JP3545888B2 - Deodorizing filter - Google Patents
Deodorizing filter Download PDFInfo
- Publication number
- JP3545888B2 JP3545888B2 JP25912196A JP25912196A JP3545888B2 JP 3545888 B2 JP3545888 B2 JP 3545888B2 JP 25912196 A JP25912196 A JP 25912196A JP 25912196 A JP25912196 A JP 25912196A JP 3545888 B2 JP3545888 B2 JP 3545888B2
- Authority
- JP
- Japan
- Prior art keywords
- deodorizing filter
- deodorizing
- sulfanilic acid
- performance
- filter according
- 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
- 230000001877 deodorizing effect Effects 0.000 title claims description 50
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical group NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 150000004982 aromatic amines Chemical class 0.000 claims description 26
- 229950000244 sulfanilic acid Drugs 0.000 claims description 26
- 239000012629 purifying agent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 150000007514 bases Chemical class 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 150000003752 zinc compounds Chemical class 0.000 claims description 11
- 125000001174 sulfone group Chemical group 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- JAZCSWFKVAHBLR-UHFFFAOYSA-N dihydrogen phosphate;phenylazanium Chemical compound OP(O)(O)=O.NC1=CC=CC=C1 JAZCSWFKVAHBLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 30
- -1 aliphatic aldehydes Chemical class 0.000 description 17
- 229910021529 ammonia Inorganic materials 0.000 description 15
- 235000019645 odor Nutrition 0.000 description 12
- 238000004332 deodorization Methods 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002781 deodorant agent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- JJSRGUCTMZWMHY-UHFFFAOYSA-N 2-aminobenzenesulfonic acid;4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1.NC1=CC=CC=C1S(O)(=O)=O JJSRGUCTMZWMHY-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- XEPNJJFNSJKTSO-UHFFFAOYSA-N azanium;zinc;chloride Chemical compound [NH4+].[Cl-].[Zn] XEPNJJFNSJKTSO-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
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- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Filtering Materials (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、脱臭フィルターに係り、特にアセトアルデヒドと他の悪臭成分とを同時に除去可能な脱臭フィルターに関するものである。
【0002】
【従来の技術】
室内や車内などの居住空間においては、様々な種類の悪臭が発生するが、中でも、近年焦点になっている煙害問題などにより、たばこ臭の除去に対する要求が高まってきている。
たばこ臭の主成分は、アセトアルデヒド、アンモニア、酢酸などであるが、この中では、アセトアルデヒドの臭気が最も強く、また、アセトアルデヒドは、他の臭気成分に比して、除去が難しい物質である。
【0003】
その理由は、アセトアルデヒドなどの低級脂肪族アルデヒドが、脱臭剤として代表的な活性炭やゼオライトなどへの吸着性が低いという特異な特性を持っているからである。
更に低級脂肪族アルデヒドは、これら活性炭やゼオライトの吸着力改善のために、表面に添着される酸や塩基性物質などとの反応性も低いという問題もある。この課題に対して、特に低級脂肪族アルデヒドの除去性能を強調した脱臭剤もしくは空気浄化剤が、従来より種々提案されてきた。
【0004】
例えば、特公昭60−54095号や特開平3−98642号では、活性炭にアニリンやリン酸アニリンを添着したものが提案されている。
また、特開平4−2350号や特開平5−23588号では、活性炭にアミノ酸やアミノ安息香酸を添着したものが提案されている。
活性炭以外には、特公平5−16299号でゼオライトなどのアルミノシリケートが、特公平6−22673号でセピオライトが、特開平7−136502号で活性炭素繊維にアミノベンゼンスルフォン酸(スルファニル酸)を添着したものが、各々提案されている。
【0005】
しかしながら、これら従来の脱臭剤もしくは空気浄化剤は、低級脂肪族アルデヒドの除去に対して実用的では無いという問題がある。
例えば、アニリンやリン酸アニリンは、低級脂肪族アルデヒドの除去性能は優れるものの、臭気が強く、一般向けの脱臭剤もしくは空気浄化剤として使用しにくい問題がある。
また、ゼオライトやセピオライトなどの金属酸化物や、アミノ酸やアミノ安息香酸などの有機物質は、活性炭と組み合わせても、低級脂肪族アルデヒドの除去性能が、アニリンよりも劣る問題がある。
更に、アミノベンゼンスルフォン酸(スルファニル酸)も、前記金属酸化物やアミノ酸類などよりは、低級脂肪族アルデヒドの除去性能に優れるものの、アニリンよりは劣るという問題がある。
【0006】
したがって、低級脂肪族アルデヒドの除去効率が高く、望ましくは、他のアンモニア、酢酸などの臭気成分の除去を同時に行えることが、この種の脱臭剤もしくは空気浄化剤に求められている技術的課題である。
【0007】
かかる事情に鑑み、特に、低級脂肪族アルデヒドの除去性能に優れるとともに、他の臭気成分も同時に除去可能な空気浄化剤を提供するため、本発明者等は、先に、特願平8−167579号として、活性炭などの多孔質体に加えて、芳香族アミン類および選択的に亜鉛化合物を含有する空気浄化剤を提案した。
この空気浄化剤は、特に、スルファニル酸などのアミノ基とスルフォン基を有する芳香族アミン類を選択した場合に、良好な脱臭性能を得ている。
【0008】
【発明が解決しようとする課題】
しかしながら、この空気浄化剤に有機バインダーを加え、押出法などにより、ハニカムなどのモノリス状の脱臭フィルターに成型した場合、成型体が乾燥後に崩壊してしまうという問題が生じる。
これは、成型のために必須の有機バインダーが、スルファニル酸などの酸性の強い芳香族アミン類により劣化し、成型体の強度確保に必要なバインダー量が不足することからくる。
そして、この問題は、▲1▼脱臭フィルター=成型体としての必要強度が得られない、▲2▼成型体必要強度を得るためにはスルファニル酸の含有量を制限する必要がある、▲3▼スルファニル酸の含有量を制限すれば、脱臭性能が落ちる、という実用上の問題につながる。
【0009】
したがって、本発明は、活性炭などの多孔質体に加えて、アミノ基とスルフォン基を有する芳香族アミン類および亜鉛化合物の両者を含有する空気浄化剤混合物の脱臭性能を落とさずに、必要強度や形状に成型可能とした脱臭フィルターを提供することを目的とするものである。
【0010】
【課題を解決するための手段】
このための、本発明の手段は、アミノ基とスルフォン基とを有する芳香族アミン類と、多孔質体とを含む空気浄化剤混合物を、有機バインダーによりモノリス状(柱状)に成型した脱臭フィルターであって、前記空気浄化剤混合物中に塩基性化合物(但し、アニリンおよびリン酸アニリンを除く)を含むことである。
【0011】
塩基性化合物を含むことで、スルファニル酸などの芳香族アミン類の一部を塩にし、酸性度を低下させて、有機バインダーの劣化を防止する。これにより、空気浄化剤に有機バインダーを加え、押出法などにより、ハニカムなどのモノリス状の脱臭フィルターに成型する場合の、成型体の強度低下を防止できる。
【0012】
この際、一方で空気浄化剤混合物の脱臭性能を落とさないよう、前記空気浄化剤混合物中の芳香族アミン類と塩基性化合物との量を調節することが好ましい。なぜなら、塩基性化合物を含ませ、スルファニル酸の一部を塩にすることで、スルファニル酸自体の脱臭性能は低下するからである。
通常、芳香族アミン類の中のアミノ基とスルフォン基が、脱臭性能に寄与しており、アセトアルデヒドに対してはアミノ基が、アンモニアに対してはスルフォン基が各々作用する。
したがって、塩基性化合物によりスルフォン基が中和されれば、スルフォン基によるアンモニア除去性能が落ちることになる。
【0013】
本発明者らの知見によれば、粉砕した成型体懸濁液(但し、水100ccに対し粉砕成型体を1gの割合で懸濁させる)のPHが3以上になるよう、空気浄化剤混合物中の芳香族アミン類と塩基性化合物との量を調節することが好ましく、この範囲に芳香族アミン類と塩基性化合物との量を調節すれば、脱臭性能を落とさずに、有機バインダーの劣化を防止できる。
【0014】
これは、PHが3以上になる領域では、有機バインダーの劣化を防止できるだけの塩基性化合物による芳香族アミン類の中和が行われており、一方、中和により減少はするものの、芳香族アミン類の絶対量も確保されているため、脱臭性能の低下が少ないものと推考される。
【0015】
【発明の実施の形態】
低級脂肪族アルデヒドの除去用に従来から提案されている芳香族アミン類は、ある程度の低級脂肪族アルデヒドの除去性能を有するが、この芳香族アミン類に、亜鉛化合物を併用すると、低級脂肪族アルデヒドの除去性能を飛躍的に向上させるとともに、他の臭気成分の除去性能も落とさず、除去可能である。
このメカニズムは定かではないが、亜鉛化合物は、芳香族アミン類とアルデヒドとの反応における触媒としての機能を発揮するためと推考される。
【0016】
本発明において、アミノ基とスルフォン基を有する芳香族アミン類としては、特にスルファニル酸などが、脱臭性能上から好ましい。
芳香族アミン類に、低級脂肪族アルデヒドの除去性能を発揮させるためには、多孔質体100重量部に対し、芳香族アミン類を3重量部以上とすることが望ましい。これ未満では、空気浄化剤としての効果の持続時間が短くなり実用的ではない。また、逆に、芳香族アミン類の添着量が50重量部を超えると、多孔質体の単体としての効果が低くなるので、これ以下の添着量とすることが好ましい。
【0017】
なお、脱臭剤の機能向上のために金属や金属化合物触媒を併用することは公知であり、例えば、特公平5−16299号にはアルミノシリケートに、鉄や銅などの遷移金属成分を保持させることが開示されている。
しかしながら、本発明者らの知見によれば、亜鉛化合物以外の、鉄や銅などの遷移金属金属化合物を用いても、芳香族アミン類とアルデヒドとの反応における触媒としての機能は無かった。
亜鉛化合物に、触媒機能を発揮させるためには、芳香族アミン類100重量部に対して、3重量部以上とすることが望ましい。これ未満では、触媒機能が小さく、反応時間が長くなり実用的ではない。
また、50重量部を超えて含有しても、触媒機能は飽和し、実用的でないので、これ以下の添着量とすることが好ましい。
【0018】
本発明において塩基性化合物としては、水酸化ナトリウムの他、水酸化カルシウム、炭酸水素ナトリウムなどのアルカリ金属化合物、炭酸アンモニウム、炭酸水素アンモニウム、などが適宜使用可能である。
【0019】
次に、亜鉛化合物について、本発明においては、亜鉛化合物として塩化亜鉛を用いることが望ましいが、酸化亜鉛、炭酸亜鉛、硝酸亜鉛、硫酸亜鉛、塩化亜鉛アンモニウムなども適用可能である。
【0020】
更に、本発明における多孔質体について、以下説明する。
多孔質体としては、活性炭、ゼオライト、活性アルミナ、シリカ、シリカゲル、ケイソウ土、炭素繊維などが適宜使用できる。これらの多孔質体は、それ自身脱臭性能を有するものが多い。
本発明において、低級脂肪族アルデヒド以外の臭気成分の除去も考慮すると、多孔質体それ自身に脱臭性能を有するものが好ましい。特に、活性炭は、低級脂肪族アルデヒド以外の他の多くの臭気成分の除去性能を有するものとして本発明における多孔質体として、特に好ましい。
【0021】
本発明における脱臭フィルターは、この多孔質体を含んでハニカムなどのモノリス状に成型されているので、室内や車内の空気清浄器内や通気口に適宜簡便に配置でき、取り替えや保守が簡単であるなどの使用上の利点が多い。
【0022】
【実施例】
まず、空気浄化剤をハニカム状モノリスに成型した脱臭フィルターを、以下の通り製作し、空気浄化剤組成の成型性に対する影響をテストした。
空気浄化剤は、多孔質体としては粉末状の活性炭、芳香族アミン類としてスルファニル酸、亜鉛化合物として塩化亜鉛、塩基性化合物として水酸化ナトリウムを各々選択した。
これらの空気浄化剤成分のうち、特に、スルファニル酸と水酸化ナトリウムとの配合比を変えたものを各々混合し、さらに、有機バインダーを加えて水で希釈し、よく混練したものを、押出成型したのち、乾燥させて、ハニカム状モノリスを得た。
【0023】
そして、得られたハニカム状モノリスを観察し、押出乾燥後にハニカムが崩壊したものを×とし、若干の亀裂が生じたが形状を保ったものを○、亀裂も無く形状も良好なものを◎として、成型性を評価した。
このハニカム状モノリスの、空気浄化剤配合条件と成型性評価結果を、表1に示す。なお、配合量は重量部で表している。また、スルファニル酸と水酸化ナトリウムとのモル比と、成型後の各ハニカム状モノリスを粉砕し、水100ccに対し粉砕成型体を1gの割合で懸濁させた成型体懸濁液のPHとの測定結果も、合わせて示す。
【0024】
表1のNo.1、2に示す、水酸化ナトリウムを含まない比較例は、成型体への成型ができなかった。
【0025】
また、No.3、7、10、14は本発明例ではあるものの、スルファニル酸に対する水酸化ナトリウムの量が少ないため、有機バインダーの劣化が若干生じており、他の本発明例に比して、成型性が若干劣っている。
【0026】
一方、No.4〜6、8〜9、11〜13、15〜16の本発明例は、スルファニル酸に対する水酸化ナトリウムの量が適正であり(成型体懸濁液のPHが3以上)スルファニル酸は、有機バインダーを劣化させない程度に、水酸化ナトリウムにより中和されており、成型性が特に良好である。また、後述する通り脱臭に必要なスルファニル酸量も確保されており、脱臭性能も十分確保されている。
【0027】
【表1】
【0028】
次に、前記表1のうち、No.4〜6、8〜9、11〜13、15〜16の本発明例であるハニカム状モノリスに成型した脱臭フィルターの、アセトアルデヒド、アンモニアの2成分に対する脱臭率の測定を行った。なお、比較例のNo.1、2、は、前記した通り、ハニカム状モノリス脱臭フィルターに成型できなかったので、脱臭率の測定は出来なかった。また、本発明例であるNo.3、7、10、14のものは、成型体に若干の亀裂が生じており、脱臭フィルターとして使用できないことはないが、脱臭率の測定対象からは除外した。
【0029】
脱臭率測定のための流通試験は、所定濃度の前記悪臭成分ガスを混合した空気を、0.2m/sの流速で脱臭フィルター内に流し、入口および出口の悪臭ガス濃度を各々測定して行い、次式を用いて脱臭率を算出した。
脱臭率(%)=〔(Ci−Co)/Ci〕×100、(但し、Ci:悪臭成分ガス入口濃度、Co:悪臭成分ガス出口濃度)、
なお、悪臭成分ガス2成分の濃度は、アセトアルデヒド、アンモニアとも15ppmとした。
【0030】
各々のフィルターの悪臭成分ガスに対する脱臭性能(除去率)と、スルファニル酸に対する水酸化ナトリウムの量(水酸化ナトリウム/スルファニル酸のモル比)との関係を、図1〜4に示す。図中の横軸に記入した番号は、各々表1の試料番号に対応している。
また、アセトアルデヒドの除去率が35%以上で、且つアンモニアの除去率が55%以上のものを○、その中でも特に除去率が高いものを◎として表1にも示した。
【0031】
図1〜4の通り、スルファニル酸に対する水酸化ナトリウムの量が増加するほど、アセトアルデヒドやアンモニアに対する脱臭性能は低下する傾向にある。
これに対して、スルファニル酸に対する水酸化ナトリウムの量が少ないほど、アセトアルデヒドやアンモニアに対する脱臭性能は優れる。
本発明ではハニカム状などのモノリス脱臭フィルターへの成型性を重視しているが、アセトアルデヒドの除去率が35%以上で、且つアンモニアの除去率が55%以上の、脱臭フィルターとしての実用的な脱臭性能を確実に確保するためには、スルファニル酸に対する水酸化ナトリウムの量、即ち、水酸化ナトリウム/スルファニル酸のモル比が0.9以下、より好ましくは0.7以下であることが好ましい。
【0032】
また、同じスルファニル酸量であっても、塩化亜鉛を含む方が(図1のスルファニル酸20重量部と、図2のスルファニル酸20重量部+塩化亜鉛0.75重量部との対比、図2のスルファニル酸30重量部と、図4のスルファニル酸30重量部+塩化亜鉛1.1重量部との対比)アセトアルデヒドやアンモニアに対する脱臭性能は優れる。
【0033】
【発明の効果】
以上説明した通り、本発明脱臭フィルターによれば、活性炭などの多孔質体に加えて、アミノ基とスルフォン基を有する芳香族アミン類を含有する空気浄化剤の脱臭性能を落とさずに、必要強度に成型した脱臭フィルターを得ることが可能である。
したがって、用途に応じて所望の形状の脱臭フィルターを得ることが可能となり、脱臭フィルターの種々の用途での実用化に道を開いた点で、その工業的価値は大きい。
【図面の簡単な説明】
【図1】本発明に係るハニカム状脱臭フィルター(表1のNo.4〜6)の、空気浄化剤組成と、アセトアルデヒドやアンモニアに対する脱臭率との関係を示す説明図である。
【図2】本発明に係るハニカム状脱臭フィルター(表1のNo.8〜9)の、空気浄化剤組成組成と、アセトアルデヒドやアンモニアに対する脱臭率との関係を示す説明図である。
【図3】本発明に係るハニカム状脱臭フィルター(表1のNo.11〜13)の、空気浄化剤組成と、アセトアルデヒドやアンモニアに対する脱臭率との関係を示す説明図である。
【図4】本発明に係るハニカム状脱臭フィルター(表1のNo.15〜16)の、空気浄化剤組成と、アセトアルデヒドやアンモニアに対する脱臭率との関係を示す説明図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a deodorizing filter, and more particularly to a deodorizing filter capable of simultaneously removing acetaldehyde and other malodorous components.
[0002]
[Prior art]
In a living space such as a room or a car, various types of odors are generated. Above all, there is an increasing demand for the removal of tobacco odors due to a focus on smoke pollution in recent years.
The main components of tobacco odor are acetaldehyde, ammonia, acetic acid, etc. Among them, acetaldehyde has the strongest odor, and acetaldehyde is a substance which is more difficult to remove than other odor components.
[0003]
The reason is that lower aliphatic aldehydes such as acetaldehyde have a unique property that they have low adsorptivity to activated carbon and zeolite, which are typical deodorants.
Further, the lower aliphatic aldehyde has a problem that reactivity with an acid or a basic substance attached to the surface is low in order to improve the adsorption power of the activated carbon and the zeolite. To address this problem, various deodorants or air purifiers that emphasize the performance of removing lower aliphatic aldehydes have been proposed in the past.
[0004]
For example, Japanese Patent Publication No. Sho 60-54095 and Japanese Patent Application Laid-Open No. 3-98642 propose an activated carbon in which aniline or aniline phosphate is impregnated.
Further, JP-A-4-2350 and JP-A-5-23588 propose an activated carbon in which an amino acid or aminobenzoic acid is impregnated.
Other than activated carbon, aluminosilicate such as zeolite in Japanese Patent Publication No. 5-16299, sepiolite in Japanese Patent Publication No. Hei 6-22673, and aminobenzenesulfonic acid (sulfanilic acid) on activated carbon fiber in Japanese Patent Application Laid-Open No. Hei 7-136502. Have been proposed.
[0005]
However, there is a problem that these conventional deodorants or air purifiers are not practical for removing lower aliphatic aldehydes.
For example, although aniline and aniline phosphate have excellent performance of removing lower aliphatic aldehydes, they have a strong odor and are difficult to use as general-purpose deodorants or air purifiers.
Further, metal oxides such as zeolite and sepiolite, and organic substances such as amino acids and aminobenzoic acid have a problem that even when combined with activated carbon, the performance of removing lower aliphatic aldehydes is inferior to that of aniline.
Further, aminobenzenesulfonic acid (sulfanilic acid) also has a problem that it is superior to aniline in removing performance of lower aliphatic aldehydes than the metal oxides and amino acids, but is inferior to aniline.
[0006]
Therefore, it is a technical problem required for this type of deodorant or air purifier that the removal efficiency of lower aliphatic aldehydes is high, and desirably that other odor components such as ammonia and acetic acid can be removed simultaneously. is there.
[0007]
In view of such circumstances, in order to provide an air purifying agent which is excellent in the performance of removing lower aliphatic aldehydes and can also remove other odor components at the same time, the present inventors first disclosed in Japanese Patent Application No. 8-167579. As an issue, an air purifier containing aromatic amines and optionally a zinc compound in addition to a porous material such as activated carbon was proposed.
This air purifier obtains good deodorizing performance particularly when aromatic amines having an amino group and a sulfone group such as sulfanilic acid are selected.
[0008]
[Problems to be solved by the invention]
However, when an organic binder is added to the air purifying agent and molded into a monolithic deodorizing filter such as a honeycomb by an extrusion method or the like, a problem occurs that the molded body collapses after drying.
This is because the organic binder essential for molding is deteriorated by strongly acidic aromatic amines such as sulfanilic acid, and the amount of binder necessary for securing the strength of the molded product is insufficient.
The problems are as follows: (1) the deodorizing filter cannot obtain the required strength as a molded body; (2) it is necessary to limit the content of sulfanilic acid to obtain the required strength of the molded body; (3) Limiting the content of sulfanilic acid leads to a practical problem that the deodorizing performance is reduced.
[0009]
Accordingly, the present invention provides the required strength and strength without lowering the deodorizing performance of an air purifier mixture containing both an aromatic amine having an amino group and a sulfone group and a zinc compound in addition to a porous body such as activated carbon. It is an object of the present invention to provide a deodorizing filter that can be formed into a shape.
[0010]
[Means for Solving the Problems]
For this purpose, a means of the present invention is a deodorizing filter in which an air purifying agent mixture containing an aromatic amine having an amino group and a sulfone group and a porous body is formed into a monolithic (columnar) shape with an organic binder. The air purifier mixture contains a basic compound (excluding aniline and aniline phosphate) .
[0011]
By containing a basic compound, a part of aromatic amines such as sulfanilic acid is converted into a salt to reduce the acidity and prevent the organic binder from deteriorating. Thereby, when the organic binder is added to the air purifying agent, and the molded article is molded into a monolithic deodorizing filter such as a honeycomb by an extrusion method or the like, a decrease in the strength of the molded article can be prevented.
[0012]
At this time, it is preferable to adjust the amounts of the aromatic amines and the basic compound in the air purifying agent mixture so as not to deteriorate the deodorizing performance of the air purifying agent mixture. This is because the deodorizing performance of sulfanilic acid itself is reduced by including a basic compound and converting a portion of sulfanilic acid into a salt.
Usually, amino groups and sulfone groups in aromatic amines contribute to deodorizing performance, and amino groups act on acetaldehyde, and sulfone groups act on ammonia.
Therefore, if the sulfone group is neutralized by the basic compound, the performance of removing ammonia by the sulfone group will be reduced.
[0013]
According to the knowledge of the present inventors, the air-purifying agent mixture is adjusted so that the PH of the pulverized molded product suspension (however, 1 g of the pulverized molded product is suspended in 100 cc of water) is 3 or more. It is preferable to adjust the amount of the aromatic amines and the basic compound in the range.If the amounts of the aromatic amines and the basic compound are adjusted in this range, the deterioration of the organic binder can be prevented without lowering the deodorizing performance. Can be prevented.
[0014]
This is because in the region where the pH is 3 or more, the aromatic amines are neutralized by a basic compound that can prevent the deterioration of the organic binder. On the other hand, the aromatic amines are reduced by the neutralization. It is assumed that the deodorizing performance does not decrease much since the absolute amount of the odors is secured.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
Aromatic amines conventionally proposed for the removal of lower aliphatic aldehydes have a certain level of lower aliphatic aldehyde removal performance. However, when a zinc compound is used in combination with these aromatic amines, the lower aliphatic aldehydes are removed. Can be removed without drastically improving the removal performance of other odor components.
Although the mechanism is not clear, it is considered that the zinc compound exhibits a function as a catalyst in the reaction between the aromatic amine and the aldehyde.
[0016]
In the present invention, the aromatic amines having an amino group and sulfone group, particularly etc. sulfanilic acid is preferred from the deodorization performance.
In order for the aromatic amines to exhibit the performance of removing lower aliphatic aldehydes, it is desirable that the aromatic amines be 3 parts by weight or more based on 100 parts by weight of the porous body. If it is less than this, the duration of the effect as an air purifying agent will be short and not practical. Conversely, if the amount of the aromatic amine added exceeds 50 parts by weight, the effect of the porous body as a simple substance is reduced.
[0017]
It is known that a metal or a metal compound catalyst is used in combination for improving the function of the deodorant. For example, Japanese Patent Publication No. 5-16299 discloses that aluminosilicate is used to hold transition metal components such as iron and copper. Is disclosed.
However, according to the findings of the present inventors, even if a transition metal metal compound such as iron or copper other than a zinc compound is used, it has no function as a catalyst in the reaction between an aromatic amine and an aldehyde.
In order for the zinc compound to exert its catalytic function, the amount is preferably 3 parts by weight or more based on 100 parts by weight of the aromatic amines. If it is less than this, the catalytic function becomes small and the reaction time becomes long, which is not practical.
If the content exceeds 50 parts by weight, the catalytic function is saturated and is not practical. Therefore, it is preferable to set the amount to be less than this.
[0018]
In the present invention, as the basic compound, in addition to sodium hydroxide, an alkali metal compound such as calcium hydroxide and sodium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate and the like can be appropriately used.
[0019]
Next, as for the zinc compound, in the present invention, it is desirable to use zinc chloride as the zinc compound, but zinc oxide, zinc carbonate, zinc nitrate, zinc sulfate, zinc ammonium chloride, and the like are also applicable.
[0020]
Further, the porous body in the present invention will be described below.
As the porous body, activated carbon, zeolite, activated alumina, silica, silica gel, diatomaceous earth, carbon fiber, and the like can be used as appropriate. Many of these porous bodies themselves have deodorizing performance.
In the present invention, in consideration of removal of odor components other than the lower aliphatic aldehyde, those having a deodorizing performance on the porous body itself are preferable. In particular, activated carbon is particularly preferable as a porous body in the present invention as having a performance of removing many odor components other than lower aliphatic aldehydes.
[0021]
Since the deodorizing filter of the present invention is formed into a monolith shape such as a honeycomb including the porous body, the filter can be appropriately and conveniently arranged in an air purifier or a vent in a room or a car, and replacement and maintenance are easy. There are many advantages in use such as.
[0022]
【Example】
First, a deodorizing filter formed by molding an air purifying agent into a honeycomb monolith was manufactured as follows, and the effect of the air purifying agent composition on moldability was tested.
As the air purifying agent, powdered activated carbon as the porous body, sulfanilic acid as the aromatic amine, zinc chloride as the zinc compound, and sodium hydroxide as the basic compound were each selected.
Among these air purifier components, in particular, the ones in which the mixing ratio of sulfanilic acid and sodium hydroxide were changed were mixed, and further, an organic binder was added, diluted with water, and well kneaded, followed by extrusion molding. After drying, a honeycomb-shaped monolith was obtained.
[0023]
Then, the obtained honeycomb-shaped monolith was observed, and those in which the honeycomb collapsed after extrusion drying were evaluated as ×, those in which some cracks were generated but the shape was maintained as ○, and those in which the shape was good without cracks were evaluated as ◎. And moldability were evaluated.
Table 1 shows the air purifier compounding conditions and the moldability evaluation results of the honeycomb monolith. In addition, the compounding amount is represented by weight part. Further, the molar ratio of sulfanilic acid to sodium hydroxide and the PH of a molded body suspension obtained by crushing each honeycomb-shaped monolith after molding and suspending the crushed molded body at a ratio of 1 g in 100 cc of water. The measurement results are also shown.
[0024]
No. 1 in Table 1. Comparative Examples 1 and 2 containing no sodium hydroxide could not be molded into a molded body.
[0025]
No. Although 3, 7, 10, and 14 are examples of the present invention, the amount of sodium hydroxide to sulfanilic acid is small, so that the organic binder is slightly deteriorated, and the moldability is lower than that of other examples of the present invention. Somewhat inferior.
[0026]
On the other hand, No. In Examples of the present invention of 4 to 6, 8 to 9, 11 to 13, and 15 to 16, the amount of sodium hydroxide to sulfanilic acid is appropriate (the PH of the molded product suspension is 3 or more). It is neutralized with sodium hydroxide to such an extent that the binder does not deteriorate, and the moldability is particularly good. Further, as described later, the amount of sulfanilic acid necessary for deodorization is ensured, and the deodorizing performance is also sufficiently ensured.
[0027]
[Table 1]
[0028]
Next, in Table 1 above, No. 4-6, 8-9, 11-13, and 15-16 The deodorizing filters formed on the honeycomb-shaped monoliths of the present invention were measured for the deodorizing rate for two components of acetaldehyde and ammonia. In addition, No. of a comparative example. As described above, Nos. 1 and 2 could not be molded into a honeycomb-shaped monolithic deodorizing filter, so that the deodorizing rate could not be measured. In addition, No. 1 of the present invention example. Samples Nos. 3, 7, 10, and 14 had some cracks in the molded product and could not be used as a deodorizing filter, but were excluded from the measurement of the deodorizing rate.
[0029]
The flow test for measuring the deodorization rate is performed by flowing air mixed with the above-mentioned malodorous component gas at a predetermined concentration into the deodorizing filter at a flow rate of 0.2 m / s, and measuring the malodorous gas concentrations at the inlet and the outlet, respectively. The deodorization rate was calculated using the following equation.
Deodorization rate (%) = [(Ci-Co) / Ci] × 100 (where Ci: concentration of odorous component gas inlet, Co: concentration of odorous component gas outlet),
The concentration of the two malodorous component gases was 15 ppm for both acetaldehyde and ammonia.
[0030]
The relationship between the deodorizing performance (removal rate) of each filter against malodorous component gases and the amount of sodium hydroxide to sulfanilic acid (molar ratio of sodium hydroxide / sulfanilic acid) is shown in FIGS. The numbers written on the horizontal axis in the figure correspond to the sample numbers in Table 1, respectively.
In addition, Table 1 also shows that the removal rate of acetaldehyde was 35% or more and that the removal rate of ammonia was 55% or more was ○.
[0031]
As shown in FIGS. 1 to 4, as the amount of sodium hydroxide with respect to sulfanilic acid increases, the deodorizing performance with respect to acetaldehyde and ammonia tends to decrease.
In contrast, the smaller the amount of sodium hydroxide with respect to sulfanilic acid, the better the deodorizing performance with respect to acetaldehyde and ammonia.
In the present invention, emphasis is placed on the moldability of a honeycomb-shaped monolithic deodorizing filter, but practical deodorizing as a deodorizing filter having an acetaldehyde removal rate of 35% or more and an ammonia removal rate of 55% or more. In order to ensure the performance, the amount of sodium hydroxide to sulfanilic acid, that is, the molar ratio of sodium hydroxide / sulfanilic acid is preferably 0.9 or less, more preferably 0.7 or less.
[0032]
In addition, even with the same amount of sulfanilic acid, the case containing zinc chloride was better (compare 20 parts by weight of sulfanilic acid in FIG. 1 with 20 parts by weight of sulfanilic acid + 0.75 parts by weight of zinc chloride in FIG. 2; (Comparison of 30 parts by weight of sulfanilic acid with that of 30 parts by weight of sulfanilic acid + 1.1 parts by weight of zinc chloride in FIG. 4) The deodorizing performance for acetaldehyde and ammonia is excellent.
[0033]
【The invention's effect】
As described above, according to the deodorizing filter of the present invention, in addition to a porous body such as activated carbon, the air purifying agent containing an aromatic amine having an amino group and a sulfone group has the required strength without deteriorating the deodorizing performance. Thus, it is possible to obtain a deodorizing filter molded in the following manner.
Therefore, it is possible to obtain a deodorizing filter having a desired shape according to the application, and the industrial value is great in that the deodorizing filter has opened the way to practical use in various applications.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram showing the relationship between the composition of an air purifier and the deodorization rate with respect to acetaldehyde and ammonia of a honeycomb-shaped deodorizing filter (Nos. 4 to 6 in Table 1) according to the present invention.
FIG. 2 is an explanatory diagram showing the relationship between the composition of an air purifying agent and the deodorization rate with respect to acetaldehyde and ammonia in the honeycomb-shaped deodorizing filters (Nos. 8 to 9 in Table 1) according to the present invention.
FIG. 3 is an explanatory diagram showing the relationship between the air purifying agent composition and the deodorization rate for acetaldehyde and ammonia of the honeycomb-shaped deodorizing filters (Nos. 11 to 13 in Table 1) according to the present invention.
FIG. 4 is an explanatory diagram showing the relationship between the air purifying agent composition and the deodorization rate for acetaldehyde and ammonia of the honeycomb-shaped deodorizing filter (No. 15 to 16 in Table 1) according to the present invention.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25912196A JP3545888B2 (en) | 1996-09-30 | 1996-09-30 | Deodorizing filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25912196A JP3545888B2 (en) | 1996-09-30 | 1996-09-30 | Deodorizing filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1099418A JPH1099418A (en) | 1998-04-21 |
| JP3545888B2 true JP3545888B2 (en) | 2004-07-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25912196A Expired - Lifetime JP3545888B2 (en) | 1996-09-30 | 1996-09-30 | Deodorizing filter |
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| JP (1) | JP3545888B2 (en) |
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| JP4617622B2 (en) * | 2001-08-20 | 2011-01-26 | 東洋紡績株式会社 | Production method of adsorbent |
| JP4378449B2 (en) * | 2002-02-20 | 2009-12-09 | 東洋紡績株式会社 | Adsorbent and production method thereof |
| JP2003299951A (en) * | 2002-04-10 | 2003-10-21 | Toyobo Co Ltd | Adsorbent and manufacturing method therefor |
| JP4952570B2 (en) * | 2007-12-26 | 2012-06-13 | 東洋紡績株式会社 | Adsorbent for aldehyde removal |
| KR102518897B1 (en) * | 2022-10-20 | 2023-04-07 | 파워카본테크놀로지(주) | Activated carbon molded article for air cleaning and method for manufacturing the same |
| CN116531931A (en) * | 2023-03-31 | 2023-08-04 | 中山市洁鼎过滤制品有限公司 | Formaldehyde purifying agent and preparation method thereof |
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1996
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