JPS6231611B2 - - Google Patents
Info
- Publication number
- JPS6231611B2 JPS6231611B2 JP54102504A JP10250479A JPS6231611B2 JP S6231611 B2 JPS6231611 B2 JP S6231611B2 JP 54102504 A JP54102504 A JP 54102504A JP 10250479 A JP10250479 A JP 10250479A JP S6231611 B2 JPS6231611 B2 JP S6231611B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- exhaust gas
- catalyst
- srfeo
- lanio
- 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
Links
- 239000003054 catalyst Substances 0.000 claims description 21
- 241000877463 Lanio Species 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 34
- 239000004065 semiconductor Substances 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 oxygen anion Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は自動車などの内燃機関、火力発電、石
油ストーブなどの各種燃焼機器の排ガス、特に一
酸化炭素、炭化水素あるいはそれらの双方を含む
排ガスの浄化に用いる排ガス浄化触媒体に関する
ものである。Detailed Description of the Invention The present invention relates to an exhaust gas purification catalyst used for purifying exhaust gas from various combustion equipment such as internal combustion engines such as automobiles, thermal power generators, and kerosene stoves, particularly exhaust gas containing carbon monoxide, hydrocarbons, or both. It's about the medium.
ガソリンエンジンの排ガスは、ガソリンと空気
の混合比やその他の要因により変化するが、石油
系の燃料を使用する限りCO、CO2、NO、NOx、
HCや中間生成物のアルデヒド、ケトンなどが酸
化されないまま排ガスとなる。その中でもCOに
ついては酸素量が理論混合比より少ない場合、す
なわち燃料過多の場合に多く出るのが一般的であ
る。この排ガス成分中、一酸化炭素、炭化水素は
還元性ガスで、NOxは酸化性ガスである。した
がつて還元性ガスと酸化性ガスの間で電子とO2-
の交換が行なわれば無公害のガスであるCO2、
H2O、N2に変化するものである。 Gasoline engine exhaust gas varies depending on the mixture ratio of gasoline and air and other factors, but as long as petroleum-based fuel is used, CO, CO 2 , NO, NOx,
HC and intermediate products such as aldehydes and ketones become exhaust gas without being oxidized. Among them, CO is generally emitted in large amounts when the amount of oxygen is less than the stoichiometric mixing ratio, that is, when there is too much fuel. Among these exhaust gas components, carbon monoxide and hydrocarbons are reducing gases, and NOx is an oxidizing gas. Therefore, electrons and O 2- are exchanged between the reducing gas and the oxidizing gas.
CO 2 , which is a non-polluting gas, if exchanged with
It changes into H 2 O and N 2 .
すなわち、CO＋2HC＋2NOx→3CO2＋H2O＋
N2と上式の反応で示される電子とO2-混合導電性
の物質を触媒として作用させることが有用である
が、ABO3構造のペロブスカイト形でＡまたはＢ
の一部を低価の金属イオンで置換するとO2-空格
子点を生成し電子−O2-導電性を示す。本発明は
この点に着目して金属的な導電性を示すペロブス
カイト形組成物において、
例えば、A+B6O3においてはKTaO3および
NaWO3、A2+B4+O3においては、SrFeO3、
CaMnO3、YVO3、SrCoO3、SrMoO3、Sr2（Fe・
Mo）O6、A3B3+O3においてはLaTiO3、
LaNiO3、LaAlO3などがある。 That is, CO+2HC+2NOx→3CO 2 +H 2 O+
It is useful to use a substance with mixed conductivity of electrons and O 2 shown in the reaction of N 2 and the above formula as a catalyst.
When part of is replaced with a low-valent metal ion, O 2- vacancies are generated and electron-O 2- conductivity is exhibited. Focusing on this point, the present invention focuses on perovskite compositions that exhibit metallic conductivity. For example, in A + B 6 O 3 , KTaO 3 and
In NaWO 3 , A 2+ B 4+ O 3 , SrFeO 3 ,
CaMnO 3 , YVO 3 , SrCoO 3 , SrMoO 3 , Sr 2 (Fe・
Mo) O 6 , A 3 B 3+ O 3 is LaTiO 3 ,
Examples include LaNiO 3 and LaAlO 3 .
従来、触媒機能を有する成形体や用法として、
活性白土やゼオライトのごとき粉末状あるいは粒
状態およびハネカム構造の貫通孔をもつた骨格構
造体において、該骨格にコージエライト2MgO・
2Al2O3・5SiO2、ムライト3Al2O3・2SiO2、γ―
Al2O3アルミナ磁器などが用いられ、1200℃以上
の高温で焼結し基礎の形をつくり、その表面に多
孔質の触媒材料を数10ミクロンから数100ミクロ
ンの間に附着させたものが主体で、その表面層は
Pt、Rh等の貴金属を薄膜状に被覆したものが用
いられていた。 Conventionally, molded bodies with catalytic functions and usage methods include:
In powdered or granular materials such as activated clay and zeolite, and skeleton structures with honeycomb-like through holes, cordierite 2MgO.
2Al 2 O 3・5SiO 2 , mullite 3Al 2 O 3・2SiO 2 , γ-
Al 2 O 3 alumina porcelain is used, which is sintered at a high temperature of 1200°C or higher to form a foundation, and a porous catalyst material is attached to the surface with a thickness of several 10 to several 100 microns. The main body, and its surface layer is
Those coated with a thin film of noble metals such as Pt and Rh were used.
したがつて触媒層が表面だけで、かつ該薄層の
厚みが不均一となり、使用中の摩耗劣化や剥離の
劣化が避けられない欠点があつた。また一部は触
媒材料と無機バインダ、たとえばアルミン酸石灰
や燐酸カルシウムのごときセメント材とを混合し
て成形されたものがあるが、有効触媒の表面積減
少や成形性の困難さ、さらに1000℃からの高温負
荷に耐えられない用途上の欠点があつた。 Therefore, the catalyst layer is only on the surface, and the thickness of the thin layer is non-uniform, resulting in the disadvantage that deterioration due to abrasion and deterioration in peeling during use cannot be avoided. Some products are molded by mixing catalyst materials and inorganic binders, such as cement materials such as lime aluminate and calcium phosphate, but they suffer from a reduction in the surface area of the effective catalyst, difficulty in moldability, and problems with temperatures exceeding 1000°C. It had the disadvantage of not being able to withstand high temperature loads.
本発明は上記の欠点を除き、従来の固体塩基固
体酸の無機材と異なり、遷移金属酸化物は電気的
には半導体と見做され、一般に化学理論比より金
属イオンが過剰、酸素アニオン欠陥がある酸化物
はｎ形半導体で、これに属するものは、CuO、
ZnO、CaO、TiO2、SnO2、Fe2O3などがあり、
このうちのFe2O3と、逆に化学理論比より酸素イ
オンが過剰、金属カチオンの欠陥のあるＰ型半導
体で、この種の金属酸化物NiO、CoO、MnO、
FeOなどのうち、NiOとよりなるSrFeO3
（SrCO3＋Fe2O3）＋LaNiO3（La2O3＋NiO）を基
材とした金属酸化物半導体の伝導度は上記の格子
欠陥濃度と比例関係にあり、欠陥濃度が大、すな
わち反応性に富んでいるゆえに電導度が低く、金
属的に近づき低抵抗体（２×10-2Ωcm程度）とな
る。したがつてｎ型半導体は酸化雰囲気で電気伝
導度が下がり、Ｐ型半導体は逆に還元雰囲気で電
気伝導度が下がる。この両性半導体の役目を有
し、酸化、還元の両性触媒的作用をする特徴を有
し、かつその結晶構造がペロブスカイト形を有す
る電子−O2-混合導電体を、連通気孔を有する構
造に形成し、焼成してなる排ガス浄化触媒体を提
供するものである。 The present invention eliminates the above-mentioned drawbacks, and unlike conventional solid base solid acid inorganic materials, transition metal oxides are electrically regarded as semiconductors, and generally have an excess of metal ions and oxygen anion defects compared to the stoichiometric ratio. Some oxides are n-type semiconductors, including CuO,
There are ZnO, CaO, TiO2 , SnO2 , Fe2O3 , etc.
Of these, Fe 2 O 3 is a P-type semiconductor with an excess of oxygen ions than the stoichiometric ratio and defects in metal cations, and this type of metal oxide NiO, CoO, MnO,
Among FeO etc., SrFeO 3 which is composed of NiO
The conductivity of a metal oxide semiconductor based on (SrCO 3 + Fe 2 O 3 ) + LaNiO 3 (La 2 O 3 + NiO) is proportional to the lattice defect concentration mentioned above. Because it is so rich, its conductivity is low, approaching that of a metal, making it a low-resistance material (approximately 2×10 -2 Ωcm). Therefore, the electrical conductivity of an n-type semiconductor decreases in an oxidizing atmosphere, and conversely, the electrical conductivity of a p-type semiconductor decreases in a reducing atmosphere. This electron-O 2 - mixed conductor, which has the role of an amphoteric semiconductor, has the characteristic of acting as an amphoteric catalyst for oxidation and reduction, and has a perovskite crystal structure, is formed into a structure with continuous pores. The present invention provides an exhaust gas purifying catalyst body obtained by firing the present invention.
すなわち、本発明の排ガス浄化触媒体は連通気
孔を有する構造体をSrFeO3とLaNiO3よりなるペ
ロブスカイト形酸化物で形成し酸化雰囲気中で焼
成したものである。 That is, the exhaust gas purification catalyst body of the present invention has a structure having communicating holes formed of a perovskite-type oxide consisting of SrFeO 3 and LaNiO 3 and fired in an oxidizing atmosphere.
以下、本発明を実施例により詳細に説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
焼成後の組成比でSrFeO3とLaNiO3とを第２図
の組成比のように配合した原料を温度1000℃で１
時間空気中で仮焼した粉末を、さらにボールミル
にて10時間湿式微粉化したのち、過、乾燥して
得た黒色微粉末を約５％濃度のバインダーを含む
溶媒中に混合分散させ均一な泥漿物を得、該泥漿
物中にポリウレタン、ポリエステル、ポリエーテ
ル、和紙などを基体とし、三次元構造の骨格組織
を有する長さ67mm、幅67mm、厚さ11mmの網状成形
体を浸漬あるいは該成形体の骨格に泥漿物を付与
して乾燥する。この操作を数回繰返し、求める肉
厚に着肉して得た成形体を温度1400℃で１時間焼
成し、ランダム形状の硬質網目架橋で、かつ立体
的空間を有する磁器体を得た。なおSrFeO3と
LaNiO3の基材に製造条件などの向上を図るため
他の物質を添加含有させてもよい。この磁器体は
黒色で、寸法は54×54×９mm３で焼成し、収縮率
は約20％であつた。 A raw material containing SrFeO 3 and LaNiO 3 in the composition ratio shown in Figure 2 after firing was heated at a temperature of 1000°C.
The powder was calcined in the air for an hour, then wet-pulverized in a ball mill for 10 hours, and then filtered and dried.The resulting black fine powder was mixed and dispersed in a solvent containing about 5% binder to form a uniform slurry. A reticular molded product having a three-dimensional skeleton structure and a length of 67 mm, a width of 67 mm, and a thickness of 11 mm is immersed in the slurry, or the molded product is immersed in the slurry. A slurry is applied to the skeleton and dried. This operation was repeated several times to obtain the desired wall thickness, and the resulting molded body was fired at a temperature of 1400° C. for 1 hour to obtain a porcelain body with a randomly shaped hard network crosslink and a three-dimensional space. Note that SrFeO 3 and
Other substances may be added to the LaNiO 3 base material in order to improve manufacturing conditions. This porcelain body was fired in black color, with dimensions of 54 x 54 x 9 mm, and had a shrinkage rate of about 20%.
このようにして得られた三次元磁器構造体の比
抵抗は約2.6×10-2Ωcmで、空孔率は85〜87％と
なり、三次元の連通気孔を有しており、これらの
磁器体を各々第１図の導入ガス試験装置に組み込
み、その変換効率を求めた結果を第２図に示す。
なお、この時の導入ガスはCOが１％vol、NOが
1000ppm、H2が１％volで、風量は0.1m2/minの
条件により求めたもので、この結果、ガスの変換
率は従来の80％程度かあるいはそれ以下のものに
比較し、大幅に向上している。すなわち、焼成後
の組成比で（１―Ｘ）SrFeO3・XLaNiO3、ただ
し0.5＞Ｘ＞0.05が最適組成で、それ以上また以
下ではガスの変換率は従来品以下となり、特に顕
著な効果を奏しない。 The specific resistance of the three-dimensional porcelain structures obtained in this way is approximately 2.6 × 10 -2 Ωcm, the porosity is 85 to 87%, and there are three-dimensional communicating holes. were installed in the introduced gas testing apparatus shown in FIG. 1, and the results of determining the conversion efficiency are shown in FIG. 2.
The gas introduced at this time was 1% vol of CO and 1% vol of NO.
It was determined under the conditions of 1000ppm, H 2 1%vol, and air flow rate 0.1m 2 /min.As a result, the gas conversion rate is significantly higher than the conventional one of about 80% or less. It's improving. In other words, the composition ratio after firing is (1-X)SrFeO 3 . Doesn't play.
さらに上記実施例により得た0.8SrFeO3・
0.2LaNiO3組成の磁器体を用いて第１図の導入ガ
ス試験装置で、一酸化炭素ガスに対する酸化触媒
能を試験し、続いて該半導体が電子−O2-混合導
電性の物質であることから還元性ガスのCO、HC
と酸化性ガスNoxの間で電子と酸素の交換が行な
われれば触媒として有用となることに着目し、さ
らにこれらの試験を行ない、その結果を第３図に
示す。図中ａなCOを還元剤としたときの2NO＋
CO＝N2＋2CO2でｂは炭化水素エチレンを還元剤
としたときの4NO＋CH4＝2N2＋CO2＋2H2O、Ｃ
はCO＋空気＝CO2＋空気の場合で、特に脱硝反
応はNOx→N2までの還元される反応が最も要求
される。なお、導入ガス量はａのとき、２％CO
と１％NO、97％N2、ｂは１％NO、２％CH4、97
％N2、Ｃは２％のCOと空気を各々0.1m2/minの
風量で第１図の装置に導入した。 Furthermore, the 0.8SrFeO 3 obtained in the above example
Using a porcelain body with a composition of 0.2LaNiO 3 , the oxidation catalytic ability of carbon monoxide gas was tested using the introduced gas test device shown in Figure 1, and then the semiconductor was confirmed to be a substance with electron-O 2 - mixed conductivity. Reducing gas CO, HC from
We focused on the fact that if electrons and oxygen were exchanged between the oxidizing gas Nox and the oxidizing gas Nox, it would be useful as a catalyst, and we further conducted these tests, and the results are shown in Figure 3. 2NO+ when CO is used as a reducing agent in the figure
CO=N 2 +2CO 2 and b is 4NO+CH 4 when hydrocarbon ethylene is used as the reducing agent. 2N 2 +CO 2 +2H 2 O, C
is the case where CO + air = CO 2 + air, and in particular, the denitrification reaction requires the most reduction reaction from NOx to N 2 . In addition, when the introduced gas amount is a, 2% CO
and 1% NO, 97% N 2 , b is 1% NO, 2% CH 4 , 97
%N 2 , C, 2% CO and air were each introduced into the apparatus shown in FIG. 1 at an air volume of 0.1 m 2 /min.
第３図のａ，ｂ，ｃの特性図より明らかなよう
にペロブスカイト型酸化物導電体の本実施例の組
成0.8SrFeO3・0.2LaNiO3は一酸化炭素CO、窒素
酸化物NOx、炭化水素HCの移動発生源である自
動車の排ガスに有効な三次触媒である。 As is clear from the characteristic diagrams a, b , and c in FIG. This is an effective tertiary catalyst for automobile exhaust gas, which is a mobile source of gas.
以上のように本発明の排ガス浄化触媒体は、排
ガスがセラミツク気孔体を流れる際、従来の触媒
体のように直通貫流でなく三次元的乱流となるた
めに触媒との未接触、未反応の残存ガス率が極め
て少ないこと、またアルミナ（Al2O3）、シリカ
（SiO2）、コージライトなどに担持された白金
（pt）、パラジウム（pd）、ロジウム（Rh）などの
貴金属を用いることがないので安価、およびハニ
カム構造などの担持体上に薄層として担持された
ものは剥離、磨耗などの劣化現象が起り触媒能の
低下をきたすことがなく、本発明の構造特徴と、
さらに表層部や中心部の骨格が同一触媒能を有す
る磁器体で形成されているので、耐熱性、耐振な
どに優れている。また、本発明品は実施例におい
て、移動発生源の自動車に有効であるとしたが、
これ以外の石油系燃料の固定発生源の排ガスの脱
硝還元および酸化の触媒、さらにダストのフイル
ター効果をも具備し、石油産業におけるゼオライ
トや活性白土の吸着、過、分離の工程および
過分離設備が省けるなどの効果を有し、単に三元
触媒に限らず、その他のものにも応用でき、工業
用利用の極めて大なるものである。 As described above, in the exhaust gas purification catalyst body of the present invention, when exhaust gas flows through the ceramic porous body, the flow is three-dimensional turbulent instead of a direct flow as in conventional catalyst bodies, so that there is no contact with the catalyst or no reaction. The residual gas rate is extremely low, and the use of noble metals such as platinum (PT), palladium (PD), and rhodium (Rh) supported on alumina (Al 2 O 3 ), silica (SiO 2 ), cordierite, etc. The structural features of the present invention are that the structure of the present invention is inexpensive, and when it is supported as a thin layer on a carrier such as a honeycomb structure, deterioration phenomena such as peeling and abrasion do not occur and the catalytic performance decreases.
Furthermore, since the surface and center skeletons are made of porcelain having the same catalytic ability, it has excellent heat resistance and vibration resistance. In addition, in the examples, it was stated that the product of the present invention is effective for automobiles, which are mobile sources, but
It also has a catalyst for denitrification, reduction and oxidation of exhaust gas from fixed sources of petroleum fuels, and also has a dust filter effect, and is suitable for the adsorption, filtration and separation processes and superseparation equipment of zeolite and activated clay in the petroleum industry. It has the effect of saving energy and can be applied not only to three-way catalysts but also to other catalysts, making it extremely useful for industrial purposes.
第１図は、排ガスの浄化試験装置の概要図、第
２図は、SrFeO3とLaNiO3の焼成後の組成比に対
するガス変換特性図、第３図は一実施例の触媒体
のガス温度一変換率特性図である。
１：加熱空気またはガス、２：添加ガス供給装
置、３：触媒体、４：温度検出器、５：反応ガス
捕集用真空ビン、６：石英管、７：ガス流量計。
Figure 1 is a schematic diagram of the exhaust gas purification test equipment, Figure 2 is a diagram of gas conversion characteristics with respect to the composition ratio of SrFeO 3 and LaNiO 3 after firing, and Figure 3 is a diagram of the gas temperature of the catalyst body of one example. It is a conversion rate characteristic diagram. 1: heated air or gas, 2: additive gas supply device, 3: catalyst body, 4: temperature detector, 5: vacuum bottle for collecting reaction gas, 6: quartz tube, 7: gas flow meter.
Claims (1)
酸化物の複合体を基材として連通気孔を有する構
造体を形成し、焼成したことを特徴とする排ガス
浄化触媒体。 ２ SrFeO3とLaNiO3の組成比が（１−Ｘ）
SrFeO3・XLaNiO3、ただしＸは0.5＞Ｘ＞0.05よ
りなる特許請求の範囲第１項記載の排ガス浄化触
媒体。[Claims] 1. An exhaust gas purification catalyst body, characterized in that a structure having continuous pores is formed using a perovskite-type oxide composite consisting of SrFeO 3 and LaNiO 3 as a base material, and then fired. 2 The composition ratio of SrFeO 3 and LaNiO 3 is (1-X)
The exhaust gas purification catalyst body according to claim 1, comprising SrFeO 3 .XLaNiO 3 , where X satisfies 0.5>X>0.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10250479A JPS5626549A (en) | 1979-08-11 | 1979-08-11 | Catalyst for cleaning exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10250479A JPS5626549A (en) | 1979-08-11 | 1979-08-11 | Catalyst for cleaning exhaust gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5626549A JPS5626549A (en) | 1981-03-14 |
| JPS6231611B2 true JPS6231611B2 (en) | 1987-07-09 |
Family
ID=14329226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10250479A Granted JPS5626549A (en) | 1979-08-11 | 1979-08-11 | Catalyst for cleaning exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5626549A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62140773A (en) * | 1985-12-12 | 1987-06-24 | 芝浦メカトロニクス株式会社 | electric bolt tightening machine |
| CN106268283B (en) * | 2016-09-14 | 2019-04-26 | 湖南省小尹无忌环境能源科技开发有限公司 | The method of cement kiln flue gas removing heavy metal and sulphur nitre pollutant and resource utilization |
| CN110465303A (en) * | 2019-08-28 | 2019-11-19 | 玉林师范学院 | A kind of LaNiO of calcium analysis3The preparation method and application of perovskite type photocatalyst |
-
1979
- 1979-08-11 JP JP10250479A patent/JPS5626549A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5626549A (en) | 1981-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3050566B2 (en) | Palladium-containing ceria-supported platinum catalyst and catalyst assembly containing the same | |
| EP1932590B1 (en) | Particulate combustion catalyst, particulate filter, and exhaust gas clean-up system | |
| JP5773337B2 (en) | Oxidation catalyst and diesel particulate filter | |
| JP5864444B2 (en) | Exhaust gas purification catalyst and exhaust gas purification catalyst structure | |
| JPH03161052A (en) | Exhaust gas purification catalyst body and its manufacturing method | |
| WO2012093599A1 (en) | Exhaust gas purifying catalyst | |
| JP2009131774A (en) | PM oxidation catalyst and exhaust gas purification catalyst using the same | |
| JP5587907B2 (en) | Purified structure containing a catalyst system supported by reduced state zircon | |
| CN103153437B (en) | Electrochemical catalyst system | |
| JPS6231611B2 (en) | ||
| JP5612795B2 (en) | Exhaust gas purification catalyst, exhaust gas purification device and filter, and method for producing the catalyst | |
| US20070054800A1 (en) | Exhaust gas purification catalyst and catalyst-equipped diesel particulate filter | |
| CN103209927B (en) | Layered mixed oxide, oxidation catalyst and diesel particulate filter | |
| JP2538010B2 (en) | Exhaust gas purification catalyst | |
| JP2000256017A (en) | Layered perovskite compound, nitrogen oxide purification catalyst material, and exhaust gas purification catalyst using the same | |
| JPH01304048A (en) | Exhaust gas purification catalyst | |
| JPH04346836A (en) | Production of catalyst for purification of exhaust gas | |
| JP2009154077A (en) | Ceramic catalyst material and exhaust purification method using the same | |
| JPH04104838A (en) | Waste gas purifying catalytic body | |
| Lu et al. | Catalytic Purification of NO x and PM by Fe-Doped CuCrO2 Catalyst Using Two Kinds of Carriers | |
| WO2026058331A1 (en) | Exhaust gas purification catalyst | |
| JPH04197446A (en) | Catalyst for exhaust purification | |
| KR20060050577A (en) | Nitrogen oxide removal materials and devices | |
| JPH01307448A (en) | Waste gas purification catalyst | |
| JPH09313941A (en) | Oxide catalyst material for removing nitrogen oxide and method for removing nitrogen oxide |