JPH06335618A - Ammonia decomposing method - Google Patents
Ammonia decomposing methodInfo
- Publication number
- JPH06335618A JPH06335618A JP5127126A JP12712693A JPH06335618A JP H06335618 A JPH06335618 A JP H06335618A JP 5127126 A JP5127126 A JP 5127126A JP 12712693 A JP12712693 A JP 12712693A JP H06335618 A JPH06335618 A JP H06335618A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ammonia
- crystalline silicate
- decomposing
- chloride
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
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する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of decomposing ammonia contained in various exhaust gases into harmless nitrogen.
【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。Ammonia is used in a wide range of fields such as a raw material for producing fertilizer and nitric acid, a refrigerant, and a reducing agent for removing nitrogen oxides in exhaust gas. Therefore, a large amount of ammonia is emitted from various chemical product manufacturing plants, waste treatment plants such as refrigerators, and combustion exhaust gas treatment facilities. Ammonia is a gas with a unique irritating odor, and its release into the atmosphere must be suppressed as much as possible. However, in many places, such as the generation of ammonia due to the decay of living organisms, the emission of ammonia from the refrigerant in waste, and the ammonia used for the reduction of nitrogen oxides in flue gas, is released into the atmosphere without reaction. At present, ammonia is released into 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。 ２ＮＨ3 ＋ 3/2Ｏ2 → Ｎ2 ＋ ３Ｈ2 Ｏ ところが、従来の触媒では前記反応以外に次のような副
反応によりＮＯ，ＮＯ 2 ，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。 ２ＮＨ3 ＋ 5/2Ｏ2 → ２ＮＯ ＋ ３Ｈ2 Ｏ ２ＮＨ3 ＋ 7/2Ｏ2 → ２ＮＯ2 ＋ ３Ｈ2 Ｏ ２ＮＨ3 ＋ ２Ｏ2 → Ｎ2 Ｏ ＋ ３Ｈ2 ＯDISCLOSURE OF THE INVENTION Ammonia emission into the atmosphere
As one of the methods to prevent the
Utilizing a catalyst in which iron oxide or nickel oxide is supported on the carrier
And decompose ammonia into harmless nitrogen by the following reaction formula
The method is known. 2 NH3+ 3 / 2O2 → N2+ 3H2O However, with conventional catalysts, in addition to the above reactions,
NO by reaction, NO 2, N2Generation of O etc. is recognized,
There was a risk of new air pollution. 2 NH3+ 5 / 2O2 → 2NO + 3H2O 2 NH3+ 7 / 2O2 → 2 NO2+ 3H2O 2 NH3+202 → N2O + 3H2O
【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を副生する恐れ
がなく、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方法を提供することにある。The object of the present invention is to solve the above-mentioned problems of the prior art, and to decompose and remove ammonia with a high yield without fear of producing nitrogen oxides as a source of air pollution as a by-product. To provide a method.
【０００５】[0005]
【課題を解決するための手段】本発明はアンモニアを含
有するガスをアンモニア分解触媒と接触させてアンモニ
アを分解除去する方法において、アンモニア分解触媒と
して、脱水された状態で （１±0.6 ）Ｒ2 Ｏ・〔ａＭ2 Ｏ3 ・ｂＡｌ2 Ｏ3 〕・
ｃＭｅＯ・ｙＳｉＯ2 （式中、Ｒはアルカリ金属イオン及び／又は水素イオ
ン、ＭはVIII族元素、希土類元素、チタン、バナジウ
ム、クロム、ニオブ、アンチモン、ガリウムからなる群
から選ばれた１種以上の元素、Ｍｅはアルカリ土類元
素、ａ≧０、ｂ≧０、ｃ≧０、ａ＋ｂ＝１、ｙ／ｃ＞１
２、ｙ＞１２）の化学組成を有し、かつ下記表１で示さ
れるＸ線回折パターンを有する結晶性シリケートに、
銅、コバルト、ニッケル、鉄、亜鉛、マンガン、クロ
ム、アルカリ土類元素、希土類元素の中から少なくとも
１種を含有させた触媒を使用することを特徴とするアン
モニア分解方法である。The present invention relates to a method for decomposing and removing ammonia by bringing a gas containing ammonia into contact with an ammonia decomposing catalyst, wherein (1 ± 0.6) R 2 in the dehydrated state is used as the ammonia decomposing catalyst. O ・ [aM 2 O 3・ bAl 2 O 3 ] ・
cMeO.ySiO 2 (wherein R is an alkali metal ion and / or a hydrogen ion, M is a group VIII element, a rare earth element, titanium, vanadium, chromium, niobium, antimony, or gallium selected from the group consisting of Element, Me is an alkaline earth element, a ≧ 0, b ≧ 0, c ≧ 0, a + b = 1, y / c> 1
2, a crystalline silicate having a chemical composition of y> 12) and an X-ray diffraction pattern shown in Table 1 below,
A method for decomposing ammonia, which comprises using a catalyst containing at least one selected from the group consisting of copper, cobalt, nickel, iron, zinc, manganese, chromium, alkaline earth elements and rare earth elements.
【０００６】本発明の方法で使用する触媒は、本質的に
は本発明者らが前に窒素酸化物（ＮＯｘ）、一酸化炭素
（ＣＯ）、炭化水素（ＨＣ）等を含有する内燃機関の排
ガスを浄化する触媒として開発したものと同一である
（特開平４−４０４５号公報、特願平３−３１９１９５
号）。前記触媒を構成する結晶性シリケートは表１に示
すようなＸ線回折パターンを示す結晶構造を有するのが
特徴である。The catalyst used in the method of the present invention is essentially the catalyst of an internal combustion engine which we have previously contained nitrogen oxides (NOx), carbon monoxide (CO), hydrocarbons (HC) and the like. It is the same as that developed as a catalyst for purifying exhaust gas (Japanese Patent Application Laid-Open No. 4-4045, Japanese Patent Application No. 3-319195).
issue). The crystalline silicate constituting the catalyst is characterized by having a crystal structure showing an X-ray diffraction pattern as shown in Table 1.
【０００７】[0007]
【表１】 [Table 1]
【０００８】前記触媒は必要によりアルミナゾル、シリ
カゾルなどのバインダー成分やコージェライト、アルミ
ナ、シリカ−アルミナ等の担体を使用し、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、１００〜６
００℃の温度で前記触媒に接触させることにより、ガス
中のアンモニアは窒素に分解される。この分解反応は選
択的に進行し、ＮＯ、ＮＯ2 、Ｎ2 Ｏ等の有害ガスが副
生することはない。It is preferable to use a binder component such as alumina sol or silica sol or a carrier such as cordierite, alumina or silica-alumina as the catalyst, if necessary, after forming a honeycomb by a wash coat method or a solid method. A gas containing ammonia is added to 100 to 6
By contacting the catalyst at a temperature of 00 ° C., ammonia in the gas is decomposed into nitrogen. This decomposition reaction proceeds selectively, and no harmful gas such as NO, NO 2 , N 2 O is produced as a by-product.
【０００９】本発明の方法で使用する触媒の結晶性シリ
ケートは該シリケートを構成する元素を含む化合物を原
料として、水熱合成法により合成することができる。ま
た、この結晶性シリケートとして予め合成した結晶性シ
リケートを母結晶とし、母結晶の表面にその母結晶と同
一の結晶構造を有するＳｉとＯよりなる結晶性シリケー
トを成長させた層状複合結晶性シリケートを使用しても
よい。この層状複合結晶性シリケートは外表面に成長し
たＳｉとＯよりなる結晶性シリケート（シリカライトと
呼ぶ）の疎水性作用により、Ｈ2 Ｏだけが該結晶性シリ
ケート内部まで浸透しにくくなる。そのためＨ2 Ｏの作
用による結晶性シリケート格子中の金属（アルミニウム
等）の脱離が抑制されて、触媒の劣化が抑制される。前
記結晶性シリケートに含有させる銅、コバルト、ニッケ
ル等の金属はイオン交換法によりこれらの金属イオンを
含有させるか、または塩化物、硝酸塩、硫酸塩等の金属
塩水溶液を含浸させる含浸法により含有させることがで
きる。The crystalline silicate of the catalyst used in the method of the present invention can be synthesized by a hydrothermal synthesis method using a compound containing an element constituting the silicate as a raw material. In addition, a layered composite crystalline silicate in which a crystalline silicate synthesized in advance as this crystalline silicate is used as a mother crystal, and a crystalline silicate composed of Si and O having the same crystal structure as the mother crystal is grown on the surface of the mother crystal. May be used. In this layered composite crystalline silicate, the hydrophobic action of the crystalline silicate consisting of Si and O (called silicalite) grown on the outer surface makes it difficult for only H 2 O to penetrate into the crystalline silicate. Therefore, desorption of metal (aluminum or the like) in the crystalline silicate lattice due to the action of H 2 O is suppressed, and deterioration of the catalyst is suppressed. Metals such as copper, cobalt and nickel contained in the crystalline silicate are contained by ion exchange method with these metal ions, or by impregnation method with which an aqueous solution of metal salt such as chloride, nitrate or sulfate is impregnated. be able to.
【００１０】[0010]
【実施例】以下実施例により本発明の方法をさらに具体
的に説明する。 （触媒の調製１）水ガラス１号（ＳｉＯ2 ：３０％）５
６１６ｇを水５４２９ｇに溶解し、この溶液を溶液Ａと
した。一方、水４１７５ｇに硫酸アルミニウム７１８．
９ｇ、塩化第二鉄１１０ｇ、酢酸カルシウム４７．２
ｇ、塩化ナトリウム２６２ｇ及び濃塩酸２０２０ｇを混
合して溶解し、この溶液を溶液Ｂとした。溶液Ａと溶液
Ｂを一定割合で供給し、沈殿を生成させ、十分攪拌して
ｐＨ＝８．０のスラリ−を得た。このスラリ−を２０リ
ットルのオートクレーブに仕込み、さらにテトラプロピ
ルアンモニウムブロマイドを５００ｇ添加し、１６０℃
にて７２時間水熱合成を行い、合成後水洗して乾燥さ
せ、さらに５００℃、３時間焼成させ結晶性シリケート
１を得た。この結晶性シリケート１は酸化物のモル比で
（結晶水を省く）下記の組成式で表され、結晶構造はＸ
線回折で前記表１にて表示されるものであった。 ０．５ＮａＯ2 ・０．５Ｈ2 Ｏ・〔０．８Ａｌ2 Ｏ3 ・
０．２Ｆｅ2 Ｏ3 ・０．２５ＣａＯ〕・２５ＳｉＯ2 EXAMPLES The method of the present invention will be described in more detail with reference to the following examples. (Preparation of catalyst 1) Water glass No. 1 (SiO 2 : 30%) 5
616 g was dissolved in 5429 g of water, and this solution was designated as solution A. On the other hand, aluminum 718.
9 g, ferric chloride 110 g, calcium acetate 47.2
g, 262 g of sodium chloride and 2020 g of concentrated hydrochloric acid were mixed and dissolved, and this solution was designated as solution B. Solution A and solution B were supplied at a constant ratio to form a precipitate, which was sufficiently stirred to obtain a slurry having a pH of 8.0. This slurry was charged into a 20 liter autoclave, and 500 g of tetrapropylammonium bromide was further added to the autoclave at 160 ° C.
After 72 hours of hydrothermal synthesis, the synthesis was followed by washing with water, drying and further firing at 500 ° C. for 3 hours to obtain crystalline silicate 1. This crystalline silicate 1 is represented by the following composition formula in terms of a molar ratio of oxides (excluding water of crystallization), and has a crystal structure of X.
It was as shown in Table 1 above by line diffraction. 0.5NaO 2 · 0.5H 2 O · [0.8Al 2 O 3 ·
0.2Fe 2 O 3 · 0.25CaO] · 25SiO 2
【００１１】この結晶性シリケート１を０．０４Ｍの酢
酸銅水溶液（３０℃）に浸漬し、２４時間攪拌し、水洗
後乾燥し、さらにくり返し、このＣｕイオン交換を２回
（合計３回）実施し、水洗、乾燥を行い粉末触媒１を得
た。この触媒の組成は１．２ＣｕＯ・〔０．８Ａｌ2 Ｏ
3 ・０．２Ｆｅ2 Ｏ3 ・０．２５ＣａＯ〕・２５ＳｉＯ
2 であった。次に、１００部の前記粉末触媒１に対し
て、バインダ−としてアルミナゾル３部、シリカゾル５
５部（ＳｉＯ2 ：２０％）及び水２００部を加え、充分
攪拌を行いウォッシュコート用スラリ−とした。次にコ
ージェライト用モノリス基材（４００セルの格子目）を
上記スラリ−に浸漬し、取り出した後余分なスラリ−を
吹きはらい２００℃で乾燥させた。コート量は基材１リ
ットルあたり２００ｇを担持させた。このコート物をハ
ニカム触媒１とする。This crystalline silicate 1 was dipped in a 0.04 M copper acetate aqueous solution (30 ° C.), stirred for 24 hours, washed with water, dried, and repeated, and this Cu ion exchange was carried out twice (total three times). Then, it was washed with water and dried to obtain a powder catalyst 1. The composition of this catalyst is 1.2CuO. [0.8Al 2 O
3・ 0.2Fe 2 O 3・ 0.25CaO] ・ 25SiO
Was 2 . Next, with respect to 100 parts of the powder catalyst 1, 3 parts of alumina sol and 5 parts of silica sol were used as a binder.
5 parts: the (SiO 2 20%) and 200 parts of water was added, the washcoat slurry perform sufficient stirring - was. Next, the monolith substrate for cordierite (lattice of 400 cells) was dipped in the above slurry, taken out, and then excess slurry was blown and dried at 200 ° C. The coating amount was 200 g per liter of the substrate. This coated material is used as a honeycomb catalyst 1.
【００１２】（触媒の調製２）触媒の調製１の結晶性シ
リケート１の合成法において塩化第二鉄の代わりに塩化
コバルト、塩化ルテニウム、塩化ロジウム、塩化ランタ
ン、塩化セリウム、塩化チタン、塩化バナジウム、塩化
クロム、塩化アンチモン、塩化ガリウム及び塩化ニオブ
を各々酸化物換算でＦｅ2 Ｏ3 と同じモル数だけ添加し
た以外は結晶性シリケート１と同様の操作を繰り返して
結晶性シリケート２〜１２を調製した。これらの結晶性
シリケートの結晶構造はＸ線回折で前記表１に表示され
るものであり、その組成は酸化物のモル比（脱水された
形態）で表わして０．５ＮａＯ2・０．５Ｈ2 Ｏ・
（０．２Ｍ2 Ｏ3 ・０．８Ａｌ2 Ｏ3 ・０．２５Ｃａ
Ｏ）・２５ＳｉＯ2 であった。ここでＭはＣｏ，Ｒｕ，
Ｒｈ，Ｌａ，Ｃｅ，Ｔｉ，Ｖ，Ｃｒ，Ｓｂ，Ｇａ，Ｎｂ
である。また、塩化第二鉄または酢酸カルシウムの代わ
りに何も添加せず結晶性シリケート１と同様の方法によ
り、結晶性シリケート１３、１４を得た。(Catalyst Preparation 2) Cobalt chloride, ruthenium chloride, rhodium chloride, lanthanum chloride, cerium chloride, titanium chloride, vanadium chloride instead of ferric chloride in the method for synthesizing crystalline silicate 1 of catalyst preparation 1 Crystalline silicates 2 to 12 were prepared by repeating the same operation as in crystalline silicate 1 except that chromium chloride, antimony chloride, gallium chloride and niobium chloride were added in the same mole number as Fe 2 O 3 in terms of oxide. . The crystal structure of these crystalline silicates is shown in Table 1 by X-ray diffraction, and its composition is expressed by the molar ratio of oxides (dehydrated form) of 0.5NaO 2 .0.5H 2. O
(0.2M 2 O 3 · 0.8Al 2 O 3 · 0.25Ca
O) .25SiO 2 . Where M is Co, Ru,
Rh, La, Ce, Ti, V, Cr, Sb, Ga, Nb
Is. Further, crystalline silicates 13 and 14 were obtained in the same manner as in crystalline silicate 1 without adding anything in place of ferric chloride or calcium acetate.
【００１３】これらの結晶性シリケート２〜１４を実施
例１と同様にＣｕイオン交換し、粉末触媒２〜１４を得
た。さらにこの粉末触媒を実施例１と同様にモノリス基
材にコートし、ハニカム触媒２〜１４を得た。These crystalline silicates 2 to 14 were subjected to Cu ion exchange in the same manner as in Example 1 to obtain powder catalysts 2 to 14. Further, this powder catalyst was coated on a monolith substrate in the same manner as in Example 1 to obtain honeycomb catalysts 2-14.
【００１４】（触媒の調製３）触媒の調製１の結晶性シ
リケート１の合成法において酢酸カルシウムの代わりに
酢酸マグネシウム、酢酸ストロンチウム、酢酸バリウム
を各々酸化物換算でＣａＯと同じモル数だけ添加した以
外は結晶性シリケート１と同様の操作を繰り返して結晶
性シリケート１５〜１７を調製した。これらの結晶性シ
リケートの結晶構造はＸ線回折で前記表１に表示される
ものであり、その組成は酸化物のモル比（脱水された形
態）で表わして０．５Ｎａ2 Ｏ・０．５Ｈ2 Ｏ・（０．
２Ｆｅ2Ｏ3 ・０．８Ａｌ2 Ｏ3 ・０．２５ＭｅＯ）・
２５ＳｉＯ2 である。ここでＭｅはＭｇ，Ｓｒ，Ｂａで
ある。これらの結晶性シリケート１５〜１７を触媒の調
製１と同様にＣｕイオン交換し粉末触媒１５〜１７を
得、さらにこの粉末触媒を触媒の調製１と同様にモノリ
ス基材にコートしてハニカム触媒１５〜１７を得た。(Catalyst Preparation 3) Except that magnesium acetate, strontium acetate, and barium acetate were added instead of calcium acetate in the same amount as CaO in terms of oxide in the method for synthesizing crystalline silicate 1 in Catalyst Preparation 1. The same operation as in crystalline silicate 1 was repeated to prepare crystalline silicates 15 to 17. The crystal structure of these crystalline silicates is shown in Table 1 by X-ray diffraction, and its composition is expressed by the molar ratio of oxides (dehydrated form) of 0.5Na 2 O · 0.5H. 2 O ・ (0.
2Fe 2 O 3 · 0.8Al 2 O 3 · 0.25MeO) ·
25 SiO 2 . Here, Me is Mg, Sr, or Ba. These crystalline silicates 15 to 17 were subjected to Cu ion exchange in the same manner as in Catalyst Preparation 1 to obtain powder catalysts 15 to 17, and the powder catalyst was coated on a monolith substrate in the same manner as in Catalyst Preparation 1 to prepare a honeycomb catalyst 15. ~ 17 were obtained.
【００１５】（触媒の調製４）触媒の調製１で得られた
結晶性シリケート１を微粉砕し、この結晶性シリケート
１を母結晶として１０００ｇを水２１６０ｇに添加し、
さらにコロイダルシリカ（ＳｉＯ2 ：２０％）４５９０
ｇを添加し、十分攪拌を行い、この溶液を溶液ａとし
た。一方、水２００８ｇに水酸化ナトリウム１０５．８
ｇを溶解させ溶液ｂを得た。溶液ａを攪拌しながら溶液
ｂを徐々に滴下し、沈殿を生成させてスラリ−を得た。
このスラリ−をオートクレーブに入れ、テトラプロピル
アンモニウムブロマイド５６８ｇを水２１０６ｇに溶解
させた溶液を添加し、１６０℃、７２時間加熱して水熱
合成を行い（２００ｒｐｍにて攪拌）、反応後、液を分
離し洗浄して乾燥後、５００℃、３時間焼成を行い、シ
リカライトを表層にコートした層状複合結晶性シリケー
ト１を得た。この層状複合結晶性シリケート１を触媒の
調製１と同様にしてＣｕイオン交換し、粉末触媒１８を
得、さらに、この粉末触媒を触媒の調製１と同様にモノ
リス基材にコートしてハニカム触媒１８を得た。以上の
ようにして調製したハニカム触媒１〜１８を表２、表３
にまとめて示す。(Catalyst Preparation 4) The crystalline silicate 1 obtained in Catalyst Preparation 1 was finely pulverized, and 1000 g of this crystalline silicate 1 as a mother crystal was added to 2160 g of water,
Further colloidal silica (SiO 2 : 20%) 4590
g was added and sufficiently stirred, and this solution was designated as solution a. Meanwhile, 105.8 sodium hydroxide was added to 2008 g of water.
g was dissolved to obtain a solution b. The solution b was gradually dropped while stirring the solution a to form a precipitate to obtain a slurry.
This slurry was placed in an autoclave, a solution of 568 g of tetrapropylammonium bromide dissolved in 2106 g of water was added, and the mixture was heated at 160 ° C. for 72 hours to perform hydrothermal synthesis (stirring at 200 rpm). After the reaction, the liquid was removed. After separation, washing and drying, firing was carried out at 500 ° C. for 3 hours to obtain a layered composite crystalline silicate 1 in which silicalite was coated on the surface. This layered composite crystalline silicate 1 was subjected to Cu ion exchange in the same manner as in Catalyst Preparation 1 to obtain a powder catalyst 18, and this powder catalyst was coated on a monolith substrate in the same manner as in Catalyst Preparation 1 to form a honeycomb catalyst 18. Got The honeycomb catalysts 1 to 18 prepared as described above are shown in Table 2 and Table 3.
Are shown together.
【００１６】[0016]
【表２】 [Table 2]
【００１７】[0017]
【表３】 [Table 3]
【００１８】（触媒の調製５）触媒の調製１で得た結晶
性シリケート１をそれぞれ０．０４Ｍの濃度に調製した
塩化コバルト水溶液、塩化ニッケル水溶液、塩化第二鉄
水溶液、塩化亜鉛水溶液、塩化マンガン水溶液、硝酸ク
ロム水溶液、塩化カルシウム水溶液、塩化バリウム水溶
液、塩化マグネシウム水溶液、塩化ランタン水溶液、塩
化セリウム水溶液に各々７０℃にて浸漬し、触媒の調製
１と同様に金属イオン交換を行い、粉末触媒１９〜２９
を得た。さらに、この粉末触媒を触媒の調製１と同様に
モノリス基材にコートしてハニカム触媒１９〜２９を得
た。以上のようにして調製したハニカム触媒１９〜２９
を表４にまとめて示した。(Catalyst Preparation 5) The crystalline silicate 1 obtained in Catalyst Preparation 1 was prepared to a concentration of 0.04 M, respectively; an aqueous solution of cobalt chloride, an aqueous solution of nickel chloride, an aqueous solution of ferric chloride, an aqueous solution of zinc chloride, and manganese chloride. The catalyst was immersed in an aqueous solution, an aqueous solution of chromium nitrate, an aqueous solution of calcium chloride, an aqueous solution of barium chloride, an aqueous solution of magnesium chloride, an aqueous solution of lanthanum chloride and an aqueous solution of cerium chloride at 70 ° C., and metal ion exchange was performed in the same manner as in Preparation 1 of the catalyst. ~ 29
Got Further, this powder catalyst was coated on a monolith substrate in the same manner as in Catalyst Preparation 1 to obtain honeycomb catalysts 19 to 29. Honeycomb catalysts 19 to 29 prepared as described above
Are summarized in Table 4.
【００１９】[0019]
【表４】 [Table 4]
【００２０】（実施例１）ハニカム触媒１〜２９を用い
てアンモニア分解試験を実施した。反応管に１５×１５
×６０ｍｍの大きさで１４４セルからなるハニカム触媒
１〜２９を入れ、次の組成のアンモニア含有ガスをＳＶ
＝１６３００ｈ-1、流量５．５４Ｎｍ3 ／ｍ2 の条件で
流し、反応温度２５０℃及び３００℃でアンモニア分解
性能を調べた。 （ガス組成） ＮＨ3 ２０ｐｐｍ ＣＯ2 ７％ Ｈ2 Ｏ ６％ Ｏ2 １４．７％ Ｎ2 残 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。 アンモニア分解率（％）＝〔（入口ＮＨ3 −出口Ｎ
Ｈ3 ）／入口ＮＨ3 〕×１００ ＮＯｘ生成率（％）＝〔（出口（Ｎ2 Ｏ×２＋ＮＯ＋Ｎ
Ｏ2 ））／入口ＮＨ3 〕×１００ これらの測定結果を表５に示す。Example 1 An ammonia decomposition test was conducted using honeycomb catalysts 1-29. 15 × 15 in the reaction tube
The honeycomb catalysts 1 to 29 each having a size of 60 mm and consisting of 144 cells were put, and an ammonia-containing gas having the following composition was added to the SV.
= 16300 h −1 and a flow rate of 5.54 Nm 3 / m 2 , the ammonia decomposition performance was examined at reaction temperatures of 250 ° C. and 300 ° C. (Gas composition) NH 3 20 ppm CO 2 7% H 2 O 6% O 2 14.7% N 2 residual performance evaluation is based on ammonia decomposition rate and NOx (NO, NO 2 , N 2 O) production rate in the initial reaction state. It was done by measuring. The ammonia decomposition rate and NOx
The production rate was calculated by the following formula. Ammonia decomposition rate (%) = [(inlet NH 3 -outlet N
H 3 ) / inlet NH 3 ] × 100 NOx production rate (%) = [(outlet (N 2 O × 2 + NO + N
O 2 )) / inlet NH 3 ] × 100 These measurement results are shown in Table 5.
【００２１】[0021]
【表５】 [Table 5]
【００２２】（実施例２）ハニカム触媒１〜２９を使用
し実施例１と同一の条件にて長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、前記ガス条件
にて１０００時間供給後においても表５と同様のアンモ
ニア分解率及びＮＯｘ生成率を維持しており、耐久性に
優れた触媒であることが確認された。(Example 2) A durability evaluation test was carried out by using honeycomb catalysts 1 to 29 and passing gas under the same conditions as in Example 1 for a long time. As a result, it was confirmed that the catalyst maintained the same ammonia decomposition rate and NOx generation rate as in Table 5 even after 1000 hours of supply under the above gas conditions, and was a catalyst with excellent durability.
【００２３】[0023]
【発明の効果】本発明のアンモニア分解方法によれば、
ＮＯｘ等の副生成物を生ずることなく、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
方法は従来無かったものであり、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 ammonia decomposition method of the present invention,
Ammonia can be decomposed into harmless nitrogen without producing by-products such as NOx. Such a decomposition treatment method has never existed before, and its industrial utility value is extremely high.
Claims (1)
分解触媒と接触させてアンモニアを分解除去する方法に
おいて、アンモニア分解触媒として、脱水された状態で （１±0.6 ）Ｒ2 Ｏ・〔ａＭ2 Ｏ3 ・ｂＡｌ2 Ｏ3 〕・
ｃＭｅＯ・ｙＳｉＯ2 （式中、Ｒはアルカリ金属イオン及び／又は水素イオ
ン、ＭはVIII族元素、希土類元素、チタン、バナジウ
ム、クロム、ニオブ、アンチモン、ガリウムからなる群
から選ばれた１種以上の元素、Ｍｅはアルカリ土類元
素、ａ≧０、ｂ≧０、ｃ≧０、ａ＋ｂ＝１、ｙ／ｃ＞１
２、ｙ＞１２）の化学組成を有し、かつ発明の詳細な説
明の項に記載の表１で示されるＸ線回折パターンを有す
る結晶性シリケートに銅、コバルト、ニッケル、鉄、亜
鉛、マンガン、クロム、アルカリ土類元素、希土類元素
の中から少なくとも１種を含有させた触媒を使用するこ
とを特徴とするアンモニア分解方法。1. A method for decomposing and removing ammonia by contacting a gas containing ammonia with an ammonia decomposing catalyst, wherein (1 ± 0.6) R 2 O. [aM 2 O 3 is used as an ammonia decomposing catalyst in a dehydrated state.・ BAl 2 O 3 ] ・
cMeO.ySiO 2 (wherein R is an alkali metal ion and / or a hydrogen ion, M is a group VIII element, a rare earth element, titanium, vanadium, chromium, niobium, antimony, or gallium selected from the group consisting of Element, Me is an alkaline earth element, a ≧ 0, b ≧ 0, c ≧ 0, a + b = 1, y / c> 1
2, y> 12), and copper, cobalt, nickel, iron, zinc, manganese in the crystalline silicate having the X-ray diffraction pattern shown in Table 1 in the detailed description of the invention. A method for decomposing ammonia, which comprises using a catalyst containing at least one of chromium, chromium, alkaline earth elements and rare earth elements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12712693A JP3241166B2 (en) | 1993-05-28 | 1993-05-28 | Ammonia decomposition method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12712693A JP3241166B2 (en) | 1993-05-28 | 1993-05-28 | Ammonia decomposition method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06335618A true JPH06335618A (en) | 1994-12-06 |
| JP3241166B2 JP3241166B2 (en) | 2001-12-25 |
Family
ID=14952258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12712693A Expired - Lifetime JP3241166B2 (en) | 1993-05-28 | 1993-05-28 | Ammonia decomposition method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3241166B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010241675A (en) * | 2009-03-17 | 2010-10-28 | Nippon Shokubai Co Ltd | Method of manufacturing hydrogen |
| JP2012161713A (en) * | 2011-02-03 | 2012-08-30 | Agc Seimi Chemical Co Ltd | Ammonia decomposition catalyst and decomposition method of ammonia |
| US8962518B2 (en) | 2009-03-17 | 2015-02-24 | Nippon Shokubai Co., Ltd. | Catalyst for production of hydrogen and process for producing hydrogen using the catalyst, and catalyst for combustion of ammonia, process for producing the catalyst and process for combusting ammonia using the catalyst |
-
1993
- 1993-05-28 JP JP12712693A patent/JP3241166B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010241675A (en) * | 2009-03-17 | 2010-10-28 | Nippon Shokubai Co Ltd | Method of manufacturing hydrogen |
| US8962518B2 (en) | 2009-03-17 | 2015-02-24 | Nippon Shokubai Co., Ltd. | Catalyst for production of hydrogen and process for producing hydrogen using the catalyst, and catalyst for combustion of ammonia, process for producing the catalyst and process for combusting ammonia using the catalyst |
| US10857523B2 (en) | 2009-03-17 | 2020-12-08 | Nippon Shokubai Co., Ltd. | Catalyst for production of hydrogen and process for producing hydrogen using the catalyst, and catalyst for combustion of ammonia, process for producing the catalyst and process for combusting ammonia using the catalyst |
| JP2012161713A (en) * | 2011-02-03 | 2012-08-30 | Agc Seimi Chemical Co Ltd | Ammonia decomposition catalyst and decomposition method of ammonia |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3241166B2 (en) | 2001-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5338715A (en) | Catalyst for exhaust gas purification | |
| CA2151229C (en) | Ammonia decomposition catalysts | |
| JP2023501862A (en) | Denitration catalyst and denitration method using the catalyst | |
| US5695728A (en) | Method for removal of nitrogen oxides | |
| JP3132959B2 (en) | Ammonia decomposition catalyst | |
| US5254515A (en) | Catalyst for decomposing nitrogen oxides and a method of purifying a waste gas containing nitrogen oxides | |
| JP3132960B2 (en) | Ammonia decomposition catalyst | |
| JP3229136B2 (en) | Ammonia decomposition method | |
| JP3241166B2 (en) | Ammonia decomposition method | |
| JP3332652B2 (en) | Ammonia decomposition removal method | |
| JP3229117B2 (en) | Ammonia decomposition method | |
| JP2778801B2 (en) | Exhaust gas treatment catalyst | |
| JP3453172B2 (en) | DeNOx method | |
| JP3510908B2 (en) | Exhaust gas purification catalyst | |
| JPH07112121A (en) | Method for removing nox | |
| JP2659840B2 (en) | Purification method of exhaust gas containing nitrogen oxides | |
| JPH07275658A (en) | Ammonia adsorbing and decomposing method | |
| JPH08266870A (en) | Denitrifying method | |
| JP3015568B2 (en) | Exhaust gas treatment catalyst | |
| JPH05317725A (en) | Exhaust gas treating catalyst and method for treating exhaust gas | |
| JP3015524B2 (en) | Exhaust gas treatment catalyst | |
| JP3482661B2 (en) | Nitrogen oxide removal method | |
| JP3300721B2 (en) | Exhaust gas purification catalyst | |
| JPH03101837A (en) | Production of catalyst for decomposition of nitrogen oxide | |
| JP2695668B2 (en) | Purification method of exhaust gas containing nitrogen oxides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20010911 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081019 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081019 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091019 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101019 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111019 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111019 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121019 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121019 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131019 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term |