JPS6146247A - Catalyst for purifying exhaust gas - Google Patents
Catalyst for purifying exhaust gasInfo
- Publication number
- JPS6146247A JPS6146247A JP59166066A JP16606684A JPS6146247A JP S6146247 A JPS6146247 A JP S6146247A JP 59166066 A JP59166066 A JP 59166066A JP 16606684 A JP16606684 A JP 16606684A JP S6146247 A JPS6146247 A JP S6146247A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carrier
- alumina
- lanthanum
- exhaust gas
- 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 88
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 85
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 238000004898 kneading Methods 0.000 claims abstract 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 abstract description 37
- 229910052703 rhodium Inorganic materials 0.000 abstract description 33
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 72
- 239000010948 rhodium Substances 0.000 description 32
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 32
- 239000002131 composite material Substances 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 241000003832 Lantana Species 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000567 combustion gas Substances 0.000 description 4
- NNLJGFCRHBKPPJ-UHFFFAOYSA-N iron lanthanum Chemical compound [Fe].[La] NNLJGFCRHBKPPJ-UHFFFAOYSA-N 0.000 description 4
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 240000008881 Oenanthe javanica Species 0.000 description 1
- 241000375392 Tana Species 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- -1 cerium nitrate Chemical class 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- VNWKDIUSXQCPGN-UHFFFAOYSA-J dicalcium tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ca+2].[Ca+2] VNWKDIUSXQCPGN-UHFFFAOYSA-J 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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〕 −この発明状、特
に内燃機関から排出されるガスを浄化するための排ガス
浄化用触媒。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] - The present invention, particularly an exhaust gas purifying catalyst for purifying gas discharged from an internal combustion engine.
従来、排ガス浄化用触媒として紘、特に自動車の内燃機
関からの排ガス浄化用の３元触媒の開発が進められてい
る。三元触媒の性能向上のために拡、０．ストシージ効
果を有するセリウムを含む担体に貴金属触媒を担持され
たものが知られている。−例えｔｆ４？開昭５２−１１
６７７９号公報、特開昭５４゜−１５９３９１号公報Ｋ
ａ・あらかじめセリウ！°を含有させた活性アルミナ粉
末をモノリス担体基材の表面に付着させた後に、白金、
ロジウム・パラジウム等の単独又は組合せてなる触媒金
属を担持させた触媒が開示されている。BACKGROUND ART Conventionally, the development of catalysts for purifying exhaust gases, particularly three-way catalysts for purifying exhaust gases from internal combustion engines of automobiles, has been progressing. To improve the performance of the three-way catalyst, it is expanded to 0. It is known that a noble metal catalyst is supported on a cerium-containing carrier that has a storage effect. -For example, TF4? Kaisho 52-11
No. 6779, JP-A-54-159391 K
a.Seriu in advance! After adhering activated alumina powder containing ° to the surface of the monolithic carrier substrate, platinum,
Catalysts are disclosed in which catalytic metals such as rhodium and palladium are supported singly or in combination.
〔発明が解決しようとする問題点〕 □かかる３
元Ｍ１ｍ紘、通常の温度域で使用する場合には、排ガス
甲の炭化水素（ＩｉＣ）、−酸化炭素（ＣＯ）、窒素酸
化物（ＮＯｘ）を高い転換率で浄化することができ、Ｈ
Ｃ，ＣＯ，ＮＯｘの転換率８０−以上を示す！燃比ゾー
ン、すなわち８０−ウィンド中が充分に確保される。し
かしながら、近年、開発中の自動車の内燃機関からの排
ガスの温度が下がる傾向があシ・このような低温の排ガ
スを排出する内燃機関の排ガスを浄化するには、かかる
触媒はＮＯｘおよびＣＯの転換率が充分でなくなる恐れ
があるという問題点があった。[Problem that the invention seeks to solve] □Such 3
When used in the normal temperature range, it can purify hydrocarbons (IiC), -carbon oxides (CO), and nitrogen oxides (NOx) in the exhaust gas with a high conversion rate, and
Shows a conversion rate of 80- or more for C, CO, and NOx! The fuel ratio zone, i.e. 80-wind, is fully secured. However, in recent years, the temperature of exhaust gas from internal combustion engines of automobiles under development has tended to decrease.In order to purify exhaust gas from internal combustion engines that emit such low-temperature exhaust gas, such catalysts are required to convert NOx and CO There was a problem that the rate might not be sufficient.
とめ発明は、このような従来の問題点に着目してなされ
たもので、鉄とランタンのペロプスカイト型酸化物又は
ニッケルとランタンのペロプスカイト型酸化物、あるい
はこれらの混合物を含む酸化ランタン粉末と、あらかじ
めセリウムを含有せしめた活性アルミナと、欧化セリウ
ム粉末と、アルミナゾルと混線して得られるスラリーを
モノリス基体に被覆して焼成した担体に、白金、パラジ
ウム、ロジウム等の単独又は組合せてなる貴金属触媒を
担持させた触媒とすることによル、前記問題点を解決す
ることを目的としている。The stop invention was made by focusing on these conventional problems, and it is based on a lanthanum oxide powder containing a perovskite-type oxide of iron and lanthanum, a perovskite-type oxide of nickel and lanthanum, or a mixture thereof. A noble metal catalyst consisting of platinum, palladium, rhodium, etc., alone or in combination, is coated on a monolithic substrate and fired with a slurry obtained by mixing activated alumina containing cerium in advance, cerium chloride powder, and alumina sol. The purpose of the present invention is to solve the above-mentioned problems by providing a catalyst supported with .
一般にδ又はｒ−アルミナを主成分とする活性アルミナ
は、触媒用担体として知られているが、高温度下では、
不活性で安定なα−アルミナに変移してしまい、触媒用
担体としては不都合となるしかし活性アルミナに適当量
のセリウムを添加すると、著しく耐熱性が向上すること
が解ったが、あｔシ少量ではその効果が弱く又あｔシ多
量では活性アルミナ自身の持つ高比表面積を低下させる
ことになシ、貴金属の分散性の面から見て不都合であっ
た。本発明では、好ましくは対アルミナ比１〜５ ｗｔ
％で特に好ましくは約３ ｗｔ％のセリウムを含有させ
ることで比表面積を低下させる事なく耐熱性を向上させ
ている。酸化セリウムはほとんど全てが４価のセリウム
の酸化物であシ一般にｃｅｏｔで表わされる。ＣＩＯ，
はそれ自体０．ストレージ効果を持ち、触媒のさらされ
る雰囲気に対し、応答雰囲気を拡げる効果を持っている
。本発明では％Ｃ１！１０゜の持つ０．ストレージ効果
をよシ有効に発揮させるために、鉄−ランタン系および
／ｌたはニッケルランタン系のペロプスカイト型複合酸
化物を含む厚を触媒担体上に塗布する。ペロブスカイト
型複合酸化物の特徴は酸素０２−の内部拡散が、陽イオ
″″拡散３きわめて太き“ことから・非常に強 １い
０．ストレージ効果が期待でき、前記ｃ ｅＱｌの０！
ストレージ効果と合わせて、触媒の活性雰囲気を拡大す
ることができる。又、特に鉄−ランタン系ペロブスカイ
ト型複合酸化物の持つＣＯ、Ｋ）ｘ Ｋ対する活性また
はニッケルーランタン系ペロブスカイト型複合酸化物の
持つＣＯに対する活性を利用することによシ、触媒の低
温時（たとえば４００℃ンでのウィンド巾を広げること
が出来る。また、上記ペロブスカイト複合酸化物を含む
コート層を、最表層部のみとすると、排ガス流のような
高Ｓｖ（？！間速度〕下で起る反応に１．ランタンを少
量でよシ有効に活性を維持させることができる。Generally, activated alumina mainly composed of δ or r-alumina is known as a catalyst support, but under high temperature,
It transforms into inactive and stable α-alumina, making it inconvenient as a catalyst carrier. However, it has been found that adding an appropriate amount of cerium to activated alumina significantly improves heat resistance. However, the effect is weak, and in large amounts, the high specific surface area of activated alumina itself is reduced, which is disadvantageous from the viewpoint of noble metal dispersibility. In the present invention, preferably the alumina ratio is 1 to 5 wt.
By containing cerium, preferably about 3 wt%, the heat resistance is improved without reducing the specific surface area. Cerium oxide is almost entirely an oxide of tetravalent cerium and is generally expressed as ceot. CIO,
is itself 0. It has a storage effect and has the effect of expanding the response atmosphere to the atmosphere to which the catalyst is exposed. In the present invention, %C1!10° has 0. In order to exhibit the storage effect more effectively, a layer containing iron-lanthanum based perovskite type composite oxide and /l or nickel lanthanum based perovskite type composite oxide is coated on the catalyst carrier. The characteristic of perovskite-type composite oxides is that the internal diffusion of oxygen 02- is very thick as cationic diffusion 3. A very strong storage effect can be expected, and the above-mentioned ceQl of 0!
Combined with the storage effect, it is possible to expand the active atmosphere of the catalyst. In addition, by utilizing the activity against CO, K) For example, it is possible to widen the window width at 400°C.Also, if the coating layer containing the above-mentioned perovskite composite oxide is applied only to the outermost layer, it is possible to increase the wind width under high Sv (? 1. The activity of lanthanum can be maintained effectively with a small amount of lanthanum.
尚、本発明で用いるペロプスカイト型複合酸化物は仄の
ように作成するのが好ましい。酸化ランタン粉末に、鉄
を、金夙換算で・酸化ランタンに対して％３ｗｔ％〜１
０ ｖｔ％ Ｋなる量の硝酸第１鉄を加”え・少量の純
水と共に混練する。その後乾燥し、還元ガス雰囲気中で
８５０℃〜９５０℃で２時間−温ステップを用いずに焼
成同雰囲気中で放冷する。この結果加えた鉄はライタン
と、一般にＬａｃｅ’ｓで示されるペロブスカイト型複
合酸化物を形成し、反応に関与しなかった余分の酸化ラ
ンタンは、そのまま残る。ニッケルについても、硝酸ニ
ッケルを用いることが異なるだけで、同様Ｋ ＬａＮｌ
０．で示されるベロプスカイ）ｆｆｌ複合欧化物を作成
することができる。ニッケルーランタン系と鉄−ランタ
ン系のペロプスカイト型複合酸化物を併用する場合には
、酸化ランタン粉末ＩＩＩ酸第１鉄と硝酸ニッケルとを
一緒に混合して還元ガス雰囲気で焼成しても良い。Incidentally, the perovskite type composite oxide used in the present invention is preferably prepared as shown below. Add iron to lanthanum oxide powder, in terms of gold, %3wt% to 1% relative to lanthanum oxide
Ferrous nitrate in an amount of 0 vt% K is added and kneaded with a small amount of pure water. After that, it is dried and fired at 850°C to 950°C in a reducing gas atmosphere for 2 hours without using a temperature step. Allow to cool in an atmosphere.As a result, the added iron forms a perovskite-type composite oxide, generally referred to as Lace's, with lanthanum, and the excess lanthanum oxide that did not participate in the reaction remains as it is.As for nickel, , KLaNl is similar, except that nickel nitrate is used.
0. It is possible to create a complex european compound (velop sky) ffl denoted by . When using nickel-lanthanum based and iron-lanthanum based perovskite type composite oxides, lanthanum oxide powder ferrous III acid and nickel nitrate may be mixed together and fired in a reducing gas atmosphere. .
又、セリウムを担持させた活性アルミナは、粉。Activated alumina loaded with cerium is powder.
末又は粒状の宿性アルミナ、例えばｒ−アルミナを・硝
酸セリウム等の水溶性セリウム塩の水溶液に含潰し、引
上げた後、１００〜２００℃の熱風中で乾燥し、次いで
５００℃以上で空気中で焼成するととくよって作成する
ことができる。Powdered or granular host alumina, such as r-alumina, is crushed in an aqueous solution of a water-soluble cerium salt such as cerium nitrate, pulled up, dried in hot air at 100 to 200°C, and then dried in air at 500°C or higher. It can be created by firing it.
ランタンを有効に用いるに社、担体の最表面部のみに存
在させるようＫすることが好ましい。そのためには、久
のように担体を作成すると良い。In order to use lanthanum effectively, it is preferable to make it exist only on the outermost surface of the carrier. For that purpose, it is good to create a carrier like Hisashi.
すなわち、ペロブスカイト型複合酸化物を含む酸化ラン
タン粉末を、あらかじめセリウムを含むδ又はｒ−アル
ミナを主成分とする活性アルミナ粒状又は粉末状担体、
市販酸化セリウム粉末、および硝酸酸性アルミナ・ゾル
と共に磁製ボールミルに投入し、粉砕混練して、スラリ
ーを得る。次に前記酸化ランタン粉末を含まない以外は
同一仕様のスラリーを作成して、コーディエライト質を
主成分とするモノリス担体に複数回に分けて所定量のコ
ーティングを行ない、最後に前記ペロプスカイト型複合
酸化物を含むスラリーのコーティングを１回のみ行う。That is, lanthanum oxide powder containing a perovskite-type composite oxide is preliminarily transferred to an activated alumina granular or powder carrier mainly composed of δ or r-alumina containing cerium,
The mixture was placed in a porcelain ball mill together with commercially available cerium oxide powder and nitric acidic alumina sol, and pulverized and kneaded to obtain a slurry. Next, a slurry with the same specifications except that it does not contain the lanthanum oxide powder is prepared, and a predetermined amount of coating is applied to the monolithic support mainly composed of cordierite in multiple steps. Coating with the slurry containing the composite oxide is performed only once.
乾燥終了後・空気気流中・又は燃焼ガス気流中６００℃
〜７５０℃望ましくは６５０℃〜７００℃で２時間以内
、同温度を保持する昇温ステップを含む、パターンで焼
成して触媒担体を得る。このように作成した担体は、排
ガスの最も接触する最表面部にのみランタンが存在する
ので、高価なランタンを少量にして充分の触媒性能を得
ることができる。After drying, in air flow, or in combustion gas flow at 600℃
A catalyst support is obtained by firing in a pattern at ~750°C, preferably at 650°C ~ 700°C for less than 2 hours, including a temperature raising step of maintaining the same temperature. Since lanthanum is present only on the outermost surface of the carrier prepared in this way, which is most in contact with exhaust gas, sufficient catalytic performance can be obtained with a small amount of expensive lanthanum.
以下実施例によシ説明する。 This will be explained below using examples.
〈実施例１〉市販酸化ランタン１０００ ｘ置部と硝酸
第１鉄１５４．５重量部を純水に溶解した溶液とを混練
し、乾燥機中１００℃で５時間乾燥した。この乾燥した
ケーキを、磁製皿に移し、水素気流中８５０℃に加熱し
た炉中に入れ、同温度を保持したまま２時間焼成した。<Example 1> 1000 parts of commercially available lanthanum oxide and a solution prepared by dissolving 154.5 parts by weight of ferrous nitrate in pure water were kneaded and dried at 100° C. for 5 hours in a dryer. This dried cake was transferred to a porcelain dish, placed in a furnace heated to 850° C. in a hydrogen stream, and baked for 2 hours while maintaining the same temperature.
焼成終了後、同雰凹気中で１００℃になるまで放冷した
後とり出した。取シ出された焼成品は、鉄−ランタン系
ペロプスカイト型複合酸化物を含む酸化ランタン粉末で
ある。この酸化ランタン粉末２３４．８Ｆとセリウムを
金属換算で対アルミナ比３ ｗｔ％含有する活性アルミ
ナ粒状担体７２０．５／、市販酸化セリウム４９１．３
Ｊ’、硝酸酸性アルミナ・ゾル２５６３ＪＦとを、磁性
ポットに投入し、１分間８０回転で８時間粉砕混合して
スラリーを得た。ζこに得たスラリーを、コーディエラ
イトを主成分とするモノリス構造体基材（４０〇七ル・
１．７ｊ）Ｋ、次の仕様のスラリーを用いて、あらかじ
めコーティングを行った担体にコーティングを行り。す
なわち、セリウムを金属換算対アルミナ比３ ｗｔ％含
有する活性アルミナ粒状担体１００６ｔ・市販酸化セリ
ウム５１６ Ｐ・硝酸酸性アルミナ １ゾル２４７８
Ｐ ｔ−磁製ボールミルに投入し毎分８０回転で６時間
粉砕混合して得たスラリーを用い、コーティング回数２
回で、コート量モノリス担体１コ当υ２００Ｐとした担
体である。該最終コート量は、モノリス担体ｌコ当シ１
４０７とした。コーティング終了後・、乾燥し・□空気
気流中、６５０℃で２時間焼成して触媒担体とした。こ
の触媒担体に塩化白金酸、塩化ロジウムの混合溶液を用
い、含浸法によシ、白金を、触媒１コ当シ１．２８６９
Ｊ’ 、ロジウムを触媒１コ当、！７ Ｇ、２１４２
Ｐ担持した後、乾燥し、燃焼ガス気流中６００℃で０
．５時間以上焼成して触媒１を得た。この触媒１は、ア
ルミナコート層２００ Ｊ’／ノで、アルミナ１２２．
７Ｐ／Ｊ、セリア６５．３ｔ／ノ、ランタナ１０．５Ｐ
／ノベロプス力イト型複合酸化物（ＬａＦｅＯｓ ）
１．５１／１と、白金０．７５７１１１ ａジウム０．
１２６ ＰＥＡを含んでいる。After the firing was completed, it was allowed to cool down to 100° C. in the same atmosphere and then taken out. The fired product taken out is a lanthanum oxide powder containing an iron-lanthanum based perovskite type composite oxide. Activated alumina granular carrier containing this lanthanum oxide powder 234.8F and cerium at a metal equivalent ratio of 3 wt% to alumina 720.5/, commercially available cerium oxide 491.3
J' and nitric acid acidic alumina sol 2563JF were placed in a magnetic pot and pulverized and mixed at 80 rpm for 8 hours to obtain a slurry. ζThe slurry obtained in this step was used as a monolithic structure base material (4007L) whose main component was cordierite.
1.7j) K, coat the previously coated carrier with a slurry having the following specifications. That is, 1006 tons of activated alumina granular carrier containing cerium at a metal equivalent to alumina ratio of 3 wt%, commercially available cerium oxide 516 P, nitric acid acidic alumina 1 sol 2478
Using a slurry obtained by pulverizing and mixing in a Pt-porcelain ball mill for 6 hours at 80 revolutions per minute, the slurry was coated 2 times.
The coating amount was υ200P per monolithic carrier. The final coating amount is 1 per monolithic carrier.
407. After coating, it was dried and fired at 650° C. for 2 hours in an air stream to obtain a catalyst carrier. A mixed solution of chloroplatinic acid and rhodium chloride was used on the catalyst carrier, and platinum was added to the catalyst by an impregnation method at a concentration of 1.2869 g per catalyst.
J', you won one rhodium catalyst! 7 G, 2142
After supporting P, it is dried and heated to 0 at 600°C in a combustion gas stream.
．． Catalyst 1 was obtained by firing for 5 hours or more. This catalyst 1 has an alumina coating layer of 200 J'/min and an alumina coating of 122.
7P/J, Seria 65.3t/no, Lantana 10.5P
/Novelops cylindrical composite oxide (LaFeOs)
1.51/1, platinum 0.757111 a, and 0.757111 a of platinum.
Contains 126 PEA.
（実施例２）
実施例ｉにおいて、最終コーティングに用いるスラリー
を、ランタン酸化物−（ランタナ） １０００重量部に
対し硝讃第１鉄２５７．８重量部混合し、焼成して得た
ペロプスカイト型複合酸化物を含むランタナ粉末２４１
．２ＪＰ、セリウムを金属換算３ ｗｔ％含む活性アル
ξす粒状担体７２０．５ Ｆ 、市販セリア４９１．３
ＪＦ、硝酸酸性アルミナゾルｚｓｓ３ｐｔ−ｍ合粉砕す
る以外同様にして触媒２を得た。この−媒２は１アルミ
ナ、コート層２００ ＰＥＡでアルミナ１２２．５Ｐ／
ｊ、セリア６５．２？／＊、ランタナ９．８Ｐ／ノ、ペ
ロプスカイト型複合酸化物（ＬａＦｅＯｓ ） ２．５
７’／ノと、白金０．７５７ｐ／ｌ、ロジウム０．１２
６ＪＰ／ノを含ん→いる。(Example 2) In Example i, the slurry used for the final coating was prepared by mixing 257.8 parts by weight of ferrous nitrate with 1000 parts by weight of lanthanum oxide (lanthana), and firing the mixture to obtain a perovskite type. Lantana powder 241 containing complex oxide
．． 2JP, activated aluminum ξ granular carrier containing 3 wt% cerium (metal equivalent) 720.5 F, commercially available ceria 491.3
Catalyst 2 was obtained in the same manner except that JF and nitric acid acidic alumina sol zss3pt-m were combined and ground. This medium 2 is 1 alumina, coated layer 200 PEA and alumina 122.5P/
j, Celia 65.2? /*, lantana 9.8P/no, perovskite type composite oxide (LaFeOs) 2.5
7'/no, platinum 0.757 p/l, rhodium 0.12
Contains 6JP/ノ.
（実施例３〕
実施例２において、白金を担体１コ当１） １．３６
Ｆ。(Example 3) In Example 2, platinum was added per carrier (1) 1.36
F.
ロジウムを担体１コ当、９０．１３６ＪＦを担持する以
外は同様にして、触媒３を得た。この触媒３は、アルミ
ナ、コート層２００１１１でアルミナ１２２．５Ｊ’ン
ノ。Catalyst 3 was obtained in the same manner except that rhodium was supported on one support and 90.136JF was supported on the support. This catalyst 3 has an alumina coating layer of 200111 and an alumina coating of 122.5J'.
セリア−６５，２Ｐ／Ｊ、ランタナ９．８７’／ノ、ペ
ロプスカイト型複合酸化物（’ＬＩＬＦＩ！Ｏｓ７２．
５１７１と、白金０．８０３１７１ 、 ロジウム０
．０８０’Ｊ’／ｊを含んでいる。Ceria-65,2P/J, Lanthana 9.87'/no, peropskite-type composite oxide ('LILFI!Os72.
5171, platinum 0.803171, rhodium 0
．． Contains 080'J'/j.
（実施例４）
実施例１において、最終コーティングに用いるスラリー
を、ランタン酸化物（ランタナ）１０００部に対し硝酸
第１鉄５１５．５重量部混合し、焼□成して得たペロプ
スカイト型複合酸化物を含むランタナ粉末２５７．３Ｊ
’、セリウムを金属換算３ ｗｔ％含む活性アルミナ粒
状担体７２０．５ Ｆ 、市販セリア４９１３ｔ、硝酸
酸性アルミナゾル２５６３ Ｊ’ 、を混合粉砕する以
外同様にして触媒４を得た。この触媒４は、アルミナコ
ート層２００７／ノで、アルミナ１２２．Ｉ Ｐ７ノ。(Example 4) In Example 1, the slurry used for the final coating was mixed with 1000 parts of lanthanum oxide (lanthana) and 515.5 parts by weight of ferrous nitrate, and the mixture was fired to obtain a perovskite-type composite. Lantana powder containing oxides 257.3J
Catalyst 4 was obtained in the same manner except that 720.5 F of active alumina granular carrier containing 3 wt% of cerium (metal equivalent), commercially available ceria 4913t, and nitric acid acidic alumina sol 2563 J' were mixed and ground. This catalyst 4 has an alumina coat layer of 2007/no and an alumina 122. I P7ノ.
セリ７６４．９Ｐ＃ 、ランタナ８． ｌ Ｐ／Ｊ、
ペロプスカイト型複合酸化物（ＬａＦｅ０ａ ） ４．
９ ／ ／ｊ と、白金０７５７７８、ロジウム０．Ｉ
Ｚ６Ｐ／Ｊを含んでいる。Seri 764.9P#, Lantana 8. l P/J,
Perovskite type composite oxide (LaFe0a) 4.
9 / /j, platinum 075778, rhodium 0. I
Contains Z6P/J.
（実施例５） 実施例４において、白金を担体１コ当シ４．３６ＪＰ。(Example 5) In Example 4, platinum was 4.36 JP per carrier.
ロジウムを担体ｌコ当シ０．１３６Ｆを担持する以外は
同様にして触媒５を得た。この触媒５は、アルミナコー
ト層２００Ｊ’／ノで、アルミナＩＺ２．ＩＰ／Ｊ 。Catalyst 5 was obtained in the same manner except that 0.136F of rhodium was supported on each carrier. This catalyst 5 has an alumina coating layer of 200 J'/no and an alumina IZ2. IP/J.
セリア６４＃／ノ、ランタナ８．１１７１ 、ペロプス
カイト型複合酸化物（ＬａＦＩＩＯｌ ） ４．９ Ｐ
／ノと、白金０．８０３Ｐ／Ｊ 、 ロジウム０．０８
０１１１を含んでいる。Ceria 64#/no, Lanthana 8.1171, Perovskite type composite oxide (LaFIIOL) 4.9 P
/not, platinum 0.803P/J, rhodium 0.08
Contains 0111.
（実施例６］
実施例４におりて、白金を担体ｌコ当１）０．７７２Ｉ
、ロジウムを担体ｌコ当Ｊ０．１２９Ｆを担持する以外
は同様にして、触媒６を得た。この触媒６は、アルミナ
コート層２００Ｐ＃でアルミナ１２２．１ Ｐ／Ｊ。(Example 6) In Example 4, platinum was added to the carrier (1) 0.772I
A catalyst 6 was obtained in the same manner except that rhodium was supported on each J0.129F carrier. This catalyst 6 has an alumina coating layer of 200P# and an alumina of 122.1 P/J.
セリア６４．９Ｐ／ｊ 、ランタナ８． Ｉ Ｐ７ノ
、ペロプスカイト型複合酸化物（ＬａＦｅ０１ ） ４
．９１７１と、白金０．４５４ｔ／ノ、ロジウム０．０
７６Ｐ／ノを含んでいる。Seria 64.9P/j, Lantana 8. I P7ノ
, perovskite type composite oxide (LaFe01) 4
．． 9171, platinum 0.454t/no, rhodium 0.0
Contains 76P/no.
（実施例７〕
実施例４において、白金を担体１＝を当ｆｉ０．８２Ｐ
。(Example 7) In Example 4, platinum was used as a carrier with a fi of 0.82P.
.
ロジウムを担体ｌコ当、６ｏ、ｏｓｚ、ｐを担持する以
外は同様にして、触媒７を得た。この触媒７はアルミナ
コート層２００１１１でアルミナ１２２．ＩＰ／ノ、セ
リア６４．９１１１ 、ランタナ８． Ｉ Ｐ／Ｊ 、
ペロプスカイト型複合酸化物（ＬａＦｅ０ｓ） ４．９
１７１と、白金０．４８２ｔ／ノ、ロジウム０．０４８
Ｐ／ｊを含んでいる。Catalyst 7 was obtained in the same manner except that rhodium was supported on one support and 6o, osz, and p were supported on the support. This catalyst 7 has an alumina coat layer of 200,111 and alumina of 122. IP/no, Seria 64.9111, Lantana 8. IP/J,
Perovskite type composite oxide (LaFe0s) 4.9
171, platinum 0.482 t/no, rhodium 0.048
Contains P/j.
（実施例８）市販酸化ランタン１０００１量部と硝酸ニ
ッケル１４８．３重量部を純水に溶解した溶液とを混疎
し、乾燥機中１００℃で５時間乾燥した。この乾燥した
ケーキを、磁製皿に移し、水素気流中８５０℃に加熱し
た炉中に入れ、同温匹を２時間保 １持した後、同
雰囲気気流中で放冷した。取シ出された焼成品はニッケ
ルーランタン系ペロプスカイト型複合酸化物を含む酸化
ランタン粉末である。(Example 8) 10,001 parts by weight of commercially available lanthanum oxide and a solution prepared by dissolving 148.3 parts by weight of nickel nitrate in pure water were mixed and dried at 100° C. for 5 hours in a dryer. This dried cake was transferred to a porcelain plate, placed in a furnace heated to 850°C in a hydrogen stream, kept at the same temperature for 2 hours, and then allowed to cool in the same atmosphere. The fired product taken out is a lanthanum oxide powder containing a nickel-lanthanum perovskite complex oxide.
この酸化ランタン粉末２３４．６ＪＦと、セリウム金属
換算で対アルミナ比３ ｖｔ−含有する活性アルミナ粒
状担体７２０．５ Ｆ 、市販１１化セｔＪ ウＡ ４
９１．３ Ｆ 。This lanthanum oxide powder 234.6JF and activated alumina granular carrier 720.5F containing 3 vt-to-alumina ratio in terms of cerium metal, commercially available 11-oxide CetJ U A 4
91.3F.
硝酸酸性アルミナゾル２５６３ ＃とを、ａＳボットに
投入し、毎分８０回転で８時間粉砕混合して・スラリー
を得る。このスラリーを、コーディエライトを主成分と
するモノリス担体ｆｒ材（ｘ、７＊。Nitric acid acidic alumina sol 2563 # was charged into an aS bot and pulverized and mixed at 80 revolutions per minute for 8 hours to obtain a slurry. This slurry is applied to a monolith carrier fr material (x, 7*) whose main component is cordierite.
４００セル）に次の仕様のスラリーを用いて、あらかじ
めコーティングを行った担体にコーティングを行う。す
なわちセリウムを金属換算対アルミナ比３ ｗｔ−含有
する活性アルミナ粒状担体１００６／。400 cells) using a slurry having the following specifications to coat the previously coated carrier. That is, activated alumina granular support 1006/ containing cerium at a metal equivalent to alumina ratio of 3 wt.
市販酸化セリウム５１６ ／硝酸酸性アルミナゾル２４
７８Ｐ ｔ−ｍｍボールミルに投入し、毎分８０回転テ
゛６時間粉砕混合して得たスラリーを用い、コーティン
グ回数２回で１コート量、モノリス担体１フ当シ２００
ｔとした担体である・該最終コート量は、モノリス担体
１：１当υ１４０ ／とした。コーティング終了後、乾
燥し・空気気流中６５０”Ｃで２時間焼成して触媒担体
とした。この触媒担体に、塩化白金ｒＲ％塩化ロジウム
の混合溶液を用い、含浸法によシ白金を触媒１コ当シ１
．２８６９Ｆ、ロジウムを触媒１コ当シ０．２１４２１
担持し友後、乾燥し、燃焼ガス気流中６００℃で０．５
時間以上焼成して触媒８を得喪。この触媒８は、アルミ
ナコート層２００ ｆ／ｌで、アルミナ１２２．７ ｆ
／ｌ 、セリア６５．３ ｆ／ｌランタナ１０．５ ｆ
／Ｌ 、ペロプスカイト型複合酸化物（ＬａＮｉＯｓ）
１．５ｆ／Ａと白金０．７５７ ｆ／ｌ 、ロジウム０
．１２６ ｆ／ｌを含んでいる。Commercially available cerium oxide 516/nitric acid acidic alumina sol 24
Using the slurry obtained by putting it in a 78P t-mm ball mill and grinding and mixing at 80 rotations per minute for 6 hours, one coating amount was obtained by coating twice, and 200 ml per monolithic carrier.
The final coating amount was 1:1 υ140/monolith support. After coating, it was dried and calcined for 2 hours at 650"C in an air stream to form a catalyst carrier. Platinum was added to the catalyst carrier by an impregnation method using a mixed solution of platinum chloride rR% rhodium chloride. Kotoshi 1
．． 2869F, rhodium per catalyst 0.21421
After supporting, dry and heat to 0.5 at 600℃ in combustion gas stream.
After firing for more than an hour, catalyst 8 was not obtained. This catalyst 8 has an alumina coating layer of 200 f/l and an alumina coating of 122.7 f/l.
/l, Seria 65.3 f/l Lantana 10.5 f
/L, perovskite type composite oxide (LaNiOs)
1.5 f/A and platinum 0.757 f/l, rhodium 0
．． Contains 126 f/l.
（実施例９）
１［例８において、最終コーティングに用いるスラリー
を、ランタン酸化物（ランタナ）１０００重量部に対し
、硝１１＝ツケル２４７．８重量部を混合し、焼成して
得たペロブスカイトＮ−合酸化物を含むランタナ粉末２
４１．１１．セリウムを金属換算３ｗｔ％を含む活性ア
ルミナ粒状担体７２０．５ ｔ 、市販セリア４９１．
３ ｔ 、硝酸酸性アルミナゾル２５６３ｆを混合粉砕
する以外同様にして触媒９を得た。この触媒９は、アル
ミナコート層２００２μで、アルミナ１２２．５ ｆ／
Ｌ 、セリア６５．２ｆ／ｌ、ランタナ９．８ｐ／ｊ、
ペロプスカイト型複合酸化物（Ｌａｌ’ＪｉＯｓ） ２
．５ｐｉｔと白金０．７５７１！７ノ、ロジウム０．１
２６Ｆ／ノを含んでいる。(Example 9) 1 [In Example 8, the slurry used for the final coating was prepared by mixing 1000 parts by weight of lanthanum oxide (lanthana) with 247.8 parts by weight of nitrate 11 = 247.8 parts by weight, and firing the mixture. -Lantana powder 2 containing synthetic oxides
41.11. 720.5 t of activated alumina granular carrier containing 3 wt% of cerium as metal, commercially available ceria 491.
Catalyst 9 was obtained in the same manner except that 3 t and nitric acid acidic alumina sol 2563f were mixed and ground. This catalyst 9 has an alumina coating layer of 2002μ and an alumina coating of 122.5f/
L, Seria 65.2f/l, Lantana 9.8p/j,
Perovskite type composite oxide (Lal'JiOs) 2
．． 5 pit and platinum 0.7571!7, rhodium 0.1
Contains 26F/no.
（実施例１０）
実施例９において、白金を触媒担体ｌコ当、り１．３６
ｔ、ロジウムを担体１コ当シ０．１３６／担持する以外
は同様にして触媒１０を得た。この触媒１０は、アルミ
ナコート層２００ Ｐ／Ｊで、アルミナ１２２．５Ｐ／
Ａ。(Example 10) In Example 9, platinum was added at 1.36 ml per 1 catalyst carrier.
Catalyst 10 was obtained in the same manner except that 0.136/t of rhodium was supported per carrier. This catalyst 10 has an alumina coating layer of 200 P/J and an alumina coating of 122.5 P/J.
A.
セリア６Ｂ、２Ｐ／Ａ 、ランタナ９．８Ｆ／ノ、ペロ
プスカイト型複合酸化物（Ｌ畠Ｎｉｄ、） ２．５ ｐ
／ノ、と白金０Ｂ０３１／ｊ、ロジウム０．０８０１／
ｊを含んでいる。Ceria 6B, 2P/A, Lanthana 9.8F/no, perovskite type composite oxide (L Hatake Nid,) 2.5 p
/ノ, platinum 0B031/j, rhodium 0.0801/
Contains j.
（実施例１１）
実施例８において、最終コーティングに用いるスラリー
を、ランタン酸化物（ランタナ）１０００重量部に対し
硝酸ニッケル４９５．６重量部混合し、焼成して得たペ
ロプスカイト型複合酸化物を含むう／タナ粉末２５６．
９／、七リクムを金属換算ａＷｔ−含む活性アルミナ粒
状担体７２０．５ Ｆ 、市販セリフ４９１．３ＪＰ、
硝酸酸性アルミナゾル２５６３ Ｐを混合粉砕する以外
同様にして触媒１１を得た・この触媒１１は、アルミナ
コート層２００ Ｐ／ｊで、アルミナ１２２．１ Ｐ／
ｊ 、セリア６４．９ Ｐ／ノ、ランタナ８，１？／ノ
。(Example 11) In Example 8, a perovskite-type composite oxide obtained by mixing 495.6 parts by weight of nickel nitrate with 1000 parts by weight of lanthanum oxide (lanthana) and firing the slurry used for the final coating was prepared. Ingredients/tana powder 256.
9/, activated alumina granular carrier containing 7 Licum in metal equivalent aWt 720.5 F, commercially available Serif 491.3JP,
Catalyst 11 was obtained in the same manner except that nitric acid acidic alumina sol 2563 P was mixed and crushed. This catalyst 11 had an alumina coat layer of 200 P/j and alumina 122.1 P/j.
j, Seria 64.9 P/no, Lantana 8.1? /of.
ペロプスカイト型複合酸化物（ＬａＮｌ０ｓ） ４．９
Ｐ／Ｊと白金０．７５７１７１ 、ロジウム０．１２
６Ｊ’／ノを含んでいる。Perovskite type composite oxide (LaNl0s) 4.9
P/J and platinum 0.757171, rhodium 0.12
Contains 6J'/ノ.
（実施例１２）
実施例１１Ｖｃおいて、白金を触媒担体１コ当シ１．３
６Ｆ、ロジウムを担体１コ当シ０．１３６Ｐを担持する
以外は同様にして、触媒１２を得た。との触媒１２は、
アルばナコー） ２００ Ｐ／ｊで、その組成は、実施
例１１で得られた触媒１１と同一であシ、白金は０．８
０３１／１ 、ロジウムは０．０８０Ｐ／ｊを含んでい
る。(Example 12) In Example 11 Vc, platinum was added per catalyst carrier at 1.3
Catalyst 12 was obtained in the same manner except that 6F and rhodium were supported in an amount of 0.136P per carrier. The catalyst 12 with
Albanako) 200 P/j, its composition was the same as catalyst 11 obtained in Example 11, and the platinum content was 0.8
031/1, rhodium contains 0.080P/j.
（実施例１３）
実施例１１において、白金を触媒担体ｌコ当シ０、’１
７２１．ロジウムを担体１コ当シ０．１２９Ｆ担持する
以外は同様にして、触媒１３を得た。この触媒１３は、
アルミナコート層２００ Ｐ／ｌで、その組 １或は実
施例１１で得た触媒１１と同一であシ、白金は０．４５
４１７１ 、ロジウムは０．０７６１！／ノを含んでい
る。(Example 13) In Example 11, platinum was applied to the catalyst carrier 0, '1
721. Catalyst 13 was obtained in the same manner except that rhodium was supported at 0.129F per carrier. This catalyst 13 is
The alumina coat layer was 200 P/l, the same as the catalyst 11 obtained in Group 1 or Example 11, and the platinum content was 0.45
4171, rhodium is 0.0761! Contains /.
（実施例１４）
実施例ｘｔにおいて、白金を触媒担体１＝ｒ当シ０．８
２？、ロジウムを担体１：２当シ０．０８２Ｆ担持する
以外は同様にして、触媒１４を得た。との触媒１４は、
アルミナコート層Ｚｏｏ Ｐ／ｊで、組成は、実施例１
１で得た触媒１１と同一であシ、白金は０．４８２Ｐ／
ｊ９日ジウムは０．０４８１７１を含んでいる。(Example 14) In Example
2? A catalyst 14 was obtained in the same manner except that rhodium was supported at 1:2/0.082F on the carrier. The catalyst 14 is
The alumina coat layer Zoo P/j has the composition of Example 1.
It is the same as the catalyst 11 obtained in 1, and the platinum content is 0.482P/
j9 day dium contains 0.048171.
（実施例１５）市販識化うンタス１０００重量部と、硝
酸第１鉄１５４．５Ｘ量部、硝酸ニッケル１４８．３重
量部を純水に溶解した溶液とを混疎し、乾燥機中１００
℃で５時間乾燥した。この乾燥したケーキを、磁製皿に
移し、水素気流中８５０℃に加熱した炉中−入れ、同温
度を保持したまま、２時間ｆｉｎａｌた。(Example 15) A solution prepared by dissolving 1000 parts by weight of commercially available nitrate, 154.5 parts by weight of ferrous nitrate, and 148.3 parts by weight of nickel nitrate in pure water,
It was dried at ℃ for 5 hours. This dried cake was transferred to a porcelain dish, placed in a furnace heated to 850°C in a hydrogen stream, and finalized for 2 hours while maintaining the same temperature.
ｔＲＩＩｔ終了後同雰囲気中で放冷し、鉄−ランタン系
およびニッケルーランタン系ペロプスカイト型複合酸化
物を含む酸化ランタン粉末を得た。この酸化ランタン粉
末２３４．８Ｆとセリウムを金属換算で対アルミナ比３
ｗｔ％含有する活性アルミナ粒状担体７２０．５Ｐ、
市販酸化セリウム粉末４９１．３Ｊ’、硝酸酸性アルミ
ナゾル２５６３ Ｆとを磁製ポットに投入する以外は実
施例１と同様にして、触媒１５を得た。この触媒１５は
、アルミナコート層２００１／Ｊで、アルミナ１２２．
７１／ｊ、セリア６５．３ ＰＨ１，、ランタナ９．０
１７１ 、ペロプスカイト型複合酸化物 。After completion of tRIIt, the mixture was allowed to cool in the same atmosphere to obtain lanthanum oxide powder containing iron-lanthanum and nickel-lanthanum perovskite complex oxides. This lanthanum oxide powder 234.8F and cerium have a metal equivalent ratio of 3 to alumina.
activated alumina granular carrier containing wt% 720.5P,
Catalyst 15 was obtained in the same manner as in Example 1 except that commercially available cerium oxide powder 491.3J' and nitric acid acidic alumina sol 2563F were placed in a porcelain pot. This catalyst 15 has alumina coat layer 2001/J and alumina 122.
71/j, Seria 65.3 PH1,, Lantana 9.0
171, Peropskite-type composite oxide.
（ＬｊＬＦ１１０畠＊ ＬｊＬＮｌｏｉ ン ３．
０ １７１ 、 （Ｆｅ：Ｎ１＝１ ： ｌ
）と、白金０．７５７Ｆ／ノ、はジクム０．１２６Ｐ／
ノを含んでいる。(LjLF110 ＊ LjLNloi in 3.
0 171, (Fe:N1=1:l
), platinum 0.757F/no, and Zikum 0.126P/
Contains no.
（比・較例１）
活性アルミナ粒状担体１４３７ Ｐ 、と硝酸酸性アル
ミナゾル２５６３ ＃とを、ａｍボールミルに投入し、
毎分８０回転で６時間粉砕した後、得られたスラリーを
、モノリス担体基材（１，７ｊ 、 ４００セルノにコ
ーティングし、空気雰囲気〒６５０℃で２時間焼成して
触媒担体とした。この時アルミナコート量は３４０ Ｐ
／ケに設定した。久にこの触媒担体を、塩化白金酸と塩
化算ジウムの混合水溶液に浸漬シ、白金、ロジウムの担
持量が、白金１．９７’イケロジウム０．１９７’／ケ
となるようＫした後、空気気流中又は燃焼ガス気流中６
００℃で２時間焼成して触媒Ａ得た。この触媒Ａは、ア
ルミナコート層２００ｔ／ノで、白金１．１２．？／ノ
、ロジウム０．１１２ Ｐ／ｊを含んでいる。(Comparison/Comparative Example 1) Activated alumina granular carrier 1437P and nitric acid acidic alumina sol 2563# were put into an am ball mill,
After pulverizing at 80 revolutions per minute for 6 hours, the resulting slurry was coated onto a monolithic carrier substrate (1,7j, 400 cels) and fired in an air atmosphere at 650°C for 2 hours to obtain a catalyst carrier. Alumina coating amount is 340P
/ke was set. The catalyst carrier was immersed in a mixed aqueous solution of chloroplatinic acid and dicalcium chloride, heated so that the amount of platinum and rhodium supported was 1.97% platinum and 0.197% chelodium, and then heated in an air stream. Medium or combustion gas stream 6
Catalyst A was obtained by calcining at 00°C for 2 hours. This catalyst A had an alumina coat layer of 200 tons/no and platinum of 1.12. ? Contains 0.112 P/j of rhodium.
（比較例２ノ
セリウムを金属換算５ ｗｔ％を含む活性アルミナ粒状
担体１４３７ ／ 、と硝酸酸性アルミナゾル２５６３
ｔとを用いる以外、比較例１と同様にして触媒Ｂを得た
。この触媒Ｂは、アルミナ；−ト層２００Ｐ／）で、ア
ルミナ１８９ Ｐ／Ｊ 、セリ、ア１１．ＯＦ／ノと白
金ｌユ２Ｐ／！、ロジウムＯ，１１２Ｆ／ノを含んでい
る。(Comparative Example 2 Activated alumina granular carrier 1437/1 containing 5 wt% of nocerium as metal, and nitric acid acidic alumina sol 2563)
Catalyst B was obtained in the same manner as Comparative Example 1 except that t was used. This catalyst B is made of alumina; OF/no and Shirokane lyu 2P/! , rhodium O, 112F/no.
（比較例３ノ
セリウムを金属換算０．５ ｗｔ−含む活性アルミナ粒
状担体１３６７．２ＪＦ、市販上リア粉末８９．Ｊ３Ｊ
Ｆ、硝駿酸性アルミナゾル２５６３ ＃を用いる以外は
、比較例１と同様にして触媒Ｃを得た。この触媒Ｃは、
アルミナコート層２００ Ｐ／Ａで、アルミナ１９０．
２Ｐ／ｊ。(Comparative Example 3 Activated alumina granular carrier 1367.2JF containing 0.5 wt of nocerium in terms of metal, commercially available rear powder 89.J3J)
Catalyst C was obtained in the same manner as in Comparative Example 1 except that F, Nitsun acidic alumina sol 2563 # was used. This catalyst C is
Alumina coat layer 200 P/A, alumina 190.
2P/j.
セリア９．８Ｐ／）、と白金１．１２ Ｐ／Ｊ 、ロジ
ウム０．１１２Ｐ／Ｊを含んでいる。□
（比較例４）
比較例３において、白金を担体１コ当シ０．７７２ｔ、
ロジウムを担体１コ当！ｐｏ、１ｚｓｐ担持させる以外
は同様にして、触媒りを得た。この触媒りは、アルミナ
コート層Ｚｏｏ Ｐ／ｊで、アルミナ１９０２１７１゜
セリア９．８ Ｐ＃ 、と白金０．４５４７’／ノ、ロ
ジウム０．０７６ｔ／ノを含んでいる。It contains 9.8 P/J of ceria, 1.12 P/J of platinum, and 0.112 P/J of rhodium. □ (Comparative Example 4) In Comparative Example 3, 0.772 t of platinum per carrier,
Win one rhodium carrier! A catalyst was obtained in the same manner except that po and 1zsp were supported. This catalyst has an alumina coat layer Zoo P/j containing 1902171° alumina and 9.8 t/h ceria, 0.4547 t/h platinum, and 0.076 t/h rhodium.
（比較例５ノ
シリカ２５６３ ？ 、セリウムを金属換算３ ｗｔ％
を含む活性アルミナ粒状担体１４３７ ＃をボールミル
に混ぜ込み、６時間粉砕の後、モノリス担体基材（１，
７ｊ ４００セルンに付着させ、６５０℃×２時間焼成
した。この時の付着量は３４０ Ｐ／ケに設定した。(Comparative Example 5 Nosilica 2563?, cerium equivalent to 3 wt% as metal)
Activated alumina granular carrier 1437 # containing activated alumina granular carrier was mixed in a ball mill and milled for 6 hours.
7j 400 Cern and baked at 650° C. for 2 hours. The adhesion amount at this time was set at 340 P/piece.
さらに、この担体を塩化白金酸と塩化ロジウムの混合水
溶液に浸漬し、Ｈ，／ Ｎ、流中で還元する。Furthermore, this carrier is immersed in a mixed aqueous solution of chloroplatinic acid and rhodium chloride, and reduced in H,/N, flow.
白金とロジウムの担持量は白金１．９Ｐｌケ、ロジウム
０．１９Ｆ／ケとなるようにした。この後６００℃×２
七焼成して触媒Ｅを得た。 −
（比較例６ノ
アルミナゾル２５６３ Ｆ 、活性アルミナ粒状担体
・１４３７ Ｊ’をボールミルで６時間粉砕した後、
モノリス担体基材（１，７Ｊ ４００セル〕に付着させ
、６５０”Ｃｐ Ｘ ２Ｈｒ焼成した。この時の付着量
は３４０ Ｐ／ケに設定した。次いで（：ｅ（ＮＯＩ）
ｓの水溶液で、セリウム金属換算２８ｔ／ケのセリウム
を付着させ、１２０℃で３時間乾燥後、６００℃Ｘ ２
Ｈｒ焼成した。さらに塩化白金酸と塩化ロジウムの混合
水溶液に浸漬し、白金１．９ Ｐ／ケ田ジウムＯ，１９
Ｐｌケとなるよう担持した後、焼成して触＠Ｆを得た。The supported amounts of platinum and rhodium were set to 1.9 Pl/kg of platinum and 0.19 F/kg of rhodium. After this, 600℃×2
After seven calcinations, Catalyst E was obtained. - (Comparative Example 6 Noalumina Sol 2563 F, activated alumina granular carrier
・After pulverizing 1437 J' in a ball mill for 6 hours,
It was deposited on a monolithic carrier substrate (1,7J 400 cells) and fired at 650"Cp x 2Hr. The amount of deposition at this time was set at 340P/piece. Then (:e(NOI)
s aqueous solution to deposit 28 t/piece of cerium in terms of cerium metal, and after drying at 120°C for 3 hours, 600°C
Fired for hr. Furthermore, it was immersed in a mixed aqueous solution of chloroplatinic acid and rhodium chloride to obtain platinum 1.9 P/kedadium O, 19
After supporting Pl, it was fired to obtain catalyst@F.
試験例
実施例１〜１５よシ得た触媒１〜１５．比較例１〜６で
得た触媒Ａ−Ｆにつき下記の条件で耐久試験を行った後
、性能評価試験を行い、その結果を、付賢に示した。Test Examples Catalysts 1 to 15 obtained from Examples 1 to 15. After carrying out a durability test on the catalysts A to F obtained in Comparative Examples 1 to 6 under the following conditions, a performance evaluation test was carried out, and the results were shown in the table below.
耐久試験条件
触、 媒 実施例のモノリス屋貴金属触媒から直径３６
５ｍ５長さ５８−ｍ’の円筒状に切シ出した小製の触媒
触媒容量 約６０ＣＣ
雰゛囲気 空気気流中
温度Ｘ時間 ７５０℃Ｘ２４時間
動的試験法 振＠ Ｚ ＝ ０．５ 振動数１回／秒
中心設定２値 ０．４ ０．７ １．０ １．２の４
点“触媒入口ガス温度 ４００℃
空間速度（ＳＶ） ２７５００Ｈｒ−’触媒容量 ６
０ＣＧ
ガス組成 モデルガス混合（１０％迅０を含む）
各２値におけ名ＮＯｘ 、 ＨＣ、ＣＯの転化率を付図
に示すようにグラフに作成した。付図は触媒８に関する
グラフである。５ＯＩＪ６ウインド幅は−Ｎｏ：Ｃ。Durability test conditions Catalyst, medium Diameter 36 from the monolith shop precious metal catalyst of the example
Small catalyst cut into a cylindrical shape with a length of 5 m5 and a length of 58 m' Catalyst capacity: Approximately 60 cc Atmosphere: Temperature x time in air flow: 750°C x 24 hours Dynamic test method Vibration @ Z = 0.5 Frequency: 1 times/second center setting 2 values 0.4 0.7 1.0 1.2 of 4
Point "Catalyst inlet gas temperature 400℃ Space velocity (SV) 27500Hr-' Catalyst capacity 6
0CG Gas Composition Model Gas Mixture (Including 10% 0CG) The conversion rates of NOx, HC, and CO at each binary value were created in a graph as shown in the attached figure. The attached figure is a graph regarding the catalyst 8. 5OIJ6 window width is -No:C.
ＨＣ，ＣＯの転化率のグラフが８０％転化率の線を横ぎ
る点の２値の、最大値と最小値の差とした。The difference between the maximum value and the minimum value of the two values at the point where the graph of the conversion rate of HC and CO crosses the line of 80% conversion rate was taken as the difference.
付図では、ＮＯｘの８０−転化率を示す２値と、ＣＯの
８０％＠化率を示す２値との差となる。In the attached figure, it is the difference between the two values indicating the 80-conversion rate of NOx and the two values indicating the 80% conversion rate of CO.
以上説明してきたようＫ、この発１１によれば、その構
成を酸化ランタンと硝酸第１鉄又は硝酸ニッケルとを混
合し、還元性ガス雰囲気中で焼成して得たペロブスカイ
トａ複合酸化物を含む酸化ランタン粉末と、あらかじめ
セリウムを含有する活性アルミナ粒状又は粉末状担体と
、酸化セリウム粉末を硝酸酸性アルミナゾルとを混線し
て得たスラリーを、無機多孔質缶ノリス基体に、コーテ
ィングし、暁成して触媒担体となした後、貴金属を担持
させるとしたため、低温にもかかわらず高い転化性能と
、高耐久性を持つことができるという効果が得られる。As explained above, according to this publication 11, the composition includes a perovskite a composite oxide obtained by mixing lanthanum oxide and ferrous nitrate or nickel nitrate and firing the mixture in a reducing gas atmosphere. A slurry obtained by mixing lanthanum oxide powder, activated alumina granular or powdered carrier containing cerium in advance, and cerium oxide powder with nitric acid acidic alumina sol is coated on an inorganic porous can Norris substrate, and then oxidized. After forming the catalyst into a catalyst carrier, noble metals are supported on the catalyst, resulting in high conversion performance and high durability despite low temperatures.
付図は、本発明の実施例８の触媒のＨＣ，Ｃｏ。 ＮＯｘの転化率を示すグラフである。 −２纏− The attached figure shows HC and Co of the catalyst of Example 8 of the present invention. It is a graph showing the conversion rate of NOx. -2 coats-
Claims (1)
とニッケルとランタンとからなるペロブスカイト型酸化
物とからなる群から選択した少くとも１種のペロブスカ
イト型酸化物を含む酸化ランタン粉末と、あらかじめセ
リウムを担持した活性アルミナと、酸化セリウム粉末と
、アルミナゾルとを混練して得られるスラリーを、モノ
リス基体に付着して焼成してなる担体に触媒金属を担持
してなることを特徴とする排ガス浄化用触媒。(1) Lanthanum oxide powder containing at least one perovskite oxide selected from the group consisting of perovskite oxides consisting of iron and lanthanum and perovskite oxides consisting of nickel and lanthanum, and cerium in advance. A catalyst for exhaust gas purification, characterized in that a slurry obtained by kneading supported activated alumina, cerium oxide powder, and alumina sol is adhered to a monolith substrate and fired, and a catalytic metal is supported on a carrier. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59166066A JPS6146247A (en) | 1984-08-08 | 1984-08-08 | Catalyst for purifying exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59166066A JPS6146247A (en) | 1984-08-08 | 1984-08-08 | Catalyst for purifying exhaust gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6146247A true JPS6146247A (en) | 1986-03-06 |
Family
ID=15824342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59166066A Pending JPS6146247A (en) | 1984-08-08 | 1984-08-08 | Catalyst for purifying exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6146247A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012125721A (en) * | 2010-12-16 | 2012-07-05 | Nissan Motor Co Ltd | Oxidation catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58156349A (en) * | 1982-03-12 | 1983-09-17 | Mitsui Mining & Smelting Co Ltd | Tertinally-component catalyst for purifying exhaust gas |
-
1984
- 1984-08-08 JP JP59166066A patent/JPS6146247A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58156349A (en) * | 1982-03-12 | 1983-09-17 | Mitsui Mining & Smelting Co Ltd | Tertinally-component catalyst for purifying exhaust gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012125721A (en) * | 2010-12-16 | 2012-07-05 | Nissan Motor Co Ltd | Oxidation catalyst |
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