JPH0510975B2 - - Google Patents
Info
- Publication number
- JPH0510975B2 JPH0510975B2 JP61013936A JP1393686A JPH0510975B2 JP H0510975 B2 JPH0510975 B2 JP H0510975B2 JP 61013936 A JP61013936 A JP 61013936A JP 1393686 A JP1393686 A JP 1393686A JP H0510975 B2 JPH0510975 B2 JP H0510975B2
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- activated carbon
- titanium
- tio
- component
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 69
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011218 binary composite Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000011206 ternary composite Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 34
- 229910010413 TiO 2 Inorganic materials 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
＜産業上の利用分野＞
本発明はオゾン分解剤に関する。
＜従来技術とその問題点＞
オゾンは強い酸化能を有し、分解すると無害な
酸素になるために脱臭、殺菌、漂白または排水中
のCOD減少等の目的でさまざまな分野において、
幅広く利用されている。しかし、処理に利用され
たオゾンは一部未反応のまま大気中に放出される
ために、光化学スモツグ等の二次公害を発生させ
る恐れがある。また、航空機が成層圏を飛行する
場合機内にオゾンを含む空気が導入されるために
乗客や搭乗員に悪影響を及ぼす危険性がある。
さらに、最近、各種の高電圧発生装置を組み込
んだ機器、例えば乾式の複写機等からのオゾンの
発生が問題となつており、これ等の機器は主に室
内に置かれるためにオゾンの発生量は微量であつ
ても室内が汚染される。
オゾンの臭いは1ppm以下の濃度で感知でき、
2ppm以上の濃度では呼吸器系に刺激を引き起こ
し、人体に有害となるために、各種の発生源から
排出されるオゾンを除去し、無害化する必要があ
る。かかるオゾンを分解除去する処理技術として
活性炭法、薬液洗浄法、熱分解法、触媒分解法が
既に知られている。
活性炭法は活性炭層でオゾンを除去する方法で
あつて、その際次の反応によつて炭酸ガスに変化
するといわれている。
2C＋2O3→2CO2＋O2
この反応は低温でも進行するため、また活性炭
は安価であるために、現在、活性炭法が広く用い
られている。しかし、活性炭法の欠点は、活性炭
を所望の形状に成形することが困難であり、かつ
オゾンとの反応により粉化し易いため工業的な利
用に支障があること、および活性炭とオゾンの反
応が強烈で発火、爆発の危険性があり取扱い上問
題があることである。
薬液洗浄法は還元性物質の水溶液で廃オゾンを
洗浄するために処理コストが高く、廃水処理の問
題が生じる。
熱分解法は分解効率を上げるためには300℃以
上の加熱が必要であり、多量の排ガスを処理する
ためには加熱費用がかかり、処理コストが高くな
るなどの欠点がある。
触媒分解法は、触媒としてニツケル、マンガ
ン、コバルト等の重金属酸化物および白金、パラ
ジウム等の貴金属を用いて、オゾンを接触的に分
解除去する方法である。
触媒分解法は前記３つの方法と比較して発火、
爆発の危険性がなく、廃水処理も不要であり、加
熱費用も不要である点からすれば、有利な方法で
ある。
しかしながら、活性炭法に比較して触媒分解法
の欠点は重金属酸化物触媒の場合、低い温度領域
でオゾン分解除去効率が低いことであり、貴金属
触媒の場合、貴金属が高価なことである。
＜発明の目的＞
本発明の目的はオゾンを分解除去するにあた
り、低温活性の優れた安価でかつ実用的なオゾン
分解剤を提供することにある。
＜問題点を解決するための手段＞
本発明者らは、上記目的に沿つて鋭意研究した
結果、本発明を完成するに至つたのである。
本発明はチタンおよびケイ素からなる二元系複
合酸化物、チタンおよびジルコニウムからなる二
元系複合酸化物および／またはチタン、ケイ素お
よびジルコニウムからなる三元系複合酸化物をＡ
成分として、活性炭をＢ成分としてなるオゾン分
解剤であつて、該オゾン分解剤の組成がＡ成分は
95〜10重量％、Ｂ成分は５〜90重量％の範囲より
なることを特徴とするオゾン分解剤である。
＜作用および効果＞
本発明にかかるオゾン分解剤の特徴はチタンお
よびケイ素からなる二元系複合酸化物（以下、
TiO2−SiO2とする）、チタンおよびジルコニウム
からなる二元系複合酸化物（以下、TiO2−ZrO2
とする）、チタン、ケイ素およびジルコニウムか
らなる三元系複合酸化物（以下、TiO2−SiO2−
ZrO2とする）をＡ成分とし、活性炭をＢ成分と
して用いる点にある。
一般に、チタンおよびケイ素からなる二元系複
合酸化物は例えば田部浩三（触媒、第17巻、No.
372頁（1975年）によつても周知のように、固体
酸として知られ、構成するおのおの単独の酸化物
には見られない顕著な酸性を示し、また高表面積
を有する。
すなわち、TiO2−SiO2は酸化チタンおよび酸
化ケイ素を単に混合したものではなく、チタンお
よびケイ素がいわゆる二元系複合酸化物を形成す
ることによりその特異な物性が発現するものと認
めることのできるものである。また、チタン、ジ
ルコニウムからなる二元系複合酸化物およびチタ
ン、ジルコニウムおよびケイ素からなる三元系複
合酸化物もTiO2−SiO2と同じような性質を有す
る複合酸化物として特定される。
さらに、上記複合酸化物はＸ線回折による分析
の結果、非晶質もしくはほぼ非晶質に近い微細構
造を有している。
これらチタンを含む複合酸化物が優れたオゾン
分解活性を有することは本発明者らがすでに出願
した特願昭60−237518号（特開昭62−97643号）
において詳細に説明しているとおりである。
次に、本発明にかかるオゾン分解剤のＢ成分と
して用いる活性炭は周知のとおり優れたオゾン分
解活性を有する。
しかし、前述したように活性炭には種々の欠点
も有している。本発明はそれらの欠点を解決し
た。すなわち、本発明にかかるオゾン分解剤がチ
タンを含む複合酸化物と活性炭からなることによ
る第１の利点は、低い温度領域でオゾン分解活性
が高いことである。
第２の利点は、所望の形状に成形することが容
易な点である。粉粒状活性炭を成形するには困難
であり、そのため種々のバイダーが検討されてい
る。しかしながら、本発明にかかる分解剤に用い
るチタンを含む複合酸化物は成形性に優れている
ために容易に所望の形状に成形することができ
る。
第３の利点は、活性炭消耗による粉化もなく、
発火等の危険性も少なく実用上優れた性能を有す
る点である。
特にオゾン濃度が高い場合、活性炭とオゾンと
の反応は発熱反応であるため反応の進行とともに
爆発の危険性があるが、本発明の脱臭剤ではチタ
ンを含む複合酸化物上に活性炭が分散しているの
で急激な温度上昇を防ぐことができ、発火、爆発
等の危険性を排除することができる。また、オゾ
ン分解と共に活性炭は消費されるが、チタンを含
む複合酸化物が形状を維持するため、粉化等によ
る圧力損失の上昇等を防止することができ、実用
上有利である。
第４の利点は、安価なことである。前述したオ
ゾン分解触媒に比べ、安価であるため、工業的な
利用に有効である。
本発明にかかるオゾン分解剤は種々の利点を有
し工業的に優れたオゾン分解剤であると言える。
本発明を構成してなるＡ成分であるTiO2−
SiO2、TiO2−ZrO2およびTiO2−SiO2−ZrO2は
いずれもその表面積が30m2／ｇ以上であることが
好ましい。
Ａ成分の組成は酸化物に換算してTiO2が20〜
95モル％、SiO2もしくはZrO2またはSiO2とZrO2
の和が５〜80モル％（いずれもTiO2＋ZrO2＋
SiO2＝100モル％に対して）の範囲にあることが
好ましい結果を与える。
本発明を構成してなるＢ成分である活性炭は特
に限定しない。通常オゾン分解剤として用いられ
ている活性炭が使用できる。
本発明にかかるオゾン分解剤の組成は、Ａ成分
が95〜10重量％、Ｂ成分は５〜90重量％の範囲よ
りなることが好ましい。特に好ましくはＡ成分が
90〜40重量％、Ｂ成分は10〜60重量％の範囲であ
る。
Ｂ成分が上記範囲未満の場合、オゾン分解活性
が不十分であり、上記範囲を越えて多く含まれる
場合は活性炭の有する欠点、すなわち、活性炭消
耗による粉化、爆発等の危険性は高まる。
本発明にかかるオゾン分解剤の調整方法は、以
上の如き原料の混練組成物を用いて、これを所望
の形状に成形し、成形物を乾燥し、更に必要なら
ば焼成するものであつて、成形手段としては、加
圧成形、押出成形を初め種々の公知手段が採用可
能であり、用途に適した種々の形状に成形され
る。
原料の混練組成物を得る際、適当な水を添加す
ることが必要である。更に必要ならば通常の種々
の成形助剤を添加するこができる。成形物の乾燥
は50〜200℃で行ない、更に必要ならば焼成する。
焼成は成形物中に可燃性の活性炭を含んでいるの
で非酸化性雰囲気中で行うことが好ましいが、可
燃性物質の少ない場合、酸化性雰囲気中でも行な
える。その焼成温度は200〜600℃で１〜10時間焼
成してオゾン分解剤を得ることができる。
また、本発明を構成してなるＡ成分、Ｂ成分以
外に担体としてアルミナ、シリカ、シリカ−アル
ミナ、ベントナイト、ケイソウ土、シリコンカー
バイド、チタニア、ジルコニア、マグネシア、コ
ーデイライト、ムライト、無機繊維などを用いる
ことができ、例えば格子状のコーデイライトにチ
タンを含む複合酸化物と粉粒状活性炭をスラリー
状としそれを含浸法により担持させる方法で調製
することができる。またオゾン分解に活性を有す
る公知の触媒をＡ成分、Ｂ成分以外に混合使用す
ることができる。もちろん、調整法はこれらの方
法に限定されるものではない。
形状としては上記のペレツト状およびハニカム
状にとどまらず円柱状、円筒状、板状、リボン
状、波板状、パイプ状、ドーナツ状、格子状、そ
の他一体化成型されたものが適宜選ばれる。
本発明の触媒によつて処理されるオゾン濃度は
ガス中に0.01〜10000ppm程度に含有するもので
あるが、必ずしもこの範囲と限定されるものでは
ない。
本発明のオゾン分解剤の使用方法はオゾンを含
有するガス、水溶液共に使用でき、一般にオゾン
分解剤を充填した層に処理すべき、ガス、液を流
過する方法が採られる。
また、本発明のオゾン分解剤の充填層と公知の
オゾン分解剤の充填層とを多段層として用いる方
法も良好な結果をもたらす。例えば、高濃度のオ
ゾンを含む排ガスよりオゾンを除去する場合、活
性炭層のみでは発火、爆発の危険性があるし、粉
化が激しく、実用に供し難いが、前段に本発明に
なるオゾン分解剤を充填しておくことによりオゾ
ン濃度を低下させ、後者の活性炭層で更にオゾン
を除去する方法など好ましい方法となる。
以下に実施例および比較例を用いて本発明をさ
らに詳細に説明するが、本発明はこれらの実施例
のみに限定されるものではない。
実施例 １
チタン及びケイ素からなる複合酸化物を以下に
述べる方法で調整した。チタン源として以下の組
成を有する硫酸チタニルの硫酸水溶液を用いた。
TiOSO4（TiO2換算） 250ｇ／
全H2SO4 1100ｇ／
別に水40にアンモニア水（NH3、25％）28
を添加し、これにスノーテツクス−NCS−30
（日産化学製シリカゾル、SiO2として約30重量％
含有）2.4Kgを加えた。得られた溶液中に、上記
硫酸チタニルの硫酸水溶液15.3を水30に添加
して稀釈したチタン含硫酸水溶液を撹拌下徐々に
滴下し、共沈ゲルを生成した。さらにそのまま15
時間放置して静置した。かくして得られたTiO2
−SiO2ゲルを過、水洗後200℃で10時間乾燥し
た。
次いで550℃で６時間空気雰囲気下で焼成した。
得られた粉体の組成はTiO2：SiO2＝４：１（モル
比）で、BET表面積は185m2／ｇであつた。ここ
で得られた粉体を以降TS−１と呼びこの粉体を
用いて以下に述べる方法でオゾン分解剤を調整し
た。
上記TS−１粉体750ｇと市販活性炭を250ｇと
を混合した後、適当量の水を添加しニーダーでよ
く混合し、混練機により充分混練し、均一な混合
物を押出し成形機で直径5.0mm、長さ6.0mmのペレ
ツトに成形し、150℃で２時間乾燥して、TiO2−
SiO2−Ｃからなるオゾン分解剤を得た。
実施例 ２
TiO2−ZrO2を以下に述べる方法で調製した。
水100にオキシ塩化ジルコニウム〔ZrOCl2・
8H2O〕1.93Kgを溶解させ、実施例１で用いたの
と同じ組成の硫酸チタニルの硫酸水溶液7.8を
添加しつつよく混合する。これを温度約30℃に維
持しつつよく撹拌しながらアンモニア水を徐々に
滴下し、PHが７になるまで加え、さらにそのまま
放置して15時間静置した。
かくして得られたTiO2−ZrO2ゲルを過し水
洗後200℃で10時間乾燥した。次いで空気雰囲気
下で550℃で６時間焼成した。得られた粉体の組
成はTiO2：ZrO2＝４：１（モル比）であり、
BET表面積は140m2／ｇであつた。ここで得られ
た粉体を以降TZ−１と呼ぶ。
TZ−１を用いて実施例１の記載の方法に準じ
てTiO2−ZrO2−Ｃからなるオゾン分解層を調製
した。
実施例 ３
実施例１及び２の方法に準じてTiO2−SiO2−
ZrO2を調製した。得られた粉体の組成はTiO2：
SiO2：ZrO2＝80：16：４（モル比）でBET表面
積は180m2／ｇであつた。ここで得られた粉体を
以降TSZ−１と呼ぶ。
TSZ−１を用いて、実施例１の記載の方法に
準じてTiO2−SiO2−ZrO2−Ｃからなるオゾン分
解剤を調製した。
実施例 ４〜６
TiO2−SiO2と活性炭の重量比を変える以外は
実施例１に準じてTiO2−SiO2−Ｃからなるオゾ
ン分解剤を調製した。得られたオゾン分解剤の組
成を表−１に示す。
比較例 １
実施例１の方法において粉粒状活性炭を使用せ
ずTS−１粉体を実施例１に準じてTiO2−SiO2の
みからなるオゾン分解剤を調製した。
比較例 ２
実施例１の方法においてTS−１粉体を使用せ
ず粉粒状活性炭を実施例１に準じて活性炭のみか
らなるオゾン分解剤を調製した。
実施例 ７
実施例１〜６及び比較例１〜２で得られた各オ
ゾン分解剤につき次のような方法でオゾン分解活
性を求めた。
内径38mmのパイレツクス製反応管に直径5.0mm、
長さ6.0mmのペレツト200c.c.を充填し、オゾンを
2000ppm、水蒸気を２％含有する空気を0.40N
m3／Hrの流速（空間速度2000Hr-1）で充填層に
導入し、反応温度20℃における充填層出口のオゾ
ン濃度を測定した。
100時間通ガス後の結果を表−２に示す。
<Industrial Application Field> The present invention relates to an ozone decomposer. <Prior art and its problems> Ozone has strong oxidizing ability and becomes harmless oxygen when decomposed, so it is used in various fields for purposes such as deodorization, sterilization, bleaching, and reducing COD in wastewater.
Widely used. However, some of the ozone used in the treatment is released into the atmosphere unreacted, which poses the risk of causing secondary pollution such as photochemical smog. Furthermore, when an aircraft flies in the stratosphere, air containing ozone is introduced into the cabin, which poses a risk of adversely affecting passengers and crew. Furthermore, recently, ozone generation from devices that incorporate various high-voltage generators, such as dry-type copying machines, has become a problem, and since these devices are mainly placed indoors, the amount of ozone generated is low. Even a small amount of this can contaminate the room. Ozone odor can be detected at concentrations below 1 ppm.
Concentrations of 2 ppm or higher cause irritation to the respiratory system and are harmful to the human body, so it is necessary to remove ozone emitted from various sources and render it harmless. Activated carbon methods, chemical cleaning methods, thermal decomposition methods, and catalytic decomposition methods are already known as treatment techniques for decomposing and removing such ozone. The activated carbon method is a method for removing ozone using an activated carbon layer, and it is said that the ozone is converted into carbon dioxide gas through the following reaction. 2C + 2O 3 → 2CO 2 + O 2The activated carbon method is currently widely used because this reaction proceeds even at low temperatures and activated carbon is inexpensive. However, the disadvantages of the activated carbon method are that it is difficult to mold activated carbon into a desired shape, and that it is easily powdered by reaction with ozone, which hinders industrial use, and that the reaction between activated carbon and ozone is intense. There is a risk of ignition and explosion, and there are problems in handling. In the chemical cleaning method, waste ozone is cleaned with an aqueous solution of a reducing substance, so the treatment cost is high and problems arise in wastewater treatment. The thermal decomposition method requires heating to 300°C or higher in order to increase decomposition efficiency, and has drawbacks such as heating costs required to process a large amount of exhaust gas, which increases processing costs. The catalytic decomposition method is a method of catalytically decomposing and removing ozone using heavy metal oxides such as nickel, manganese, and cobalt and noble metals such as platinum and palladium as catalysts. Compared to the above three methods, the catalytic decomposition method is less prone to ignition and
This is an advantageous method since there is no danger of explosion, no waste water treatment is required, and no heating costs are required. However, the drawbacks of the catalytic decomposition method compared to the activated carbon method are that the ozone decomposition removal efficiency is low in the low temperature range in the case of heavy metal oxide catalysts, and that the precious metals are expensive in the case of noble metal catalysts. <Object of the Invention> An object of the present invention is to provide an inexpensive and practical ozonolytic agent with excellent low-temperature activity for decomposing and removing ozone. <Means for Solving the Problems> As a result of intensive research in line with the above objectives, the present inventors have completed the present invention. The present invention provides A binary composite oxide consisting of titanium and silicon, a binary composite oxide consisting of titanium and zirconium, and/or a ternary composite oxide consisting of titanium, silicon, and zirconium.
An ozone decomposing agent comprising activated carbon as component B, and the composition of the ozone decomposing agent is component A.
It is an ozone decomposer characterized by comprising 95 to 10% by weight of the ozone decomposition agent and 5 to 90% by weight of component B. <Functions and Effects> The ozonolytic agent according to the present invention is characterized by a binary composite oxide (hereinafter referred to as
TiO 2 −SiO 2 ), a binary composite oxide consisting of titanium and zirconium (hereinafter referred to as TiO 2 −ZrO 2
TiO 2 −SiO 2 −
ZrO 2 ) is used as the A component and activated carbon is used as the B component. In general, binary composite oxides consisting of titanium and silicon are described, for example, by Kozo Tabe (Catalysts, Vol. 17, No.
As is well known from P. 372 (1975), it is known as a solid acid, exhibits remarkable acidity not seen in the constituent oxides alone, and has a high surface area. In other words, it can be recognized that TiO 2 -SiO 2 is not simply a mixture of titanium oxide and silicon oxide, but that its unique physical properties are expressed when titanium and silicon form a so-called binary composite oxide. It is something. Furthermore, a binary composite oxide consisting of titanium and zirconium and a ternary composite oxide consisting of titanium, zirconium and silicon are also specified as composite oxides having properties similar to TiO 2 -SiO 2 . Further, as a result of X-ray diffraction analysis, the above composite oxide has an amorphous or nearly amorphous microstructure. The fact that these composite oxides containing titanium have excellent ozonolytic activity is disclosed in Japanese Patent Application No. 60-237518 (Japanese Unexamined Patent Publication No. 62-97643) filed by the present inventors.
As explained in detail in . Next, as is well known, the activated carbon used as component B of the ozonolytic agent according to the present invention has excellent ozonolytic activity. However, as mentioned above, activated carbon also has various drawbacks. The present invention has solved those drawbacks. That is, the first advantage of the ozonolytic agent according to the present invention comprising a titanium-containing composite oxide and activated carbon is that the ozonolytic activity is high in a low temperature range. The second advantage is that it is easy to mold into a desired shape. It is difficult to mold powdered activated carbon, and therefore various binders are being considered. However, the titanium-containing composite oxide used in the decomposing agent according to the present invention has excellent moldability and can be easily molded into a desired shape. The third advantage is that there is no powdering due to activated carbon consumption.
It has excellent practical performance with little risk of ignition. Especially when the ozone concentration is high, the reaction between activated carbon and ozone is exothermic and there is a risk of explosion as the reaction progresses. However, in the deodorizer of the present invention, activated carbon is dispersed on a composite oxide containing titanium. This prevents a sudden rise in temperature and eliminates the risk of fire, explosion, etc. Further, although the activated carbon is consumed with ozone decomposition, since the composite oxide containing titanium maintains its shape, it is possible to prevent an increase in pressure loss due to powdering, etc., which is advantageous in practice. The fourth advantage is that it is inexpensive. Since it is cheaper than the ozone decomposition catalyst described above, it is effective for industrial use. The ozone decomposer according to the present invention has various advantages and can be said to be an industrially excellent ozone decomposer. TiO 2 − which is the A component constituting the present invention
It is preferable that SiO 2 , TiO 2 -ZrO 2 and TiO 2 -SiO 2 -ZrO 2 all have a surface area of 30 m 2 /g or more. The composition of component A is TiO 2 from 20 to 20 in terms of oxide.
95 mol%, SiO2 or ZrO2 or SiO2 and ZrO2
The sum of 5 to 80 mol% (both TiO 2 + ZrO 2 +
(based on SiO 2 =100 mol %) gives preferable results. Activated carbon, which is component B constituting the present invention, is not particularly limited. Activated carbon, which is commonly used as an ozone decomposer, can be used. The composition of the ozonolytic agent according to the present invention is preferably such that component A is in a range of 95 to 10% by weight and component B is in a range of 5 to 90% by weight. Particularly preferably, component A is
90 to 40% by weight, and component B ranges from 10 to 60% by weight. If component B is less than the above range, the ozonolytic activity will be insufficient, and if the content exceeds the above range, the disadvantages of activated carbon, ie, the risk of pulverization and explosion due to activated carbon consumption, will increase. The method for preparing an ozonolytic agent according to the present invention uses a kneaded composition of raw materials as described above, molds it into a desired shape, dries the molded product, and further bakes it if necessary, As the molding means, various known methods including pressure molding and extrusion molding can be employed, and the material is molded into various shapes suitable for the purpose. When obtaining a kneaded composition of raw materials, it is necessary to add an appropriate amount of water. Furthermore, if necessary, various conventional molding aids can be added. The molded product is dried at 50 to 200°C, and is further fired if necessary.
Since the molded article contains flammable activated carbon, firing is preferably carried out in a non-oxidizing atmosphere, but it can also be carried out in an oxidizing atmosphere if there is little combustible material. The ozone decomposer can be obtained by firing at a temperature of 200 to 600°C for 1 to 10 hours. In addition to components A and B that constitute the present invention, alumina, silica, silica-alumina, bentonite, diatomaceous earth, silicon carbide, titania, zirconia, magnesia, cordierite, mullite, inorganic fibers, etc. are used as carriers. For example, it can be prepared by making a slurry of a titanium-containing composite oxide and powdery activated carbon onto a lattice of cordierite, and supporting the slurry by impregnation. In addition, a known catalyst having activity in ozone decomposition may be mixed and used in addition to the A component and the B component. Of course, the adjustment method is not limited to these methods. The shape is not limited to the above-mentioned pellet shape and honeycomb shape, but may be suitably selected from columnar, cylindrical, plate, ribbon, corrugated, pipe, donut, lattice, and other integrally molded shapes. The ozone concentration treated by the catalyst of the present invention is contained in the gas in a range of about 0.01 to 10,000 ppm, but it is not necessarily limited to this range. The ozone decomposer of the present invention can be used with both ozone-containing gas and aqueous solutions, and generally a method is adopted in which the gas or liquid to be treated passes through a bed filled with the ozone decomposer. Further, a method in which a packed layer of the ozonolytic agent of the present invention and a packed layer of a known ozonolytic agent are used as a multistage layer also brings about good results. For example, when removing ozone from exhaust gas containing a high concentration of ozone, there is a risk of ignition and explosion if only the activated carbon layer is used, and it is difficult to put into practical use because it becomes powdery. A preferable method is to reduce the ozone concentration by filling the activated carbon layer with carbon and further remove ozone using the latter activated carbon layer. The present invention will be explained in more detail below using Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 A composite oxide consisting of titanium and silicon was prepared by the method described below. A sulfuric acid aqueous solution of titanyl sulfate having the following composition was used as a titanium source. TiOSO 4 (TiO 2 conversion) 250g / Total H 2 SO 4 1100g / Separately, water 40 and ammonia water (NH 3 , 25%) 28
Add Snowtex-NCS-30 to this
(Silica sol manufactured by Nissan Chemical, approximately 30% by weight as SiO 2
(Contains) 2.4Kg was added. A titanium-containing aqueous sulfuric acid solution diluted by adding 15.3 parts of the titanyl sulfate aqueous sulfuric acid solution to 30 parts of water was gradually dropped into the obtained solution while stirring to produce a coprecipitated gel. 15 more as is
It was left to stand still for some time. The TiO 2 thus obtained
-The SiO 2 gel was filtered, washed with water, and then dried at 200°C for 10 hours. Then, it was fired at 550°C for 6 hours in an air atmosphere.
The composition of the obtained powder was TiO 2 :SiO 2 =4:1 (mole ratio), and the BET surface area was 185 m 2 /g. The powder thus obtained was hereinafter referred to as TS-1 and was used to prepare an ozone decomposer using the method described below. After mixing 750 g of the above TS-1 powder and 250 g of commercially available activated carbon, add an appropriate amount of water, mix well with a kneader, thoroughly knead with a kneader, and extrude the homogeneous mixture with a diameter of 5.0 mm. Formed into pellets with a length of 6.0 mm and dried at 150°C for 2 hours to form TiO 2 −
An ozonolytic agent consisting of SiO 2 -C was obtained. Example 2 TiO2 - ZrO2 was prepared by the method described below. Zirconium oxychloride [ZrOCl 2・
8H 2 O] was dissolved, and 7.8 kg of a sulfuric acid aqueous solution of titanyl sulfate having the same composition as used in Example 1 was added and mixed well. While maintaining the temperature at about 30°C and stirring well, ammonia water was gradually added dropwise to the mixture until the pH reached 7, and the mixture was left to stand still for 15 hours. The thus obtained TiO 2 -ZrO 2 gel was filtered, washed with water, and then dried at 200°C for 10 hours. Then, it was fired at 550° C. for 6 hours in an air atmosphere. The composition of the obtained powder was TiO 2 :ZrO 2 =4:1 (molar ratio),
The BET surface area was 140 m 2 /g. The powder obtained here is hereinafter referred to as TZ-1. An ozonolysis layer consisting of TiO2 - ZrO2 -C was prepared using TZ-1 according to the method described in Example 1. Example 3 TiO 2 −SiO 2 − according to the method of Examples 1 and 2
ZrO2 was prepared. The composition of the obtained powder is TiO2 :
The BET surface area was 180 m 2 /g with SiO 2 :ZrO 2 =80:16:4 (molar ratio). The powder obtained here is hereinafter referred to as TSZ-1. Using TSZ-1, an ozonolytic agent consisting of TiO2 - SiO2 -ZrO2 - C was prepared according to the method described in Example 1. Examples 4 to 6 Ozone decomposers made of TiO 2 -SiO 2 -C were prepared according to Example 1 except that the weight ratio of TiO 2 -SiO 2 and activated carbon was changed. The composition of the obtained ozone decomposer is shown in Table 1. Comparative Example 1 An ozonolytic agent consisting only of TiO 2 -SiO 2 was prepared according to the method of Example 1 using TS-1 powder without using granular activated carbon. Comparative Example 2 An ozonolytic agent consisting only of activated carbon was prepared in the same manner as in Example 1, except that the TS-1 powder was not used and granular activated carbon was used. Example 7 The ozonolytic activity of each of the ozonolytic agents obtained in Examples 1 to 6 and Comparative Examples 1 and 2 was determined by the following method. A Pyrex reaction tube with an inner diameter of 38 mm and a diameter of 5.0 mm.
Fill with 200c.c. of pellets with a length of 6.0mm and add ozone.
2000ppm, air containing 2% water vapor at 0.40N
It was introduced into the packed bed at a flow rate of m 3 /Hr (space velocity 2000 Hr -1 ), and the ozone concentration at the outlet of the packed bed at a reaction temperature of 20°C was measured. Table 2 shows the results after passing gas for 100 hours.
【表】【table】
【表】【table】
Claims (1)
物、チタンおよびジルコニウムからなる二元系複
合酸化物および／またはチタン、ケイ素およびジ
ルコニウムからなる三元系複合酸化物をＡ成分と
し、活性炭をＢ成分としてなるオゾン分解剤であ
つて、該オゾン分解剤の組成はＡ成分が95〜10重
量％、Ｂ成分が５〜90重量％の範囲よりなること
を特徴とするオゾン分解剤。1 A binary composite oxide consisting of titanium and silicon, a binary composite oxide consisting of titanium and zirconium, and/or a ternary composite oxide consisting of titanium, silicon, and zirconium as the A component, and activated carbon as the B component. 1. An ozone decomposing agent characterized in that the composition of the ozone decomposing agent is 95 to 10% by weight of component A and 5 to 90% by weight of component B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61013936A JPS62176541A (en) | 1986-01-27 | 1986-01-27 | Ozone decomposing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61013936A JPS62176541A (en) | 1986-01-27 | 1986-01-27 | Ozone decomposing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62176541A JPS62176541A (en) | 1987-08-03 |
| JPH0510975B2 true JPH0510975B2 (en) | 1993-02-12 |
Family
ID=11847079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61013936A Granted JPS62176541A (en) | 1986-01-27 | 1986-01-27 | Ozone decomposing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62176541A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01262944A (en) * | 1988-04-11 | 1989-10-19 | Nippon Shokubai Kagaku Kogyo Co Ltd | Deodorization catalyst |
-
1986
- 1986-01-27 JP JP61013936A patent/JPS62176541A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62176541A (en) | 1987-08-03 |
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