JP3219613B2 - Ammonia decomposition catalyst and method for decomposing and removing ammonia - Google Patents
Ammonia decomposition catalyst and method for decomposing and removing ammoniaInfo
- Publication number
- JP3219613B2 JP3219613B2 JP27906094A JP27906094A JP3219613B2 JP 3219613 B2 JP3219613 B2 JP 3219613B2 JP 27906094 A JP27906094 A JP 27906094A JP 27906094 A JP27906094 A JP 27906094A JP 3219613 B2 JP3219613 B2 JP 3219613B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- catalyst
- decomposing
- decomposition catalyst
- 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
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- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は各種排ガス等に含まれる
アンモニアを無害な窒素に分解除去する触媒及び同触媒
を使用してアンモニアを分解除去する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for decomposing and removing ammonia contained in various exhaust gases and the like into harmless nitrogen and a method for decomposing and removing ammonia using the catalyst.
【0002】[0002]
【従来の技術】アンモニアは肥料や硝酸の製造原料、冷
媒、排ガス中の窒素酸化物除去用還元剤等幅広い分野で
使用されている。したがって、各種化学品製造工場、冷
凍機等の廃棄物処理工場あるいは燃焼排ガス処理施設等
からは多量のアンモニアが排出される。アンモニアは特
異な刺激臭を有する気体であり大気中への放出は極力抑
える必要がある。しかし、生物の腐敗によるアンモニア
の生成や廃棄物中の冷媒からのアンモニアの放散、さら
に煙道排ガス中の窒素酸化物の還元に用いられるアンモ
ニアが未反応のまま大気放出される等、多くの場所でア
ンモニアが大気放出されているのが現状である。2. Description of the Related Art Ammonia is used in a wide variety of fields such as raw materials for producing fertilizers and nitric acid, refrigerants, and reducing agents for removing nitrogen oxides from exhaust gas. Therefore, a large amount of ammonia is discharged from various chemical manufacturing plants, a waste treatment plant such as a refrigerator, or a combustion exhaust gas treatment facility. Ammonia is a gas having a peculiar pungent odor, and its release into the atmosphere must be minimized. However, in many places, such as the production of ammonia due to the decay of organisms, the emission of ammonia from refrigerants in waste, and the release of ammonia used for the reduction of nitrogen oxides in flue gas without being reacted to the atmosphere At present, ammonia is released to the atmosphere.
【0003】[0003]
【発明が解決しようとする課題】アンモニアの大気放出
を防ぐ方法の一つとしてアルミナやシリカ−アルミナ系
担体に酸化鉄や酸化ニッケルを担持させた触媒を利用し
て次の反応式によりアンモニアを無害な窒素に分解する
方法が知られている。As one of the methods for preventing the release of ammonia into the atmosphere, ammonia is made harmless by the following reaction formula using a catalyst in which iron oxide or nickel oxide is supported on an alumina or silica-alumina carrier. There is known a method of decomposing into nitrogen.
【化1】 2NH3 + 3/2O2 → N2 + 3H2 O ところが、従来の触媒では400℃以下の低温での反応
活性が乏しく、さらに前記反応以外に次のような副反応
によりNO,NO2 ,N2 O等の生成が認められ、新た
に大気汚染を生じる恐れがあった。2NH 3 + 3 / 2O 2 → N 2 + 3H 2 O However, the conventional catalyst has poor reaction activity at a low temperature of 400 ° C. or lower, and further has NO, Generation of NO 2 , N 2 O and the like was recognized, and there was a possibility that air pollution would newly occur.
【化2】 2NH3 + 5/2O2 → 2NO + 3H2 O 2NH3 + 7/2O2 → 2NO2 + 3H2 O 2NH3 + 2O2 → N2 O + 3H2 OEmbedded image 2NH 3 + 5 / 2O 2 → 2NO + 3H 2 O 2NH 3 + 7 / 2O 2 → 2NO 2 + 3H 2 O 2NH 3 + 2O 2 → N 2 O + 3H 2 O
【0004】本発明の目的は前記従来技術の問題点を解
決し、大気汚染のもととなる窒素酸化物の副生を極力抑
え、高い収率でアンモニアを分解除去することのできる
アンモニア分解触媒及び同触媒を使用したアンモニア分
解除去方法を提供することにある。An object of the present invention is to solve the above-mentioned problems of the prior art, and to minimize the by-product of nitrogen oxides, which cause air pollution, and to decompose and remove ammonia with a high yield. And a method for decomposing and removing ammonia using the same catalyst.
【0005】[0005]
【課題を解決するための手段】本発明は チタン酸化
物担体上に、バナジウム、タングステン及びモリブデン
よりなる群から選ばれた元素の酸化物の少なくとも1種
以上と白金及び/又はイリジウムを担持させてなること
を特徴とするアンモニア分解触媒及び 上記記載の
アンモニア分解触媒にアンモニア含有ガスを接触させる
ことを特徴とするアンモニア含有ガスのアンモニアの分
解除去方法である。According to the present invention, at least one oxide of an element selected from the group consisting of vanadium, tungsten and molybdenum and platinum and / or iridium are supported on a titanium oxide carrier. A method for decomposing and removing ammonia from an ammonia-containing gas, comprising contacting an ammonia-containing gas with the ammonia decomposition catalyst described above.
【0006】本発明の触媒はチタン酸化物担体上にアン
モニアの分解活性に優れた白金及び/又はイリジウム
と、アンモニアを還元剤としたときに脱硝活性に優れた
バナジウム、タングステン及びモリブデンよりなる群か
ら選ばれた少なくとも1種類の元素の酸化物より構成さ
れる。各々の反応式は下記のとおりである。[0006] The catalyst of the present invention is selected from the group consisting of platinum and / or iridium having excellent ammonia decomposition activity on a titanium oxide carrier and vanadium, tungsten and molybdenum having excellent denitration activity when ammonia is used as a reducing agent. It is composed of an oxide of at least one selected element. Each reaction formula is as follows.
【化3】 2NH3 + 5/2O2 → 2NO + 3H2 O ・・・ 4NH3 +4NO+O2 → 4N2 + 6H2 O ・・・Embedded image 2NH 3 + 5 / 2O 2 → 2NO + 3H 2 O 4NH 3 + 4NO + O 2 → 4N 2 + 6H 2 O
【0007】すなわち、式は白金及び/又はイリジウ
ムが300℃付近の低温域にて高活性を有し、式は担
体であるチタン酸化物及びバナジウム、タングステン及
びモリブデンよりなる群から選ばれた少なくとも1種類
以上の元素の酸化物が高活性を有する。すなわち、式
と式の反応を逐次的に進行することができれば、アン
モニアを選択的にN2 に分解することが可能である。白
金及び/又はイリジウムは種々の担体にて含浸法等によ
り調製し、高いNH 3 分解活性を示し、とりわけ脱硝触
媒として使用されているチタニア(TiO2)担体上で
十分な活性を示す。また、バナジウム、タングステン及
びモリブデンよりなる群から選ばれた1種類以上の元素
の酸化物は通常脱硝触媒として使用されており、チタニ
ア担体上にV2 O5 ,WO3 ,MoO3 のうち1種以上
が含浸法又は共沈法により担持される。That is, the formula is platinum and / or iridium.
Has high activity in the low temperature range around 300 ° C,
Titanium oxide and vanadium, tungsten and
At least one selected from the group consisting of molybdenum and molybdenum
Oxides of the above elements have high activity. That is, the expression
If the reaction of the formula can proceed sequentially,
Monia selectively NTwoCan be decomposed into White
Gold and / or iridium can be impregnated with various carriers by impregnation, etc.
High NH ThreeShows decomposition activity, especially denitration
Titania (TiO 2) used as a mediumTwo) On the carrier
Shows sufficient activity. Vanadium, tungsten and
At least one element selected from the group consisting of molybdenum and molybdenum
Oxides are usually used as denitration catalysts,
V on the carrierTwoOFive, WOThree, MoOThreeOne or more of
Is supported by an impregnation method or a coprecipitation method.
【0008】[0008]
【作用】前記触媒は必要によりチタニアゾル、アルミナ
ゾル、シリカゾルなどのバインダ成分やコージェライト
等の基材を使用し、ウォッシュコート法又はソリッド法
によりハニカム化して使用するのが好ましい。アンモニ
アを含有するガスを、100〜600℃の温度で前記触
媒に接触させることにより、ガス中のアンモニアは主に
窒素に分解される。この分解反応は選択的に進行し、N
O、NO2 、N2 O等の有害ガスはほとんど副生しな
い。さらに、本触媒はSO2 が共存する排ガスにおいて
も、アンモニア分解活性が低下することなく安定なアン
モニア分解性能を保つ。また、SO2 をSO3 へ酸化さ
せる能力は低いため酸性硫酸アンモニウム生成の不具合
点も見られない。The above catalyst is preferably used as a honeycomb by a wash coat method or a solid method using a binder component such as titania sol, alumina sol, silica sol or the like or a base material such as cordierite, if necessary. By bringing the gas containing ammonia into contact with the catalyst at a temperature of 100 to 600 ° C., the ammonia in the gas is mainly decomposed into nitrogen. This decomposition reaction proceeds selectively, and N
Hazardous gases such as O, NO 2 and N 2 O are hardly produced as by-products. Further, the present catalyst maintains a stable ammonia decomposition performance without reducing the ammonia decomposition activity even in an exhaust gas in which SO 2 coexists. Further, since the ability to oxidize SO 2 to SO 3 is low, there is no problem in producing acidic ammonium sulfate.
【0009】[0009]
【実施例】以下、実施例により本発明の触媒及びアンモ
ニアの分解除去方法を具体的に説明する。EXAMPLES Hereinafter, the catalyst and the method for decomposing and removing ammonia of the present invention will be described in detail with reference to examples.
【0010】(例1)チタニア(TiO2 )担体にメタ
バナジン酸アンモニウム(NH4 VO3 )、パラタング
ステン酸アンモニウム{(NH4 )10H10W12O46・6
H2 O}を各々10%メチルアミン水溶液で溶かし、V
2 O5 で4wt%、WO3 で8wt%を含浸法により担
持させ、蒸発・乾固して500℃×6時間焼成して粉末
触媒を得た。さらに、この粉末触媒に塩化イリジウム
(IrCl4 ・H2 O)水溶液に含浸させIrを0.5
wt%担持させ、蒸発・乾固後、500℃、6時間焼成
して粉末触媒1を得た。(Example 1) On a titania (TiO 2 ) carrier, ammonium metavanadate (NH 4 VO 3 ), ammonium paratungstate {(NH 4 ) 10 H 10 W 12 O 46.6
H 2 O} is dissolved in a 10% aqueous solution of methylamine.
4 wt% of 2 O 5 and 8 wt% of WO 3 were supported by impregnation, evaporated, dried and calcined at 500 ° C. for 6 hours to obtain a powdered catalyst. Further, this powder catalyst was impregnated with an iridium chloride (IrCl 4 .H 2 O) aqueous solution to reduce Ir to 0.5%.
wt%, and evaporated and dried, and then calcined at 500 ° C. for 6 hours to obtain a powder catalyst 1.
【0011】得られた粉末触媒100部に対してバイン
ダとしてチタニアゾル40部(TiO2 :20wt%)
及び水200部を加え、スラリとして7.6mmピッ
チ、壁厚コージェライトハニカム基材にウォッシュコー
トして、基材表面積当り200g/m2 のコート量を担
持した。得られた触媒をハニカム触媒1とする。For 100 parts of the obtained powder catalyst, 40 parts of titania sol as a binder (TiO 2 : 20 wt%)
Then, 200 parts of water and 200 parts of water were added thereto, and the slurry was wash-coated on a 7.6 mm pitch, wall thickness cordierite honeycomb substrate to carry a coating amount of 200 g / m 2 per substrate surface area. The obtained catalyst is referred to as “honeycomb catalyst 1”.
【0012】(例2)上記ハニカム触媒1の調製法でV
2 O5 の担持量を5wt%、WO3 の担持量を9wt%
として他は例1と同様な方法で調製してハニカム触媒2
を得た。(Example 2) In the preparation method of the honeycomb catalyst 1 described above, V
5% by weight of 2 O 5 supported and 9% by weight of WO 3 supported
Other than that, the honeycomb catalyst 2 was prepared in the same manner as in Example 1 and
I got
【0013】また、上記ハニカム触媒1の調製法でパラ
タングステン酸アンモニウムの代わりにモリブデン酸ア
ンモニウム{(NH4 )2 MoO4 }を用いてMoO3
で8wt%担持させた他は例1と同様な方法で調製して
ハニカム触媒3を得た。Further, in the above-mentioned method for preparing the honeycomb catalyst 1, MoO 3 was replaced by ammonium molybdate {(NH 4 ) 2 MoO 4 } instead of ammonium paratungstate.
The honeycomb catalyst 3 was prepared in the same manner as in Example 1 except that the catalyst was supported by 8 wt%.
【0014】さらに、上記ハニカム触媒1の調製法で塩
化イリジウム水溶液の代わりに塩化白金酸を用い白金担
持量(Pt)で0.05wt%担持させた他は例1と同
様な方法で調製してハニカム触媒4を得た。Further, a honeycomb catalyst was prepared in the same manner as in Example 1 except that chloroplatinic acid was used in place of the iridium chloride aqueous solution and 0.05% by weight of platinum was supported (Pt). A honeycomb catalyst 4 was obtained.
【0015】加えて、上記ハニカム触媒1の調製法でパ
ラタングステン酸アンモニウムを使用しない他は例1と
同様な方法で調製してハニカム触媒5を得た。In addition, a honeycomb catalyst 5 was obtained in the same manner as in Example 1, except that ammonium paratungstate was not used.
【0016】(例3)上記ハニカム触媒1の調製法にお
いてチタニア担体上にメタバナジン酸アンモニウム、パ
ラタングステン酸アンモニウム、塩化イリジウムを同時
にメチルアミン水溶液に溶かし、V2 O5 、WO3 、I
rO2 を共含浸させ、例1と同様の組成にて、焼成処理
を行い粉末触媒6及びハニカム触媒6を得た。(Example 3) In the preparation method of the above-mentioned honeycomb catalyst 1, ammonium metavanadate, ammonium paratungstate and iridium chloride were simultaneously dissolved in a methylamine aqueous solution on a titania carrier, and V 2 O 5 , WO 3 , I
The mixture was impregnated with rO 2 and calcined at the same composition as in Example 1 to obtain a powder catalyst 6 and a honeycomb catalyst 6.
【0017】(例4)40mm×50mm×150mm
Lのアンモニア分解触媒3本を直列に設置し、反応試験
を実施した。実験条件は下記の表1のとおりである。(Example 4) 40 mm × 50 mm × 150 mm
Three L ammonia decomposition catalysts were installed in series, and a reaction test was performed. The experimental conditions are as shown in Table 1 below.
【0018】[0018]
【表1】 [Table 1]
【0019】性能評価は反応初期状態におけるアンモニ
ア分解率及びNOx(NO、NO2、N2 O)生成率及
びSO2 酸化率を測定することによって行なった。な
お、アンモニア分解率及びNOx生成率は次の式により
求めた。The performance was evaluated by measuring the ammonia decomposition rate, NOx (NO, NO 2 , N 2 O) production rate and SO 2 oxidation rate in the initial state of the reaction. The ammonia decomposition rate and the NOx generation rate were determined by the following equations.
【0020】〇 アンモニア分解率(%)=〔(入口N
H3 −出口NH3 )/入口NH3 〕×100〇 Ammonia decomposition rate (%) = [(Inlet N
H 3 -outlet NH 3 ) / inlet NH 3 ] × 100
【0021】〇 NOx生成率(%)=〔出口(N2 O
×2+NO+NO2 )/入口NH3 〕×100〇 NOx generation rate (%) = [outlet (N 2 O
× 2 + NO + NO 2 ) / Inlet NH 3 ] × 100
【0022】〇 SO2 酸化率(%)=〔出口SO3 /
入口SO2 〕×100酸化 SO 2 oxidation rate (%) = [outlet SO 3 /
Inlet SO 2 ] × 100
【0023】結果を下記表2に示した。本発明脱硝触媒
を用いたアンモニア分解方法においては、アンモニア分
解率は約90%、NOx生成率は2〜3%、SO2 酸化
率は約1%と何れも高性能を有することを確認した。The results are shown in Table 2 below. In the ammonia decomposition method using the present invention denitration catalyst, the ammonia decomposition rate is about 90%, NOx formation rate is 2 to 3%, SO 2 oxidation rate was confirmed to have about 1% and both high performance.
【0024】[0024]
【表2】 [Table 2]
【0025】(例5)ハニカム触媒1〜5を使用し例4
と同一の条件にて3000時間通ガスすることにより耐
久性評価試験を実施した。その結果を表3に示す。前記
ガス条件にて3000時間供給後においてもほぼ表2と
同様のアンモニア分解率、NOx生成率及びSO2 酸化
率を維持しており、耐久性に優れた触媒であることが確
認された。Example 5 Example 4 using honeycomb catalysts 1 to 5
A durability evaluation test was performed by passing gas for 3,000 hours under the same conditions as described above. Table 3 shows the results. Almost Table 2 the same ammonia decomposition rate even after supply 3000 hours the gas conditions, maintains the NOx generation rate and SO 2 oxidation rate, it was confirmed that excellent catalysts in durability.
【0026】[0026]
【表3】 [Table 3]
【0027】[0027]
【発明の効果】本発明によれば、SO2 の酸化やNOx
等の副生成物を極力抑制して、アンモニアを無害な窒素
に分解することができる。このような分解処理方法は従
来なかったものであり、その産業上の利用価値は極めて
大きいものがある。According to the present invention, oxidation of SO 2 and NOx
And other by-products can be suppressed as much as possible to decompose ammonia into harmless nitrogen. Such a decomposition treatment method has not been available in the past, and its industrial utility value is extremely large.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) B01J 21/00 - 38/74 B01D 53/86 B01D 53/94 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) B01J 21/00-38/74 B01D 53/86 B01D 53/94
Claims (2)
ングステン及びモリブデンよりなる群から選ばれた元素
の酸化物の少なくとも1種以上と白金及び/又はイリジ
ウムを担持させてなることを特徴とするアンモニア分解
触媒。Ammonia characterized in that at least one oxide of an element selected from the group consisting of vanadium, tungsten and molybdenum and platinum and / or iridium are supported on a titanium oxide carrier. Cracking catalyst.
ンモニア含有ガスを接触させることを特徴とするアンモ
ニア含有ガスのアンモニアの分解除去方法。2. A method for decomposing and removing ammonia from an ammonia-containing gas, comprising bringing the ammonia-containing gas into contact with the ammonia decomposition catalyst according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27906094A JP3219613B2 (en) | 1994-11-14 | 1994-11-14 | Ammonia decomposition catalyst and method for decomposing and removing ammonia |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27906094A JP3219613B2 (en) | 1994-11-14 | 1994-11-14 | Ammonia decomposition catalyst and method for decomposing and removing ammonia |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08131832A JPH08131832A (en) | 1996-05-28 |
JP3219613B2 true JP3219613B2 (en) | 2001-10-15 |
Family
ID=17605851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27906094A Expired - Lifetime JP3219613B2 (en) | 1994-11-14 | 1994-11-14 | Ammonia decomposition catalyst and method for decomposing and removing ammonia |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3219613B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8202481B2 (en) | 2007-08-22 | 2012-06-19 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst and exhaust gas treatment system |
EP3578247A1 (en) * | 2018-06-06 | 2019-12-11 | Clariant International Ltd | Honeycomb catalytic converter, method for the oxidation of carbon monoxide and organic air pollutants using the honeycomb catalytic converter and use of the honeycomb catalytic converter |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7393511B2 (en) * | 2005-02-16 | 2008-07-01 | Basf Catalysts Llc | Ammonia oxidation catalyst for the coal fired utilities |
WO2015087495A1 (en) | 2013-12-13 | 2015-06-18 | 日本電気株式会社 | Digital filter device, digital filter processing method, and storage medium having digital filter program stored thereon |
JP7492743B2 (en) | 2018-12-27 | 2024-05-30 | 日揮ユニバーサル株式会社 | Ammonia decomposition catalyst and exhaust gas treatment method |
-
1994
- 1994-11-14 JP JP27906094A patent/JP3219613B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8202481B2 (en) | 2007-08-22 | 2012-06-19 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst and exhaust gas treatment system |
EP3578247A1 (en) * | 2018-06-06 | 2019-12-11 | Clariant International Ltd | Honeycomb catalytic converter, method for the oxidation of carbon monoxide and organic air pollutants using the honeycomb catalytic converter and use of the honeycomb catalytic converter |
Also Published As
Publication number | Publication date |
---|---|
JPH08131832A (en) | 1996-05-28 |
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