JP2866928B2 - Catalyst for decomposing nitrous oxide and method for removing nitrous oxide - Google Patents

Catalyst for decomposing nitrous oxide and method for removing nitrous oxide

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Publication number
JP2866928B2
JP2866928B2 JP8236717A JP23671796A JP2866928B2 JP 2866928 B2 JP2866928 B2 JP 2866928B2 JP 8236717 A JP8236717 A JP 8236717A JP 23671796 A JP23671796 A JP 23671796A JP 2866928 B2 JP2866928 B2 JP 2866928B2
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JP
Japan
Prior art keywords
catalyst
rhodium
ion
nitrous oxide
metal oxide
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
Application number
JP8236717A
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Japanese (ja)
Other versions
JPH1080633A (en
Inventor
潤子 大井
存 小渕
敦 尾形
暁 櫛山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
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Agency of Industrial Science and Technology
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Priority to JP8236717A priority Critical patent/JP2866928B2/en
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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/10Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、N2O分解用触媒
及びその触媒を用いるN2Oの除去方法に関するもので
ある。
The present invention relates to relates to a method for removing N 2 O using the N 2 O decomposition catalyst and the catalyst.

【0002】[0002]

【従来の技術】N2Oは大気汚泥物質であることから、
2Oを含むガスからそれを除去する方法に多くの研究
が向けられている。N2Oを除去するための実用的方法
として、N2Oを含むガスをN2O分解用触媒と接触さ
せ、ガス中に含まれるN2Oを酸素と窒素とに分解する
方法が知られている。この方法におけるN2O分解効率
は、その触媒性能に依存することから、N2O分解効率
の高い触媒の開発が強く要望されている。特開平7−1
63870号公報によれば、2価金属イオンと3価金属
イオンを含むハイドロタルサイト型化合物の焼成物から
なる複合金属酸化物がN2Oの分解触媒として有効であ
ることが示されている。この公報に示された実施例を見
ると、2価金属イオンとしてコバルトイオンとマグネシ
ウムイオンを含み、3価金属イオンとしてアルミニウム
イオンを含むハイドロタルサイト型化合物の焼成物及び
2価金属イオンとしてコバルトイオンを含み、3価金属
イオンとしてロジウムイオンとアルミニウムイオンを含
むハイドロタルサイト型化合物の焼成物がN2Oに対し
て高い分解活性を有することが理解される。しかしなが
ら、これらの触媒は、その活性が未だ不十分である上、
水分の共在下においてはその触媒活性が著しく小さいと
いう欠点を有している。
2. Description of the Related Art Since N 2 O is an air sludge substance,
It has been directed much research on how to remove it from the gas containing N 2 O. As a practical method for removing N 2 O, the gas containing N 2 O is contacted with N 2 O decomposing catalyst, methods for decomposing is known N 2 O contained in the gas into oxygen and nitrogen ing. Since the N 2 O decomposition efficiency in this method depends on the catalyst performance, development of a catalyst having high N 2 O decomposition efficiency is strongly demanded. JP-A-7-1
No. 63870 discloses that a composite metal oxide comprising a calcined product of a hydrotalcite-type compound containing a divalent metal ion and a trivalent metal ion is effective as a catalyst for decomposing N 2 O. According to the examples shown in this publication, a calcined product of a hydrotalcite-type compound containing cobalt ions and magnesium ions as divalent metal ions and aluminum ions as trivalent metal ions, and a cobalt ion as divalent metal ions It is understood that a calcined product of a hydrotalcite-type compound containing rhodium ions and aluminum ions as trivalent metal ions has a high decomposition activity for N 2 O. However, these catalysts still have insufficient activity,
It has the disadvantage that its catalytic activity is extremely low in the presence of moisture.

【0003】[0003]

【発明が解決しようとする課題】本発明は、高い触媒活
性を有し、水分の共存下においてもN2Oに対する十分
な分解活性を有するN2O分解用触媒及びその触媒を用
いるガス中に含まれるN2Oの除去方法を提供すること
をその課題とする。
[0008] The present invention is higher has a catalytic activity, in the gas using the N 2 O decomposition catalyst and the catalyst has sufficient cracking activity for N 2 O even the presence of water An object of the present invention is to provide a method for removing N 2 O contained therein.

【0004】[0004]

〔発明の詳細な説明〕[Detailed description of the invention]

【0005】[0005]

【発明の実施の形態】本発明の触媒は、2価金属イオン
として亜鉛(II)イオン(Zn2+)を含み、3価金属イ
オンとしてロジウム(III)イオン(Rh3+)とアルミニ
ウム(III)イオン(Al3+)を含むハイドロタルサイト
型化合物の焼成物(複合金属酸化物)からなるものであ
る。この複合金属酸化物は、その原料として用いるハイ
ドロタルサイト型化合物に由来する亜鉛、ロジウム及び
アルミニウムを含有する。本発明においては、その亜鉛
とアルミニウムとの原子比Zn/Alを1以上、好まし
くは5以上に規定するのがよい。そのZn/Al原子比
の上限値は特に制約されないが、通常10〜50程度で
ある。Zn/Al原子比が前記範囲より小さくなると、
水蒸気存在下での触媒活性が大きく低下するので好まし
くない。複合金属酸化物に含まれるロジウムの量は、金
属ロジウムとして0.5〜5重量%、好ましくは0.8
〜3.5重量%である。ロジウム含有量が前記範囲より
小さくなると、十分な触媒活性が得られなくなり、一
方、前記範囲を超えても、触媒活性の格別の向上は得ら
れず、触媒コストが高くなる。
BEST MODE FOR CARRYING OUT THE INVENTION The catalyst of the present invention contains zinc (II) ion (Zn 2+ ) as a divalent metal ion, and rhodium (III) ion (Rh 3+ ) and aluminum (III) as a trivalent metal ion. ) It is composed of a calcined product (composite metal oxide) of a hydrotalcite-type compound containing ions (Al 3+ ). This composite metal oxide contains zinc, rhodium and aluminum derived from a hydrotalcite-type compound used as a raw material. In the present invention, the atomic ratio Zn / Al between zinc and aluminum is set to 1 or more, preferably 5 or more. The upper limit of the Zn / Al atomic ratio is not particularly limited, but is usually about 10 to 50. When the Zn / Al atomic ratio is smaller than the above range,
It is not preferable because the catalytic activity in the presence of steam is greatly reduced. The amount of rhodium contained in the composite metal oxide is 0.5 to 5% by weight as metal rhodium, preferably 0.8% by weight.
~ 3.5% by weight. If the rhodium content is smaller than the above range, sufficient catalytic activity cannot be obtained. On the other hand, if the rhodium content exceeds the range, no particular improvement in catalytic activity can be obtained, and the catalyst cost increases.

【0006】前記ハイドロタルサイト型化合物の焼成に
際しての焼成温度は、300〜800℃、好ましくは4
00〜500である。焼成雰囲気は特に制約されない
が、酸素を含む酸化雰囲気の使用が好ましい。焼成物
は、酸化亜鉛と酸化ロジウムと酸化アルミニウムからな
る複合金属酸化物であるが、この場合、酸化ロジウムと
酸化アルミニウムは非晶質の形態で存在し、酸化亜鉛の
みが結晶状態で存在する。前記複合金属酸化物からなる
本発明のN2O分解用触媒の形状は、粉末状の他、顆粒
状、ペレット状、球形状、筒体状等の各種の形状である
ことができる。また、本発明の触媒は、支持体上に支持
させた被膜(微粉末層)状で用いることができる。
The firing temperature for firing the hydrotalcite type compound is 300 to 800 ° C., preferably 4 to 800 ° C.
00 to 500. The firing atmosphere is not particularly limited, but an oxidizing atmosphere containing oxygen is preferably used. The fired product is a composite metal oxide composed of zinc oxide, rhodium oxide, and aluminum oxide. In this case, rhodium oxide and aluminum oxide exist in an amorphous form, and only zinc oxide exists in a crystalline state. The shape of the catalyst for decomposing N 2 O of the present invention comprising the composite metal oxide may be various shapes such as a granular shape, a pellet shape, a spherical shape, and a cylindrical shape, in addition to the powder shape. Further, the catalyst of the present invention can be used in the form of a film (fine powder layer) supported on a support.

【0007】本発明の触媒を用いてガス中に含まれるN
2Oを除去するには、N2O含有ガスを、250〜600
℃、好ましくは350〜500℃で本発明触媒と接触さ
せればよい。この場合の触媒床の方式は、固定床、沸騰
床、流動床等の各種の方式が採用され、特に制約されな
い。ガス中に含まれるN2Oの濃度は、通常、0.1〜
30vol%である。
[0007] Using the catalyst of the present invention, N contained in gas
To remove 2 O, a N 2 O-containing gas is used at 250 to 600
C., preferably 350 to 500 ° C., may be brought into contact with the catalyst of the present invention. In this case, various types of catalyst beds, such as a fixed bed, a boiling bed, and a fluidized bed, are adopted and are not particularly limited. The concentration of N 2 O contained in the gas is usually 0.1 to
30 vol%.

【0008】N2Oを含むガス中には、通常、0.1〜
10vol%の水蒸気が含まれる場合が多いが、本発明
の触媒は、このような水蒸気共存下においても高い触媒
活性を有する。また、N2Oを含むガス中には、0.0
1〜1vol%のNOx(NO、NO2)が含まれる場
合も多いが、本発明の触媒は、このようなNOxの共存
下でも高い触媒活性を有する。本発明の触媒のN2O分
解活性は、そのN2O分解温度にも依存し、その温度が
高くなるにつれて向上する。従って、水蒸気やNO2
共存下でのN2O分解活性が不十分であっても、そのN2
O分解温度を上昇させることによって高い触媒活性を得
ることができる。
The gas containing N 2 O usually contains 0.1 to
Although 10 vol% of steam is often contained, the catalyst of the present invention has high catalytic activity even in the presence of such steam. Further, in a gas containing N 2 O, 0.02
1~1Vol% of NOx (NO, NO 2) is also often included, but the catalyst of the present invention has a high catalytic activity even in the presence of such NOx. The N 2 O decomposition activity of the catalyst of the present invention also depends on its N 2 O decomposition temperature, and increases as the temperature increases. Therefore, even in insufficient N 2 O decomposition activity in the presence of water vapor and NO 2, the N 2
By increasing the O decomposition temperature, high catalytic activity can be obtained.

【0009】[0009]

【実施例】次に本発明を実施例によりさらに詳細に説明
する。
Next, the present invention will be described in more detail with reference to examples.

【0010】触媒調製例1 (1)硝酸亜鉛水和物〔Zn(NO3)2・H2O〕0.0
375モル(11.1551g)、硝酸アルミニウム・
9水和物〔Al(NO3)3・9H2O〕0.0125モル
(4.6891g)、硝酸ロジウム〔Rh(NO3)3〕3
wt%水溶液0.0681gをビーカーに入れ、これに
イオン交換水100ml加えて溶液Aを作る。 (2)炭酸ナトリウム(Na2CO3)1.325gをイ
オン交換水250mlに溶かして溶液Bを作る。 (3)水酸化ナトリウム(NaOH)10gをイオン交
換水125ccに溶かして溶液Cを作る。 (4)溶液Bに撹拌下において溶液A及び溶液Cを滴下
する。この場合、得られる混合液のpHを10に保持す
る。この溶液混合により、共沈物が形成される。 (5)共沈物を含む溶液を一晩以上放置して共沈物を熟
成する。 (6)共沈物を含む溶液を遠心分離処理した後、デカン
テーションにより水を分離する。次いで、イオン交換水
を加えて遠心分離処理した後、デカンテーションにより
水を分離する。このようなイオン交換水の添加と遠心分
離処理とデカンテーションからなる一連の操作を10回
繰返して、精製共沈物を得る。 (7)得られた精製共沈物をシャーレに入れ、オーブン
中で100℃で一晩以上乾燥させる。 以上のようにして、Zn2+とAl3+とRh3+を含むハイ
ドロタルサイト型化合物を得る。次に、このハイドロタ
ルサイト型化合物を、空気雰囲気下で500℃で2時間
焼成して複合金属酸化物(触媒I)を得た。この複合金
属酸化物において、そのZn/Al原子比は3であり、
そのRh含有量は1.4wt%である。また、この複合
金属酸化物において、亜鉛は結晶状態のZnOとして存
在し、その他の金属は非晶質状態の酸化物として存在す
ることがX線回析分析により確認された。
Catalyst Preparation Example 1 (1) Zinc nitrate hydrate [Zn (NO 3 ) 2 .H 2 O] 0.0
375 mol (11.551 g), aluminum nitrate
Nonahydrate [Al (NO 3) 3 · 9H 2 O ] 0.0125 mol (4.6891g), rhodium nitrate [Rh (NO 3) 3] 3
0.0681 g of a wt% aqueous solution is placed in a beaker, and 100 ml of ion-exchanged water is added thereto to prepare a solution A. (2) Solution B is prepared by dissolving 1.325 g of sodium carbonate (Na 2 CO 3 ) in 250 ml of ion-exchanged water. (3) Solution C is prepared by dissolving 10 g of sodium hydroxide (NaOH) in 125 cc of ion-exchanged water. (4) The solution A and the solution C are added dropwise to the solution B with stirring. In this case, the pH of the resulting mixture is maintained at 10. This solution mixing forms a coprecipitate. (5) The solution containing the coprecipitate is left to stand overnight or more to mature the coprecipitate. (6) After centrifuging the solution containing the coprecipitate, water is separated by decantation. Next, after ion-exchanged water is added and centrifuged, water is separated by decantation. A series of operations including the addition of the ion-exchanged water, the centrifugation, and the decantation is repeated 10 times to obtain a purified coprecipitate. (7) The obtained purified coprecipitate is placed in a petri dish and dried in an oven at 100 ° C overnight or more. As described above, a hydrotalcite-type compound containing Zn 2+ , Al 3+, and Rh 3+ is obtained. Next, this hydrotalcite-type compound was calcined at 500 ° C. for 2 hours in an air atmosphere to obtain a composite metal oxide (catalyst I). In this composite metal oxide, its Zn / Al atomic ratio is 3,
Its Rh content is 1.4 wt%. Further, in this composite metal oxide, it was confirmed by X-ray diffraction analysis that zinc was present as ZnO in a crystalline state and other metals were present as oxides in an amorphous state.

【0011】触媒調製例2 実施例1において、硝酸ロジウム3wt%水溶液0.1
36gを用いた以外は同様にして実験を行い、Zn/A
l原子比が3でロジウム含有率が3.3wt%の複合金
属酸化物(触媒II)を得た。
Catalyst Preparation Example 2 In Example 1, a 3 wt% rhodium nitrate aqueous solution 0.1
An experiment was conducted in the same manner except that 36 g of Zn / A was used.
A composite metal oxide (catalyst II) having an atomic ratio of 3 and a rhodium content of 3.3 wt% was obtained.

【0012】触媒調製例3 実施例1において、硝酸ロジウム3wt%水溶液0.2
043gを用いた以外は同様にして実験を行い、Zn/
Al原子比が3でロジウム含有率が4.7wt%の複合
金属酸化物(触媒III)を得た。
Catalyst Preparation Example 3 In Example 1, a 3 wt% rhodium nitrate aqueous solution 0.2
An experiment was conducted in the same manner except that 043 g was used, and Zn /
A composite metal oxide (catalyst III) having an Al atomic ratio of 3 and a rhodium content of 4.7 wt% was obtained.

【0013】触媒調製例4 触媒調製例1において、硝酸ロジウム3wt%水溶液
0.0340gを用いた以外は同様にして実験を行い、
Zn/Al原子比が3でロジウム含有率が0.8wt%
の複合金属酸化物(触媒IV)を得た。
Catalyst Preparation Example 4 An experiment was carried out in the same manner as in Catalyst Preparation Example 1 except that 0.0340 g of a 3 wt% aqueous solution of rhodium nitrate was used.
Zn / Al atomic ratio is 3 and rhodium content is 0.8wt%
Was obtained (catalyst IV).

【0014】触媒調製例5 触媒調製例1において、硝酸ロジウム水溶液を使用しな
い以外は同様にして実験を行い、Zn/Al原子比が3
でロジウム含有率がゼロ%の複合金属酸化物(触媒V)
を得た。
Catalyst Preparation Example 5 An experiment was conducted in the same manner as in Catalyst Preparation Example 1 except that an aqueous rhodium nitrate solution was not used.
Metal oxide with no rhodium content (catalyst V)
I got

【0015】触媒調製例6 触媒調製例1において、硝酸ロジウム水溶液を使用せ
ず、また硝酸亜鉛の代りに硝酸コバルトを用いた以外は
同様にして実験を行い、Co/Al原子比が3でロジウ
ム含有率がゼロ%の複合金属酸化物(触媒VI)を得た。
Catalyst Preparation Example 6 An experiment was carried out in the same manner as in Catalyst Preparation Example 1 except that an aqueous rhodium nitrate solution was not used and cobalt nitrate was used instead of zinc nitrate. A composite metal oxide (catalyst VI) having a content of 0% was obtained.

【0016】反応例1 粉末状触媒0.05gをガラス管(内径:0.6cm、
長さ:2cm)に充填し、その上下端にガラスウールを
詰めて、触媒反応管を作製した。この反応管に、950
volppmN2Oと5vol%O2を含むヘリウムガス
(ガスA)、950volppmN2Oと5vol%O2
と0.5vol%H2Oを含むヘリウムガス(ガスB)
又は950volppmN2Oと5vol%O2と0.1
vol%NO2を含むヘリウムガス(ガスC)を、40
0℃の条件で、50ml/分の流速で流通させてN2
の分解実験を行った。この実験におけるN2Oの分解速
度(μmol/g−cat/h)を測定し、その結果を
示す。なお、N2Oの分解速度は触媒活性の指標となる
もので、N2O分解速度が大きい触媒ほど触媒活性の高
いことを示す。
Reaction Example 1 0.05 g of a powdery catalyst was placed in a glass tube (inner diameter: 0.6 cm,
(Length: 2 cm), and the upper and lower ends were filled with glass wool to prepare a catalyst reaction tube. Add 950 to this reaction tube.
volppmN 2 O and 5 vol% helium gas containing O 2 (gas A), 950volppmN 2 O and 5 vol% O 2
Helium gas containing 0.5 vol% H 2 O and (gas B)
Or 950 vol ppm N 2 O, 5 vol% O 2 and 0.1
Helium gas containing vol% NO 2 (gas C), 40
Under the condition of 0 ° C., N 2 O was circulated at a flow rate of 50 ml / min.
Was decomposed. The decomposition rate (μmol / g-cat / h) of N 2 O in this experiment was measured, and the results are shown. Note that the decomposition rate of N 2 O is an index of the catalytic activity, and a catalyst having a higher N 2 O decomposition rate indicates a higher catalytic activity.

【0017】[0017]

【表1】 [Table 1]

【0018】反応例2 触媒調整例1において硝酸亜鉛と硝酸アルミニウムとの
モル比を種々変化させた以外は同様にして実験を行い、
種々のZn/Al原子比を有するロジウム含有率が1.
4wt%の複合金属酸化物を調製した。これらの各種の
触媒を用いた以外は反応例1と同様にして実験を行っ
た。触媒中のZn/Al原子比とN2O分解速度との関
係を表2に示す。
Reaction Example 2 An experiment was conducted in the same manner as in Catalyst Preparation Example 1 except that the molar ratio between zinc nitrate and aluminum nitrate was changed variously.
Rhodium content with various Zn / Al atomic ratios is 1.
A 4 wt% composite metal oxide was prepared. An experiment was conducted in the same manner as in Reaction Example 1 except that these various catalysts were used. Table 2 shows the relationship between the atomic ratio of Zn / Al in the catalyst and the decomposition rate of N 2 O.

【0019】[0019]

【表2】 [Table 2]

【0020】反応例3 反応例1において、N2Oの分解温度を500℃とした
以外は同様にして実験を行った。その結果を表3に示
す。
Reaction Example 3 An experiment was conducted in the same manner as in Reaction Example 1, except that the decomposition temperature of N 2 O was changed to 500 ° C. Table 3 shows the results.

【0021】[0021]

【表3】 [Table 3]

【0022】[0022]

【発明の効果】本発明の触媒は、水蒸気やNO2の共存
下でも高いN2O分解活性を有し、本発明の触媒を用い
ることにより、N2Oを含む各種のガス中からN2Oを効
率良く分解除去することができる。
The catalyst of the present invention according to the present invention has a high N 2 O decomposition activity in the presence of water vapor and NO 2, by using the catalyst of the present invention, N 2 from a variety of gas containing N 2 O O can be efficiently decomposed and removed.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 櫛山 暁 茨城県つくば市小野川16番3 工業技術 院資源環境技術総合研究所内 (56)参考文献 特開 平8−224474(JP,A) 特開 平5−245384(JP,A) (58)調査した分野(Int.Cl.6,DB名) B01J 23/60 B01D 53/94──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akira Kushiyama 16-3 Onogawa, Tsukuba, Ibaraki Pref. National Institute of Advanced Industrial Science and Technology (56) References JP-A-8-224474 (JP, A) 5-245384 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) B01J 23/60 B01D 53/94

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 亜鉛(II)イオン、ロジウム(III)イオ
ン及びアルミニウム(III)イオンを含むハイドロタルサ
イト型化合物を焼成して得られる酸化亜鉛のみが結晶状
態で存在する複合金属酸化物からなり、該複合金属酸化
物に含まれる亜鉛とアルミニウムとの原子比Zn/Al
が3以上でかつロジウム含有率が0.5〜3重量%であ
るN2O分解用触媒。
1. A composite metal oxide in which only zinc oxide obtained by calcining a hydrotalcite-type compound containing zinc (II) ion, rhodium (III) ion and aluminum (III) ion exists in a crystalline state. , The atomic ratio of zinc to aluminum contained in the composite metal oxide, Zn / Al
N 2 O decomposition catalyst but 3 or more and rhodium content is from 0.5 to 3 wt%.
【請求項2】 ガス中に含まれるN2Oを除去する方法
において、該ガスを250〜600℃の温度において請
求項1の触媒と接触させて酸素と窒素とに分解すること
を特徴とするN2Oの除去方法。
2. A method for removing N 2 O contained in a gas, comprising contacting the gas with the catalyst of claim 1 at a temperature of 250 to 600 ° C. to decompose it into oxygen and nitrogen. A method for removing N 2 O.
【請求項3】 該ガスが、水蒸気及び/又はNO2を含
む請求項2の方法。
3. The method of claim 2 , wherein said gas comprises water vapor and / or NO 2 .
JP8236717A 1996-09-06 1996-09-06 Catalyst for decomposing nitrous oxide and method for removing nitrous oxide Expired - Lifetime JP2866928B2 (en)

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WO2011040787A3 (en) * 2009-09-30 2011-09-09 상명대학교 산학협력단 Lean nitrogen oxide breakdown method employing a high-adsorption mixed metal oxide catalyst

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