JPH10180042A - Treatment of hydrazine-containing steam and catalyst for same - Google Patents
Treatment of hydrazine-containing steam and catalyst for sameInfo
- Publication number
- JPH10180042A JPH10180042A JP8341898A JP34189896A JPH10180042A JP H10180042 A JPH10180042 A JP H10180042A JP 8341898 A JP8341898 A JP 8341898A JP 34189896 A JP34189896 A JP 34189896A JP H10180042 A JPH10180042 A JP H10180042A
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- JP
- Japan
- Prior art keywords
- hydrazine
- catalyst
- steam
- oxygen
- containing steam
- 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.)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ヒドラジン含有水
蒸気の処理方法及びその触媒に関する。[0001] The present invention relates to a method for treating hydrazine-containing steam and a catalyst thereof.
【０００２】[0002]
【従来の技術】ボイラーで水蒸気を発生させる際、水中
の溶存酸素が配管等の腐食の原因となる。ボイラーにお
ける配管等の腐食を抑制するために、水に脱酸素剤とし
てヒドラジンやアスコルビン酸（ビタミンＣ）等が添加
され、ボイラーで使用されている。ヒドラジンは微生物
や細胞での実験で強い変異原性が認められることが知ら
れている。2. Description of the Related Art When steam is generated in a boiler, dissolved oxygen in the water causes corrosion of piping and the like. Hydrazine, ascorbic acid (vitamin C) and the like are added to water as an oxygen scavenger in order to suppress corrosion of piping and the like in a boiler, and are used in boilers. Hydrazine is known to have strong mutagenic properties in experiments with microorganisms and cells.
【０００３】ヒドラジンを脱酸素剤に使用する場合、人
体に有害な影響を与えるヒドラジンがボイラーで発生し
た水蒸気中に混入することになる。ヒドラジンを含む水
蒸気が使用される場合、大気中放出されたり、工業的に
使用されると環境破壊や人体（生物）に悪影響を与える
ため、水蒸気中からヒドラジンを除去する技術が求めら
れている。[0003] When hydrazine is used as an oxygen scavenger, hydrazine which has a harmful effect on the human body is mixed into steam generated in a boiler. When water vapor containing hydrazine is used, it is released into the air, or when used industrially, it has a detrimental effect on the environment and adverse effects on human bodies (living organisms). Therefore, a technique for removing hydrazine from water vapor is required.
【０００４】[0004]
【発明が解決しようとする課題】水蒸気中に含むヒドラ
ジンを除去し、環境や人体に悪影響を与えない。The hydrazine contained in the water vapor is removed so that the environment and the human body are not adversely affected.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、鋭意検討
を重ねた結果、ヒドラジンを含む水蒸気に特定の触媒と
接触させることにより、環境や人体に悪影響を与えない
レベルまで水蒸気中からヒドラジンを除去することを見
いだし、本発明の完成に至った。Means for Solving the Problems As a result of intensive studies, the present inventors have made it possible to bring hydrazine-containing water vapor into contact with a specific catalyst so that hydrazine can be converted from water vapor to a level that does not adversely affect the environment and the human body. To complete the present invention.
【０００６】すなわち、本発明はヒドラジン含有水蒸気
を触媒と接触させることを特徴とするヒドラジン含有水
蒸気の処理方法及びその触媒に関する。That is, the present invention relates to a method for treating hydrazine-containing steam, which comprises contacting hydrazine-containing steam with a catalyst, and a catalyst for the same.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明でいうヒドラジン含有水蒸気を触媒と接触させる
とは、触媒層をヒドラジン含有水蒸気を通気させ、触媒
により水蒸気中のヒドラジンを分解し、ヒドラジンを処
理することをいう。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The term “contacting the hydrazine-containing steam with the catalyst” as used in the present invention means that the catalyst layer is aerated with the hydrazine-containing steam and the catalyst decomposes hydrazine in the steam to treat the hydrazine.
【０００８】本発明で使用する触媒としては銅、鉄、亜
鉛、コバルト、モリブテン、イリジウム、ニッケル、マ
ンガン、クロム、パラジウム、銀、白金及びこれらの化
合物、ゼオライト、アルミナ、ヘリパック、ラヒシリン
グ、ディクソンパッキンの少なくとも一種類以上を含む
触媒を使用することが有用である。本発明での金属化合
物は酸化物、硝酸塩、塩化物等が挙げられる。また、ア
ルミナやゼオライトにイリジウム、パラジウム、銀、白
金等を少なくとも１種類以上を担持した触媒を用いても
良い。本発明で用いる触媒が粉末の場合、打錠成形、押
し出し成形等の方法で成形した成形体を用いる。[0008] The catalyst used in the present invention includes copper, iron, zinc, cobalt, molybdenum, iridium, nickel, manganese, chromium, palladium, silver, platinum and compounds thereof, zeolites, alumina, helipaks, Lahischilling, and Dixon packing. It is useful to use a catalyst containing at least one or more. The metal compound in the present invention includes oxides, nitrates, chlorides and the like. Further, a catalyst in which at least one kind of iridium, palladium, silver, platinum or the like is supported on alumina or zeolite may be used. When the catalyst used in the present invention is a powder, a molded product formed by a method such as tableting and extrusion is used.
【０００９】本発明ではヒドラジン含有水蒸気を触媒と
接触させ、水蒸気中のヒドラジンを除去する際の条件と
しては空間速度（以下、ＳＶと記す）が１．０×１０３
〜９．０×１０５ｈｒ−１が好ましい。ＳＶが１．０×
１０３ｈｒ−１未満では、水蒸気中のヒドラジンを十分
除去できるものの、使用する触媒量が多量になりコスト
高になり好ましくない。また、ＳＶが９．０×１０５ｈ
ｒ−１を超えると、ヒドラジン含有水蒸気を触媒と接触
させる際、ヒドラジンが長時間、安定して分解しないの
で好ましくない。In the present invention, the condition for contacting the hydrazine-containing steam with the catalyst and removing the hydrazine in the steam is such that the space velocity (hereinafter referred to as SV) is 1.0 × 10 3.
-9.0 * 10 < 5 > hr < -1 > is preferable. SV is 1.0 ×
If it is less than 10 3 hr −1 , hydrazine in the water vapor can be sufficiently removed, but the amount of the catalyst to be used increases and the cost increases, which is not preferable. In addition, the SV is 9.0 × 10 5 h
If it exceeds r −1 , it is not preferable because hydrazine is not stably decomposed for a long time when hydrazine-containing steam is brought into contact with the catalyst.
【００１０】触媒を長時間、安定して維持するために
は、ヒドラジン含有水蒸気中に空気又は酸素を添加する
ことにより、より効果的にヒドラジンを水蒸気中から除
去できる。In order to maintain the catalyst stably for a long time, hydrazine can be more effectively removed from the hydrazine-containing steam by adding air or oxygen to the hydrazine-containing steam.
【００１１】空気又は酸素の添加量はＳＶ、反応温度、
酸素の滞留時間等により一概に言えないが、水蒸気中の
酸素の濃度が１０ｐｐｍ〜１０容量％が好ましく、更に
好ましくは、１００ｐｐｍ〜５容量％が好適である。酸
素の濃度が１０ｐｐｍ未満では、酸素が希薄であるため
ヒドラジンとの接触効率が低く、ヒドラジンの分解反応
が進行しにくく、所望の濃度まで除去できないので好ま
しくない。また、１０容量％を超えると所望の濃度まで
除去できるものの、ヒドラジン除去への高い効果が認め
られないので好ましくない。さらには、溶存酸素が多量
になるため、配管等の腐食の原因となるので好ましくな
い。The amount of air or oxygen to be added is SV, reaction temperature,
The concentration of oxygen in the steam is preferably 10 ppm to 10% by volume, more preferably 100 ppm to 5% by volume, although it cannot be said unconditionally due to the residence time of oxygen or the like. If the oxygen concentration is less than 10 ppm, the contact efficiency with hydrazine is low because the oxygen is diluted, and the decomposition reaction of hydrazine hardly proceeds, and it cannot be removed to a desired concentration. If it exceeds 10% by volume, it can be removed to a desired concentration, but a high effect on hydrazine removal is not recognized. Further, since a large amount of dissolved oxygen causes corrosion of piping and the like, it is not preferable.
【００１２】また、触媒としてヘリパック、ラヒシリン
グ、ディクソンパッキンを使用した場合、これらのもの
は触媒としての活性は殆どないので、水蒸気に空気又は
酸素を添加する必要がある。ヘリパック、ラヒシリン
グ、ディクソンパッキンは他の触媒と異なり、触媒界面
で酸素によるヒドラジンの分解反応だけでヒドラジンの
低減を行う。そのため、他の触媒のように触媒劣化のよ
るヒドラジン分解能力低下ということがないので、ヒド
ラジンの分解能力を長時間、安定して維持することがで
きる。When Helipak, Rahischilling, or Dickson packing is used as a catalyst, these have almost no activity as a catalyst, so that it is necessary to add air or oxygen to steam. Unlike other catalysts, Helipak, Lahischilling and Dixon packing reduce hydrazine only by the decomposition reaction of hydrazine by oxygen at the catalyst interface. Therefore, unlike other catalysts, there is no decrease in hydrazine decomposition ability due to catalyst deterioration, and the hydrazine decomposition ability can be stably maintained for a long time.
【００１３】この際、水蒸気中からヒドラジンを除去す
る条件としてはＳＶが１．０×１０ ３ｈｒ−１以上で水
蒸気中の酸素の濃度が１０ｐｐｍ〜１０容量％になるよ
うに空気または酸素を水蒸気中に添加することが好まし
い。更に好ましくは水蒸気中の酸素濃度が２００ｐｐｍ
〜７容量％となるのが好適である。ＳＶが１．０×１０
３ｈｒ−１未満では、水蒸気中のヒドラジンを十分除去
できるものの、使用する触媒量が多量になりコスト高に
なり好ましくない。また酸素の濃度が１０ｐｐｍ未満で
は、酸素が希薄であるためヒドラジンとの接触効率が低
く、ヒドラジンの分解反応が進行しにくく、所望の濃度
まで除去できないので好ましくない。また、１０容量％
を超えると所望の濃度まで除去できるものの、ヒドラジ
ン除去への高い効果が認められないので好ましくない。
さらには、溶存酸素が多量になるため、配管等の腐食の
原因となるので好ましくない。At this time, hydrazine is removed from the steam.
As a condition, SV is 1.0 × 10 3hr-1Water over
The concentration of oxygen in the steam will be 10ppm to 10% by volume
It is preferable to add air or oxygen to the steam
No. More preferably, the oxygen concentration in the steam is 200 ppm
It is preferably about 7% by volume. SV is 1.0 × 10
3hr-1If less than, hydrazine in water vapor is sufficiently removed
Although it can be used, the amount of catalyst used increases and the cost increases
It is not preferable. If the oxygen concentration is less than 10 ppm
Has low contact efficiency with hydrazine due to the low oxygen content
Hydrazine decomposition reaction does not progress easily and the desired concentration
It is not preferable because it cannot be removed to the maximum. 10% by volume
If it exceeds, it can be removed to the desired concentration,
This is not preferable because a high effect on the removal of the resin is not recognized.
Furthermore, since the amount of dissolved oxygen becomes large, corrosion of piping etc.
It is not preferable because it causes.
【００１４】ヒドラジン含有水蒸気中に空気又は酸素を
添加すると前述したように、配管等の腐食の原因となる
ので、ヒドラジン含有水蒸気中と触媒層を接触させる
際、触媒のできるだけ近い上流側に添加するのがよい。
また、空気又は酸素の添加付近を特殊な材質を用いるこ
ともできる。As described above, if air or oxygen is added to hydrazine-containing steam, it causes corrosion of piping and the like. Therefore, when the catalyst layer is brought into contact with hydrazine-containing steam, the air or oxygen is added as close as possible to the upstream side of the catalyst. Is good.
In addition, a special material can be used in the vicinity of the addition of air or oxygen.
【００１５】水蒸気中に空気又は酸素を添加する方法と
しては、水蒸気の流れに対して並流でも向流のどちらで
も良い。空気又は酸素が存在することにより、ヒドラジ
ンが容易に分解され、触媒への負荷が減少し、触媒のラ
イフが延びる効果がある。特に触媒として金属酸化物を
使用している場合、ヒドラジンの分解により触媒表面の
酸素が消費され、触媒活性が低下するが、空気又は酸素
を水蒸気に添加し、空気又は酸素存在下でヒドラジンの
処理を行うと、消費された酸素が補充され、触媒のライ
フを延長する効果もある。また、処理温度は１００〜２
００℃が好ましく、圧力は特に制限するものではない。The method of adding air or oxygen to steam may be either cocurrent or countercurrent to the steam flow. The presence of air or oxygen has the effect of easily decomposing hydrazine, reducing the load on the catalyst, and extending the life of the catalyst. Especially when a metal oxide is used as a catalyst, oxygen on the surface of the catalyst is consumed by the decomposition of hydrazine and the catalytic activity is reduced.However, treatment of hydrazine in the presence of air or oxygen by adding air or oxygen to steam is performed. Is performed, the consumed oxygen is replenished, and there is also an effect of extending the life of the catalyst. The processing temperature is 100 to 2
00 ° C. is preferable, and the pressure is not particularly limited.
【００１６】本発明で用いる反応器としては固定層触媒
反応器が挙げられるがこれに限定するものではない。反
応器は水蒸気配管の途中に取り付け、水蒸気中のヒドラ
ジンの処理を行う方法が挙げられる。反応器は加熱を行
っても良いし、水蒸気自身の熱で反応を行ってもよい。The reactor used in the present invention includes, but is not limited to, a fixed-bed catalytic reactor. The reactor may be installed in the middle of a steam pipe to process hydrazine in steam. The reactor may be heated, or the reaction may be performed with the heat of steam itself.
【００１７】[0017]
【実施例】以下、本発明を実施例にて詳細に説明する。
本発明の水蒸気中のヒドラジンの含有量は、ｐ−ジメチ
ルアミノベンズアルデヒド吸光光度法で水蒸気の凝集水
中ヒドラジンを定量する方法で測定した。 実施例１ 触媒として東洋ＣＣＩ社製Ｃ１８（ＣｕＯ／ＺｎＯ）を
用いて、ＳＶ＝５．０×１０３ｈｒ−１、処理温度１３
０℃で水蒸気中に含まれる１００ｐｐｂのヒドラジンの
除去を行った。その結果を表１に示す。The present invention will be described below in detail with reference to examples.
The content of hydrazine in the water vapor of the present invention was measured by a method of quantifying hydrazine in water agglomerated with water vapor by p-dimethylaminobenzaldehyde absorption spectrophotometry. Example 1 Using C18 (CuO / ZnO) manufactured by Toyo CCI as a catalyst, SV = 5.0 × 10 3 hr −1 , treatment temperature 13
At 0 ° C., 100 ppb of hydrazine contained in steam was removed. Table 1 shows the results.
【００１８】実施例２〜３ ＳＶをそれぞれ５．０×１０４ｈｒ−１、５．０×１０
５ｈｒ−１に変更した以外は実施例１と同様の方法で水
蒸気中のヒドラジンの除去を行った。その結果を表１に
示す。Examples 2 to 3 SV was 5.0 × 10 4 hr −1 and 5.0 × 10 4 respectively.
The hydrazine in the steam was removed in the same manner as in Example 1 except that the hydrazine was changed to 5 hr -1 . Table 1 shows the results.
【００１９】実施例４ 処理温度を１７５℃に変更した以外は実施例１と同様の
方法で水蒸気中のヒドラジンの除去を行った。その結果
を表１に示す。Example 4 Hydrazine in water vapor was removed in the same manner as in Example 1 except that the treatment temperature was changed to 175 ° C. Table 1 shows the results.
【００２０】実施例５〜７ 水蒸気中のヒドラジン含有量に対し、酸素濃度をそれぞ
れ１００ｐｐｍ、３，０００ｐｐｍ及び３％添加した以
外は、実施例３と同様の方法で水蒸気中のヒドラジンの
除去を行った。その結果を表１に示す。Examples 5 to 7 The removal of hydrazine in water vapor was carried out in the same manner as in Example 3 except that the oxygen concentration was 100 ppm, 3,000 ppm and 3%, respectively, based on the hydrazine content in the water vapor. Was. Table 1 shows the results.
【００２１】実施例８〜１０ 触媒をそれぞれ東洋ＣＣＩ社製Ｃ１２（Ｆｅ２Ｏ３／Ｃ
ｒ２Ｏ３）、東洋ＣＣＩ社製ＣＯＲ−２−０２（Ｐｄ／
Ｐｔ／Ａｌ２Ｏ３）及びゼオライトに変更した以外は、
実施例１と同様の方法で水蒸気中のヒドラジンの除去を
行った。その結果を表１に示す。Examples 8 to 10 The catalyst was C12 (Fe 2 O 3 / C manufactured by Toyo CCI Co., Ltd.).
r 2 O 3 ), COR-2-02 (Pd /
Pt / Al 2 O 3 ) and zeolite
The hydrazine in the water vapor was removed in the same manner as in Example 1. Table 1 shows the results.
【００２２】実施例１１〜１３ 触媒を東洋ＣＣＩ社製Ｃ１８（ＣｕＯ／ＺｎＯ）からヘ
リパックに変更した以外は実施例５〜７と同様の方法で
水蒸気中のヒドラジンの除去を行った。その結果を表１
に示す。Examples 11 to 13 Hydrazine in steam was removed in the same manner as in Examples 5 to 7 except that the catalyst was changed from C18 (CuO / ZnO) manufactured by Toyo CCI to Helipak. Table 1 shows the results.
Shown in
【００２３】実施例１４ 触媒をヘリパックからラヒシリングに変更した以外は実
施例１２と同様の方法で水蒸気中のヒドラジンの除去を
行った。その結果を表１に示す。Example 14 The removal of hydrazine in steam was carried out in the same manner as in Example 12 except that the catalyst was changed from Helipak to Rahichilling. Table 1 shows the results.
【００２４】[0024]
【表１】 Ｃ１８：ＣｕＯ／ＺｎＯ、Ｃ１２：Ｆｅ２Ｏ３／Ｃｒ２
Ｏ３、ＣＯＲ−２−０２：Ｐｄ／Ｐｔ／Ａｌ２Ｏ３ [Table 1] C18: CuO / ZnO, C12: Fe 2 O 3 / Cr 2
O 3 , COR-2-02: Pd / Pt / Al 2 O 3
【００２５】[0025]
【発明の効果】本発明のヒドラジン含有水蒸気の処理方
法は、特定の触媒を用いることにより、ヒドラジン含有
水蒸気中のヒドラジンを処理し、環境や人体に悪影響を
与えることのない水蒸気を得ることができる。また、空
気又は酸素を添加することにより、より効果的に水蒸気
中からヒドラジンを除去でき、更に触媒のライフを延長
することができる。本発明のヒドラジン含有水蒸気の処
理方法により水蒸気中からヒドラジンを除去できるの
で、環境破壊や人体へ健康被害等の問題を解決できる。According to the method for treating hydrazine-containing steam of the present invention, hydrazine in hydrazine-containing steam can be treated by using a specific catalyst to obtain steam that does not adversely affect the environment or the human body. . In addition, by adding air or oxygen, hydrazine can be more effectively removed from steam, and the life of the catalyst can be further extended. Since hydrazine can be removed from water vapor by the method for treating hydrazine-containing water vapor of the present invention, problems such as environmental destruction and health damage to the human body can be solved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 23/70 Ｂ０１Ｊ 23/70 Ｍ Ｆ２２Ｂ 37/00 Ｆ２２Ｂ 37/00 Ａ (72)発明者 志村 和也 山口県下関市彦島迫町七丁目１番１号 三 井東圧化学株式会社内────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification code FI B01J 23/70 B01J 23/70 M F22B 37/00 F22B 37/00 A (72) Inventor Kazuya Shimura Shiko Hikoshima, Shimonoseki City, Yamaguchi Prefecture 7-1-1, Machi-cho, Mitsui Toatsu Chemicals Co., Ltd.
Claims (5)
せることを特徴とするヒドラジン含有水蒸気の処理方
法。1. A method for treating hydrazine-containing steam, comprising contacting hydrazine-containing steam with a catalyst.
素を添加する請求項１記載のヒドラジン含有水蒸気の処
理方法。2. The method for treating hydrazine-containing steam according to claim 1, wherein air or oxygen is added to the hydrazine-containing steam.
気又は酸素が、１０ｐｐｍ〜１０容量％である請求項１
または２記載のヒドラジン含有水蒸気の処理方法。3. The method according to claim 1, wherein the amount of air or oxygen added to the hydrazine-containing steam is 10 ppm to 10% by volume.
Or the method for treating hydrazine-containing steam according to 2 above.
リブテン、イリジウム、ニッケル、マンガン、クロム、
パラジウム、銀、白金及びこれらの化合物、ゼオライ
ト、アルミナ、ヘリパック、ラヒシリング、ディクソン
パッキンの少なくとも一種類以上を含む請求項１〜３項
のいずれか１項に記載のヒドラジン含有水蒸気の処理方
法。4. The catalyst comprises copper, iron, zinc, cobalt, molybdenum, iridium, nickel, manganese, chromium,
The method for treating hydrazine-containing steam according to any one of claims 1 to 3, wherein the method comprises at least one of palladium, silver, platinum, and compounds thereof, zeolite, alumina, helipak, Lahischilling, and Dixon packing.
蒸気中のヒドラジンを処理する触媒。5. A catalyst for treating hydrazine in steam by contacting hydrazine-containing steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8341898A JPH10180042A (en) | 1996-12-20 | 1996-12-20 | Treatment of hydrazine-containing steam and catalyst for same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8341898A JPH10180042A (en) | 1996-12-20 | 1996-12-20 | Treatment of hydrazine-containing steam and catalyst for same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10180042A true JPH10180042A (en) | 1998-07-07 |
Family
ID=18349604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8341898A Pending JPH10180042A (en) | 1996-12-20 | 1996-12-20 | Treatment of hydrazine-containing steam and catalyst for same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10180042A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100712637B1 (en) | 2005-12-23 | 2007-04-30 | 한국항공우주연구원 | Method for preparing iridium catalyst for decomposition of hydrazine for a space vehicle thruster having high strength characteristics using bauxite and iridium catalyst obtained therefrom |
| JP2007269514A (en) * | 2006-03-30 | 2007-10-18 | Toyota Tsusho Corp | Hydrogen production method and hydrogen production apparatus |
| JP2007269529A (en) * | 2006-03-30 | 2007-10-18 | Toyota Tsusho Corp | Hydrogen production apparatus |
| JP2011041894A (en) * | 2009-08-20 | 2011-03-03 | Taiyo Nippon Sanso Corp | Method for treating exhaust gas and detoxifying agent |
-
1996
- 1996-12-20 JP JP8341898A patent/JPH10180042A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100712637B1 (en) | 2005-12-23 | 2007-04-30 | 한국항공우주연구원 | Method for preparing iridium catalyst for decomposition of hydrazine for a space vehicle thruster having high strength characteristics using bauxite and iridium catalyst obtained therefrom |
| JP2007269514A (en) * | 2006-03-30 | 2007-10-18 | Toyota Tsusho Corp | Hydrogen production method and hydrogen production apparatus |
| JP2007269529A (en) * | 2006-03-30 | 2007-10-18 | Toyota Tsusho Corp | Hydrogen production apparatus |
| JP2011041894A (en) * | 2009-08-20 | 2011-03-03 | Taiyo Nippon Sanso Corp | Method for treating exhaust gas and detoxifying agent |
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