１と同じである。結果を第６表に示す。
この結果、ｏ−アミノ安息香酸を担持したセピ
オライトは、吸着性能の劣化が少なくアルデヒド
を吸着し耐久性があることを示している。
実施例 ５
以下に述べる方法でNo.23からNo.27の５種類の除
去剤を作製した。No.23はセピオライト９ｇと、ｏ
−アミノ安息香酸１ｇをそれぞれ微粉砕して混合
した。No.24は、ｏ−アミノ安息香酸１ｇをエチル
アルコール20mlに溶解し、この溶液にセピオライ
ト９ｇを加えてセピオライトにｏ−アミノ安息香
酸−エチルアルコ[Table] The rate and adsorption amount were determined. The results are shown in Table 5.
The measurement conditions of the gas chromatograph are as in Example 1.
It was made the same as. The blank was made under similar conditions without the removal agent, and the acetaldehyde concentration was
It was 178ppm. As a result, in No. 9 in which the amount of o-aminobenzoic acid supported was 0.1% by weight or less, the removal rate was lower than that in Comparative Example C6. Further, even in No. 21, in which the supported amount was 95% by weight, the removal rate was lower than that of comparative example C6, indicating that the supported amount of aromatic amino acids in the range of 1.0 to 90% by weight is effective. In particular, a range in which the supported amount of aromatic amino acids Nos. 12 to 19 is 5 to 80% by weight is more effective as the removal rate of lower aldehydes is 90% or more. Example 4 1 g of o-aminobenzoic acid was weighed into a beaker,
Add 9g of sepiolite and stir well. Next, add 20 ml of ethyl alcohol, seal, stir for about 5 minutes using an ultrasonic cleaner, and then place in a dryer at 70°C.
After heating for about 30 minutes, the package was opened and dried at 100°C to prepare remover No. 22. This lower aldehyde remover was packed into the deodorizing column 1 of the cyclic test device shown in Figure 1, and air containing acetaldehyde was passed through the column to examine the deterioration of the lower aldehyde removal performance. This test device consists of an air supply pipe 5 in which a circulation pump 7 and an odorant vaporizer 3 are installed in a 25-capacity container 2, and an air supply pipe in which a circulation pump 6, a flow meter, and a deodorizing column 1 are installed in the middle. 4, and the container 2 and deodorizing column 1 are kept at a constant temperature in a constant temperature bath. The air containing lower aldehydes in the container 2 is constantly sent to the deodorizing column 1 via the circulation pump 6 and circulated to maintain an equilibrium adsorption state. The amount of removing agent in the deodorizing column 1 is 3 g. Test conditions are gas flow rate: 50/min, pressure drop: 18mm.
H2O , temperature: 25±1℃, deodorizing column: 30×30×
The air inside the container 2 was circulated at a filling length of 240 mm and a filling length of 8 mm. First, an aqueous solution of acetaldehyde diluted approximately 10 times was poured into the odorant vaporizer 3, air was circulated for 20 minutes, and then an acetaldehyde aqueous solution was again injected from the odorant vaporizer 3.
I did it twice. At this time, the injection amount was 20μ for the 1st to 8th injections, and 40μ for the 9th and 10th injections. Also,
The concentration of acetaldehyde after injection was 0, 1, 3,
Measurements were made using a gas chromatograph after 5, 10, 15, and 20 minutes. The measurement conditions of the gas chromatograph were the same as in Example 1. The results are shown in Table 6. The results show that sepiolite supporting o-aminobenzoic acid adsorbs aldehydes with little deterioration in adsorption performance and is durable. Example 5 Five types of removers No. 23 to No. 27 were prepared by the method described below. No.23 is sepiolite 9g and o
- 1 g of aminobenzoic acid was pulverized and mixed. No. 24 is prepared by dissolving 1 g of o-aminobenzoic acid in 20 ml of ethyl alcohol, adding 9 g of sepiolite to this solution, and adding o-aminobenzoic acid-ethyl alcohol to the sepiolite.
【表】
ール溶液を含浸させた。次に、これを乾燥器にい
れ100℃で乾燥させた。No.25は、ｏ−アミノ安息
香酸１ｇをエチルアルコール15ml、水５mlの混合
溶媒に溶解し、この溶液にセピオライト９ｇを加
えて含浸させた。次に100℃の乾燥器で乾燥させ
た。No.26は、ｏ−アミノ安息香酸１ｇとセピオラ
イト９ｇを混合し、エチルアルコール20mlを加え
た。これを超音波洗浄器を用いて約５分間撹拌
し、さらに密封して70℃で約30分間加熱した。次
いで開封し、乾燥器で100℃で乾燥した。No.277
は、ｏ−アミノ安息香酸１ｇとセピオライト９ｇ
を混合し、エチルアルコール15ml、水15mlの混合
溶液を加えた。この混合溶液を超音波洗浄器で約
５分間撹拌し、さらに密封して70℃で約30分間加
熱した。次いで開封し、乾燥器で100℃で乾燥し
た。
この除去剤について低級アルデヒドの吸収除去
性能の試験を次のようにしておこなつた。試料
（No.23〜27）をそれぞれ0.2ｇ、比較例としてセピ
オライトのみを0.2ｇ（C7）秤り取り、５容量
のガス非透過性の袋にいれ、さらにアセトアルデ
ヒド（10倍に稀釈した水溶液）10μを気化させ
ながら加えた。約４時間後に除去性を評価した。
この場合のブランクの濃度は125ppmである。結
果は第７表に示す。この結果ｏ−アミノ安息香酸
のセピオライトへの担持方法を変えても、除去性
能には影響がないことを示している。
実施例 ６
ここでは多孔性担体のセピオライトとヤシガラ
活性炭とを比較した。No.28は、ｏ−アミノ安息香
酸１ｇをエチルアルコール20mlに溶解し、この溶
液にセピオライト９ｇを加えて含浸させた後、
100℃で乾燥した。No.29は、ｏ−アミノ安息香酸
１ｇをエチルアルコール20mlに溶解し、この溶液
にヤシガラ活性炭９ｇを加えて含浸させた後100
℃で乾燥した。この除去剤を、それぞれ0.2ｇず
つ秤り取り、５容量のガス非透過性の袋にいれ
た。このようにして、[Table] Impregnated with mol solution. Next, this was placed in a dryer and dried at 100°C. In No. 25, 1 g of o-aminobenzoic acid was dissolved in a mixed solvent of 15 ml of ethyl alcohol and 5 ml of water, and 9 g of sepiolite was added to this solution for impregnation. Next, it was dried in a dryer at 100°C. No. 26 was prepared by mixing 1 g of o-aminobenzoic acid and 9 g of sepiolite, and adding 20 ml of ethyl alcohol. This was stirred for about 5 minutes using an ultrasonic cleaner, then sealed and heated at 70° C. for about 30 minutes. The package was then opened and dried in a dryer at 100°C. No.277
is 1 g of o-aminobenzoic acid and 9 g of sepiolite.
A mixed solution of 15 ml of ethyl alcohol and 15 ml of water was added. This mixed solution was stirred in an ultrasonic cleaner for about 5 minutes, then sealed and heated at 70° C. for about 30 minutes. The package was then opened and dried in a dryer at 100°C. The ability of this remover to absorb and remove lower aldehydes was tested as follows. Weigh out 0.2 g of each sample (No. 23 to 27) and 0.2 g of sepiolite (C7) as a comparative example, place them in a 5-volume gas-impermeable bag, and add acetaldehyde (an aqueous solution diluted 10 times). 10μ was added with vaporization. After about 4 hours, removability was evaluated.
The blank concentration in this case is 125 ppm. The results are shown in Table 7. This result shows that even if the method of supporting o-aminobenzoic acid on sepiolite is changed, the removal performance is not affected. Example 6 Here, porous carriers sepiolite and coconut shell activated carbon were compared. No. 28 was prepared by dissolving 1 g of o-aminobenzoic acid in 20 ml of ethyl alcohol, adding 9 g of sepiolite to this solution and impregnating it.
Dry at 100°C. No. 29 was prepared by dissolving 1 g of o-aminobenzoic acid in 20 ml of ethyl alcohol, adding 9 g of coconut shell activated carbon to this solution and impregnating it.
Dry at °C. 0.2 g of each of the removers was weighed out and placed in a 5-capacity gas-impermeable bag. In this way,
【表】
各試料に対してそれぞれ７袋およびブランク７袋
を作製した。次に、これらの袋に濃度が異なるよ
うに約10倍に稀釈したアセトアルデヒド水溶液を
第８表に示す量だけ加え、約４時間放置後のアセ
トアルデヒド濃度をガスクロマトグラフで測定
し、試料のアセトアルデヒド吸着量をもとめた。
ガスクロマトグラフの測定条件は、実施例１と同
じである。結果を第８表に示す。またブランクの
濃度については第９表に示す。
このようにして求めた吸着平衡線図から、担体
としてヤシガラ活性炭よりもセピオライトを用い
た方が、アセトアルデヒドの吸着量が大きく、除
去性がよい。
実施例 ７
ｏ−アミノ安息香酸１ｇをエチルアルコール20
mlに溶解し、ここへセピオライト９ｇを加え含浸
させた後100℃で乾燥し、乳鉢で粉砕して除去剤
を得た。
この除去剤を0.2ｇ秤り取り、５容量のガス
非透過性の袋に入れ、さらにホルムアルデヒド[Table] Seven bags and seven blank bags were prepared for each sample. Next, add acetaldehyde aqueous solutions diluted approximately 10 times to different concentrations in the amounts shown in Table 8 to these bags, and after standing for approximately 4 hours, measure the acetaldehyde concentration using a gas chromatograph to determine the amount of acetaldehyde adsorbed by the sample. I asked for.
The measurement conditions of the gas chromatograph were the same as in Example 1. The results are shown in Table 8. The blank density is shown in Table 9. From the adsorption equilibrium diagram obtained in this manner, the use of sepiolite as a carrier rather than coconut shell activated carbon allows for a larger amount of acetaldehyde to be adsorbed and better removability. Example 7 1 g of o-aminobenzoic acid was mixed with 20 ml of ethyl alcohol.
ml, 9 g of sepiolite was added thereto for impregnation, dried at 100°C, and ground in a mortar to obtain a remover. Weigh out 0.2g of this remover, put it in a 5-capacity gas-impermeable bag, and add formaldehyde to it.
【表】【table】
【表】
を約10倍に稀釈したホルムアルデヒド水溶液50μ
を入れて約４時間放置後に、ホルムアルデヒド
の残留濃度を北川式ガス検知管で測定した。この
結果をNo.30として第10表に示す。
同様に、アセトアルデヒド、ｎ−ブチルアルデ
ヒドについても検討した。なお、アセトアルデヒ
ドは約10倍に稀釈した水溶液を10μ、ｎ−ブチ
ルアルデヒドは約10倍に稀釈した水溶液を27μ
いれ、ガスクロマトグラフを用いて残留濃度を測
定した。これらをNo.31.No.32として第10表に示す。
比較品としてセピオライト0.2ｇづつを５容
量のガス非透過性の袋にいれ、ホルムアルデヒ
ド、アセトアルデヒド、ｎ−ブチルアルデヒド水
溶液をそれぞれ本実施例と同量入れ、残留濃度を
ガスクロマトグラフを用いて測定した（C8、C9、
C10）。結果を第10表に示す。なお、ブランクの
濃度はホルムアルデヒドが129ppm、アセトアル
デヒドが113ppm、ｎ−ブチルアルデヒド151ppm
である。ガスクロマトグ[Table] 50μ formaldehyde aqueous solution diluted approximately 10 times
After leaving it for about 4 hours, the residual concentration of formaldehyde was measured using a Kitagawa gas detection tube. This result is shown in Table 10 as No. 30. Similarly, acetaldehyde and n-butyraldehyde were also investigated. For acetaldehyde, an aqueous solution diluted approximately 10 times is diluted to 10μ, and for n-butyraldehyde, an aqueous solution diluted approximately 10 times is diluted 27μ.
The residual concentration was measured using a gas chromatograph. These are shown in Table 10 as No. 31 and No. 32. As a comparative product, 0.2 g of sepiolite was placed in a 5-volume gas-impermeable bag, and the same amounts of formaldehyde, acetaldehyde, and n-butyraldehyde aqueous solutions as in this example were added, and the residual concentration was measured using a gas chromatograph ( C8, C9,
C10). The results are shown in Table 10. The blank concentration is 129 ppm for formaldehyde, 113 ppm for acetaldehyde, and 151 ppm for n-butyraldehyde.
It is. gas chromatog
【表】【table】
【表】
ラフの測定条件は、実施例１と同じである。本実
施例の除去剤は、97％以上の除去率をしめしてい
る。特にホルムアルデヒド、ｎ−ブチルアルデヒ
ドは100％の除去率を示している。C10の留濃度
9.01ppmで除去率94.0％吸着量10.5ppmとあるが
対応するNo.32は、それぞれ0ppm、100％、11.1
mg／ｇであり吸着量がさらに向上した。
実施例 ８
ｏ−アミノ安息香酸10ｇをビーカーに秤り取
り、さらにエチルアルコール90ｇを加えて、ｏ−
アミノ安息香酸のエチルアルコール溶液を作製し
た。次に、活性炭素繊維シート（大阪ガス(株)製、
商品名：繊維状活性炭ACF Ａ−10、23.6cm×
23.6cm×0.3mm）に前記のエチルアルコール溶液
を均一に含浸するように、ピペツトで注意深く滴
下し、次いで、含浸した活性炭素繊維シートを乾
燥器で100℃、16時間加熱乾燥してエチルアルコ
ールを除去し低級アルデヒド類の除去剤を得た。
ｏ−アミノ息香酸の担持量は５重量％であつた。
アルデヒドの除去性能試験を次のようにおこな
つた。シートを５mm角に切出し、この切片2.5ｇ
を秤り取り、実施例４の第１図に示す装置の脱臭
カラム１に充填し、約10倍に稀釈したアセトアル
デヒド水溶液80μを臭気物質気化器３から導入
し、気化させた。つぎに実施例４と同様の実験条
件で装置内の空気を循環した。このときの容器２
内のガスを時間を追つて採気口からマイクロシリ
ンジで採気し、ガスクロマトグラフにより、容器
中のアセトアルデヒドの濃度を測定した。ガスク
ロマトグラフの条件は実施例１と同じである。結
果を第２図の線図Ａに示す。
なお、比較品としてｏ−アミノ安息香酸を全く
担持しない活性炭素繊維シートのみについても前
記の実施例と全く同一のアセトアルデヒドの除去
性能試験をおこなつた。結果は第２図に併記した
（線図Ｂ）。比較例に比べて本例はアセトアルデヒ
ドの濃度が時間とともに減少していることを示し
ている。
実施例 ９
実施例８の活性炭素繊維シートの代りにセピオ
ライトとパルプとからなる紙（21.8cm×21.8cm×
0.13mm）を用いることを除いては、実施例８と全
く同じ方法でｏ−アミノ安息香酸５重量％担持の
試料を作製した。
アルデヒドの除去性能試験についても、実施例
８と全く同一の方法でおこなつた。結果を第３図
の線図Ｃに示す。
なお、比較品としてｏ−アミノ安息香酸を全く
担持しない紙のみについても同一の試験を行つ
た。結果を第３図に併記した（線図Ｄ）。
このセピオライトとパルプとからなる紙にｏ−
アミノ安息香酸を担持したものは、時間の経過と
ともにアセトアルデヒドの濃度が著しく減少して
おり除去性能が優れている。[Table] The rough measurement conditions are the same as in Example 1. The removal agent of this example shows a removal rate of 97% or more. In particular, formaldehyde and n-butyraldehyde have a removal rate of 100%. C10 concentration
It says that the removal rate is 94.0% and the adsorption amount is 10.5ppm at 9.01ppm, but the corresponding No. 32 is 0ppm, 100%, and 11.1%, respectively.
mg/g, which further improved the adsorption amount. Example 8 Weigh out 10 g of o-aminobenzoic acid in a beaker, add 90 g of ethyl alcohol, and add o-aminobenzoic acid.
An ethyl alcohol solution of aminobenzoic acid was prepared. Next, activated carbon fiber sheet (manufactured by Osaka Gas Co., Ltd.,
Product name: Fibrous activated carbon ACF A-10, 23.6cm×
23.6cm x 0.3mm) with a pipette so as to uniformly impregnate the ethyl alcohol solution, and then heat-dry the impregnated activated carbon fiber sheet in a dryer at 100°C for 16 hours to remove the ethyl alcohol. A lower aldehyde remover was obtained.
The amount of o-aminozoic acid supported was 5% by weight. An aldehyde removal performance test was conducted as follows. Cut the sheet into 5mm square pieces and weigh 2.5g
was weighed out and packed into the deodorizing column 1 of the apparatus shown in FIG. 1 of Example 4, and 80μ of an acetaldehyde aqueous solution diluted approximately 10 times was introduced from the odorant vaporizer 3 and vaporized. Next, the air inside the apparatus was circulated under the same experimental conditions as in Example 4. Container 2 at this time
The gas inside the container was collected over time using a microsyringe through the intake port, and the concentration of acetaldehyde in the container was measured using a gas chromatograph. The gas chromatograph conditions were the same as in Example 1. The results are shown in diagram A in FIG. As a comparative product, an activated carbon fiber sheet that did not support any o-aminobenzoic acid was also subjected to the same acetaldehyde removal performance test as in the above example. The results are also shown in Figure 2 (diagram B). Compared to the comparative example, this example shows that the concentration of acetaldehyde decreases over time. Example 9 Instead of the activated carbon fiber sheet of Example 8, a paper made of sepiolite and pulp (21.8 cm x 21.8 cm x
A sample carrying 5% by weight of o-aminobenzoic acid was prepared in exactly the same manner as in Example 8, except that 0.13 mm) was used. The aldehyde removal performance test was also conducted in exactly the same manner as in Example 8. The results are shown in diagram C in FIG. In addition, as a comparison product, the same test was conducted using only paper that did not carry any o-aminobenzoic acid. The results are also shown in Figure 3 (diagram D). This paper made of sepiolite and pulp has an o-
Those carrying aminobenzoic acid have excellent removal performance, with the concentration of acetaldehyde decreasing significantly over time.
第１図は実施例の繰返し吸着除去の試験装置の
説明図、第２図は実施例８のアセトアルデヒドの
時間の経過による濃度変化を示す線図、第３図は
実施例９のアセトアルデヒドの時間の経過による
濃度変化を示す線図である。
１……脱臭カラム、２……容器、３……臭気物
質気化器、４，５……送気パイプ、６，７……循
環ポンプ。
Figure 1 is an explanatory diagram of the test device for repeated adsorption and removal in Example, Figure 2 is a diagram showing the concentration change over time of acetaldehyde in Example 8, and Figure 3 is a graph showing the change in concentration over time of acetaldehyde in Example 9. FIG. 3 is a diagram showing changes in concentration over time. 1... Deodorizing column, 2... Container, 3... Odorous substance vaporizer, 4, 5... Air supply pipe, 6, 7... Circulation pump.
Claims (1)
類の少なくとも１種を有効成分とする低級アルデ
ヒド類の除去剤。 ２ 芳香族アミノ酸、および芳香族アミノ酸の塩
類は、Ｏ−、ｍ−またはｐ−アミノ安息香酸、ｐ
−アミノサリチル酸及びその塩類から選ばれる少
なくとも１種からなる特許請求の範囲第１項記載
の低級アルデヒド類の除去剤。 ３ 多孔性担体に芳香族アミノ酸、および芳香族
アミノ酸の塩類の少なくとも１種を有効成分とし
て担持してなる低級アルデヒド類の除去剤。 ４ 多孔性担体は、セピオライト、パリゴルスカ
イト、活性炭、ゼオライトから選ばれる少なくと
も１種からなる特許請求の範囲第３項記載の低級
アルデヒド類の除去剤。 ５ 多孔性担体は、シート状、ハニカム状、顆粒
状、粉末状、粒状、板状、繊維状から選ばれる少
なくとも１種からなる特許請求の範囲第３項記載
の低級アルデヒド類の除去剤。 ６ 芳香族アミノ酸、および芳香族アミノ酸の塩
類は、ｏ−、ｍ−またはｐ−アミノ安息香酸、ｐ
−アミノサリチル酸及びその塩から選ばれる少な
くとも１種からなる特許請求の範囲第３項記載の
低級アルデヒド類の除去剤。[Scope of Claims] 1. A lower aldehyde remover containing at least one of an aromatic amino acid and a salt of an aromatic amino acid as an active ingredient. 2 Aromatic amino acids and salts of aromatic amino acids include O-, m- or p-aminobenzoic acid, p-
- The lower aldehyde remover according to claim 1, which comprises at least one member selected from aminosalicylic acid and its salts. 3. A lower aldehyde remover comprising at least one of an aromatic amino acid and a salt of an aromatic amino acid supported as an active ingredient on a porous carrier. 4. The lower aldehyde remover according to claim 3, wherein the porous carrier comprises at least one selected from sepiolite, palygorskite, activated carbon, and zeolite. 5. The lower aldehyde removing agent according to claim 3, wherein the porous carrier is at least one selected from sheet, honeycomb, granule, powder, granule, plate, and fibrous shapes. 6 Aromatic amino acids and salts of aromatic amino acids include o-, m- or p-aminobenzoic acid, p-aminobenzoic acid,
- The lower aldehyde removing agent according to claim 3, which comprises at least one selected from aminosalicylic acid and its salts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266632A JPH02115020A (en) | 1988-10-22 | 1988-10-22 | Removing agent for lower aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266632A JPH02115020A (en) | 1988-10-22 | 1988-10-22 | Removing agent for lower aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02115020A JPH02115020A (en) | 1990-04-27 |
| JPH0439368B2 true JPH0439368B2 (en) | 1992-06-29 |
Family
ID=17433525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63266632A Granted JPH02115020A (en) | 1988-10-22 | 1988-10-22 | Removing agent for lower aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02115020A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031248A1 (en) * | 2007-09-05 | 2009-03-12 | Daicel Chemical Industries, Ltd. | Composition containing amino compound and silica gel, and tobacco filter |
Families Citing this family (12)
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| JP3078850B2 (en) * | 1990-12-28 | 2000-08-21 | 日揮ユニバーサル株式会社 | Adsorption composition containing zeolite and adsorption decomposition composition containing this adsorption composition |
| JP3348498B2 (en) * | 1992-12-08 | 2002-11-20 | 株式会社豊田中央研究所 | Stink remover |
| JP3271380B2 (en) * | 1993-06-23 | 2002-04-02 | 株式会社デンソー | Deodorant and method for producing the same |
| DE4433139A1 (en) * | 1994-09-16 | 1996-03-21 | Thera Ges Fuer Patente | Hydrophilized dental impression materials |
| JP2818929B2 (en) * | 1995-04-20 | 1998-10-30 | 大和化学工業株式会社 | Deodorant, deodorant fiber, method for producing the same, and deodorized processed body |
| JPH0956800A (en) * | 1995-08-24 | 1997-03-04 | Toyota Central Res & Dev Lab Inc | Deodorant and deodorizing method |
| WO2002011777A1 (en) * | 2000-08-08 | 2002-02-14 | Bridgestone Corporation | Deodorizers and deodorizing filter medium |
| JP2002085539A (en) * | 2000-09-20 | 2002-03-26 | Toyota Central Res & Dev Lab Inc | Deodorant and method for indicating aldehyde adsorption degree |
| US8500880B2 (en) * | 2009-11-24 | 2013-08-06 | Corning Incorporated | Amino acid salt articles and methods of making and using them |
| CN104436999B (en) * | 2013-09-24 | 2017-04-05 | 宁波市雨辰环保科技有限公司 | A kind of formaldehyde absorbent and its using method |
| US20210039067A1 (en) * | 2018-03-30 | 2021-02-11 | Unitika Ltd. | Deodorizing Material, Method for Producing the Same, Deodorization Method, and Deodorizing Sheet |
| CN109529569A (en) * | 2018-12-06 | 2019-03-29 | 佛山市顺德区阿波罗环保器材有限公司 | A kind of compound deodorizer and preparation method thereof |
-
1988
- 1988-10-22 JP JP63266632A patent/JPH02115020A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031248A1 (en) * | 2007-09-05 | 2009-03-12 | Daicel Chemical Industries, Ltd. | Composition containing amino compound and silica gel, and tobacco filter |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02115020A (en) | 1990-04-27 |
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