JPH01317542A - Preparation of catalyst for exhaust gas clean-up - Google Patents
Preparation of catalyst for exhaust gas clean-upInfo
- Publication number
- JPH01317542A JPH01317542A JP63149308A JP14930888A JPH01317542A JP H01317542 A JPH01317542 A JP H01317542A JP 63149308 A JP63149308 A JP 63149308A JP 14930888 A JP14930888 A JP 14930888A JP H01317542 A JPH01317542 A JP H01317542A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- average particle
- compound
- molar ratio
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 19
- 239000000446 fuel Substances 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 description 23
- 230000000694 effects Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 5
- 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 5
- 239000010410 layer Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 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
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 241000252095 Congridae Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 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
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Ｈ、Ｓ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。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a catalyst for purifying automobile exhaust gas, and more particularly, to a method for producing a catalyst for purifying exhaust gas that does not generate H and S gases that cause off-odors. This relates to a manufacturing method.
〔従来の技術」
近年、自動車の二／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シ上げられるに至り、現在ではエン
ジン排気系に、炭化水素（ｎｃ）、−酸化炭素（ＣＯ〕
、窒素酸化物（ＮＯ３Ｃ）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っている。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。[Conventional technology] In recent years, exhaust gases emitted from automobile engines have come to be widely discussed as a pollution problem, and now engine exhaust systems contain hydrocarbons (NC) and -carbon oxides (CO).
It has become common to install a catalytic converter to detoxify nitrogen oxides (NO3C) and the like. On the other hand, secondary air is also introduced for the purpose of completely combusting 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
能低下環の原因となるので、エンジン高負荷時には制御
装置によって二次空気の導入を停止させたり、燃料の供
給を増加させたシしている。In such vehicles equipped with a catalytic converter, if secondary air is introduced to increase exhaust gas combustion efficiency when the engine is under high load, the catalytic converter will be heated abnormally, causing damage to the catalyst and deterioration of its function. When the engine is under high load, the control device stops the introduction of secondary air or increases the fuel supply.
しかしその場合には排気ガスの窒燃比がリッチ側（燃料
過剰側）となシ、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ＳＯ，が還元されてＨ，Ｓが
生成しく ８ ｔｈ Ｉｎｔ。However, in that case, the nitrogen-fuel ratio of the exhaust gas is on the rich side (fuel excess side), and in the catalytic converter, which has become a reducing atmosphere, the SO adsorbed on the catalyst bed is reduced and H and S are no longer produced. 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った。その対策として、
Ｈ，Ｓ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。Congr, Catal (see Proceedings of the 8th International Catalysis Conference, March 1984 issue, pp. 453-463),
There was a problem that a strange odor was generated. As a countermeasure,
Utility Model Application Publication No. 54-31210 requires the installation of H and S processing equipment.
It is proposed in the Publication No.
このＨ，Ｓ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Ｈ，Ｓ酸化用触媒装置
と二次空気注入系のエアスイッチングバルブを、触媒コ
ンバータｔ ／＜イパスさせて連通し、上記エアスイッ
チングバルブを、触媒コンバータへの二次空気の注入ｔ
−遮断したときに二次空気が前記Ｈ，Ｓ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,S treatment device is equipped with a H2S oxidation catalyst device behind the catalytic converter, and communicates the H,S oxidation catalyst device with the air switching valve of the secondary air injection system by passing through the catalytic converter. Then, the air switching valve is used to inject secondary air into the catalytic converter.
- It can be freely switched so that when it is shut off, secondary air is guided to the H, S oxidation catalyst device.
又、本出願人は特願昭６２−１７０３３２号明細書に記
載された、耐火性担体に、Ａｔ ： Ｃｅ ： Ｃｏ、
Ｎｉ％Ｆｅの少なくとも１種： Ｌａ ｆ、２：［Ｌ１
〜α６：α０３〜２．０：ｃＬ０１〜Ｃ１，１のモル比
で含んテする酸化物コート層を形成させ、Ｐｔ、 Ｐｄ
、 Ｒｈ の少なくとも１樗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 present applicant has added At:Ce:Co,
At least one type of Ni%Fe: La f, 2: [L1
An oxide coating layer containing Pt, Pd in a molar ratio of ~α6:α03~2.0:cL01~C1,1 is formed.
We have proposed an exhaust gas purifying catalyst characterized by supporting at least one inch of precious metals such as , and Rh.
しかし実開昭５４−３１２１０号公報に記載されたよう
なＨ，Ｓ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、自動車の製造によシ以上のコスト
が強いられることとなる。However, providing a separate H and S treatment device as described in Japanese Utility Model Application Publication No. 54-31210 makes the exhaust gas purification system even more complicated, and increases the cost of manufacturing automobiles.
又、特願昭６２−１７０５５２号明細書記載の触媒は、
ＣｅとＣ０１Ｎｉ、Ｆｅの少なくとも１攬とが必ずしも
隣接してはいなかったため、このような触媒系が有する
リッチ側でのＨ，Ｓの生成抑制効果をまだ充分に発揮さ
せたものではなかった。In addition, the catalyst described in Japanese Patent Application No. 170552/1987 is
Since Ce and at least one of C01Ni and Fe were not necessarily adjacent to each other, the effect of suppressing the production of H and S on the rich side of such a catalyst system was not yet sufficiently exhibited.
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ッチ側における
Ｉ（、Ｓの発生を抑制するとともにＨＣ，Ｃｏ及びＮＯ
ｘ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 intended to solve the problems in the prior art described above, and its purpose is to suppress the generation of I(, S) on the rich side, and to suppress the generation of HC, Co, and NO.
An object of the present invention is to provide an easy method for producing an exhaust gas purifying catalyst that has excellent x purifying performance.
〔課題を解決するだめの手段」
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α１μｍ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ｒＬ１μｍ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、Ａｔ： Ｃｅ ： Ｎｉ、 Ｃｏ、
Ｆｅのうちの少なくとも１ ’ａ ： Ｌａ ｉ、２
： ０．ｌ 〜（１６：α０１〜１．２：α０１〜ＩＩ
Ｌ１のモル比で含んでなる酸化物コート層を形成し、
次いで該酸化物コート層にＰｔ、 Ｐｄ、 Ｒｈのうち
の少なくともＩＩＩを担持してなることを特徴とする。[Another means to solve the problem] In other words, the method for producing an exhaust gas purifying catalyst of the present invention is to add Ni, Co to a Ce compound powder having an average particle size of α1 μm or more.
, using a compound powder prepared by supporting at least one of Fe or supporting Ce on a compound powder consisting of at least one of Ni, Co, and Fe with an average particle size rL1 μm or more. , on a refractory carrier, At: Ce: Ni, Co,
At least 1'a of Fe: La i, 2
: 0. l ~(16:α01~1.2:α01~II
The present invention is characterized in that an oxide coat layer containing L1 in a molar ratio is formed, and then at least III of Pt, Pd, and Rh is supported on the oxide coat layer.
Ｃｅの化合物粉末又はＮｉ、 Ｃｏ、 Ｆｅのうちの少
なくとも１穐からなる化合物粉末は、平均粒径があまり
小さいとＣｅとＮｉ％Ｃｏ％Ｆｅのうちの少なくとも１
穐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Ｈ，Ｓの捕捉効果が低下するので、平
均粒径［１１μｍ以上のものを使用する必要がある。担
持方法は浸漬法などの慣用の方法であってよい。If the average particle size is too small, the compound powder of Ce or the compound powder consisting of at least one of Ni, Co, and Fe may contain at least one of Ce and Ni%Co%Fe.
If the grains are not sufficiently adjacent to the grains, interactions with other components will occur, reducing the H and S trapping effect, so it is necessary to use grains with an average diameter of 11 μm or more. . The supporting method may be a conventional method such as a dipping method.
耐火性担体としてはセラミック裂例えばコージェライト
裏、耐熱性金属製等のペレット又は一体性担体等を使用
することができる。As the refractory carrier, ceramic cracks such as cordierite backing, pellets or monolithic carriers made of heat-resistant metals, etc. can be used.
Ｍはアルミナ例えばγ−Ｍ２０３であってよい。M may be alumina, such as γ-M203.
Ｃｅ、 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Ｈ，Ｓの発生抑制性能
及び浄化性能等の点で具合がよい。Ce, Ni, Co, Fe or La is used in a desired form such as oxide or salt. Further, the ratio of each metal component is suitable in terms of the H and S generation suppression performance and purification performance of the catalyst in which the above-mentioned ratio is obtained.
Ｐｔ、Ｐｄ又ＦｉＲｈＦｉ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。A predetermined amount is supported on an oxide coat layer formed on a Pt, Pd or FiRhFi refractory carrier by a dipping method or the like.
以下にＮｉ’！！−例としてＨ，Ｓの生成抑制機構を説
明する。なお、Ｃｏ及びＦｅも同様である。り一ン側で
は下記反応式（１）の反応が、リッチ側では下記反応式
１ｉｔ）の反応が起る。Ni' below! ! - As an example, the mechanism for suppressing the generation of H and S will be explained. Note that the same applies to Co and Fe. On the rich side, a reaction expressed by the following reaction formula (1) occurs, and on the rich side, a reaction expressed by the following reaction formula 1it) occurs.
Ａｔ２ｏ３＋ Ｃｅｎｔ ＋ ５ ＳＯｘ ＋ ２０ｘ
→ｋＬｔｃＳＯａ）ｓ ＋ Ｃｅ（ＳＯＪ ｘ Ｉ
ＩＪＡ７２（ＳＯ４）３ ＋ Ｃｅ（Ｓｏｎ）＊ ＋
１５Ｈ２＋ ５．Ｎｉ→５ Ｎｉ Ｓ ＋ Ａｔ２０３
＋ ＣｅＯ２＋ １５ Ｈ２Ｏ（Ｉｌｌ上記反応（
ＩＩ）において、ＮｉとＣｅとが隣接して存在すればＮ
ｉＳ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Ｎ２０．と反応して
Ｍ、Ｎｔｏ、全形成してＮｉのＨ，Ｓ生成抑制効果が失
われたり、浄化性能低下の原因となったりするのを防止
する作用がある。At2o3+ Cent + 5 SOx + 20x
→kLtcSOa)s + Ce(SOJ x I
IJA72(SO4)3 + Ce(Son)* +
15H2+ 5. Ni → 5 Ni S + At203
+ CeO2+ 15 H2O (Ill the above reaction (
In II), if Ni and Ce exist adjacent to each other, N
This is advantageous for iS generation. Another effect when Ni and Ce are adjacent to each other is that Ni is N20. It has the effect of preventing Ni from reacting with Ni to completely form M, Nto, and thereby losing the H and S production suppressing effect of Ni and causing deterioration of purification performance.
なお、他の金属成分のうち、Ｐｔ、Ｐｄ又ｔｉ Ｒｈは
ＨＣ，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。Of the other metal components, Pt, Pd, or TiRh exhibits a purifying effect on HC, Co, or NOx, and La exhibits a cocatalyst effect 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 explained in further detail in the following Examples and Comparative Examples. Note that the present invention is not limited to the following examples.
実施例１
平均粒径２μｍのＣｅＯ鵞粉末にＮｉ （Ｎ０ｘ）＊溶
液を含浸添加したものと、Ｌａ（ＮＯｓ）ｓ溶液を予め
含浸させたｒ −ｕ、ｏ、のスラリーとを均一に混合し
、これを市販のコージェライト質ハニカム担体にウォッ
シュコートして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 powder with an average particle size of 2 μm was impregnated with a Ni (NO This was wash-coated onto a commercially available cordierite honeycomb carrier, dried at 100°C for 1 hour, and then fired at 700°C for 2 hours. Next, a noble metal was supported on this to make it a catalyst.
実施例２
Ｃｅ０２粉末の代シに平均粒径２ μｍのＣｅ （Ｃ０
Ｂ）２を使用すること以外は実施例１と同様にして行っ
た。Example 2 Ce (C0
The same procedure as Example 1 was carried out except that B)2 was used.
実施例５
平均粒径２ μｍ１１のＣｅ０１粉末にＮ１（ＮＯｓ）
ｘ溶液を含浸添加したものをスラリー化−してコージェ
ライト質ハニカム担体にウォッシュコートして１００℃
で１時間乾燥後７００℃で２時間焼成した。Example 5 N1 (NOs) was added to Ce01 powder with an average particle size of 2 μm11
The slurry obtained by impregnating and adding x solution was washed coated on a cordierite honeycomb carrier and heated at 100°C.
After drying for 1 hour, it was fired at 700°C for 2 hours.
次いでこの上に、Ｌａ（ＮＯ，）３溶液を予め含浸させ
ｆｔ ｒ Ａ４０ｓのスラリーをウォッシュフートし
て１００℃で１時間乾燥後７００℃で２時間焼成した。Next, a slurry of ft r A40s which had been pre-impregnated with La(NO,)3 solution was washed onto this, dried at 100°C for 1 hour, and then fired at 700°C for 2 hours.
次いで、これに貴金属を担持して触媒化した。Next, a noble metal was supported on this to make it a catalyst.
実施例４
平均粒径２ ｔｓｍのＮｉＯ粉末にＣ６（ＮＯ３）＊溶
液を含浸させたものをｒ −Ａｔ、Ｏ８のスラリーに添
加して均一に混合し、コージェライト質ハニカム担体に
ウォッシュコートして１００℃で１時間乾燥後７００℃
で２時間焼成した６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 NiO powder with an average particle size of 2 tsm impregnated with a C6(NO3)* solution was added to a slurry of r-At and O8, mixed uniformly, and washed coated on a cordierite honeycomb carrier. 700℃ after drying at 100℃ for 1 hour
Then, it was impregnated with a La(No3)3 solution, dried and fired in the same manner, and then a noble metal was supported and catalyzed.
上記実施例１〜４において、担体１を当りの各成分の相
持量を下記第１表に示す。In Examples 1 to 4 above, the amount of each component supported per carrier 1 is shown in Table 1 below.
第１表 担体１を当りの各成分の担持置注） ＮｉＯ又
１ｄ Ｎｉ （ＮＯｘ、ｈについては各実施例について
上記の如く濃度を変化させて触媒を得た。Table 1: Loading of each component per carrier 1 (Note) NiO or 1d Ni (For NOx and h, catalysts were obtained by varying the concentrations as described above for each example.
コージェライト質Ｉ・ニカム担体の寸法としては３０り
ｘ ５０ Ｌ （ａｔ）のテストピース及び１．７ｔの
フルサイズの２徨類を使用して、本発明の方法によって
排気ガス浄化用触媒を得た。A catalyst for exhaust gas purification was obtained by the method of the present invention using a test piece of 30 L x 50 L (at) and a 1.7 t full-size cordierite Nicum carrier. Ta.
なお、上記実施例１〜４において、Ｎｉ化他の代りにＣ
ｏ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 addition, in the above Examples 1 to 4, C was used instead of Ni.
Catalysts can be similarly obtained using o or Fe compounds.
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 1-4 Catalysts of Comparative Examples 1-4 were obtained in the same manner as Examples 1-4 except that no Ni compound was used.
性能評価試験
＋１） Ｈ，Ｓ抑制効果の評価
テストピース触媒に、イオウ分を０． １ ｗｉ％含有
したガソリン使用時のモデルガスをＡ／Ｆ＝１ａＯで１
時間流通させた後Ａ／Ｆ ＝ １五〇で５分間流通させ
、Ｈ，Ｓ生成量を測定した。結果を第２表に示す。Performance evaluation test +1) H, S suppression effect test piece catalyst with sulfur content of 0. Model gas when using gasoline containing 1 wi% at A/F = 1aO
After flowing for a time, the mixture was allowed to flow for 5 minutes at A/F = 150, and the amounts of H and S produced were measured. The results are shown in Table 2.
第２表 各触媒のＨ，Ｓ生成量（ｐｐｍ）第２表から明
らかな如く、本発明の製造方法によって得た触媒は比較
例の触媒に比べてＨ，Ｓ生成量が少ない。又、Ｎｉ添加
量が多くなるにつれてＨ，Ｓは更に減少し、Ｎｉ添加量
がαＩ Ｍ／ｌ・担体以上ではＨ，Ｓは全く発生しない
のが判る。Table 2 Amounts of H and S produced by each catalyst (ppm) As is clear from Table 2, the amount of H and S produced by the catalyst obtained by the production method of the present invention is smaller than that of the catalyst of the comparative example. It is also seen that as the amount of Ni added increases, H and S decrease further, and when the amount of Ni added exceeds αI M/l·carrier, H and S are not generated at all.
（２）浄化性能の評価
３ｔ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、２０００ ｒｐｍ 。(2) Evaluation of purification performance The full-size catalysts of Example 1 and Comparative Example 1 were installed in the exhaust system of a 3-ton engine, and the engine was operated at 2000 rpm.
−３６０ｍＨｇ 、 ３００℃の測定条件下で、初期及
び床温９００℃、５０００ ｒｐｍ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。Under measurement conditions of -360 mHg and 300°C, the purification rates of HC, CO, and NOx were measured at the initial stage and after 100 hours of durability at a bed temperature of 900°C and 5000 rpm. The results are shown in Table 3.
第３表 各触媒のＨＣ，ＣＯ及びＮＯｘ浄化率（チ〕第
３表に示す如く、本発明の製造方法によって得た触媒は
比較例の触媒に比べて同等の浄化率を有している。Table 3 HC, CO, and NOx purification rate of each catalyst (H) As shown in Table 3, the catalyst obtained by the production method of the present invention has a purification rate equivalent to that of the catalyst of the comparative example.
ＮｉＳ生成の確認
Ｈ，Ｓ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
九。Confirmation of NiS production After measuring the amounts of H and S produced, the catalyst of the example was crushed and subjected to FTIR
When observing the adsorption state of Ni and S, a peak of NiS bonding was confirmed, indicating that they are chemically bonded.9.
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（１１μｍ以上の
Ｃｅの化合物粉末にＮｉ、 Ｃｏ。As mentioned above, in the method for producing an exhaust gas purifying catalyst of the present invention, when forming an oxide coat layer of a predetermined composition for supporting a noble metal on a refractory carrier, a Ce compound having an average particle size (11 μm or more) Ni and Co in the powder.
Ｆｅのうちの少なくとも１徨を担持するか、又は平均粒
径Ｑ、１μｍ以上のＮｉ、Ｃｏ％Ｆｅのうちの少なくと
４ｂ１１１ｉからなる化合物粉末にＣｅを担射ることに
よシ調製し九化合物粉末を使用するため、本発明の方法
によっ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、リッ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、リッチ側の雰囲気にお
けるＨ、Ｓの生成が抑制される。又、Ｎｉ、Ｃｏ又はＦ
ｅとＡｔ、０． 、との反応が抑制されるので、それに
よるＨ１Ｓ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ＮＯｘの浄化性能も従来の排
気ガス浄化用触媒と同等で娶るので、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。A compound powder prepared by supporting at least one of Fe, or by supporting Ce on a compound powder consisting of at least 4b111i of Ni and Co%Fe with an average particle size Q of 1 μm or more. Therefore, in the catalyst produced by the method of the present invention, Ce and Ni, Co, or Fe are adjacent to each other, and in the rich atmosphere, Ni
, Co, or Fe becomes easy to form, so the sulfur content in the exhaust gas is efficiently captured, and the generation of H and S in the rich atmosphere is suppressed. Also, Ni, Co or F
e and At, 0. Since the reaction with , is suppressed, a decrease in the H1S suppressing effect and a decrease in purification performance due to this is prevented. Furthermore, since the purification performance of HC, CO and NOx is comparable to that of conventional exhaust gas purification catalysts, by using the method of the present invention, it is possible to easily obtain an exhaust gas purification catalyst with excellent overall performance.
特許出願人 トヨタ自動車株式会社Patent applicant: Toyota Motor Corporation
Claims (1)
ｏ、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、
Ａｌ：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
形成し、 一次いで該酸化物コート層にＰｔ、Ｐｄ、Ｒｈのうちの
少なくとも、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。[Claims] Ni, C and Ce compound powder with an average particle size of 0.1 μm or more
o, Fe, or a compound powder prepared by supporting Ce on a compound powder consisting of at least one of Ni, Co, and Fe with an average particle size of 0.1 μm or more. on a refractory carrier using
Al:Ce:At least one of Ni, Co, and Fe:La, 2:0.1~0.6:0.01~1.2:0
．． 01 to 0.1 molar ratio is formed, and then the oxide coat layer supports at least a species of Pt, Pd, and Rh. A method for producing a catalyst for gas purification.
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 true JPH01317542A (en) | 1989-12-22 |
| JPH0653230B2 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) |
Cited By (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 |
| EP0773056A1 (en) * | 1995-11-08 | 1997-05-14 | Toyota Jidosha Kabushiki Kaisha | Method for purifying an exhaust gas from a diesel engine |
-
1988
- 1988-06-17 JP JP63149308A patent/JPH0653230B2/en not_active Expired - Fee Related
Cited By (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 |
| EP0773056A1 (en) * | 1995-11-08 | 1997-05-14 | Toyota Jidosha Kabushiki Kaisha | Method for purifying an exhaust gas from a diesel engine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653230B2 (en) | 1994-07-20 |
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