JPS63158130A - Catalyst for purifying exhaust gas - Google Patents
Catalyst for purifying exhaust gasInfo
- Publication number
- JPS63158130A JPS63158130A JP61306973A JP30697386A JPS63158130A JP S63158130 A JPS63158130 A JP S63158130A JP 61306973 A JP61306973 A JP 61306973A JP 30697386 A JP30697386 A JP 30697386A JP S63158130 A JPS63158130 A JP S63158130A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carrier
- exhaust gas
- element selected
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 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
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 consisting of A Inorganic materials 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は各種の燃焼機器や内燃機関の排気ガスに含まれ
るCo、HC等の有害ガスを002やH2Oに変化させ
るとともに、還元雰囲気下ではNOxも浄化することの
できる触媒体に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention converts harmful gases such as Co and HC contained in the exhaust gas of various combustion devices and internal combustion engines into 002 and H2O, and also converts NOx in a reducing atmosphere. This invention relates to a catalyst body that can be purified.
従来の技術
従来、この種の触媒としてはPt、Pd等の貴金属触媒
やCuo9Mno2.co304等の酸化物触媒が用い
られている。前者は、三元触媒として用いられており、
Co、HC等の酸化や還元雰囲気下でのNo 浄化を行
うことができるが高価である。後者!
は、高温、還元雰囲気下では容易に還元され触媒活性が
低下するので主として酸素存在下でのC09HC等の酸
化触媒として用いられている。゛発明が解決しようとす
る問題点
触媒を実際に使用する場合、触媒材料を触媒担体に担持
する必要がある。通常、アルミナやシリカ等を主成分と
するセラミックス製担体に担持す、るがコバルト酸化物
を含む触媒あるいはコバルトを含む複合酸化物からなる
触媒の場合、コバルトがアルミナやシリカ等と高温で容
易に反応し触媒活性の低い複合酸化物を生成する0また
、セラミックス製担体の場合、衝撃に対してもろく、機
械加工が容易でない欠点を有している。BACKGROUND OF THE INVENTION Conventionally, this type of catalyst includes noble metal catalysts such as Pt and Pd, Cuo9Mno2. Oxide catalysts such as CO304 are used. The former is used as a three-way catalyst,
Although it is possible to perform No purification in an oxidizing or reducing atmosphere using Co, HC, etc., it is expensive. the latter! is easily reduced and its catalytic activity decreases at high temperatures and in a reducing atmosphere, so it is mainly used as an oxidation catalyst for CO9HC and the like in the presence of oxygen. Problems to be Solved by the Invention When the catalyst is actually used, it is necessary to support the catalyst material on a catalyst carrier. Usually, catalysts containing cobalt oxide or composite oxides containing cobalt are supported on a ceramic carrier mainly composed of alumina, silica, etc., but cobalt easily forms with alumina, silica, etc. at high temperatures. Furthermore, in the case of a ceramic carrier, it has the disadvantage that it is brittle against impact and cannot be easily machined.
問題点を解決するための手段
本発明は上記の問題点を解決するために触媒担体として
Ni、Fe、Tiから選ぶ少くとも一種の元素を構成要
素とし、それにコバルトを含む酸化触媒を担持させたも
のである。Means for Solving the Problems In order to solve the above problems, the present invention uses at least one element selected from Ni, Fe, and Ti as a catalyst carrier, and supports an oxidation catalyst containing cobalt on it. It is something.
作 用
本発明になる触媒体は、熱により生成される金属担体表
面の酸化物と酸化コバルトを含む酸化物触媒及び一般式
La1−rAxCo1□MeyO3−δ(AはCe。Function The catalyst body of the present invention is an oxide catalyst containing an oxide on the surface of a metal carrier generated by heat and cobalt oxide, and a general formula La1-rAxCo1□MeyO3-δ (A is Ce).
Ca、Baから選ぶ少くとも一種の元素、MeはFe。At least one element selected from Ca and Ba; Me is Fe.
Mn、Cr、Vから選ぶ少くとも一種の元素、0≦x≦
1.0≦y≦1)で表わされる酸化物触媒とをその接触
部分において反応させて担持するものであるが、アルミ
ナやシリカと異なシ触媒活性の低い生成物を生ずること
がなく、触媒を担体に焼付けてもほとんど触媒活性が低
下することがない。また金属担体として耐熱性金属を用
いれば高温雰囲気での使用にも十分機械的強度をもった
触媒体を得ることができ、しかも穴あけ、打抜き9曲げ
などの機械加工が金属担体であることから容易にできる
。At least one element selected from Mn, Cr, and V, 0≦x≦
The catalyst is supported by reacting with the oxide catalyst represented by 1.0≦y≦1) in the contact area, but unlike alumina and silica, it does not produce products with low catalytic activity, and the catalyst is Even if the carrier is baked, the catalytic activity hardly decreases. In addition, if a heat-resistant metal is used as the metal carrier, it is possible to obtain a catalyst body with sufficient mechanical strength for use in a high-temperature atmosphere, and machining processes such as drilling, punching, and bending are easy because the metal carrier is used. Can be done.
実施例
本実施例では、各金属塩を均一に混合溶解した水溶液か
ら水酸化ナトリウム、アミン類としゆう酸を用いて各金
属のしゅう酸塩及び水酸化物を沈殿させ、空気中で焼成
してL ao 、 sS r o 、5Coo3−δ酸
化物触媒を合成した。Example In this example, oxalates and hydroxides of each metal were precipitated from an aqueous solution containing uniformly mixed and dissolved metal salts using sodium hydroxide, amines, and citric acid, and then calcined in air. L ao , sS r o , 5Coo3-δ oxide catalysts were synthesized.
上記酸化物触媒を水に分散し、発泡ニッケルよりなる担
体に含浸し、乾燥後熱処理して焼付は触媒体を作製した
。このように作製した触媒体の排ガス浄化能と熱に対す
る触媒特性の安定性を調べた0
排ガス浄化能試験として、該触媒体を管状電気炉にとう
した石英ガラス管内に設置し、空気とCOハ、からなる
混合ガス、空気とl5O−C4H10//N2からなる
混合ガスを用いて各温度におけるCO及びZ So −
C4H、。の酸化率の測定を行った。また、熱に対する
触媒特性の安定性の確認試験として、触媒体をaOO℃
雰囲気下におき1o時間おきに300℃でのCOの酸化
率の測定を行った。比較のためにムライト製担体゛に同
重量の酸化物触媒を担持した触媒体についても同様の試
験を行った。The above-mentioned oxide catalyst was dispersed in water, impregnated into a support made of foamed nickel, dried, and then heat-treated to produce a baked catalyst body. The exhaust gas purification ability of the catalyst body prepared in this way and the stability of the catalytic properties against heat were investigated.0 As an exhaust gas purification ability test, the catalyst body was placed in a quartz glass tube placed in a tubular electric furnace, and air and CO were removed. , CO and Z So − at each temperature using a mixed gas consisting of air and l5O−C4H10//N2.
C4H. The oxidation rate was measured. In addition, as a test to confirm the stability of the catalyst properties against heat, the catalyst body was
The oxidation rate of CO was measured at 300° C. every 1 hour in an atmosphere. For comparison, a similar test was conducted on a catalyst body in which the same weight of oxide catalyst was supported on a mullite carrier.
各温度におけるCOの酸化率の結果を第1図に、各温度
における1so−C4H1゜の酸化率の結果を第2図に
、また、800℃雰囲気下での触媒特性の安定性の結果
を第3図にそれぞれ示した。Co及び1so−C4H1
゜の酸化率は、次式より求めた。The results of the oxidation rate of CO at each temperature are shown in Figure 1, the results of the oxidation rate of 1so-C4H1° at each temperature are shown in Figure 2, and the results of the stability of catalyst properties in an atmosphere of 800°C are shown in Figure 1. They are shown in Figure 3. Co and 1so-C4H1
The oxidation rate in ° was calculated from the following formula.
第1図と第2図に示した結果より発泡ニッケルを担体と
した触媒体は、ムライト製担体を用いた触媒体より60
〜100℃低い温度がらCo、is。From the results shown in Figures 1 and 2, the catalyst body using foamed nickel as a carrier was 60% lower than the catalyst body using mullite carrier.
Co, is at ~100°C lower temperature.
−C4H1゜の酸化が起こり、担持による触媒能の低下
はほとんど認められなかった。また、第3図の熱に対す
る触媒特性の安定性の結果からも発泡ニッケルを担体と
した触媒体の方が触媒活性の低い化合物を生成すること
がないためムライト製担体を用いた触媒体よりも安定し
ていることが認められる。-C4H1° oxidation occurred, and almost no decrease in catalytic ability was observed due to the support. Also, from the results of the stability of catalyst properties against heat shown in Figure 3, the catalyst using foamed nickel as a carrier does not produce compounds with low catalytic activity, so it is better than the catalyst using mullite as a carrier. It is recognized that it is stable.
次に、酸素量に対してCO量の過剰な還元雰囲気にNo
x/N2ガスを混合し、各温度におけるNOx消去率の
測定を行った。その結果を第4図に示した。NO工消去
率は次式より求めた。Next, the No.
x/N2 gas was mixed and the NOx elimination rate was measured at each temperature. The results are shown in Figure 4. The NO eradication rate was determined from the following formula.
NOx消去率についても第4図より発泡ニッケルを担体
とした触媒体の方が60℃程度低い温度よりNo工を消
去した。Regarding the NOx elimination rate, FIG. 4 shows that the catalyst body using foamed nickel as a carrier eliminated NOx at a temperature about 60° C. lower.
以上のように本発明になる触媒体は、排ガス中のCo
、 HC(還元雰囲気ではN0x)の浄化能が高く、熱
に対しても安定である。さらに、実施例ではL a o
、 s S r o 、 6COOa −,5酸化物
触媒を発泡ニッケルに担持した場合について述べたが、
コバルトを含む酸化物触媒、AにSrのかわシにCe。As described above, the catalyst body of the present invention can reduce CO in exhaust gas.
, has a high purifying ability for HC (N0x in a reducing atmosphere) and is stable against heat. Furthermore, in the example, L a o
, s S r o , 6COOa -,5 oxide catalyst is supported on foamed nickel,
An oxide catalyst containing cobalt, consisting of A, Sr, and Ce.
Ca、Baを添加した場合、Co f M eとしてF
e、Mn。When Ca and Ba are added, F as Co f M e
e, Mn.
、Cr、Vで置換した場合にも同様な効果が得られた。, Cr, and V were substituted with similar effects.
また、金属担体としては、Fe(耐熱性ステンレス)。Moreover, as a metal carrier, Fe (heat-resistant stainless steel) is used.
Ti およびこれらを主成分として含む合金の場合にも
同様の効果を得ることができた。Similar effects could be obtained in the case of Ti and alloys containing these as main components.
発明の効果
本発明は、金属をコバルト系酸化物触媒の触媒担体とし
て用いることで排ガス中のCo 、 HC(還元雰囲気
ではN0x)の浄化能も高く、熱に対しても触媒活性の
低い反応物を生成せず触媒特性の安定した触媒体を得る
ことができ、しかも、金属担体であることから穴あけ、
打抜き9曲げなどの機械加工を容易に行うことができる
。Effects of the Invention The present invention uses a metal as a catalyst carrier for a cobalt-based oxide catalyst, which has a high ability to purify Co and HC (N0x in a reducing atmosphere) in exhaust gas, and is a reactant with low catalytic activity against heat. It is possible to obtain a catalyst body with stable catalytic properties without producing any
Machining such as punching and bending can be easily performed.
第1図は本発明の一実施例の触媒体の各温度におけるC
Oの駿化率特性図、第2図は同触媒体の各温度における
1so−C4H1゜の酸化率特性図、第3図は同触媒体
の800°Cに対する安定性特性図、第4図は還元雰囲
気下での各温度におけるNo!消去率特性図である。
代理人の氏名 弁理士 中 尾 敏 男 ほか1名第1
図
温 潰 (”C)
第2図
温 り雫己 (Dこ、ン
第3図Figure 1 shows the C of the catalyst body of one embodiment of the present invention at various temperatures.
Figure 2 is the oxidation rate characteristic diagram of 1so-C4H1° at various temperatures of the same catalyst, Figure 3 is the stability characteristic diagram of the same catalyst at 800°C, and Figure 4 is the characteristic diagram of the oxidation rate of O. No. at each temperature under reducing atmosphere! It is an erasure rate characteristic diagram. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure 2 (D) Figure 3
Claims (2)
ら選ぶ少くとも一種を構成要素とする担体に担持したこ
とを特徴とする排ガス浄化用触媒体。(1) A catalyst body for exhaust gas purification, characterized in that an oxide catalyst containing cobalt is supported on a carrier having at least one component selected from Ni, Fe, and Ti.
_1_−_yMe_yO_3_−_δ(ただしAはCe
、Sr、Ca、Baから選ぶ少くとも一種の元素、Me
はFe、Mn、Cr、Vから選ぶ少くとも一種の元素、
0≦x≦1、0≦y≦1)で表わされる酸化物であるこ
とを特徴とする特許請求の範囲第1項記載の排ガス浄化
用触媒体。(2) The oxide catalyst has the general formula La_1_-_xA_xCo
_1_-_yMe_yO_3_-_δ (A is Ce
, at least one element selected from Sr, Ca, Ba, Me
is at least one element selected from Fe, Mn, Cr, and V,
The catalyst body for exhaust gas purification according to claim 1, characterized in that it is an oxide represented by 0≦x≦1, 0≦y≦1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61306973A JPS63158130A (en) | 1986-12-23 | 1986-12-23 | Catalyst for purifying exhaust gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61306973A JPS63158130A (en) | 1986-12-23 | 1986-12-23 | Catalyst for purifying exhaust gas |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63158130A true JPS63158130A (en) | 1988-07-01 |
Family
ID=17963493
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61306973A Pending JPS63158130A (en) | 1986-12-23 | 1986-12-23 | Catalyst for purifying exhaust gas |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63158130A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5318937A (en) * | 1990-06-21 | 1994-06-07 | The United States Of America As Represented By The Administrator Of The U.S. Environmental Protection Agency | Ruthenium-containing perovskite materials, catalysts and methods |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58156350A (en) * | 1982-03-12 | 1983-09-17 | Matsushita Electric Ind Co Ltd | Apparatus for purifying exhaust gas |
JPS6030909A (en) * | 1983-08-01 | 1985-02-16 | Matsushita Electric Ind Co Ltd | Method of cleaning exhaust gas from gas burner |
JPS6082138A (en) * | 1983-10-07 | 1985-05-10 | Doudensei Muki Kagoubutsu Gijutsu Kenkyu Kumiai | Catalyst body for purifying waste gas |
JPS6118434A (en) * | 1984-07-06 | 1986-01-27 | Doudensei Muki Kagoubutsu Gijutsu Kenkyu Kumiai | Catalytic body for purifying exhaust gas |
JPS6197032A (en) * | 1984-10-19 | 1986-05-15 | Doudensei Muki Kagoubutsu Gijutsu Kenkyu Kumiai | Catalyst body for purifying exhaust gas |
JPS61283349A (en) * | 1985-06-05 | 1986-12-13 | Tech Res Assoc Conduct Inorg Compo | Catalyst for purifying exhaust gas |
JPS61283350A (en) * | 1985-06-05 | 1986-12-13 | Tech Res Assoc Conduct Inorg Compo | Catalyst for purifying exhaust gas |
-
1986
- 1986-12-23 JP JP61306973A patent/JPS63158130A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58156350A (en) * | 1982-03-12 | 1983-09-17 | Matsushita Electric Ind Co Ltd | Apparatus for purifying exhaust gas |
JPS6030909A (en) * | 1983-08-01 | 1985-02-16 | Matsushita Electric Ind Co Ltd | Method of cleaning exhaust gas from gas burner |
JPS6082138A (en) * | 1983-10-07 | 1985-05-10 | Doudensei Muki Kagoubutsu Gijutsu Kenkyu Kumiai | Catalyst body for purifying waste gas |
JPS6118434A (en) * | 1984-07-06 | 1986-01-27 | Doudensei Muki Kagoubutsu Gijutsu Kenkyu Kumiai | Catalytic body for purifying exhaust gas |
JPS6197032A (en) * | 1984-10-19 | 1986-05-15 | Doudensei Muki Kagoubutsu Gijutsu Kenkyu Kumiai | Catalyst body for purifying exhaust gas |
JPS61283349A (en) * | 1985-06-05 | 1986-12-13 | Tech Res Assoc Conduct Inorg Compo | Catalyst for purifying exhaust gas |
JPS61283350A (en) * | 1985-06-05 | 1986-12-13 | Tech Res Assoc Conduct Inorg Compo | Catalyst for purifying exhaust gas |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5318937A (en) * | 1990-06-21 | 1994-06-07 | The United States Of America As Represented By The Administrator Of The U.S. Environmental Protection Agency | Ruthenium-containing perovskite materials, catalysts and methods |
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