JPH1080633A - Nitrous oxide decomposing catalyst and removing method of nitrous oxide - Google Patents
Nitrous oxide decomposing catalyst and removing method of nitrous oxideInfo
- Publication number
- JPH1080633A JPH1080633A JP8236717A JP23671796A JPH1080633A JP H1080633 A JPH1080633 A JP H1080633A JP 8236717 A JP8236717 A JP 8236717A JP 23671796 A JP23671796 A JP 23671796A JP H1080633 A JPH1080633 A JP H1080633A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ion
- rhodium
- gas
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 11
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title 4
- 239000001272 nitrous oxide Substances 0.000 title 2
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 239000010948 rhodium Substances 0.000 claims abstract description 17
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 238000010304 firing Methods 0.000 abstract description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum ions Chemical class 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【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、
Ｎ2Ｏ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]
【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 above 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の
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 addition of ion-exchanged water, centrifugation, and 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, the 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Ｎ2Ｏ
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 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akira Kushiyama 16-3 Onogawa Tsukuba, Ibaraki Pref.
Claims (3)
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%.
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.
む請求項２の方法。3. The method of claim 2 , wherein said gas comprises water vapor and / or NO 2 .
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| JP8236717A JP2866928B2 (en) | 1996-09-06 | 1996-09-06 | Catalyst for decomposing nitrous oxide and method for removing nitrous oxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8236717A JP2866928B2 (en) | 1996-09-06 | 1996-09-06 | Catalyst for decomposing nitrous oxide and method for removing nitrous oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1080633A true JPH1080633A (en) | 1998-03-31 |
| JP2866928B2 JP2866928B2 (en) | 1999-03-08 |
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ID=17004739
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11137999A (en) * | 1997-11-12 | 1999-05-25 | Jisedai Haigas Shokubai Kenkyusho:Kk | Purification catalyst for waste gas and its production |
| JP2000262863A (en) * | 1999-03-17 | 2000-09-26 | Jisedai Haigas Shokubai Kenkyusho:Kk | Exhaust gas cleaning catalyst combination device |
| JP2002153734A (en) * | 2000-09-08 | 2002-05-28 | Showa Denko Kk | Nitrous oxide decomposition catalyst, its manufacturing method and decomposition method of nitrous oxide |
| WO2006095001A1 (en) * | 2005-03-09 | 2006-09-14 | Albemarle Netherlands Bv | Fluid catalytic cracking additive |
| KR100638835B1 (en) | 2005-05-30 | 2006-10-25 | 장길상 | Decomposition Method of Nitrogen Oxide Using Double Reactor |
| KR100654885B1 (en) | 2005-06-01 | 2006-12-06 | 장길상 | Decomposition Method of Nitrogen Oxide Using Carbon Monoxide |
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| KR101029642B1 (en) * | 2009-09-30 | 2011-04-15 | 상명대학교 산학협력단 | Decomposition Method of Dilute Nitrogen Oxide Using Highly Adsorbable Mixed Metal Oxide Catalyst |
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1996
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11137999A (en) * | 1997-11-12 | 1999-05-25 | Jisedai Haigas Shokubai Kenkyusho:Kk | Purification catalyst for waste gas and its production |
| JP2000262863A (en) * | 1999-03-17 | 2000-09-26 | Jisedai Haigas Shokubai Kenkyusho:Kk | Exhaust gas cleaning catalyst combination device |
| JP4573320B2 (en) * | 2000-09-08 | 2010-11-04 | 昭和電工株式会社 | Nitrous oxide decomposition catalyst, production method thereof, and decomposition method of nitrous oxide |
| JP2002153734A (en) * | 2000-09-08 | 2002-05-28 | Showa Denko Kk | Nitrous oxide decomposition catalyst, its manufacturing method and decomposition method of nitrous oxide |
| WO2006095001A1 (en) * | 2005-03-09 | 2006-09-14 | Albemarle Netherlands Bv | Fluid catalytic cracking additive |
| KR100638835B1 (en) | 2005-05-30 | 2006-10-25 | 장길상 | Decomposition Method of Nitrogen Oxide Using Double Reactor |
| KR100654885B1 (en) | 2005-06-01 | 2006-12-06 | 장길상 | Decomposition Method of Nitrogen Oxide Using Carbon Monoxide |
| JP2013505830A (en) * | 2009-09-30 | 2013-02-21 | サンミュン大学校産学協力団 | Mixed metal oxide catalyst for nitrogen oxide decomposition |
| KR101029680B1 (en) | 2009-10-26 | 2011-04-15 | 상명대학교 산학협력단 | Storage and Decomposition of Dilute Nitrogen Oxides Using Mixed Metal Oxide Catalysts |
| WO2011052920A3 (en) * | 2009-10-26 | 2011-09-15 | 상명대학교 산학협력단 | Method for adsorbing and decomposing lean nitrogen oxide using a mixed metal oxide catalyst |
| WO2011052921A3 (en) * | 2009-10-26 | 2011-11-03 | 상명대학교 산학협력단 | Method for decomposing lean nitrogen oxide through a parallel arrangement of mixed metal oxide catalysts having highly adsorptive properties |
| JP2013508139A (en) * | 2009-10-26 | 2013-03-07 | 祥明大学校産学協力団 | Method for occluding and decomposing dilute nitrogen oxides using mixed metal oxide catalysts |
| US8512662B2 (en) | 2009-10-26 | 2013-08-20 | Sangmyung University, Council For Industry Academic Cooperation | Method for adsorbing and decomposing lean nitrogen oxide using a mixed metal oxide catalyst |
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