JPH01317541A - Oxidizing catalyst - Google Patents
Oxidizing catalystInfo
- Publication number
- JPH01317541A JPH01317541A JP63150629A JP15062988A JPH01317541A JP H01317541 A JPH01317541 A JP H01317541A JP 63150629 A JP63150629 A JP 63150629A JP 15062988 A JP15062988 A JP 15062988A JP H01317541 A JPH01317541 A JP H01317541A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- complex oxide
- perovskite type
- type complex
- support
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title abstract description 25
- 230000001590 oxidative effect Effects 0.000 title abstract 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052878 cordierite Inorganic materials 0.000 abstract description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 abstract description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 230000003252 repetitive effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 230000010718 Oxidation Activity Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は各種燃焼器から排出される未燃焼の炭化水素、
−酸化炭素を完全燃焼し、炭酸ガスと水にする酸化触媒
に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to unburned hydrocarbons discharged from various combustors,
- It relates to an oxidation catalyst that completely burns carbon oxide and converts it into carbon dioxide gas and water.
従来の技術
一般に未燃焼の炭化水素、−酸化炭素を空気の存在下で
炭酸ガスと水蒸気に完全酸化させる酸化触媒においては
、白金、パラジウム、ロジウムなどの白金族金属をアル
ミナ、シリカなどの無機耐熱材料に担持させた触媒体が
最も活性が高いとされ広く使用されている。Conventional technology In general, in oxidation catalysts that completely oxidize unburned hydrocarbons and carbon oxides into carbon dioxide gas and water vapor in the presence of air, platinum group metals such as platinum, palladium, and rhodium are combined with heat-resistant inorganic materials such as alumina and silica. Catalysts supported on materials are said to have the highest activity and are widely used.
一方、コバルト、ニッケル、鉄などの金属については、
最近では単独の金属酸化物よりも各種複合酸化物が検討
されている。これらの検討の中で、化学式ＡＢＯ，で表
わされるペロブスカイト型結晶構造を持つものが活性が
高いとされ、注目されている。このペロブスカイト型構
造を有する複合酸化物の中では、ＬａＣａＯ，、ＬａＭ
ｎ０．が活性が高イコと、さらにＡ位置の一部を２価の
アルカリ土類金属元素（たとえばストロンチウム）で置
換すると酸化活性が向上することについてすでに報告が
ある。On the other hand, for metals such as cobalt, nickel, and iron,
Recently, various composite oxides have been studied rather than single metal oxides. Among these studies, those having a perovskite crystal structure represented by the chemical formula ABO are said to have high activity and are attracting attention. Among the complex oxides having this perovskite structure, LaCaO, LaM
n0. There have already been reports that the oxidation activity is improved by substituting a part of the A position with a divalent alkaline earth metal element (eg, strontium).
発明が解決しようとする課題
一般に酸化触媒の活性を上げるには触媒自身の表面積を
大きくすること、あるいは触媒の組成を最適な組成に構
成することが考えられる。前者の表面積の増大について
はアルコキシド法、超音波微粒子法などが検討され、現
在２０〜３０ ｄ／ｆ程度のものが工業用として入手可
能となっている。一方触媒の組成については、上記した
ようにＡ位置の一部を置換することが系統的に検討され
ている。Problems to be Solved by the Invention Generally, in order to increase the activity of an oxidation catalyst, it is possible to increase the surface area of the catalyst itself or to configure the composition of the catalyst to an optimum composition. Regarding the former method of increasing the surface area, methods such as the alkoxide method and the ultrasonic particle method have been studied, and those with a surface area of about 20 to 30 d/f are currently available for industrial use. On the other hand, regarding the composition of the catalyst, as described above, substitution of part of the A position has been systematically studied.
これらの結果ペロブスカイト型複合酸化物からなる酸化
触媒の活性はかなり向上されてきた。しかしながら従来
の白金系触媒に比較すると酸化活性、特に低温活性は不
十分である。As a result, the activity of oxidation catalysts made of perovskite-type composite oxides has been considerably improved. However, compared to conventional platinum-based catalysts, oxidation activity, especially low-temperature activity, is insufficient.
本発明は上記の課題を解決するもので、酸化触媒として
、より活性の向上したペロブスカイト型複合酸化物から
なる酸化触媒を提供することを目的とするものである。The present invention solves the above problems, and aims to provide an oxidation catalyst made of a perovskite-type composite oxide with improved activity.
課題を解決するための手段
上記の課題を解決するために本発明の酸化触媒は、化学
式ＡＭｎ （ｌ−ｙ ） ＣｕｙＯ８（ただしＡはアル
カリ土類金属元素の少なくとも一種類の元素、ｙ＝０．
１〜０．５）で示されるペロブスカイト型複合酸化物か
らなるものである。Means for Solving the Problems In order to solve the above problems, the oxidation catalyst of the present invention has the chemical formula AMn (ly) CuyO8 (where A is at least one kind of alkaline earth metal element, y=0.
1 to 0.5).
作用
上記構成の酸化触媒を各種燃焼排気ガス気流中に設置し
て完全酸化に必要な温度まで加熱すれば、加熱された触
媒上を通過する排気ガス中の未燃焼の炭化水素、−酸化
炭素は触媒上に酸素と共に接触し、完全酸化される。Effect: If an oxidation catalyst with the above configuration is installed in the airflow of various types of combustion exhaust gas and heated to the temperature required for complete oxidation, unburned hydrocarbons and carbon oxides in the exhaust gas passing over the heated catalyst will be It comes into contact with oxygen on the catalyst and is completely oxidized.
実施例
実施例１
断面が格子状の３００ ｃｅ １１／ｉ ｎｃｈ２のコ
ージライト製ハニカム担体に、硝酸ストロンチウム、硝
酸銅。Examples Example 1 Strontium nitrate and copper nitrate were placed on a cordierite honeycomb carrier of 300 ce 11/inch 2 having a grid-like cross section.
硝酸マンガンを出発物質としてアルカリ沈殿法で作製し
たペロブスカイト型複合酸化物であるＳｒＭｎｏ−ａ
Ｃｕｅ−＊ Ｏｓを酸化触媒として、無機バインダであ
るアルミナゾルと共に担持させた後、８００°Ｃで焼成
して触媒体とした。前記ペロブスカイト型複合酸化物の
担持量は５％であった。この触媒体について、通常の固
定床流通式でメタン１％空気バランスの酸化活性を調べ
たところ、３００°Ｃでの酸化活性は４５％であり、還
元雰囲気下に曝露しても性能の劣化はなかった。SrMno-a is a perovskite-type composite oxide prepared by an alkaline precipitation method using manganese nitrate as a starting material.
Cue-*Os was supported as an oxidation catalyst together with alumina sol as an inorganic binder, and then fired at 800°C to obtain a catalyst body. The amount of the perovskite type composite oxide supported was 5%. When we investigated the oxidation activity of this catalyst in a conventional fixed bed flow system with 1% methane in air balance, the oxidation activity at 300°C was 45%, and there was no deterioration in performance even when exposed to a reducing atmosphere. There wasn't.
実施例２
断面が格子状の３００ｃｅｌｌ／ｉ ｎｃｈ”のコージ
ライト製ハニカム担体を、硝酸ストロンチウム、硝酸銅
。Example 2 A cordierite honeycomb carrier with a grid-like cross section and a capacity of 300 cells/inch was prepared using strontium nitrate and copper nitrate.
硝酸マンガンをＳｒ ： Ｃｕ ：Ｍｎの比が１０：２
：８になるように調製した混合溶液に浸漬した後、乾燥
し、８００°Ｃで５時間空気中で焼成した。これにより
ハニカム担体上にペロブスカイト型複合酸化物であるＳ
ｒＭｎ０．、 ｃｕ＠−！ｏ３が生成し、その担持量は
８％であった。Manganese nitrate with a Sr:Cu:Mn ratio of 10:2
: After immersing in a mixed solution prepared to have a concentration of 8, it was dried and calcined in air at 800°C for 5 hours. As a result, S, which is a perovskite-type composite oxide, is placed on the honeycomb carrier.
rMn0. , cu@-! o3 was produced, and its supported amount was 8%.
この触媒体について、通常の固定床流通式でメタン１％
空気バランスの酸化活性を調べたところ、３００°Ｃで
の酸化活性は３５％であり、また還元雰囲気下でも安定
であった。Regarding this catalyst body, 1% methane was produced using a normal fixed bed flow system.
When the oxidation activity in air balance was examined, the oxidation activity at 300°C was 35%, and it was stable even in a reducing atmosphere.
発明の効果
以上のように本発明の酸化触媒は化学式ＡＭｎ（ｔ−ｙ
）Ｃｕｙ（Ｊ３で示されるペロブスカイト型複合酸化物
からなり、酸化活性が極めて良好で、しかも還元雰囲気
に対して強く、酸化、還元をくり返す雰囲気下での使用
が可能である。Effects of the Invention As described above, the oxidation catalyst of the present invention has the chemical formula AMn(t-y
)Cuy (composed of a perovskite-type composite oxide represented by J3, has extremely good oxidation activity, is resistant to reducing atmospheres, and can be used in an atmosphere where oxidation and reduction are repeated.
代地人 轟本義弘Representative Yoshihiro Todoroki
Claims (1)
アルカリ土類金属元素の少なくとも一種類の元素、ｙ＝
０．１〜０．５）で示されるペロブスカイト型複合酸化
物からなる酸化触媒。1. Chemical formula AMn(1-y)CuyO_3 (where A is at least one alkaline earth metal element, y=
0.1 to 0.5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63150629A JPH01317541A (en) | 1988-06-17 | 1988-06-17 | Oxidizing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63150629A JPH01317541A (en) | 1988-06-17 | 1988-06-17 | Oxidizing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01317541A true JPH01317541A (en) | 1989-12-22 |
Family
ID=15501034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63150629A Pending JPH01317541A (en) | 1988-06-17 | 1988-06-17 | Oxidizing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01317541A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443807A (en) * | 1990-07-26 | 1995-08-22 | Peking University | Conversion of carbon monoxide utilizing a perovskite-type rare earth complex oxide catalyst |
-
1988
- 1988-06-17 JP JP63150629A patent/JPH01317541A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443807A (en) * | 1990-07-26 | 1995-08-22 | Peking University | Conversion of carbon monoxide utilizing a perovskite-type rare earth complex oxide catalyst |
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