JP2625811B2 - Ozone decomposition catalyst - Google Patents
Ozone decomposition catalystInfo
- Publication number
- JP2625811B2 JP2625811B2 JP63021292A JP2129288A JP2625811B2 JP 2625811 B2 JP2625811 B2 JP 2625811B2 JP 63021292 A JP63021292 A JP 63021292A JP 2129288 A JP2129288 A JP 2129288A JP 2625811 B2 JP2625811 B2 JP 2625811B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- manganese oxide
- paper
- corotron
- supported
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims description 32
- 238000000354 decomposition reaction Methods 0.000 title claims description 20
- 239000003054 catalyst Substances 0.000 title claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 119
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 86
- 239000000835 fiber Substances 0.000 claims description 29
- 239000003063 flame retardant Substances 0.000 claims description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 4
- 239000000123 paper Substances 0.000 description 71
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 40
- 239000011572 manganese Substances 0.000 description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 24
- 229910052748 manganese Inorganic materials 0.000 description 24
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 229920000049 Carbon (fiber) Polymers 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- -1 cellulose fiber Chemical class 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 7
- 229920003043 Cellulose fiber Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002696 manganese Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 241000272814 Anser sp. Species 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005949 ozonolysis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 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
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- ONXPZLFXDMAPRO-UHFFFAOYSA-N decachlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl ONXPZLFXDMAPRO-UHFFFAOYSA-N 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- AIRPJJGSWHWBKS-UHFFFAOYSA-N hydroxymethylphosphanium;chloride Chemical compound [Cl-].OC[PH3+] AIRPJJGSWHWBKS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 208000013220 shortness of breath Diseases 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はオゾン分解触媒、詳しく言えば効率よくオゾ
ンを分解し、かつ長期間安定して使用することができる
オゾン分解触媒に関する。Description: FIELD OF THE INVENTION The present invention relates to an ozonolysis catalyst, and more particularly to an ozonolysis catalyst that can efficiently decompose ozone and can be used stably for a long period of time.
［従来の技術及びその問題点］ 一般に、オゾンはフッ素に次いで強力な酸化作用を有
するため、廃液中の有機物質の分解や殺菌、あるいは硫
化水素、メルカプタンやトリメチルアミン等の悪臭の物
質の分解あるいは脱硝用酸化剤として優れた効果を発揮
している。しかしオゾンは非常に臭いの強い気体であ
り、かつ空気中に0.1ppm存在すると息切れ、めまい、頭
痛、吐き気を催すなど、人体に対して有害な生理作用を
有している。[Conventional technology and its problems] In general, ozone has a strong oxidizing effect next to fluorine, so ozone decomposes or disinfects organic substances in waste liquid, or decomposes or denitrates odorous substances such as hydrogen sulfide, mercaptan and trimethylamine. It has an excellent effect as an oxidizing agent. However, ozone is an extremely odorous gas, and when present at 0.1 ppm in the air, it has harmful physiological effects on the human body, such as shortness of breath, dizziness, headache and nausea.
従って、廃水処理、脱臭、脱硝等の処理にオゾンを利
用する場合には未反応オゾンを分解して無害化すること
が必要である。Therefore, when using ozone for wastewater treatment, deodorization, denitration, etc., it is necessary to decompose unreacted ozone to make it harmless.
また、電子写真複写機や電機集塵式空気清浄機器類で
もコロナ放電の条件によりオゾンを発生するので、これ
らの機器類を備えた室内で作業する者は有害なオゾンを
吸入する危険があり、オゾンを無害化することは環境衛
生上重要である。In addition, electrophotographic copiers and electric dust-collecting air purifying devices also generate ozone due to corona discharge conditions, and therefore, workers working in rooms equipped with these devices may inhale harmful ozone, Detoxification of ozone is important for environmental health.
従来、オゾンの処理方法としては活性炭や金属酸化物
等の固体吸着剤による吸着や分解あるいは加熱や燃焼に
よる熱分解あるいはアルカリ溶液による薬液分解等が知
られている。Conventionally, as a method of treating ozone, adsorption or decomposition by a solid adsorbent such as activated carbon or metal oxide, thermal decomposition by heating or combustion, or decomposition of a chemical by an alkaline solution are known.
これらのうち固体吸着剤による吸着や分解に関して
は、例えば活性炭を利用する場合には、分解効率は非常
に高いが、オゾンとの間で燃焼反応が起るために損失が
あり、長期間の使用に際しては活性炭を補給する必要が
あり、微粉化による汚染対策も必要である。また活性炭
を再生するには高温の水蒸気が必要であり、再生は容易
でない。Among these, regarding adsorption and decomposition by the solid adsorbent, for example, when activated carbon is used, the decomposition efficiency is very high, but there is a loss due to the combustion reaction with ozone, and long-term use In that case, it is necessary to supply activated carbon, and it is necessary to take measures against contamination by pulverization. Regeneration of activated carbon requires high-temperature steam, and regeneration is not easy.
他方、金属酸化物を利用する場合には活性炭より経済
的であり、かつオゾン分解効率も同程度であるが、寿命
が短いという欠点がある。On the other hand, when a metal oxide is used, it is more economical than activated carbon and has the same ozone decomposition efficiency, but has the drawback of a short life.
さらに、パラジウム、白金あるいは銀を活性炭に担持
させたのも提案されているが、これらの金属は高価であ
り、しかもこれらの金属を担持させた活性炭はオゾンの
除去率、寿命等の点で必ずしも満足できるものはなかっ
た。Further, it has been proposed to support palladium, platinum or silver on activated carbon. However, these metals are expensive, and the activated carbon supporting these metals is not necessarily satisfactory in terms of ozone removal rate, service life, and the like. There was nothing.
従って、この本発明の目的は、前記した従来技術の欠
点を解消し、オゾンの分解効率が高く、長寿命でコスト
の低いオゾン分解触媒を提供することにある。Accordingly, an object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide an ozone decomposing catalyst having high ozone decomposition efficiency, a long life and low cost.
［問題点を解決するための手段］ 本発明者は酸化マンガンを担持せしめた活性炭素がオ
ゾンの分解効率の高い優れた触媒であることを見出し、
更に難燃化剤を担持させることにより活性炭素の燃焼性
を抑えることに成功し、本発明を完成した。[Means for Solving the Problems] The present inventor has found that activated carbon loaded with manganese oxide is an excellent catalyst having high ozone decomposition efficiency,
Further, by supporting a flame retardant, the combustibility of activated carbon was successfully suppressed, and the present invention was completed.
すなわち、本発明は活性炭素に酸化マンガン及び難燃
化剤を担持せしめてなるオゾン分解触媒である。That is, the present invention is an ozone decomposition catalyst obtained by supporting manganese oxide and a flame retardant on activated carbon.
本発明による酸化マンガンを担持せしめた活性炭素に
は、粉末状及び繊維状のものがある。The activated carbon loaded with manganese oxide according to the present invention includes powdery and fibrous forms.
これらは種々の形で、例えば粉末状の活性炭素はフェ
ルト、ペーパー、ハニカム（段ボール）あるいはクロス
の面に付着せしめたり、オゾン発生域で使用する機械本
体（金属）面に直接コートしたりして使用することがで
きる。These are in various forms, for example, powdered activated carbon is attached to felt, paper, honeycomb (cardboard) or cloth surface, or directly coated on machine body (metal) surface used in ozone generating area. Can be used.
また繊維状の活性炭素は、フエルト状、ペーパー状、
ハニカム状、コート状、クロス状に加工したり、繊維を
機械本体に直接コートしたりして使用することができ
る。In addition, fibrous activated carbon is felt, paper,
It can be used in the form of a honeycomb, a coat, or a cloth, or can be used by directly coating a machine body with fibers.
しかし、活性炭素粉末をペーパーやフェルト面に付着
させ、また活性炭素繊維をペーパー状やフェルト状に加
工した場合には燃焼性であることが判明した。そこで種
々検討を行なった結果このような欠点は難燃化剤を含有
させた活性炭素を使用することによって解決できた。However, it was found that when the activated carbon powder was attached to the paper or felt surface and the activated carbon fiber was processed into a paper or felt shape, it was flammable. Therefore, as a result of various studies, such a drawback could be solved by using activated carbon containing a flame retardant.
以下、本発明の構成を詳しく説明する。 Hereinafter, the configuration of the present invention will be described in detail.
本発明において用いられる活性炭素粉末あるいは繊維
は、従来公知の任意の方法によって製造することができ
る。そして活性炭素粉末の場合には酸化マンガンを担持
後にフェルト、ペーパー、ハニカム、クロスあるいは金
属面に付着せしめることができ、活性炭素繊維の場合に
は酸化マンガンを担持後または担持前に、フェルト状、
ペーパー状、ハニカム状、クロス状、コート状（バイン
ダーに活性炭素繊維を混入したものを塗布して製造）に
容易に加工することができる。The activated carbon powder or fiber used in the present invention can be produced by any conventionally known method. And in the case of activated carbon powder, after carrying manganese oxide, it can be made to adhere to felt, paper, honeycomb, cloth or a metal surface, and in the case of activated carbon fiber, after or before carrying manganese oxide, felt-like,
It can be easily processed into paper, honeycomb, cloth, and coat (manufactured by applying a mixture of activated carbon fibers to a binder).
以下にまず、活性炭素粉末の場合について説明する。 First, the case of activated carbon powder will be described.
酸化マンガンを活性炭素粉末に付着含有（担持）せし
める方法としては、例えばマンガンの塩化物、硝酸塩な
どの水溶液に活性炭素粉末を含浸させた後、焼成してマ
ンガン塩をマンガン酸化物にする方法、あるいは活性炭
素粉末の原料にマンガンの塩化物や硝酸塩の溶液を含浸
後、焼成、賦活化して活性炭素粉末を作ると共にマンガ
ン塩をマンガン酸化物にする方法、あるいは、マンガン
の硝酸塩、硫酸塩などの水溶液に活性炭素粉末を含浸さ
せた後、水酸化ナトリウムを加えて水酸化マンガンと
し、これを加熱してマンガン酸化物とする方法等があ
る。Examples of a method for adhering and containing (supporting) manganese oxide on activated carbon powder include, for example, a method in which an activated carbon powder is impregnated with an aqueous solution of manganese chloride, nitrate, etc., followed by firing to convert the manganese salt into manganese oxide; Alternatively, the raw material of the activated carbon powder is impregnated with a solution of manganese chloride or nitrate, and then calcined and activated to produce the activated carbon powder and convert the manganese salt to manganese oxide, or a method such as manganese nitrate or sulfate. There is a method of impregnating an aqueous solution with activated carbon powder, adding sodium hydroxide to form manganese hydroxide, and heating this to form manganese oxide.
なお、本発明で活性炭素粉末に担持せしめる酸化マン
ガンは、完全な酸化物であるMnO2やMnOに限らず不飽和
あるいは過飽和酸化状態のものや含水酸基酸化物を含包
するものでもよいが、特にMn2O3またはMn3O4またはそれ
らの混合物が有効である。The manganese oxide to be supported on the activated carbon powder in the present invention is not limited to MnO 2 or MnO which is a complete oxide, but may be one containing an unsaturated or supersaturated oxidized state or a hydrated oxide. In particular, Mn 2 O 3 or Mn 3 O 4 or a mixture thereof is effective.
この酸化マンガンの担持量は、担持可能な量であれば
特に制限はないが、活性炭素粉末に対して0.001〜30重
量％、好ましくは0.1〜20重量％が実用的である。The amount of manganese oxide supported is not particularly limited as long as it can be supported, but is practically 0.001 to 30% by weight, preferably 0.1 to 20% by weight, based on the activated carbon powder.
次に活性炭素繊維の場合には、例えば、ポリアクロニ
トリル繊維を酸化処理した後、あるいはセルロース繊
維、ピッチ繊維、フェノール樹脂繊維を予備酸化して炭
化した後、濃度が5Vol％以上、好ましくは80Vol％以上
の賦活ガス（例えば、水蒸気、二酸化炭素、アンモニア
ガス、あるいはこれらの混合物等）を用いて350℃以上
の高温雰囲気中で１分間乃至３時間賦活して製造され
る。Next, in the case of activated carbon fibers, for example, after oxidizing polyacrylonitrile fibers, or after pre-oxidizing and carbonizing cellulose fibers, pitch fibers, and phenol resin fibers, the concentration is 5 Vol% or more, preferably 80 Vol%. % Of an activation gas (eg, steam, carbon dioxide, ammonia gas, or a mixture thereof) in a high-temperature atmosphere of 350 ° C. or more for 1 minute to 3 hours.
しかし、活性炭素繊維の製造方法は上気の方法に限定
されるものではない。However, the method for producing the activated carbon fiber is not limited to the above method.
本発明で用いられる活性炭素繊維は吸着面積が300〜
2,000m2/gのものである。このような活性炭素繊維は、
粒状の活性炭に比べて、約1.5倍〜数倍の平衡吸着量
と、10〜100倍の吸着速度を有している。The activated carbon fiber used in the present invention has an adsorption area of 300 to
2,000 m 2 / g. Such activated carbon fibers are
Compared to granular activated carbon, it has an equilibrium adsorption amount of about 1.5 to several times and an adsorption speed of 10 to 100 times.
このような活性炭繊維は安価に製造することができ、
粉末状活性炭の焼結品のように活性炭の脱離による粉塵
化が殆どなく、繊維としての特性を利用して、前記した
ように酸化マンガンを担持後または担持前に、フェルト
状、ペーパー状、ハニカム状、クロス状、コート状に容
易に加工することができる。Such activated carbon fibers can be manufactured at low cost,
As in the case of powdered activated carbon sintered products, there is almost no dusting due to desorption of activated carbon, and utilizing the properties as fibers, after or before supporting manganese oxide as described above, felt, paper, It can be easily processed into a honeycomb, cloth, or coat.
酸化マンガンを活性炭素繊維に付着含有（担持）せし
める方法としては、例えばマンガンの塩化物、硝酸塩な
どの水溶液に活性炭素繊維を含浸させた後、焼成してマ
ンガン塩をマンガン酸化物にする方法、あるいは活性炭
素繊維の原料繊維、例えばセルローズ繊維にマンガンの
塩化物や硝酸塩の溶液を含浸後、焼成、賦活化して活性
炭素繊維を作ると共にマンガン塩をマンガン酸化物にす
る方法、あるいはさらに紡糸液にマンガン塩を溶解、混
合後紡糸し、焼成賦活化する方法、あるいは、マンガン
の硝酸塩、硫酸塩などの水溶液に活性炭素繊維を含浸さ
せた後、水酸化ナトリウムを加えて水酸化マンガンと
し、これを加熱してマンガン酸化物とする方法等があ
る。Examples of a method for causing manganese oxide to adhere to (support) activated carbon fibers include, for example, a method of impregnating an activated carbon fiber with an aqueous solution of manganese chloride or nitrate, followed by firing to convert the manganese salt into manganese oxide; Alternatively, a raw material fiber of activated carbon fiber, such as cellulose fiber, is impregnated with a solution of manganese chloride or nitrate, and then fired and activated to produce activated carbon fiber and manganese salt to manganese oxide, or further into a spinning solution. A method of dissolving and mixing a manganese salt, spinning, and activating by firing, or impregnating an activated carbon fiber with an aqueous solution of manganese nitrate or sulfate, and then adding sodium hydroxide to form manganese hydroxide. There is a method of heating to manganese oxide.
なお、本発明で活性炭素繊維に担持せしめる酸化マン
ガンは、活性炭素粉末の場合に述べたのと同様に完全な
酸化物であるMnO2やMnOに限らず不飽和あるいは過飽和
酸化状態のもの（Mn2O3、Mn3O4等）や含水酸基酸化物を
含包するものでもよい。酸化マンガンの担持量も、活性
炭素粉末の場合と同様活性炭素繊維に対して0.001〜30
重量％、好ましくは0.1〜20重量％である。The manganese oxide supported on the activated carbon fiber in the present invention is not limited to the complete oxide MnO 2 or MnO, as described in the case of the activated carbon powder, but may be in the unsaturated or supersaturated oxidized state (MnO 2). 2 O 3 , Mn 3 O 4, etc.) or a hydrated oxide. The loading amount of manganese oxide is also 0.001 to 30 with respect to the activated carbon fiber as in the case of the activated carbon powder.
%, Preferably 0.1 to 20% by weight.
活性炭素粉末あるいは繊維を難燃性にする難燃化剤し
ては公知の物質を用いることができる。Known substances can be used as the flame retardant for making the activated carbon powder or the fiber flame-retardant.
例えば、テトラキス・ヒドロキシメチル・ホスホニウ
ム・クロライド［（CH2OH）4PCl］等のリン系化合物、
デカクロロビフェニル［C12Cl10］等の塩化物、リン酸
グアニジン［（NH2）2C・NH・H3PO4］等のグアニジン化
合物、三酸化アンチモン［Sb2O3］等が有効である。こ
れらの難燃化剤は活性炭素粉末あるいは繊維に酸化マン
ガンを担持後、フェルト状、ペーパー状、ハニカム状、
クロス状、コート状等に成型時に塗布、スプレー、浸
漬、又は難燃化剤と酸化マンガン担持活性炭素粉末ある
いは繊維の混合物のコート等によって酸化マンガン担持
活性炭素粉末あるいは繊維に含有させることができる。
含有量は活性炭素粉末あるいは繊維に対して0.01〜30重
量％が可能であるが、あまり少ない含有量では難燃化の
効果がなく、またあまり多い含有量ではオゾン分解率が
触媒の表面積低下によって悪くなるために、１〜20重量
％が実用的である。For example, phosphorus compounds such as tetrakis hydroxymethyl phosphonium chloride [(CH 2 OH) 4 PCl],
Chloride such as decachlorobiphenyl [C 12 Cl 10 ], guanidine compound such as guanidine phosphate [(NH 2 ) 2 C • NH • H 3 PO 4 ], antimony trioxide [Sb 2 O 3 ], etc. are effective. is there. These flame retardants support manganese oxide on activated carbon powder or fiber, then felt, paper, honeycomb,
The manganese oxide-carrying activated carbon powder or fiber can be contained by applying, spraying, dipping, or coating a mixture of a flame retardant and manganese oxide-carrying activated carbon powder or fiber at the time of molding into a cloth or a coat.
The content can be 0.01 to 30% by weight with respect to the activated carbon powder or fiber. However, if the content is too small, there is no flame retardant effect. For worsening, 1-20% by weight is practical.
本発明による酸化マンガンを担持した活性炭素粉末あ
るいは繊維は、いずれもO3を効率よく分解するととも
に、長寿命であり、かつO3以外の有害な気体をも有効に
吸着する。また導電性であるため電極を兼ねた使用が可
能であり、特に難燃化剤で処理したものは燃焼する危険
性がないのでそのような用途に好適である。The activated carbon powder or fiber carrying manganese oxide according to the present invention both decomposes O 3 efficiently, has a long life, and effectively adsorbs harmful gases other than O 3 . In addition, since it is conductive, it can be used also as an electrode. Particularly, a material treated with a flame retardant has no danger of burning, and is suitable for such use.
［実施例］ 次に実施例として、ペーパー状に加工された本発明の
活性炭素粉末紙、活性炭素繊維紙及びそれらを用いたコ
ロトロンについて説明する。[Examples] Next, as examples, activated carbon powder paper and activated carbon fiber paper of the present invention processed into paper, and a corotron using them will be described.
実施例 １ 粉末状活性炭素をフイブリル化したパルプ繊維、雁皮
パルプ繊維等のセルロース系繊維（紙基材）に混合した
後、通常の湿式抄紙法で抄造する。この活性炭素粉末紙
に、所定量の硝酸マンガンを溶解した溶液に浸漬する。Example 1 After powdered activated carbon is mixed with a fibrilized pulp fiber or a cellulosic fiber (paper base material) such as a goose pulp fiber, papermaking is performed by an ordinary wet papermaking method. This activated carbon powder paper is immersed in a solution in which a predetermined amount of manganese nitrate is dissolved.
次にNaOH溶液に浸漬した後水洗し、これを予備乾燥し
た後、110℃にて加熱を行う。以上の操作によって15重
量％の酸化マンガンを活性炭素粉末紙に担持した。Next, it is immersed in a NaOH solution, washed with water, preliminarily dried, and then heated at 110 ° C. By the above operation, 15% by weight of manganese oxide was supported on the activated carbon powder paper.
この酸化マンガン担持紙１を第１図に示すようにコロ
トロンシールド２の少なくとも表面に接着する。The manganese oxide-carrying paper 1 is adhered to at least the surface of the corotron shield 2 as shown in FIG.
第１図の例では、厚さ1mmのアルミニウムシールド２
に厚さ0.1mmの酸化マンガン担持活性炭素粉末紙を接着
剤により貼り付け、コロトロン内面が酸化マンガン担持
炭素粉末紙となるように加工したものである。In the example of FIG. 1, a 1 mm thick aluminum shield 2
A manganese oxide-supported activated carbon powder paper having a thickness of 0.1 mm was adhered to the substrate with an adhesive, and processed so that the inner surface of the corotron became a manganese oxide-supported carbon powder paper.
このコロトロンと、このコロトロント同様の構造で酸
化マンガンを担持しない活性炭素粉末紙を貼り付けたシ
ールドからなるコロトロン、及びアルミニウムシールド
のみからなるコロトロンとを電子写真複写機に装着し
て、コロトロンをマイナス放電したときに複写機の排気
ファンから放出するO3量について比較したところ、本発
明によるコロトロンは、アルミニウムシールドのみから
なるコロトロンにくらべてO3分解は、酸化マンガンを担
持しない活性炭素粉末紙を設けたシールドコロトロンが
75％であったのに対し、80％の高率を示した。This corotron, a corotron consisting of a shield having the same structure as this corotron and affixed with activated carbon powder paper not carrying manganese oxide, and a corotron consisting of only an aluminum shield are mounted on an electrophotographic copying machine, and the corotron is minus. Comparing the amount of O 3 released from the exhaust fan of the copying machine when discharged, the corotron according to the present invention decomposes O 3 compared to a corotron consisting only of an aluminum shield, and uses activated carbon powder paper that does not carry manganese oxide. The provided shield corotron
Compared to 75%, it was as high as 80%.
また、酸化マンガンを担持しない活性炭素粉末紙で
は、５万枚コピー後には分解率が40％まで低下したのに
対し、本発明による酸化マンガン担持炭素粉末紙を用い
たコロトロンでは分解率は75％までしか低下せず、極め
て劣化が少ないことが判明した。In addition, in the case of activated carbon powder paper not supporting manganese oxide, the decomposition rate was reduced to 40% after 50,000 copies, whereas in the case of corotron using the manganese oxide-supported carbon powder paper according to the present invention, the decomposition rate was 75%. It was found that the deterioration was only low and the deterioration was extremely small.
上記実施例の他に、酸化マンガン担持活性炭素粉末紙
を作り、これをシート状に成形した後ハニカム状のエア
・フィルターを作成した。In addition to the above examples, a manganese oxide-supported activated carbon powder paper was prepared and formed into a sheet, after which a honeycomb air filter was prepared.
このようにして得られたフィルターと酸化マンガンを
担持しない活性炭素粉末紙によるフィルターとについ
て、0.2ppmオゾンを含有する排気ガスを0.35m3/secの風
量で流したところ、本発明によるフィルターの初期オゾ
ン除去率は95％であったのに対し、酸化マンガン担持な
しフィルターでは88％であった。また100時間後の除去
率は、本発明によるフィルターでは91％であったが、酸
化マンガン担持なしフィルターでは50％で、除去率が低
下した。When the exhaust gas containing 0.2 ppm ozone was flown at a flow rate of 0.35 m 3 / sec with respect to the filter obtained in this way and the filter using activated carbon powder paper not supporting manganese oxide, the filter according to the present invention was initialized. The ozone removal rate was 95%, while the filter without manganese oxide was 88%. The removal rate after 100 hours was 91% in the filter according to the present invention, but was 50% in the filter without manganese oxide support, and the removal rate was reduced.
実施例 ２ 粉末状活性炭素をフイブリル化したパルプ繊維、雁皮
パルプ繊維等のセルローズ系繊維（紙基材）に混合した
後、通常の湿式抄紙法で抄造する。この活性炭素粉末紙
に、所定量の硝酸マンガンを溶解した溶液に浸漬する。Example 2 After powdered activated carbon was mixed with a cellulose fiber (paper base) such as fibrillated pulp fiber or goose pulp fiber, papermaking was performed by a usual wet papermaking method. This activated carbon powder paper is immersed in a solution in which a predetermined amount of manganese nitrate is dissolved.
次にNaOH溶液に浸漬した後水洗し、次にリン酸グアニ
ジン水溶液に浸漬する。これを予備乾燥した後、110℃
にて加熱を行う。以上の操作によって15重量％の酸化マ
ンガンと10重量％のリン酸グアニジンを活性炭素紙に担
持した。Next, it is immersed in a NaOH solution, washed with water, and then immersed in an aqueous solution of guanidine phosphate. After pre-drying this, 110 ° C
Perform heating. By the above operation, 15% by weight of manganese oxide and 10% by weight of guanidine phosphate were supported on activated carbon paper.
この酸化マンガン−リン酸グアニジン担持紙１を第１
図に示すように、厚さ1mmのアルミニウムシールド２に
厚さ0.1mmの酸化マンガン−リン酸グアニジン担持活性
炭素粉末紙を接着剤により貼り付け、コロトロン内面が
酸化マンガン−リン酸グアニジン担持炭素繊維紙となる
ように加工した。This manganese oxide-guanidine phosphate supporting paper 1 is first
As shown in the figure, a 0.1 mm-thick manganese oxide-guanidine phosphate-supported activated carbon powder paper is adhered to an aluminum shield 2 having a thickness of 1 mm with an adhesive, and the inner surface of the corotron is a manganese oxide-guanidine phosphate-supported carbon fiber paper. It was processed to become.
このコロトロンと、このコロトロンと同様の構造でリ
ン酸グアニジンを担持しない酸化マンガン担持活性炭素
粉末紙を貼り付けたシールドからなるコロトロン、及び
アルミニウムシールドのみからなるコロトロンとを複写
機に装着してコロトロンをマイナス放電したときに複写
機の排気ファンから放出するO3量について比較したとこ
ろ、本発明によるコロトロンは、アルミニウムシールド
のみからなるコロトロンに比べてO3分解は、リン酸グア
ニジンを担持しない酸化マンガン担持活性炭素粉末紙を
設けたシールドコロトロンが80％であったのとほぼ同等
の78％の高率を示した。また、リン酸グアニジンを担持
しない酸化マンガン担持活性炭素粉末紙では、10万枚コ
ピー後には分解率が75％までしか低下しなかったのとほ
ぼ同様に酸化マンガン−リン酸グアニジン担持炭素粉末
紙を用いたコロトロンでも分解率は70％までしか低下せ
ず、極めて劣化が少ないことが判明した。A corotron consisting of a shield having the same structure as that of the corotron and having a manganese oxide-carrying activated carbon powder paper not carrying guanidine phosphate attached thereto, and a corotron consisting of an aluminum shield alone were mounted on a copying machine to form a corotron. Comparing the amount of O 3 released from the exhaust fan of the copier when a minus discharge occurs, the corotron according to the present invention decomposes O 3 compared to a corotron consisting only of an aluminum shield. Shielded corotron with activated carbon powdered paper showed a high rate of 78%, almost the same as 80%. In addition, in the case of manganese oxide-supported activated carbon powder paper that does not support guanidine phosphate, the manganese oxide-guanidine phosphate-supported carbon powder paper was used in almost the same manner as the decomposition rate decreased to only 75% after 100,000 copies. Even with the corotron used, the decomposition rate was reduced only to 70%, indicating that the degradation was extremely small.
またこれらの活性炭素粉末紙をUL（Underwriters Lab
oratories）燃焼試験法に従って試験をしたところ、リ
ン酸グアニジンを担持しない酸化マンガン担持活性炭素
粉末紙は炎は出さないものの完全に燃焼したのに対し、
酸化マンガン−リン酸グアニジン担持活性炭素繊維紙は
燃焼せずUL規格でもっともきびしいVoレベルにもパスし
た。In addition, these activated carbon powder papers have been used by UL (Underwriters Lab).
oratories) When tested in accordance with the combustion test method, manganese oxide-supported activated carbon powder paper not supporting guanidine phosphate did not produce a flame, but burned completely,
Manganese oxide - phosphate guanidine supported active carbon fiber paper has also passed the most stringent V o level UL standard does not burn.
上記の例の他に、酸化マンガン担持活性炭素粉末を作
り、これをシート状に成形しさらにリン酸グアニジンを
含有させた後ハニカム状のエア・フィルターを作成し
た。In addition to the above examples, a manganese oxide-supported activated carbon powder was prepared, formed into a sheet, and further containing guanidine phosphate, followed by preparing a honeycomb-shaped air filter.
このようにして得られたフィルターとリン酸グアニジ
ンを担持しない酸化マンガン担持活性炭素粉末紙による
フィルターとについて、0.2ppmオゾンを含有する排気ガ
スを0.35m3/secの風量で流したところ、本発明によるフ
ィルターの初期オゾン除去率は93％であったのに対し、
リン酸グアニジン担持なしフィルターでは95％であっ
た。また100時間後の除去後は、本発明によるフィルタ
ーでは89％であったが、リン酸グアニジン担持なしフィ
ルターでは91％で、難燃化処理した本発明によるフィル
ターは難燃化剤を用いない可燃性のフィルターとほぼ同
様の特性を示した。When the exhaust gas containing 0.2 ppm ozone was flown at an air flow of 0.35 m 3 / sec with respect to the filter thus obtained and the filter using manganese oxide-supported activated carbon powder paper not supporting guanidine phosphate, the present invention The initial ozone removal rate of the filter by was 93%,
It was 95% for the filter without guanidine phosphate loading. After removal after 100 hours, the filter of the present invention was 89%, whereas the filter without guanidine phosphate support was 91%. The characteristics were almost the same as those of the sex filter.
なお、上記の実施例において、酸化マンガン及びリン
酸グアニジンを担持しない活性炭素粉末紙は使用時にオ
ゾンとの反応による消耗が原因と考えられる活性炭の微
粉末による脱離がみられたが、本発明による活性炭素粉
末紙については活性炭の粉末脱離は見られなかった。In the above example, activated carbon powder paper not supporting manganese oxide and guanidine phosphate was desorbed by fine powder of activated carbon, which was considered to be caused by reaction with ozone during use. No activated carbon powder was desorbed from the activated carbon powder paper.
以上を総括すると、酸化マンガンを担持しないリン酸
グアニジン担持活性炭素粉末紙では難燃性はあるものの
寿命が短くリン酸グアニジンを担持しない酸化マンガン
担持活性炭素粉末紙は寿命は長いものの難燃性がなく、
酸化マンガンとリン酸グアニジンを組合わせて使用する
ことが長寿命でかつ難燃性である担持活性炭素粉末紙に
不可欠であることになる。Summarizing the above, guanidine phosphate-supported activated carbon powder paper that does not support manganese oxide has flame retardancy, but has a short life, and manganese oxide-supported active carbon powder paper that does not support guanidine phosphate has a long life but has flame retardancy. Not
The use of a combination of manganese oxide and guanidine phosphate is indispensable for a long-lived and flame-retardant supported activated carbon powder paper.
実施例 ３ 繊維状活性炭素を粉砕した後、フイブリル化したパル
プ繊維、雁皮パルプ繊維等のセルローズ系繊維（紙基
材）に混合した後、通常の湿式抄紙法で抄造する。この
活性炭素繊維紙に、所定量の硝酸マンガンを溶解した溶
液に浸漬する。Example 3 After fibrous activated carbon was pulverized, it was mixed with cellulose fibers (paper base material) such as fibrillated pulp fiber and goose pulp fiber, and then made by a usual wet papermaking method. The activated carbon fiber paper is immersed in a solution in which a predetermined amount of manganese nitrate is dissolved.
次にNaOH溶液に浸漬した後水洗し、これを予備乾燥し
た後、110℃にて加熱を行う。以上の操作によって15重
量％の酸化マンガンを活性炭素紙に担持した。Next, it is immersed in a NaOH solution, washed with water, preliminarily dried, and then heated at 110 ° C. By the above operation, 15% by weight of manganese oxide was supported on the activated carbon paper.
この酸化マンガン担持紙１を実施例１と同様に第１図
に示すコロトロンシールド２の少なくとも表面に接着す
る。The manganese oxide-carrying paper 1 is adhered to at least the surface of the corotron shield 2 shown in FIG.
この例でも、厚さ1mmのアルミニウムシールド２に厚
さ0.1mmの酸化マンガン担持活性炭素繊維紙を接着剤に
より貼り付け、コロトロン内面が酸化マンガン担持炭素
繊維紙となるように加工した。Also in this example, manganese oxide-supported activated carbon fiber paper having a thickness of 0.1 mm was adhered to an aluminum shield 2 having a thickness of 1 mm with an adhesive, and the inner surface of the corotron was processed so as to be manganese oxide-supported carbon fiber paper.
このコロトロンと、このコロトロント同様の構造で酸
化マンガンを担持しない活性炭素繊維紙を貼り付けたシ
ールドからなるコロトロン、及びアルミニウムシールド
のみからなるコロトロンとを電子写真複写機に装着し
て、コロトロンをマイナス放電したときに複写機の排気
ファンから放出するO3量について比較したところ、本発
明によるコロトロンは、アルミニウムシールドのみから
成るコロトロンにくらべてO3分解は、酸化マンガンを担
持しない活性炭素繊維紙を設けたシールドコロトロンが
77％であったのに対し、81％の高率を示した。This corotron, a corotron consisting of a shield having the same structure as this corotron and affixed with activated carbon fiber paper not carrying manganese oxide, and a corotron consisting only of an aluminum shield are attached to an electrophotographic copying machine, and the corotron is minus. Comparing the amount of O 3 released from the exhaust fan of the copier when discharged, the corotron according to the present invention decomposes O 3 compared to a corotron consisting of only an aluminum shield, and uses activated carbon fiber paper that does not carry manganese oxide. The provided shield corotron
The rate was 81%, compared to 77%.
また、酸化マンガンを担持しない活性炭素繊維紙で
は、５万枚オピー後には分解率が44％まで低下したのに
対し、本発明による酸化マンガン担持炭素繊維紙を用い
たコロトロンでは分解率は78％までしか低下せず、極め
て劣化が少ないことが判明した。In addition, in the case of activated carbon fiber paper not supporting manganese oxide, the decomposition rate decreased to 44% after 50,000 sheets of oppy, whereas in the case of corotron using manganese oxide-supported carbon fiber paper according to the present invention, the decomposition rate was 78%. It was found that the deterioration was only low and the deterioration was extremely small.
上記実施例の他に、セルロース繊維を硝酸マンガン溶
液に含浸後、焼成、賦活化して酸化マンガン担持活性炭
素繊維を作り、これをシート状に成形した後ハニカム状
のエア・フィルターを作成した。In addition to the above examples, a cellulose fiber was impregnated with a manganese nitrate solution, fired and activated to produce a manganese oxide-supported activated carbon fiber, which was formed into a sheet, and then a honeycomb air filter was formed.
このようにして得られたフィルターと酸化マンガンを
担持しない活性炭素繊維紙によるフィルターとについ
て、0.2ppmオゾンを含有する排気ガスを0.35m3/secの風
量で流したところ、本発明によるフィルターの初期オゾ
ン除去率は98％であったのに対し、酸化マンガン担持な
しフィルターでは99％であった。また100時間後の除去
率は、本発明によるフィルターでは94％であったが、酸
化マンガン担持なしフィルターでは55％で、除去率が低
下した。When the exhaust gas containing 0.2 ppm ozone was flown at a flow rate of 0.35 m 3 / sec with respect to the filter thus obtained and the filter made of activated carbon fiber paper not carrying manganese oxide, the filter according to the present invention was initialized. The ozone removal rate was 98%, while the filter without manganese oxide was 99%. Further, the removal rate after 100 hours was 94% in the filter according to the present invention, but was 55% in the filter without manganese oxide supported, and the removal rate was reduced.
実施例 ４ 繊維状活性炭素を粉砕した後、フイブリル化したパル
プ繊維、雁皮パルプ繊維等のセルローズ系繊維（紙基
材）に混合した後、通常の湿式抄紙法で抄造する。この
活性炭素繊維紙に、所定量の硝酸マンガンを溶解した溶
液に浸漬する。Example 4 After fibrous activated carbon was pulverized, the fibrous activated carbon was mixed with cellulosic fibers (paper base material) such as fibrillated pulp fiber and goose pulp fiber, and then made by a usual wet papermaking method. The activated carbon fiber paper is immersed in a solution in which a predetermined amount of manganese nitrate is dissolved.
次にNaOH溶液に浸漬した後水洗し、次にリン酸グアニ
ジン水溶液に浸漬する。これを予備乾燥した後、110℃
にて加熱を行う。以上の操作によって15重量％の酸化マ
ンガンと10重量％のリン酸グアニジンを活性炭素紙に担
持した。Next, it is immersed in a NaOH solution, washed with water, and then immersed in an aqueous solution of guanidine phosphate. After pre-drying this, 110 ° C
Perform heating. By the above operation, 15% by weight of manganese oxide and 10% by weight of guanidine phosphate were supported on activated carbon paper.
この酸化マンガン−リン酸グアニジン担持紙１を第１
図に示すように、厚さ1mmのアルミニウムシールド２に
厚さ0.1mmの酸化マンガン−リン酸グアニジン担持活性
炭素繊維紙を接着剤により貼り付け、コロトロン内面が
酸化マンガン−リン酸グアニジン担持炭素繊維紙となる
ように加工した。This manganese oxide-guanidine phosphate supporting paper 1 is first
As shown in the figure, a manganese oxide-guanidine phosphate-supported activated carbon fiber paper having a thickness of 0.1 mm is adhered to an aluminum shield 2 having a thickness of 1 mm with an adhesive, and the inner surface of the corotron is coated with a manganese oxide-guanidine phosphate-supported carbon fiber paper. It was processed to become.
このコロトロンと、このコロトロンと同様の構造でリ
ン酸グアニジンを担持しない酸化マンガン担持活性炭素
繊維紙を貼り付けたシールドからなるコロトロン、及び
アルミニウムシールドのみからなるコロトロンとを複写
機に装着してコロトロンをマイナス放電したときに複写
機の排気ファンから放出するO3量について比較したとこ
ろ、本発明によるコロトロンは、アルミニウムシールド
のみから成るコロトロンに比べてO3分解は、リン酸グア
ニジンを担持しない酸化マンガン担持活性炭素繊維紙を
設けたシールドコロトロンが83％であったのとほぼ同等
の80％の高率を示した。また、リン酸グアニジンを担持
しない酸化マンガン担持活性炭素繊維紙では、10万枚コ
ピー後には分解率が77％までしか低下しなかったのとほ
ぼ同様に酸化マンガン−リン酸グアニジン担持炭素繊維
紙を用いたコロトロンでも分解率は72％までしか低下せ
ず、極めて劣化が少ないことが判明した。A corotron consisting of a shield having the same structure as the corotron and having a manganese oxide-carrying activated carbon fiber paper that does not carry guanidine phosphate and a corotron consisting only of an aluminum shield attached to a copier. Comparing the amount of O 3 released from the exhaust fan of the copier when a minus discharge occurs, the corotron according to the present invention decomposes O 3 compared to a corotron consisting only of an aluminum shield. Shielded corotron with activated carbon fiber paper showed a high rate of 80%, almost the same as 83%. In the case of manganese oxide-supported activated carbon fiber paper not supporting guanidine phosphate, the manganese oxide-guanidine phosphate-supported carbon fiber paper was almost completely degraded after 100,000 copies, as the decomposition rate decreased only to 77%. Even with the corotron used, the decomposition rate was reduced only to 72%, indicating that the degradation was extremely small.
またこれらの活性炭素繊維紙をUL（Underwriters Lab
oratories）燃焼試験法に従って試験をしたところ、リ
ン酸グアニジンを担持しない酸化マンガン担持活性炭素
繊維紙は炎は出さないものの完全に燃焼したのに対し、
酸化マンガン−リン酸グアニジン担持活性炭素繊維紙は
燃焼せずUL規格のVoレベルにパスした。In addition, these activated carbon fiber papers are UL (Underwriters Lab)
oratories) When tested according to the combustion test method, manganese oxide-supported activated carbon fiber paper that did not support guanidine phosphate did not produce a flame, but burned completely,
Manganese oxide - phosphate guanidine supported active carbon fiber paper has passed V o level of UL Standard does not burn.
上記の例の他に、セルロース繊維を硝酸マンガン溶液
に含浸後、焼成、賦活化して酸化マンガン担持活性炭素
繊維を作り、これをシート状に成形しさらにリン酸グア
ニジンを含有させた後ハニカム状のエア・フィルターを
作成した。In addition to the above examples, after impregnating the cellulose fibers with a manganese nitrate solution, baking and activating them to produce manganese oxide-supported activated carbon fibers, forming this into a sheet shape, and further containing guanidine phosphate, followed by a honeycomb shape. Created an air filter.
このようにして得らてたフィルターとリン酸グアニジ
ンを担持しない酸化マンガン担持活性炭素繊維紙による
フィルターとについて、0.2ppmオゾンを含有する排気ガ
スを0.35m3/secの風量で流したところ、本発明によるフ
ィルターの初期オゾン除去率は95％であったのに対し、
リン酸グアニジン担持なしフィルターでは98％であっ
た。また100時間後の除去率は、本発明によるフィルタ
ーでは90％であったが、リン酸グアニジン担持なしフィ
ルターでは94％で、難燃化処理した本発明によるフィル
ターは難燃化剤を用いない可燃性のフィルターとほぼ同
様の特性を示した。When the exhaust gas containing 0.2 ppm ozone was flown at a flow rate of 0.35 m 3 / sec with respect to the filter obtained in this manner and the filter using manganese oxide-supported activated carbon fiber paper not supporting guanidine phosphate, The initial ozone removal rate of the filter according to the invention was 95%,
It was 98% for the filter without guanidine phosphate loading. The removal rate after 100 hours was 90% with the filter according to the present invention, but was 94% with the filter without guanidine phosphate support. The characteristics were almost the same as those of the sex filter.
［発明の効果］ 本発明は活性炭素粉末または繊維に酸化マンガンを担
持させたオゾン分解触媒を提供したものであり、本発明
の触媒は安価に製造できること、活性炭素粉の脱離によ
る粉塵を殆ど生じないこと、繊維の場合には繊維として
の特性を利用して、また粉末の場合にも他の繊維に付着
させて抄紙加工したり粉末の接着法等によりフエルト
状、ペーパー状、ハニカム状、コート状、クロス状等種
々の形に容易に成形できること、オゾンの分解率が高
く、かつオゾン以外の有害な気体も有効に吸着し、かつ
長期間性能が低下しないこと、更に活性炭素粉末あるい
は繊維に酸化マンガンと同時に難燃化剤を含有せしめる
ことにより、上記の効果を損うことなく難燃化できるこ
と等の特徴を有する。[Effects of the Invention] The present invention provides an ozonolysis catalyst in which manganese oxide is supported on activated carbon powder or fiber. The catalyst of the present invention can be manufactured at low cost, and almost no dust is generated due to desorption of activated carbon powder. In the case of fibers, utilizing the properties of fibers in the case of fibers, and also in the case of powders, by adhering to other fibers, paper making or bonding with powders, etc., felt, paper, honeycomb, It can be easily formed into various shapes such as coats and cloths, has a high ozone decomposition rate, effectively adsorbs harmful gases other than ozone, and does not deteriorate for a long period of time. By incorporating a flame retardant together with manganese oxide into manganese, flame retardancy can be achieved without impairing the above effects.
また導電性であるため電極を兼ねた使用が可能であ
り、特に難燃化剤で処理したものは燃焼する危険性がな
いのでそのような用途に好適である。In addition, since it is conductive, it can be used also as an electrode. Particularly, a material treated with a flame retardant has no danger of burning, and is suitable for such use.
第１図は本発明の１例である酸化マンガン担持活性炭素
紙を貼付したコロナ帯電器の断面図である。 図中符号： １……酸化マンガン担持紙;2……アルミニウム製シール
ド;3……コロナ放電電極線。FIG. 1 is a cross-sectional view of a corona charger to which an activated carbon paper carrying manganese oxide, which is an example of the present invention, is adhered. Symbols in the figure: 1 ... Manganese oxide-carrying paper; 2 ... Aluminum shield; 3 ... Corona discharge electrode wire.
Claims (2)
持せしめてなるオゾン分解触媒。An ozone decomposition catalyst comprising manganese oxide and a flame retardant supported on activated carbon.
る特許請求の範囲第１項に記載のオゾン分解触媒。2. The ozone decomposition catalyst according to claim 1, wherein the activated carbon is in the form of powder and / or fiber.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4039787 | 1987-02-25 | ||
| JP20303787 | 1987-08-17 | ||
| JP62-40397 | 1987-08-17 | ||
| JP62-203037 | 1987-08-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01127040A JPH01127040A (en) | 1989-05-19 |
| JP2625811B2 true JP2625811B2 (en) | 1997-07-02 |
Family
ID=26379858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63021292A Expired - Lifetime JP2625811B2 (en) | 1987-02-25 | 1988-02-02 | Ozone decomposition catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2625811B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5628747B2 (en) * | 2011-06-01 | 2014-11-19 | 住江織物株式会社 | Flame-retardant deodorant filter and method for producing the same |
| CN109603817A (en) * | 2018-12-18 | 2019-04-12 | 中山大学 | A kind of manganese oxide catalyst and preparation method thereof that catalysis ozone decomposes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5933410B2 (en) * | 1977-01-12 | 1984-08-15 | 武田薬品工業株式会社 | How to remove ozone |
| JPS60225640A (en) * | 1984-04-25 | 1985-11-09 | Toyobo Co Ltd | Activated carbon paper for adsorbing gas |
-
1988
- 1988-02-02 JP JP63021292A patent/JP2625811B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01127040A (en) | 1989-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0523591A (en) | Ozone filter and production thereof | |
| US20060205592A1 (en) | Catalytic adsorbents for mercury removal from flue gas and methods of manufacture therefor | |
| US5698165A (en) | Ozone filter and process for producing the same | |
| JPS5824340A (en) | Filter | |
| US11806665B2 (en) | Sorbents for the oxidation and removal of mercury | |
| US5817427A (en) | Titanium oxide-containing paper, corrugated board, and deodorizing element | |
| JP2011200857A (en) | Optically regenerable adsorbing material and utilization thereof | |
| KR20070113287A (en) | Adsorbents for mercury removal from flue gas | |
| JPS5881425A (en) | Apparatus for removing ozone | |
| JP2625811B2 (en) | Ozone decomposition catalyst | |
| KR20020009353A (en) | Complex Catalysts Used For Removing Nitrogen Oxides And Other Harmful Materials Among Flue Gases And Method For Preparing The Sames | |
| JPS6331253B2 (en) | ||
| JP4806108B2 (en) | Deodorizing device | |
| JPH09249824A (en) | Air-purifying coating material using photocatalyst | |
| JPH10235129A (en) | Filter | |
| JPS5919727B2 (en) | Manufacturing method of activated carbon adsorption unit | |
| JPS5933410B2 (en) | How to remove ozone | |
| JP2995608B2 (en) | Ozone filter and its manufacturing method | |
| JP2001170497A (en) | Catalyst for cleaning air | |
| JPH10235130A (en) | Filter | |
| JP3029764B2 (en) | Deodorant | |
| JPS63208070A (en) | Corona discharger | |
| JP2008238077A (en) | Dehumidification element, manufacturing method of dehumidification element and dehumidifier | |
| JP3126012B2 (en) | How to Prevent Odor Generation from Ozone Filter | |
| JP2827627B2 (en) | Deodorizing catalyst |