JPH0653230B2 - Exhaust gas purification catalyst manufacturing method - Google Patents
Exhaust gas purification catalyst manufacturing methodInfo
- Publication number
- JPH0653230B2 JPH0653230B2 JP63149308A JP14930888A JPH0653230B2 JP H0653230 B2 JPH0653230 B2 JP H0653230B2 JP 63149308 A JP63149308 A JP 63149308A JP 14930888 A JP14930888 A JP 14930888A JP H0653230 B2 JPH0653230 B2 JP H0653230B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- average particle
- particle size
- compound powder
- 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 - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000746 purification Methods 0.000 title description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052878 cordierite Inorganic materials 0.000 description 7
- 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 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241000252095 Congridae Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は自動車の排気ガス浄化用触媒の製造方法、更に
詳しくは、異臭の原因となるH2Sガスを生成させない排
気ガス浄化用触媒の製造方法に関するものである。The present invention relates to a method for producing a catalyst for purifying exhaust gas of an automobile, more specifically, a catalyst for purifying exhaust gas which does not generate H 2 S gas causing an offensive odor. The present invention relates to a manufacturing method.
近年、自動車のエンジンから排出される排気ガスが公害
問題として大きく取り上げられるに至り、現在ではエン
ジン排気系に、炭化水素(HC)、一酸化炭素(CO)、窒素酸
化物(NOx)等を無害化処理するための触媒コンバータを
装着することが一般的となつている。一方、エンジン中
の未燃焼ガスを完全燃焼させる目的で二次空気を導入す
ることも行なわれている。In recent years, exhaust gas emitted from automobile engines has come to be widely taken up as a pollution problem, and now hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx), etc. are harmless to the engine exhaust system. It is common to equip a catalytic converter for chemical treatment. On the other hand, secondary air is also introduced for the purpose of completely burning unburned gas in the engine.
そのような触媒コンバータ付自動車では、エンジン高負
荷時に更に二次空気を導入して排気ガス燃焼効率を高め
ると触媒コンバータが異常に加熱され、触媒損傷、機能
低下等の原因となるので、エンジン高負荷時には制御装
置によつて二次空気の導入を停止させたり、燃料の供給
を増加させたりしている。In such a vehicle with a catalytic converter, if secondary air is further introduced to increase exhaust gas combustion efficiency when the engine is under heavy load, the catalytic converter will be abnormally heated, causing damage to the catalyst and deterioration of its function. At the time of load, the control device stops the introduction of the secondary air or increases the fuel supply.
しかしその場合には排気ガスの空燃比がリツチ側（燃料
過剰側）となり、還元雰囲気となつた触媒コンバータ内
では触媒床に吸着していたSO2が還元されてH2Sが生成し
（8th Int.Congr.Catal.〈第８回国際触媒会議予稿集〉
1984年３月号、第453〜463頁参照）、異臭が発生すると
いう問題があつた。その対策として、H2S処理装置を設
けることが実開昭54-31210号公報に提案されている。However, in that case, the air-fuel ratio of the exhaust gas becomes the rich side (fuel excess side), and the SO 2 adsorbed on the catalyst bed is reduced within the catalytic converter in the reducing atmosphere to produce H 2 S (8th Int.Congr.Catal. <8th International Catalysis Conference Proceedings>
March 1984 issue, pp. 453-463), there was a problem that an offensive odor was generated. As a countermeasure, it is proposed in Japanese Utility Model Publication No. 54-31210 to provide an H 2 S processing device.
このH2S処理装置は、触媒コンバータ後方にH2S酸化用触
媒装置を設けると共に、該H2S酸化用触媒装置と二次空
気注入系のエアスイツチングバルブを、触媒コンバータ
をバイパスさせて連通し、上記エアスイツチングバルブ
を、触媒コンバータへの二次空気の注入を遮断したとき
に二次空気が前記H2S酸化用触媒装置に導かれるように
切替自在としたものである。This H 2 S treatment device is provided with a catalyst device for H 2 S oxidation at the rear of the catalytic converter, and bypasses the catalytic converter for the H 2 S oxidation catalyst device and the air switching valve of the secondary air injection system. In communication with each other, the air switching valve is switchable so that the secondary air is guided to the H 2 S oxidation catalyst device when the injection of the secondary air into the catalytic converter is interrupted.
又、本出願人は特願昭62-170332号明細書（特開昭64-15
138号公報）に記載された、耐火性担持体に、Ａ：C
e：Co、Ni、Feの少なくとも１種：Laを、２：0.1〜0.6：
0.03〜2.0：0.01〜0.1のモル比で含んでなる酸化物コー
ト層を形成させ、Pt、Pd、Rhの少なくとも１種の貴金属を
担持させたことを特徴とする排気ガス浄化用触媒を提案
した。In addition, the applicant of the present invention is directed to Japanese Patent Application No. 62-170332
No. 138), the refractory carrier described in A: C
e: at least one of Co, Ni and Fe: La, 2: 0.1 to 0.6:
An exhaust gas purifying catalyst characterized in that an oxide coat layer containing 0.03 to 2.0: 0.01 to 0.1 in a molar ratio is formed and at least one precious metal of Pt, Pd, and Rh is supported is proposed. .
しかし実開昭54-31210号公報に記載されたようなH2S処
理装置を別途設けることは排気ガス浄化システムを一層
複雑化し、自動車の製造により以上のコストが強いられ
ることとなる。However, the additional provision of the H 2 S treatment device as described in Japanese Utility Model Laid-Open No. 54-31210 further complicates the exhaust gas purification system, and the above cost is imposed on the automobile manufacturing.
又、特願昭62-170332号明細書記載の触媒は、CeとCo、N
i、Feの少なくとも１種とが必ずしも隣接してはいなかつ
たため、このような触媒系が有するリツチ側でのH2Sの
生成抑制効果をまだ充分に発揮させたものではなかつ
た。The catalyst described in Japanese Patent Application No. 62-170332 is Ce, Co, N.
Since at least one of i and Fe was not necessarily adjacent to each other, the effect of suppressing the generation of H 2 S on the latch side, which such a catalyst system had, was not yet sufficiently exerted.
本発明は上記従来技術における問題点を解決するための
ものであり、その目的とするところはリツチ側における
H2Sの発生を抑制するとともにHC、CO及びNOxの浄化性能
に優れた排気ガス浄化用触媒の容易な製造方法を提供す
ることにある。The present invention is to solve the problems in the above-mentioned prior art, and the purpose thereof is on the latch side.
An object of the present invention is to provide a method for easily producing an exhaust gas purification catalyst that is excellent in purification performance of HC, CO and NOx while suppressing generation of H 2 S.
すなわち本発明の排気ガス浄化用触媒の製造方法は、平
均粒径0.1μｍ以上のCeの化合物粉末にNi、Co、Feのうち
の少なくとも１種を担持するか、又は平均粒径0.1μｍ
以上のNi、Co、Feのうちの少なくとも１種からなる化合物
粉末にCeを担持することにより調製した化合物粉末を使
用して、 耐火性担持上に、Ａ：Ce：Ni、Co、Feのうちの少なくと
も１種：Laを、２：0.1〜0.6：0.01〜1.2：0.01〜0.1の
モル比で含んでなる酸化物コート層を浸漬法により形成
し、 次いで該酸化物コート層にPt、Pd、Rhのうちの少なくとも
１種を担持してなることを特徴とする。That is, in the method for producing an exhaust gas purifying catalyst of the present invention, a compound powder of Ce having an average particle size of 0.1 μm or more is loaded with at least one of Ni, Co and Fe, or an average particle size of 0.1 μm.
Using a compound powder prepared by supporting Ce on a compound powder consisting of at least one of the above Ni, Co, and Fe, A: Ce: Ni, Co, Fe Of at least one kind of: La at a molar ratio of 2: 0.1 to 0.6: 0.01 to 1.2: 0.01 to 0.1 is formed by a dipping method, and then Pt, Pd, It is characterized by supporting at least one of Rh.
Ceの化合物粉末又はNi、Co、Feのうちの少なくとも１種か
らなる化合物粉末は、平均粒径があまり小さいとCeとN
i、Co、Feのうちの少なくとも１種とが充分に隣接せず、
他の構成成分との間の相互作用の影響がでてきてH2Sの
補捉効果が低下するので、平均粒径0.1μｍ以上のもの
を使用する必要がある。担持方法は浸漬法を用いる。The compound powder of Ce or the compound powder consisting of at least one of Ni, Co, and Fe has Ce and N when the average particle size is too small.
At least one of i, Co and Fe is not sufficiently adjacent to each other,
It is necessary to use particles having an average particle size of 0.1 μm or more, because the effect of interaction with other constituents appears and the trapping effect of H 2 S decreases. A dipping method is used as a supporting method.
耐火性担体としてはセラミツク製例えばコージエライト
製、耐熱性金属製等のペレツト又は一体性担体等を使用
することができる。As the refractory carrier, a pellet made of ceramic, for example, cordierite, a heat-resistant metal, or an integral carrier can be used.
Ａはアルミナ例えばγ−Ａ２Ｏ３であつてよい。C
e、Ni、Co、Fe又はLaは酸化物、塩などの所望の形態のもの
を使用する。又、各金属成分の比率は前記比率が得られ
る触媒のH2Sの発生抑制性能及び浄化性能等の点で具合
がよい。A may be alumina such as γ-A 2 O 3 . C
As e, Ni, Co, Fe or La, those in a desired form such as oxides and salts are used. Further, the ratio of each metal component is good in terms of the H 2 S generation suppressing performance and purification performance of the catalyst that can obtain the above ratio.
Pt、Pd又はRhは耐火性担体上に形成した酸化物コート層
に浸漬法などにより所定量担持する。Pt, Pd, or Rh is supported in a predetermined amount on the oxide coating layer formed on the refractory carrier by a dipping method or the like.
以下にNiを例としてH2Sの生成抑制機構を説明する。な
お、Co及びFeも同様である。リーン側では下記反応(I)
の反応が、リツチ側では下記反応式(II)の反応が起る。The mechanism of H 2 S production suppression is explained below using Ni as an example. The same applies to Co and Fe. On the lean side, the following reaction (I)
On the side of the latch, the reaction of the following reaction formula (II) occurs.
上記反応(II)において、NiとCeとが隣接して存在すれば
NiSの生成に有利である。又、NiとCeとが隣接している
場合の他の作用として、NiがＡ２Ｏ３と反応してＡ
２ＮｉＯ４を形成してNiのH2S生成抑制効果が失われた
り、浄化性能低下の原因となつたりするのを防止する作
用がある。なお、他の金属成分のうち、Pt、Pd又はRhはH
C、CO又はNOxの浄化作用を示し、又、Laはこの際の助触
媒作用を示す。 In the above reaction (II), if Ni and Ce are adjacent to each other,
It is advantageous for the production of NiS. As another effect when Ni and Ce are adjacent to each other, Ni reacts with A 2 O 3 to form A
It has an effect of preventing 2 NiO 4 from being formed and losing the H 2 S production suppressing effect of Ni, and causing the deterioration of the purification performance. Among other metal components, Pt, Pd or Rh is H
It exhibits a purifying action for C, CO or NOx, and La exhibits a co-catalyst action in this case.
以下の実施例及び比較例において本発明を更に詳細に説
明する。なお、本発明は下記実施例に限定されるもので
はない。The present invention will be described in more detail in the following examples and comparative examples. The present invention is not limited to the examples below.
実施例１ 平均粒径２μｍのCeO2粉末にNi(NO3)2溶液を含浸添加し
たものと、La(NO3)3溶液を予め含浸させたγ−Ａ２Ｏ
３のスラリーとを均一に混合し、これを市販のコージエ
ライト質ハニカム担体にウオツシユコートして100℃で
１時間乾燥後700℃で２時間焼成した。次いで、これに
貴金属を担持して触媒化した。Example 1 CeO 2 powder having an average particle size of 2 μm impregnated with a Ni (NO 3 ) 2 solution and γ-A 2 O impregnated with a La (NO 3 ) 3 solution in advance
The slurry of No. 3 was uniformly mixed, and this was coated on a commercially available cordierite honeycomb carrier with a washcoat, dried at 100 ° C. for 1 hour, and then calcined at 700 ° C. for 2 hours. Then, a noble metal was supported on this to be catalyzed.
実施例２ CeO2粉末の代りに平均粒径２μｍのCe(CO3)2を使用する
こと以外は実施例１と同様にして行つた。Example 2 The procedure of Example 1 was repeated, except that Ce (CO 3 ) 2 having an average particle size of 2 μm was used instead of the CeO 2 powder.
実施例３ 平均粒径２μｍのCeO2粉末にNi(NO3)2溶液を含浸添加し
たものをスラリー化してコージエライト質ハニカム担体
にウオツシユコートして100℃で１時間乾燥後700℃で２
時間焼成した。次いでこの上に、La(NO3)3溶液を予め含
浸させたγ−Ａ２Ｏ３のスラリーをウオツシユコート
して100℃で１時間乾燥後700℃で２時間焼成した。次い
で、これに貴金属を担持して触媒化した。Example 3 A CeO 2 powder having an average particle size of 2 μm impregnated with a Ni (NO 3 ) 2 solution was slurried to form a slurry on a cordierite honeycomb carrier, which was dried at 100 ° C. for 1 hour and then at 700 ° C. for 2 hours.
Burned for hours. Then, a slurry of γ-A 2 O 3 pre-impregnated with a La (NO 3 ) 3 solution was applied onto this in a wash-coating manner, dried at 100 ° C. for 1 hour, and then calcined at 700 ° C. for 2 hours. Then, a noble metal was supported on this to be catalyzed.
実施例４ 平均粒径２μｍのNiO粉末にCe(NO3)2溶液を含浸させた
ものをγ−Ａ２Ｏ３のスラリーに添加して均一に混合
し、コージエライト質ハニカム担体にウオツシユコート
して100℃で１時間乾燥後700℃で２時間焼成した。次い
でこれにLa(NO3)3溶液を含浸させて同様に乾燥、焼成
後、貴金属を担持して触媒化した。Example 4 A NiO powder having an average particle diameter of 2 μm impregnated with a Ce (NO 3 ) 2 solution was added to a slurry of γ-A 2 O 3 and uniformly mixed, and a cordierite honeycomb carrier was coated with a washcoat. And dried at 100 ° C. for 1 hour and then calcined at 700 ° C. for 2 hours. Next, this was impregnated with a La (NO 3 ) 3 solution, dried and calcined in the same manner, and then supported with a noble metal to form a catalyst.
上記実施例１〜４において、担体１当りの各成分の担
持量を下記第１表に示す。In the above Examples 1 to 4, the supported amounts of each component per carrier 1 are shown in Table 1 below.
コージエライト質ハニカム担体の寸法としては３０φ×
５０Ｌ(mm)のテストピース及び1.7のフルサイズの２
種類を使用して、本発明の方法によつて排気ガス浄化用
触媒を得た。 The size of the cordierite honeycomb carrier is 30φ ×
50L (mm) test piece and 1.7 full size 2
An exhaust gas purifying catalyst was obtained by the method of the present invention by using various kinds.
なお、上記実施例１〜４において、Ni化合物の代りにCo
又はFe化合物を使用しても同様に触媒を得ることができ
る。In the above Examples 1 to 4, Co was used instead of the Ni compound.
Alternatively, a catalyst can be obtained in the same manner by using an Fe compound.
比較例１〜４ Ni化合物を使用しないこと以外は実施例１〜４と同様に
して比較例１〜４の触媒を得た。Comparative Examples 1 to 4 Catalysts of Comparative Examples 1 to 4 were obtained in the same manner as in Examples 1 to 4 except that the Ni compound was not used.
性能評価試験１ (1) H2S抑制効果の評価 テストピース触媒に、イオウ分を0.1wt%含有したガソリ
ン使用時のモデルガスをA/F＝15.0で１時間流通させた
後A/F＝13.0で５分間流通させ、H2S生成量を測定した。
結果を第２表に示す。Performance evaluation test 1 (1) Evaluation of H 2 S suppression effect A model gas when gasoline containing 0.1 wt% of sulfur was used in the test piece catalyst at A / F = 15.0 for 1 hour and then A / F = It was circulated at 13.0 for 5 minutes, and the amount of H 2 S produced was measured.
The results are shown in Table 2.
第２表から明らかな如く、本発明の製造方法によつて得
た触媒は比較例の触媒に比べてH2S生成量が少ない。
又、Ni添加量が多くなるにつれてH2Sは更に減少し、Ni
添加量が0.1Ｍ／・担体以上ではH2Sは全く発生しない
のが判る。 As is clear from Table 2, the catalyst obtained by the production method of the present invention produces less H 2 S than the catalyst of the comparative example.
In addition, H 2 S decreases further as the amount of Ni added increases.
It can be seen that H 2 S is not generated at all when the added amount is 0.1 M / · carrier or more.
(2) 浄化性能の評価 ３エンジンの排気系に実施例１及び比較例１のフルサ
イズ触媒を取り付け、2000rpm、−360mmHg、300℃の測
定条件下で、初期及び床温度900℃、5000rpmで100時間
耐久後のHC、CO及びNOxの浄化率を測定した。結果を第３
表に示す。(2) Evaluation of purification performance 3 Full-sized catalysts of Example 1 and Comparative Example 1 were attached to the exhaust system of an engine, and the initial and floor temperatures were 900 ° C and 5000rpm at 100 rpm under measurement conditions of 2000 rpm, -360 mmHg, and 300 ° C. The purification rates of HC, CO and NOx after the endurance time were measured. The result is the third
Shown in the table.
第３表に示す如く、本発明の製造方法によつて得た触媒
は比較例の触媒に比べて同等の浄化率を有している。 As shown in Table 3, the catalyst obtained by the production method of the present invention has an equivalent purification rate as compared with the catalyst of the comparative example.
NiS生成の確認 H2S生成量測定後の実施例の触媒を粉砕し、FTIRでNiと
Ｓとの吸着状態を観察したところ、NiSの結合のピーク
が確認でき、化学的に結合しているのが判つた。Confirmation of NiS production When the catalyst of the example after measuring the amount of H 2 S produced was pulverized and the adsorption state of Ni and S was observed by FTIR, the peak of NiS binding was confirmed and it was chemically bound. I found out.
実施例５ 平均粒径５μｍのＦｅ２Ｏ３粉末にＣｅ（ＮＯ３）３溶
液を含浸させたものを、γ−Ａ２Ｏ３粒子と共に均一
に混合してスラリー化し、コージエライト質ハニカム担
体にウオツシユコートして１００℃で１時間乾燥後、６
００℃で２時間焼成した。以下、実施例４と同様にして
触媒化した。Example 5 A Fe 2 O 3 powder having an average particle size of 5 μm impregnated with a Ce (NO 3 ) 3 solution was uniformly mixed with γ-A 2 O 3 particles to form a slurry, and a cordierite honeycomb carrier was coated with woo. Tissue coat and dry at 100 ° C for 1 hour, then 6
It was baked at 00 ° C. for 2 hours. Thereafter, the same procedure as in Example 4 was carried out to obtain a catalyst.
実施例６ 平均粒径５μｍのＣｏ２Ｏ３粉末にＣｅ（ＮＯ３）３溶
液を含浸させたものを、γ−Ａ２Ｏ３粒子と共に均一
に混合してスラリー化し、コージエライト質ハニカム担
体にウオツシユコートして１００℃で１時間乾燥後、６
００℃で２時間焼成した。以下、実施例４と同様にして
触媒化した。Example 6 Co 2 O 3 powder having an average particle size of 5 μm impregnated with a Ce (NO 3 ) 3 solution was uniformly mixed with γ-A 2 O 3 particles to form a slurry, and a cordierite honeycomb carrier was coated with wow. Tissue coat and dry at 100 ° C for 1 hour, then 6
It was baked at 00 ° C. for 2 hours. Thereafter, the same procedure as in Example 4 was carried out to obtain a catalyst.
実施例５及び実施例６の触媒における担体１当たりの
各成分の担持量を下記第４表に示す。Table 4 below shows the amounts of the respective components supported per carrier in the catalysts of Examples 5 and 6.
性能評価試験２ 実施例５及び実施例６の触媒に関して、前記性能評価試
験１と同様にして性能評価試験２を行なった。Ｈ２Ｓ抑
制効果及び浄化性能の評価結果を下記第５表にまとめて
示す。 Performance Evaluation Test 2 With respect to the catalysts of Example 5 and Example 6, performance evaluation test 2 was performed in the same manner as in the performance evaluation test 1. The evaluation results of the H 2 S suppression effect and the purification performance are summarized in Table 5 below.
〔発明の効果〕 上述の如く、本発明の排気ガス浄化用触媒の製造方法
は、耐火性担体上に貴金属を担持するための所定組成の
酸化物コート層を形成する際、平均粒径0.1μｍ以上のC
eの化合物粉末にNi、Co、Feのうちの少なくとも１種を担
持するか、又は平均粒径0.1μｍ以上のNi、Co、Feのうち
の少なくとも１種からなる化合物粉末にCeを担持するこ
とにより調製した化合物粉末を使用するため、本発明の
方法によつて製造した触媒ではCeとNi、Co又はFeとが隣
接することとなり、リツチ側の雰囲気においてNi、Co又
はFeの硫化物形成が容易となるので排気ガス中の硫黄分
が効率よく捕捉され、リツチ側の雰囲気におけるH2Sの
生成が抑制される。又、Ni、Co又はFeとＡ２Ｏ３との
反応が抑制されるので、それによるH2S抑制効果の低下
や浄化性能の低下が防止される。更に、HC、CO及びＮＯ
ｘの浄化性能も従来の排気ガス浄化用触媒と同等である
ので、本発明の方法を用いれば総合的性能が優れた排気
ガス浄化用触媒を容易に得ることができる。 [Advantages of the Invention] As described above, the method for producing an exhaust gas purifying catalyst of the present invention has an average particle diameter of 0.1 μm when forming an oxide coating layer of a predetermined composition for supporting a noble metal on a refractory carrier. C above
Supporting at least one of Ni, Co and Fe on the compound powder of e, or supporting Ce on the compound powder of at least one of Ni, Co and Fe having an average particle size of 0.1 μm or more. In order to use the compound powder prepared by, the catalyst produced by the method of the present invention, Ce and Ni, Co or Fe will be adjacent to each other, Ni, Co or Fe sulfide formation in the atmosphere of the Rich side Since it becomes easy, the sulfur content in the exhaust gas is efficiently captured, and the generation of H 2 S in the atmosphere on the latch side is suppressed. In addition, since the reaction between Ni, Co or Fe and A 2 O 3 is suppressed, it is possible to prevent a decrease in the H 2 S suppression effect and a decrease in the purification performance due to the reaction. Furthermore, HC, CO and NO
Since the purification performance of x is the same as that of the conventional exhaust gas purifying catalyst, the exhaust gas purifying catalyst having excellent overall performance can be easily obtained by using the method of the present invention.
Claims (1)
にＮｉ、Ｃｏ、Ｆｅのうちの少なくとも１種を担持する
か、又は平均粒径0.1μｍ以上のＮｉ、Ｃｏ、Ｆｅのう
ちの少なくとも１種からなる化合物粉末にＣｅを担持す
ることにより調製した化合物粉末を使用して、 耐火性担体上にＡ：Ｃｅ：Ｎｉ、Ｃｏ、Ｆｅのうちの
少なくとも１種：Ｌａを、２：0.1〜0.6：0.01〜1.2：
0.01〜0.1のモル比で含んでなる酸化物コート層を浸漬
法により形成し、次いで該酸化物コート層にＰｔ、Ｐ
ｄ、Ｒｈのうちの少なくとも１種を担持してなることを
特徴とする排気ガス浄化用触媒の製造方法。1. A compound powder of Ce having an average particle size of 0.1 μm or more carrying at least one of Ni, Co and Fe, or at least one of Ni, Co and Fe having an average particle size of 0.1 μm or more. At least one of A: Ce: Ni, Co, and Fe: La is used on a refractory carrier by using a compound powder prepared by supporting Ce on a compound powder consisting of one kind: 2: 0.1 to. 0.6: 0.01 ~ 1.2:
An oxide coating layer containing a molar ratio of 0.01 to 0.1 is formed by a dipping method, and then Pt and P are added to the oxide coating layer.
A method for producing an exhaust gas purifying catalyst, which comprises carrying at least one of d and Rh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63149308A JPH0653230B2 (en) | 1988-06-17 | 1988-06-17 | Exhaust gas purification catalyst manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63149308A JPH0653230B2 (en) | 1988-06-17 | 1988-06-17 | Exhaust gas purification catalyst manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01317542A JPH01317542A (en) | 1989-12-22 |
| JPH0653230B2 true JPH0653230B2 (en) | 1994-07-20 |
Family
ID=15472292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63149308A Expired - Fee Related JPH0653230B2 (en) | 1988-06-17 | 1988-06-17 | Exhaust gas purification catalyst manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653230B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02102739A (en) * | 1988-10-07 | 1990-04-16 | Toyota Motor Corp | Catalyst for purification of exhaust gas |
| JP3381489B2 (en) * | 1995-11-08 | 2003-02-24 | トヨタ自動車株式会社 | Exhaust gas purification catalyst and purification device for diesel engine |
-
1988
- 1988-06-17 JP JP63149308A patent/JPH0653230B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01317542A (en) | 1989-12-22 |
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