JPS62262747A - Composite oxide catalytic body - Google Patents
Composite oxide catalytic bodyInfo
- Publication number
- JPS62262747A JPS62262747A JP61107082A JP10708286A JPS62262747A JP S62262747 A JPS62262747 A JP S62262747A JP 61107082 A JP61107082 A JP 61107082A JP 10708286 A JP10708286 A JP 10708286A JP S62262747 A JPS62262747 A JP S62262747A
- Authority
- JP
- Japan
- Prior art keywords
- composite oxide
- catalyst
- ceramic honeycomb
- honeycomb carrier
- lanthanum
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 11
- 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 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims abstract 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 229910002254 LaCoO3 Inorganic materials 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 150000002823 nitrates Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- -1 unburned Jf5't Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 101150106671 COMT gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は家庭用燃焼器、自動車あるいは工業用各種炉か
ら排出される一酸化炭素（Ｃｏ）、炭化水素（ＣｘＨｙ
）など不完全燃焼物や未燃Ｊｆ５′ｔ、物を炭酸ガス（
Ｃｏ２）、水（Ｈ２Ｏ）などｊ！ｉｌ； ｇ すも（７
］Ｃ’ｉ換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 is applicable to carbon monoxide (Co) and hydrocarbons (CxHy) discharged from household combustors, automobiles, and various industrial furnaces.
) and other incompletely combusted materials, unburned Jf5't, and materials with carbon dioxide gas (
Co2), water (H2O), etc.j! il; g sumo (7
] This relates to an oxidation catalyst for converting C'i.
従来の技術
従来この棟の用途に用いる触媒は白金（Ｐｔ）、パラジ
ウム（Ｐｄ）、ロジウム（Ｒｈ）なト貴金ＦＥ、に利用
し５たものが多い。しかし貴金属系の触・煤は高７晶で
長時間使用すると、シンクリング金起こし、１＋！ｒ
ｌ：Ｉ：劣化につながり、しかもコスト的にも非常に高
ｂｌｌｉ テ；ｈ ル。マタコバルＩ・（Ｃｏ）、ニッ
ケル（Ｎ ｉ ）、マンガン（Ｍｎ）など単独の４移金
属酸化物もある程度のｔ６性を有するが、高温にすると
酸化を占性度の小さな酸化物の形となったり、アルミナ
など担体成分との間でヌビネ）Ｖｆ影形成て劣化の方向
に進む。Prior Art Conventionally, the catalysts used for this purpose are often made of precious metals such as platinum (Pt), palladium (Pd), and rhodium (Rh). However, if you use precious metals and soot for a long time with a high 7 crystal, it will cause a sink ring and 1+! r
l: I: Leads to deterioration and is also extremely costly. Single tetra-transfer metal oxides such as Matacovar I (Co), nickel (N i ), and manganese (Mn) also have some degree of t6 property, but at high temperatures, they oxidize into the form of oxides with low occupancy. Otherwise, Vf shadows (Nubine) are formed with support components such as alumina, leading to deterioration.
Ｌａなどの希土類とＮ ｉ 、Ｃｏ など遷移金属酸
化物とのベロゲスカイト複合酸化物は従来より高活性と
耐熱性を兼ねセ１１１えた触媒としてよく知られている
が、貴金属系の触１楳と比較するとその活性は良いとは
言えない。Vergeskite composite oxides of rare earth elements such as La and transition metal oxides such as Ni and Co are well known as catalysts that have both high activity and heat resistance. Then, the activity cannot be said to be good.
発明が解決しようとする問題点
ペロプスカイト複合酸化物触媒のと記の欠点を解消する
ためにはベロゲスカイト複合酸化物の活性点であるコバ
ルトが効率良く触媒表面とに露出していなく−ｃはなら
ない。Ｌａ Ｃｏ ０３ （Ｌａ＋３の一部にＣｅ＋４
あるいはＳｒ＋２ を導入した複合酸化物でも同じ挙動
であるが）系ベロゲスカイトは原料のＬａ とＣＯ全当
量比に混合させて触媒粉末を作成するとマクロ的にはＬ
ａ Ｃｏ ０３のベロプヌカイト構凸ができるが、触媒
の極く表面（１１でばＣｏＶこ比Ｉ咬してＬａの濃度が
高く、ＣＯが表面に出にくい性質がある。従って本発明
はこの点を解決しようとするものである。Problems to be Solved by the Invention In order to solve the following drawbacks of perovskite composite oxide catalysts, it is necessary that cobalt, which is an active site of vergeskite composite oxide, is not efficiently exposed to the catalyst surface. . La Co 03 (Ce+4 in part of La+3
Alternatively, the behavior is the same with composite oxides containing Sr+2), but when the velogesite system is mixed with the raw materials La and CO in the total equivalent ratio to create a catalyst powder, macroscopically L
a Co 03 has a velopnukite structure convexity, but the very surface of the catalyst (11 has a high concentration of La compared to CoV and has a property that makes it difficult for CO to come out to the surface. Therefore, the present invention addresses this point. This is what we are trying to solve.
問題点を解決するだめの手段
上記の問題全解決するためにＡサイトのＬａあるいはＬ
ａ＋Ｃｅ又はＬａ＋Ｓｒの合計量に比べてＢサイ１−の
Ｃｏの梠を（ｊくわずか増加させた触媒を作成すること
により、当量比からなる触媒に比して圧倒的に高活性の
ものが得られる。Means to solve the problem In order to solve all the above problems, set La or L of A site.
By creating a catalyst in which the amount of Co in B size 1- is slightly increased by (j) compared to the total amount of a+Ce or La+Sr, a catalyst with overwhelmingly high activity can be obtained compared to a catalyst with an equivalent ratio. It will be done.
作 用
Ｌａ Ｃｏ○３系ペロブスカイト複合酸化物のＢサイト
Ｃ０ｆＩｉをわずか（１，０１〜１．０６）増加するこ
とにより、ペロプスカイト複合酸化物表面の組成を本来
のＬａ ＣａＯ２の様にＬａ：Ｃｏの当１１１比が１：
１近くなり、活性が向丘する。また過剰にＢサイトのＣ
ｏｆ、加えすぎると複合酸化物［なりきれないフリーの
Ｃｏ酸化物が触媒表面に存在することになり、温度をと
げると活性の、悲いＣａＯとなってかえって触媒の活性
を悪くする傾向になる。Effect By slightly increasing the B site C0fIi of the LaCo○3-based perovskite composite oxide (1.01 to 1.06), the composition of the surface of the perovskite composite oxide can be changed to La:Co like the original LaCaO2. The ratio of 111 is 1:
It becomes close to 1, and the activity increases. Also, excessive C of site B
Of, if too much is added, complex oxide [free Co oxide that cannot be formed will exist on the catalyst surface, and if the temperature is raised, it becomes active CaO, which tends to worsen the activity of the catalyst. .
実施例 以下本発明による実施例を説明する。Example Examples according to the present invention will be described below.
（１）酢酸ランタンと酢酸コバルトをそれぞれの金属の
モル比が１：１．ＯＯ〜１．０６になる採水溶液を調整
し、ローグリ−エバポレータで乾燥し、４００′Ｃで仮
焼し、さらに８５０°Ｃ，５時間空気中で焼成し、ペロ
ブスカイト複合酸化物微粉末を作成した。作成した微粉
末の化学反応は図１に示した通りで、通常の流通反応装
雁（常圧、反応ガス組成：Ｃｏ １９ｆ＝ ／ Ａ ｉ
ｒバランス、流量３００ｃｔｄ ／ ＪｎｉＡ ）を
用いた。触媒昂は０．１８：ゾとし石英砂で希釈後、全
光合２．ａｃｆｆｌとした。反応管は内径１０ｍｍの石
英管を用いた。生成ガスの分析ばガヌクロマｉ−グラフ
ィーにより行なった。なおＬａの一部にＣｅ あるいは
３ｒを導入したもの（Ｌａ Ｏ，９Ｃｅ０．Ｉ ＣａＯ
２、Ｌａ Ｏ，８Ｓｒ Ｏ，２ＣａＯ２）についても同
様の触媒粉未作成法を行なった結果も併せて第１図に示
す。第１図の結果からも分る様にへサイ１−レこ比較し
゛〔Ｂサイトのセル比全僅かに増加させるだけで活性を
大巾に増加させることができる。特にＢサイトの量が１
．０２〜１．０３の特級もその効果が著しい。(1) Lanthanum acetate and cobalt acetate in a molar ratio of each metal of 1:1. A sampled water solution with a concentration of OO~1.06 was prepared, dried in a Roguery evaporator, calcined at 400'C, and further calcined in air at 850°C for 5 hours to create perovskite composite oxide fine powder. . The chemical reaction of the prepared fine powder is as shown in Fig. 1, using a normal flow reaction system (atmospheric pressure, reaction gas composition: Co 19f = / A i
r balance, flow rate 300 ctd/JniA) was used. Catalytic concentration is 0.18: after diluting with quartz sand, total photopolymerization is 2. acffl. A quartz tube with an inner diameter of 10 mm was used as the reaction tube. Analysis of the produced gas was carried out by Ganuchromatography. In addition, those in which Ce or 3r is introduced into a part of La (La O, 9Ce0.I CaO
2, LaO, 8SrO, 2CaO2), the same method without catalyst powder was performed and the results are also shown in FIG. As can be seen from the results in FIG. 1, the activity can be greatly increased by only a slight increase in the total cell ratio of the B site. Especially the amount of B site is 1
．． The special grade of 02 to 1.03 also has a remarkable effect.
次に実用的なコーディエライトハニカム担体上に１１１
行させた粉末担持法（２）の例と直接担持法（３）の例
を示す。Next, 111 on a practical cordierite honeycomb carrier
An example of the powder loading method (2) and an example of the direct loading method (3) are shown below.
（２）硝酸ランタンと硝酸コバルトをそれぞれの金属の
モル比が１：１．ＯＯ〜ＬＯ６＆こなる採水溶液を調整
したものｔ大過剰の水酸化す） ＩＪウム水溶液に若干
の過酸化水素水を加えたものの中に混合攪拌し、水酸物
を生成沈澱させる。この沈澱物？十分水洗し、アルカリ
分を除去し、８５０°Ｃ５時間空気中で焼成し、ペロプ
スカイト複合酸化物微粉末を作成する。さらに水洗いを
行ない、適ｉｉｉのコロイダルアルミナと混合させ、特
殊なミ／ｌ／により十分混練させ、触媒微粉末スラリー
を作成する。(2) Lanthanum nitrate and cobalt nitrate in a molar ratio of each metal of 1:1. OO to LO6 & the prepared water collection solution containing a large excess of hydroxide) is mixed and stirred into an aqueous solution of IJ and a small amount of hydrogen peroxide to form and precipitate hydroxide. This sediment? Thoroughly wash with water to remove alkaline content, and calcinate in air at 850°C for 5 hours to produce fine perovskite composite oxide powder. The mixture is further washed with water, mixed with appropriate colloidal alumina, and sufficiently kneaded using a special micro/l/ to create a catalyst fine powder slurry.
ＩＩｌ！１１楳徽わ）末ヌラリーを水で希釈させ、この
中にコーディエライトハニカムを含浸させる。コーディ
エライトハニカム中に存在するｇＩｆｆｆｌｌ孔に水が
吸収するトキコーディエライトハニカム表面上に；独１
毘微粉末が吸い寄せられ、その箇所でアルミナゾルと共
に触媒粉末が固着させられる。触媒会固盾したハニカム
を８００°Ｃ，５分以と空気中で焼成することによりペ
ロブスカイト複合酸化物触媒体を作成する。第２図にこ
のｌ１ｌｌｉｌ媒体のプロパン（Ｃ３Ｈ８）における変
換率２示す。試験袋費は通常の流通反応装散（常圧、反
応ガス組成；Ｃ３ＨＢ１％／ Ａ ｉ ｒ バランス
、流量３００ｃｔ／ｍ１ＪＩ） ｆｆ：用いた。触媒体
は直径２０ ｍｍ ｓ厚みを１０ｍｍとした。IIl! 11) Dilute the slurry with water and impregnate the cordierite honeycomb in it. On the surface of the cordierite honeycomb where water is absorbed into the pores present in the cordierite honeycomb; Germany 1
The fine powder is attracted, and the catalyst powder is fixed together with the alumina sol at that location. A perovskite composite oxide catalyst body is prepared by firing the honeycomb solidified with the catalyst in air at 800°C for 5 minutes or more. FIG. 2 shows the conversion rate 2 of this lllil medium in propane (C3H8). The cost of the test bag was determined by using a normal flow reaction device (normal pressure, reaction gas composition: C3HB1%/Air balance, flow rate 300ct/m1JI). The catalyst body had a diameter of 20 mm and a thickness of 10 mm.
反応管は内径は２０＋＋＋＋＋＋の石英管を用いた。生
成ガスの分析はガスクロマトグラフィーにより行なった
。第２図の結果からも分る様にＢサイトの量が１．０３
の時最もその効果が著しい。A quartz tube with an inner diameter of 20++++ was used as the reaction tube. The produced gas was analyzed by gas chromatography. As can be seen from the results in Figure 2, the amount of B site is 1.03
The effect is most significant when
（３）その内部に多数の徽紬孔が存在するコーディエラ
イトハニカム担体を硝酸第一セリウム溶液（硝酸第一セ
リウム６水塩７５０ ｇ ／ １ ｅ Ｈ２Ｏ）の中に
３０分以上含浸させ、付着水乞振り落し、よく乾燥し、
４００°Ｃで仮焼成した後、９００°Ｃ１時間空気中で
焼成させる。次にこの担体を硝酸ランタンと硝酸コバル
トヲそれぞれの金属のモル比が１：１．ＯＯ〜１．０６
にさせた水溶液を調整したものの中に３０分以上含身さ
せ、付着水を振り落し、よく乾燥し、４００°Ｃで仮焼
成した後、８００°Ｃ１２時間空気中で焼成させてベロ
プス力−（ト複合酸化物触媒体を作成する。第３図にこ
の触媒体のプロパン（Ｃ３ＨＢ）における変換率を示す
。試験装置及び試験方法は交）の場合と同じであるので
省略する。第３図の結果からも分る様にＢサイトの量が
１．０４の時最もその効果が著しい。(3) A cordierite honeycomb carrier with a large number of pores inside is impregnated in a cerous nitrate solution (cerous nitrate hexahydrate 750 g / 1 e H2O) for more than 30 minutes, and then adhered. Shake off the water, dry thoroughly,
After pre-baking at 400°C, it is fired at 900°C in air for 1 hour. Next, this carrier was mixed with lanthanum nitrate and cobalt nitrate in a metal molar ratio of 1:1. OO~1.06
The aqueous solution was immersed in the prepared material for 30 minutes or more, the adhering water was shaken off, the water was thoroughly dried, and the mixture was pre-calcined at 400°C, and then fired in the air at 800°C for 12 hours to obtain a veloping force -( A composite oxide catalyst body is prepared. Figure 3 shows the conversion rate of this catalyst body in propane (C3HB). The test equipment and test method are the same as in the case of (2), and will therefore be omitted. As can be seen from the results in Figure 3, the effect is most significant when the amount of B site is 1.04.
第４図及び第５図にベロプヌ力イト粉末担持触媒体とベ
ログヌカイト直接担持触媒体のモデル図を示す。第４図
及び第５図においてコーディエライト担体１内には小さ
な細孔２が多数存在する。FIG. 4 and FIG. 5 show model diagrams of a catalyst supported on berognite powder and a catalyst supported directly on berognukite. In FIGS. 4 and 5, a large number of small pores 2 are present in the cordierite carrier 1.
粉末４１！持の場合用体表面３において触媒微粉末（ペ
ロブスカイト複合酸化物微粉末）４がアルミナゾルを焼
成した際にできる多孔質アルミナ５によって付着されて
いる。なお粉末担持の場合細孔２内には触媒ａ粉末４は
存在しない。Powder 41! In this case, catalyst fine powder (perovskite composite oxide fine powder) 4 is adhered to the surface 3 of the body by porous alumina 5 formed when alumina sol is fired. In addition, in the case of powder support, the catalyst a powder 4 does not exist in the pores 2.
直接相持の場合細孔２内の壁面６も含めコーディエライ
ト材質が露出している而はＣｅ Ｏ２あるいはＺｒＯ２
からなる保護膜７により被われている。In the case of direct interaction, the cordierite material, including the wall surface 6 inside the pore 2, is exposed, which means CeO2 or ZrO2.
It is covered with a protective film 7 consisting of.
さらにこの保護膜７の上に触媒直接合成物８が生成され
ている。Furthermore, a catalytic direct composition 8 is produced on this protective film 7.
以上示した各側からも、その作成方法の違いにもかかわ
らず、ペロブスカイト複合酸化物触媒のＡサイト：Ｂサ
イトが１：１．０１〜１．０６の時、その効果が大きく
、中でもＢサイトが１．０２〜１．０４の時、その効果
が著しい。From each side shown above, despite the differences in their preparation methods, when the A site:B site ratio of the perovskite composite oxide catalyst is 1:1.01 to 1.06, the effect is large, especially the B site. When is 1.02 to 1.04, the effect is remarkable.
その原因としては第６図に示した触媒粉末の表面用の組
成〔Ｘ線光電子分光（ｘｐｓ）で測定〕と触媒粉末バル
クの組成〔螢光Ｘ線分析（ＸＲＦＳ ）で測定〕の結果
を示す。ＡサイトのＬａとＢサイトのＣＯが当量比の場
合、バルク内のＣＯはほぼ計算値通りの値であるのに対
し、触媒表面相ではＣｏ１１が著しく少ない。つまりＣ
ｏは表面に出にくい性質となっている。Ｃｏｍ’を僅か
づつ増やす 。The reason for this is shown in Figure 6, which shows the composition of the surface of the catalyst powder [measured by X-ray photoelectron spectroscopy (XPS)] and the composition of the bulk catalyst powder [measured by X-ray fluorescence spectroscopy (XRFS)]. . When La at the A site and CO at the B site are in an equivalent ratio, the CO in the bulk is approximately the same as the calculated value, but the amount of Co11 in the catalyst surface phase is extremely low. In other words, C
o has a property that it is difficult to appear on the surface. Increase Com' little by little.
とそれに応じて表面用のＣＯは増加し、ＣＯＯ１２０３
近辺でほぼ理論値？とり、触媒活性は最高値をとる。さ
らにＣＯ量が増加すると、フリーのＣＯ酸化物が触媒表
面に存在することになり、高ｎｕ′１に加熱するとＣｏ
ｏとなり触媒活性度をかえって落とすことになるものと
考える。and the surface CO increases accordingly, COO1203
Near theoretical value? and the catalytic activity takes the highest value. Furthermore, as the amount of CO increases, free CO oxides will exist on the catalyst surface, and when heated to a high nu'1, Co
It is thought that this results in a decrease in the catalyst activity.
発明の効果
本発明による効果として以下列記する様なことが挙げら
れる。Effects of the Invention The effects of the present invention include the following.
（１） コバルト徂の割合をほんの僅か増加させるだ
けで、圧倒的に高い高活性を有する触媒体を得ることが
できる。(1) By only slightly increasing the proportion of cobalt, a catalyst having overwhelmingly high activity can be obtained.
（２）触媒体作成の如何を問わず、Ｂサイトにコバール
トを用いたペロブスカイト複合酸化物触媒体は本方法を
利用することができ、工業的作成方法として活性用度が
大きい。(2) Regardless of how the catalyst is prepared, the present method can be used to produce a perovskite composite oxide catalyst using cobalt at the B site, and the method is highly useful as an industrial preparation method.
（３）貴金属を使用していないので、しかも貴金属触媒
並みの高活性が期待でき、併せて耐熱性の高い触媒体が
可能となる。(3) Since no precious metals are used, high activity comparable to that of noble metal catalysts can be expected, and a catalyst body with high heat resistance can be produced.
キ、図面のｆ７ｉ’ｉ ｆｌ’ｉな説明第１図はペロブ
スカイト複合酸化物触媒のＣ○酸化反応（２５０’Ｃ）
における過剰Ｃｏの効果をを表わした特性図、第２図は
ペロプスカイト粉末４１１４−：“１触媒体のＣ３Ｈ８
変換：＋−を示す図、第３図はべロブスカイト直接相持
触媒体のＣ３ＨＢ変換率を示す図、第４図はペロブスカ
イト粉末担荷触媒モデル図、第５図はペロプスカイト直
接担持触媒モデル図、第６図はペロブスカイト複合酸化
物触媒（Ｌａ Ｃｏ ０３ ）のコバルト過剰にした場
合の触媒組成及びバルク内の組成を表した特性図である
。G, f7i'i fl'i explanation of the drawings Figure 1 shows the C○ oxidation reaction (250'C) of a perovskite composite oxide catalyst.
Figure 2 is a characteristic diagram showing the effect of excess Co on perovskite powder 4114-:1 catalyst of C3H8
Conversion: A diagram showing +-, Figure 3 is a diagram showing the C3HB conversion rate of berovskite directly supported catalyst, Figure 4 is a model diagram of perovskite powder supported catalyst, Figure 5 is a diagram of perovskite directly supported catalyst model, FIG. 6 is a characteristic diagram showing the catalyst composition and bulk composition when cobalt is excessive in a perovskite composite oxide catalyst (La Co 03 ).
１・・・・・・コーディエライト担体、２・・・・・・
細孔、４・・・・・・触媒微粉末、７・・・・・・保護
膜、８・・・・・・触媒直接合成物。1... Cordierite carrier, 2...
Pores, 4... Catalyst fine powder, 7... Protective film, 8... Catalyst direct composite.
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第１
図
グロブス刀１日支合舌文イこ物触縣のＣＯＭｔ友ノー（
２ＳＯ”Ｃ） ＩＺ Ｆｌ゛１７５ｇＬテＩ Ｃ６ｕ
；＠Ｌ第２図
触謀展次／’Ｃ
第３図
第４図
ｔｂ）Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure Globus sword 1 day support tongue pattern Ikomono touch comt friend no (
2SO”C) IZ Fl゛175gLteI C6u
;@L Figure 2 Takushi Exhibition/'C Figure 3 Figure 4 tb)
Claims (4)
化物において、Ａはランタン（Ｌａ）、Ｂはコバルト（
Ｃｏ）を用い、Ａ：Ｂのモル比を１：１．０１〜１．０
６にさせたものをコーディエライトなどセラミックハニ
カム担体に相持させた複合酸化物触媒体。(1) In the perovskite composite oxide having the structure ABO_3, A is lanthanum (La) and B is cobalt (
Co), and the molar ratio of A:B is 1:1.01 to 1.0.
A composite oxide catalyst made by supporting 6 on a ceramic honeycomb carrier such as cordierite.
の構造を有するペロブスカイト複合酸化物微粉末をアル
ミナゾルなど担持助剤と共にセラミックハニカム担体の
表面にコーティングさせた特許請求の範囲第１項記載の
複合酸化物触媒体。(2) LaCoO_3 (Co increase 1.01-1.06)
The composite oxide catalyst body according to claim 1, wherein the perovskite composite oxide fine powder having the structure is coated on the surface of a ceramic honeycomb carrier together with a supporting agent such as alumina sol.
酸第１セリウム、酢酸第１セリウムなどセリウム塩水溶
液に含浸させた後、焼成させた安定化担体上に焼成する
ことによってＬａＣｏＯ＿３（Ｃｏ増量１．０１〜１．
０６）の複合酸化物が得られる硝酸塩混合液中に含浸さ
せ、乾燥し、焼成して作成した特許請求の範囲第１項記
載の複合酸化物触媒体。(3) A ceramic honeycomb carrier with a large number of pores is impregnated with an aqueous solution of cerium salt such as cerous nitrate or cerous acetate, and then fired on a fired stabilizing carrier to increase the amount of LaCoO_3 (Co .01~1.
2. The composite oxide catalyst body according to claim 1, which is prepared by impregnating the composite oxide in a nitrate mixture obtained in 06), drying, and calcining it.
にセリウム（Ｃｅ）あるいはストロンチウム（Ｂｒ）を
導入させた特許請求の範囲第１項、第２項または第３項
記載の複合酸化物触媒体。(4) The composite oxide catalyst according to claim 1, 2 or 3, in which cerium (Ce) or strontium (Br) is introduced into a part of the lanthanum (La) at the A site of ABO_3. Medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61107082A JPH0653228B2 (en) | 1986-05-09 | 1986-05-09 | Complex oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61107082A JPH0653228B2 (en) | 1986-05-09 | 1986-05-09 | Complex oxide catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62262747A true JPS62262747A (en) | 1987-11-14 |
| JPH0653228B2 JPH0653228B2 (en) | 1994-07-20 |
Family
ID=14450020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61107082A Expired - Fee Related JPH0653228B2 (en) | 1986-05-09 | 1986-05-09 | Complex oxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653228B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304046A (en) * | 1988-06-01 | 1989-12-07 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPH01307447A (en) * | 1988-06-06 | 1989-12-12 | Matsushita Electric Ind Co Ltd | Waste gas purification catalyst |
| CN111054368A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for processing oxidation tail gas of PTA device and application |
| CN111054355A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for catalytic combustion treatment of PTA tail gas |
| CN111054352A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof |
-
1986
- 1986-05-09 JP JP61107082A patent/JPH0653228B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304046A (en) * | 1988-06-01 | 1989-12-07 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPH01307447A (en) * | 1988-06-06 | 1989-12-12 | Matsushita Electric Ind Co Ltd | Waste gas purification catalyst |
| CN111054368A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for processing oxidation tail gas of PTA device and application |
| CN111054355A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for catalytic combustion treatment of PTA tail gas |
| CN111054352A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof |
| CN111054368B (en) * | 2018-10-16 | 2022-07-12 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for processing oxidation tail gas of PTA device and application |
| CN111054355B (en) * | 2018-10-16 | 2022-10-11 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for catalytic combustion treatment of PTA tail gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653228B2 (en) | 1994-07-20 |
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