JPH0555185B2 - - Google Patents
Info
- Publication number
- JPH0555185B2 JPH0555185B2 JP63148170A JP14817088A JPH0555185B2 JP H0555185 B2 JPH0555185 B2 JP H0555185B2 JP 63148170 A JP63148170 A JP 63148170A JP 14817088 A JP14817088 A JP 14817088A JP H0555185 B2 JPH0555185 B2 JP H0555185B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ozone
- titanium
- oxide
- 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
- 239000003054 catalyst Substances 0.000 claims description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- TWWPCKXWXDAZOR-UHFFFAOYSA-N [Zr].[Ti].[Si] Chemical compound [Zr].[Ti].[Si] TWWPCKXWXDAZOR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005949 ozonolysis reaction Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 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 claims description 2
- 239000000306 component Substances 0.000 claims 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 31
- 238000000034 method Methods 0.000 description 17
- 238000000354 decomposition reaction Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005437 stratosphere Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 moisture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
＜産業上の利用分野＞
本発明は、オゾン分解処理に使用された使用済
触媒を再生する方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for regenerating a spent catalyst used in ozone decomposition treatment.
＜従来技術とその問題点＞
オゾンは強い酸化能を有していて分解すると無
害な酸素になるため、脱臭、殺菌、漂白、排水中
のCOD減少等の目的で幅広く利用されている。
しかし、オゾンは2ppm以上の濃度では人体に有
害とされており、あるいは処理に使用したオゾン
が一部未反応のまま大気中に放出されると光化学
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、成層圏で
はオゾンが多く存在しており、機内にオゾンを含
む空気が導入されて乗客や乗員に悪影響を及ぼす
危険性がある。更に、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
オゾンが発生し、これらの機器は主に室内に置か
れるため室内の汚染が問題となつている。以上述
べたごとく、オゾンを利用する場合、あるいはオ
ゾンが発生する環境下においてはオゾンを分解除
去し、無害化する必要がある。<Prior art and its problems> Ozone has strong oxidizing ability and becomes harmless oxygen when decomposed, so it is widely used for purposes such as deodorization, sterilization, bleaching, and reducing COD in wastewater.
However, ozone is considered harmful to the human body at concentrations of 2 ppm or higher, and if some of the ozone used for treatment is released into the atmosphere unreacted, it may cause secondary pollution such as photochemical smog. .
Furthermore, when an aircraft flies in the stratosphere, there is a large amount of ozone present in the stratosphere, and there is a risk that air containing ozone may be introduced into the aircraft cabin and have a negative impact on passengers and crew. Furthermore, recently, ozone is generated from equipment incorporating various high voltage generators, such as dry type copying machines, and since these equipment are mainly placed indoors, indoor pollution has become a problem. As mentioned above, when using ozone or in an environment where ozone is generated, it is necessary to decompose and remove ozone to make it harmless.
従来行なわれてきたオゾンの処理技術として
は、活性炭法、薬液洗浄法および熱分解法があ
る。活性炭法は低濃度オゾンの処理に利用されて
いるが、オゾン分解の進行に従つて活性炭が消耗
し補充する必要があり、また高濃度のオゾンを処
理する場合は反応熱により活性炭自身が発火、燃
焼する危険性があり、取扱上問題がある。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
方法で薬液の費用が高く、また排水処理の問題が
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
処理するには問題がある。 Conventional ozone treatment techniques include an activated carbon method, a chemical cleaning method, and a thermal decomposition method. The activated carbon method is used to treat low-concentration ozone, but as ozone decomposition progresses, the activated carbon is consumed and needs to be replenished, and when treating high-concentration ozone, the activated carbon itself ignites due to the heat of reaction. There is a danger of combustion and there are problems in handling. The chemical cleaning method is a method in which waste ozone is cleaned with an aqueous solution of a reducing substance, and the cost of the chemical is high and there are problems in wastewater treatment. In order to increase the decomposition efficiency of the pyrolysis method,
It requires heating to over 300°C, which poses a problem in processing large amounts of exhaust gas.
一方、近年廃オゾン処理方法として触媒分解法
が研究されており、該方法は発火、爆発の危険性
がなく、排水処理も不要で、安価にオゾンを分解
除去でき、有利な方法とされている。しかし、こ
の方法においても、長期間の使用により触媒のオ
ゾン分解活性がしだいに低下し、触媒の再生が必
要となる問題がある。触媒の再生に関しては例え
ば、特開昭53−14688号公報によれば該公報の製
法で得られたのオゾン分解用触媒は500〜700℃に
加熱することによつて活性が回復することが示さ
れている。 On the other hand, in recent years, catalytic decomposition methods have been studied as a waste ozone treatment method, and this method is considered to be an advantageous method because it has no risk of ignition or explosion, does not require wastewater treatment, and can decompose and remove ozone at low cost. . However, even in this method, there is a problem that the ozone decomposition activity of the catalyst gradually decreases after long-term use, and the catalyst needs to be regenerated. Regarding the regeneration of the catalyst, for example, according to JP-A-53-14688, it has been shown that the activity of the ozone decomposition catalyst obtained by the production method of the publication can be recovered by heating it to 500 to 700°C. has been done.
また、本発明者らはオゾン分解触媒として、チ
タン−珪素からなる二元系酸化物、チタン−ジル
コニウムからなる二元系酸化物、チタン−珪素−
ジルコニウムからなる三元系酸化物よりなる群か
ら選ばれる少なくとも１種を必須成分とする触媒
が低温活性等で優れていることを見いだした（特
開昭62−97643号公報）。しかし、上記触媒におい
ても長期間の使用によりオゾン分解活性がしだい
に低下し、触媒の再生が必要となつてくる。 In addition, the present inventors have developed a titanium-silicon binary oxide, a titanium-zirconium binary oxide, and a titanium-silicon binary oxide as an ozone decomposition catalyst.
It has been found that a catalyst containing at least one element selected from the group consisting of ternary oxides of zirconium as an essential component has excellent low-temperature activity (Japanese Patent Laid-Open No. 62-97643). However, even in the above catalyst, the ozone decomposition activity gradually decreases after long-term use, and it becomes necessary to regenerate the catalyst.
＜発明が解決しようとしている問題点＞
本発明の目的は、オゾン分解活性等の優れた、
チタン−珪素からなる二元系酸化物、チタン−ジ
ルコニウムからなる二元系酸化物、チタン−珪素
−ジルコニウムからなる三元系酸化物よりなる群
から選ばれる少なくとも１種を必須成分とする触
媒を再生するにあたり、簡便な触媒再生方法を提
供することにある。<Problems to be Solved by the Invention> The purpose of the present invention is to provide a solution that has excellent ozonolysis activity, etc.
A catalyst containing at least one element selected from the group consisting of a binary oxide consisting of titanium-silicon, a binary oxide consisting of titanium-zirconium, and a ternary oxide consisting of titanium-silicon-zirconium as an essential component. The purpose of this invention is to provide a simple catalyst regeneration method.
＜問題点を解決するための手段＞
本発明者等は、上記目的に沿つて鋭意研究した
結果、本発明を完成したものである。即ち本発明
は、オゾン分解処理に使用された、チタン−珪素
からなる二元系酸化物、チタン−ジルコニウムか
らなる二元系酸化物およびチタン−珪素−ジルコ
ニウムからなる三元系酸化物よりなる群から選ば
れる少なくとも１種を触媒Ａ成分とし、マンガ
ン、鉄、コバルト、ニツケル、亜鉛、銀、白金、
パラジウムおよびロジウムよりなる群から選ばれ
る少なくとも１種の元素を触媒Ｂ成分としてなる
触媒であつて、該触媒の組成が触媒Ａ成分は酸化
物の重量％で40〜100％、触媒Ｂ成分はマンガン、
鉄、コバルト、ニツケル、亜鉛および銀について
は酸化物としての重量％で０〜60％、白金、パラ
ジウムおよびロジウムについては金属元素として
の重量％で０〜10％の範囲よりなる触媒を再生す
るにあたり、空気中もしくは酸素中で100〜450
℃、好ましくは200〜400℃で焼成する触媒再生方
法である。<Means for Solving the Problems> The present inventors have completed the present invention as a result of intensive research in accordance with the above objectives. That is, the present invention relates to a group consisting of a binary oxide consisting of titanium-silicon, a binary oxide consisting of titanium-zirconium, and a ternary oxide consisting of titanium-silicon-zirconium, which are used in ozone decomposition treatment. The catalyst A component is at least one selected from manganese, iron, cobalt, nickel, zinc, silver, platinum,
A catalyst comprising at least one element selected from the group consisting of palladium and rhodium as a catalyst B component, wherein the catalyst A component is 40 to 100% by weight of oxide, and the catalyst B component is manganese. ,
For regenerating a catalyst, the range is 0 to 60% by weight as an oxide for iron, cobalt, nickel, zinc, and silver, and 0 to 10% by weight as a metal element for platinum, palladium, and rhodium. , 100-450 in air or oxygen
℃, preferably 200 to 400 ℃ is a catalyst regeneration method.
本発明が特定する触媒は、オゾン分解活性等が
優れるものであるが、本発明者らは再生において
も触媒活性の回復が容易で、従来の触媒に比較し
てはるかに低い温度で焼成することにより再生す
ることができることを見いだしたものである。本
発明の方法に従つて再生することにより、再生に
要するエネルギーが従来より少なくてすみ、装置
も簡略化でき、再生処理が簡便に行なえる。 The catalyst specified by the present invention has excellent ozone decomposition activity, etc., but the inventors have found that the catalyst activity can be easily recovered during regeneration, and that it can be fired at a much lower temperature than conventional catalysts. It was discovered that it can be reproduced by By regenerating according to the method of the present invention, less energy is required for regeneration than before, the equipment can be simplified, and the regeneration process can be performed easily.
本発明において、触媒の再生は空気中もしくは
酸素中で100〜450℃、好ましくは200〜400℃で焼
成して行なう。一般的に触媒のオゾン分解活性の
低下原因として、触媒表面の金属カチオンとオゾ
ンが反応し、過酸化物が生成し蓄積することが考
えられる。また処理ガス中に含まれるダストや水
分、ミストの触媒表面への付着も原因の一つと考
えられる。単純な水分吸着など触媒の活性劣化度
合が小さい場合には100〜150℃程度での乾燥でも
十分であるが、通常の場合は200〜400℃で焼成す
るのがよい。450℃を越える温度で焼成しても触
媒再生効果は増加せず、装置が大がかりになつた
りエネルギーが余計に必要になつたりして不利で
ある。 In the present invention, the catalyst is regenerated by firing in air or oxygen at 100 to 450°C, preferably 200 to 400°C. Generally, the cause of the decrease in the ozonolysis activity of a catalyst is thought to be the reaction between metal cations on the surface of the catalyst and ozone, resulting in the production and accumulation of peroxides. It is also thought that one of the causes is the adhesion of dust, moisture, and mist contained in the process gas to the catalyst surface. If the degree of deterioration of catalyst activity is small, such as when the catalyst is simply adsorbed with water, drying at a temperature of about 100 to 150°C is sufficient, but in normal cases, it is better to calcinate at a temperature of 200 to 400°C. Calcining at a temperature exceeding 450°C does not increase the catalyst regeneration effect and is disadvantageous in that the equipment becomes bulky and additional energy is required.
以下、実施例により本発明をさらに詳細に説明
するが、本発明は実施例のみに限定されるもので
はない。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited only to the Examples.
＜実施例＞
オゾン分解用触媒として、チタン−珪素からな
る二元系酸化物と酸化マンガンとからなり、各々
の組成比が重量比で85：15である触媒を用いた。
該触媒にオゾンを60ppm含有する空気を室温下、
空間速度50000hr-1にて通じ、空気中のオゾン分
解処理を行なつた。処理を開始してから2000時間
後オゾン分解効率を測定したところ、52％であつ
た。触媒を取り出し、電気加熱式焼成炉に入れて
加熱、350℃、３時間焼成し、触媒の再生を行な
つた。再生後の触媒を前回と同じ条件下でオゾン
分解処理に用いた。処理開始直後のオゾン分解効
率は95％であり、オゾン分解活性が回復してい
た。<Example> As an ozone decomposition catalyst, a catalyst was used which was composed of a binary oxide of titanium-silicon and manganese oxide, and the composition ratio of each was 85:15 by weight.
Air containing 60 ppm of ozone was added to the catalyst at room temperature.
It was conducted at a space velocity of 50,000 hr -1 to decompose ozone in the air. When the ozone decomposition efficiency was measured 2000 hours after starting the treatment, it was 52%. The catalyst was taken out, placed in an electrically heated calcining furnace, heated, and calcined at 350°C for 3 hours to regenerate the catalyst. The regenerated catalyst was used for ozone decomposition treatment under the same conditions as before. Immediately after the start of treatment, the ozone decomposition efficiency was 95%, indicating that the ozone decomposition activity had recovered.
Claims (1)
からなる二元系酸化物、チタン−ジルコニウムか
らなる二元系酸化物およびチタン−珪素−ジルコ
ニウムからなる三元系酸化物よりなる群から選ば
れる少なくとも１種を触媒Ａ成分とし、マンガ
ン、鉄、コバルト、ニツケル、亜鉛、銀、白金、
パラジウムおよびロジウムよりなる群から選ばれ
る少なくとも１種の元素を触媒Ｂ成分としてなる
触媒であつて、該触媒の組成が触媒Ａ成分は酸化
物の重量％で40〜100％、触媒Ｂ成分はマンガン、
鉄、コバルト、ニツケル、亜鉛および銀について
は酸化物としての重量％で０〜60％、白金、パラ
ジウムおよびロジウムについては金属元素として
の重量％で０〜10％の範囲よりなる触媒を再生す
るにあたり、空気中もしくは酸素中で100〜450℃
で焼成することを特徴とする触媒再生方法。1 At least one selected from the group consisting of a binary oxide consisting of titanium-silicon, a binary oxide consisting of titanium-zirconium, and a ternary oxide consisting of titanium-silicon-zirconium used in the ozonolysis treatment. One type is catalyst A component, manganese, iron, cobalt, nickel, zinc, silver, platinum,
A catalyst comprising at least one element selected from the group consisting of palladium and rhodium as a catalyst B component, wherein the catalyst A component is 40 to 100% by weight of oxide, and the catalyst B component is manganese. ,
For regenerating a catalyst, the range is 0 to 60% by weight as an oxide for iron, cobalt, nickel, zinc, and silver, and 0 to 10% by weight as a metal element for platinum, palladium, and rhodium. , 100-450℃ in air or oxygen
A catalyst regeneration method characterized by calcination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63148170A JPH01317543A (en) | 1988-06-17 | 1988-06-17 | Regeneration of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63148170A JPH01317543A (en) | 1988-06-17 | 1988-06-17 | Regeneration of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01317543A JPH01317543A (en) | 1989-12-22 |
| JPH0555185B2 true JPH0555185B2 (en) | 1993-08-16 |
Family
ID=15446813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63148170A Granted JPH01317543A (en) | 1988-06-17 | 1988-06-17 | Regeneration of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01317543A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010105537A (en) * | 2000-05-15 | 2001-11-29 | 박성호 | Ceramic catalyst for producing the radicals and method of prepartion for the same |
-
1988
- 1988-06-17 JP JP63148170A patent/JPH01317543A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01317543A (en) | 1989-12-22 |
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