JPS63218254A - Production of catalyst carrier - Google Patents
Production of catalyst carrierInfo
- Publication number
- JPS63218254A JPS63218254A JP5115087A JP5115087A JPS63218254A JP S63218254 A JPS63218254 A JP S63218254A JP 5115087 A JP5115087 A JP 5115087A JP 5115087 A JP5115087 A JP 5115087A JP S63218254 A JPS63218254 A JP S63218254A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- carrier
- slurry
- water
- rare earth
- 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 57
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 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 90
- 239000002002 slurry Substances 0.000 claims abstract description 39
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 27
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 3
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 abstract 2
- 159000000013 aluminium salts Chemical class 0.000 abstract 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000005352 clarification Methods 0.000 abstract 1
- 229910052746 lanthanum Inorganic materials 0.000 description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 15
- 239000000969 carrier Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052878 cordierite Inorganic materials 0.000 description 10
- 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 10
- 239000002245 particle Substances 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 7
- 229910052788 barium Inorganic materials 0.000 description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000000694 effects Effects 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、排気ガス浄化用触媒に用いる。高温耐久性に
優れた触媒担体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is used in a catalyst for purifying exhaust gas. The present invention relates to a method for producing a catalyst carrier having excellent high-temperature durability.
内燃機間の排気ガス浄化用触媒は１時として１０００℃
以上の高温に曝されることがある。そのため、その担体
には、高温における耐久性が要求される。The exhaust gas purifying catalyst between internal combustion engines is heated to 1000℃ at one hour.
May be exposed to higher temperatures. Therefore, the carrier is required to have durability at high temperatures.
従来、高温耐久性に優れた触媒用担体としては。Traditionally, it has been used as a catalyst carrier with excellent high-temperature durability.
希土類或いはアルカリ土類で安定化された安定化アルミ
ナが知られている（特開昭６ｌ−２３８３４１）。Stabilized alumina stabilized with rare earth or alkaline earth elements is known (Japanese Patent Laid-Open No. 61-238341).
一方、触媒担体を製造する場合、担体としての機能を向
上させるため、コーディエライト等の担体基材の表面に
、触媒成分を担持させるための担体表面層を付着形成す
る方法が採られている。この表面層形成方法による担体
の製造法としては。On the other hand, when manufacturing a catalyst carrier, a method is adopted in which a carrier surface layer for supporting catalyst components is formed on the surface of a carrier base material such as cordierite in order to improve its functionality as a carrier. . A method for manufacturing a carrier using this surface layer forming method is as follows.
例えば１粒状活性アルミナに貴金属を分散担持さ・せた
触媒と、希土類金属の硝酸塩、希土類金属酸化物粉末及
び硝酸水溶液とを混合粉砕し、スラリー化して担体基材
表面に付着させ乾燥、焼成する方法がある（特開昭６Ｏ
−９９３４０）。For example, a catalyst in which a precious metal is dispersed and supported on a single particle of activated alumina, a rare earth metal nitrate, a rare earth metal oxide powder, and an aqueous nitric acid solution are mixed and ground, formed into a slurry, and adhered to the surface of a carrier base material, dried, and fired. There is a method (Unexamined Japanese Patent Publication No. 6O
-99340).
しかしながら、前記安定化アルミナ粉末を用いて。However, with the stabilized alumina powder.
これをスラリー化し、担体基材表面に付着、乾燥。This is made into a slurry, adhered to the surface of the carrier base material, and dried.
焼成する場合には、高温耐久性に優れた担体を製造する
ことができない、その原因は、スラリーの形成、付着、
乾燥の間に、安定化アルミナ中に固溶していた上記希土
類元素が溶出し、その結果アルミナの高温における変態
を引き起こし、担体表面の表面積を減少させるためであ
る。When firing, it is not possible to produce a carrier with excellent high-temperature durability, due to the formation of slurry, adhesion,
This is because the above-mentioned rare earth elements dissolved in the stabilized alumina are eluted during drying, causing transformation of the alumina at high temperatures and reducing the surface area of the carrier surface.
［発明が解決しようとする問題点〕
本発明は、上記従来技術の問題点を解決しようとするも
ので、安定化したアルミナ中から希土類あるいはアルカ
リ土類が溶出することを防ぎ、高温における触媒担体の
安定性を図り、耐久性に。[Problems to be Solved by the Invention] The present invention attempts to solve the above-mentioned problems of the prior art, and is intended to prevent rare earth or alkaline earth elements from leaching out of stabilized alumina, and to prevent catalyst carriers from being eluted at high temperatures. Stability and durability.
優れた排気ガス浄化用触媒担体を提供しようとするもの
である。The present invention aims to provide an excellent catalyst carrier for purifying exhaust gas.
本発明は、希土類あるいはアルカリ土類の１種以上を含
んだ安定化アルミナ粉末、水溶性アルミニウム塩並びに
酸の一方又は双方と、水溶性希土類塩と、水とを混合し
てスラリーを形成し、該スラリーを触媒担体基材表面に
付着させた後、乾燥。In the present invention, a slurry is formed by mixing one or both of a stabilized alumina powder, a water-soluble aluminum salt, and an acid containing one or more types of rare earth or alkaline earth, the water-soluble rare earth salt, and water; After the slurry is applied to the surface of the catalyst carrier base material, it is dried.
焼成して、前記触媒担体基材表面に安定化アルミナ層を
形成することを特徴とする触媒担体の製造方法にある。A method for producing a catalyst carrier, which comprises firing to form a stabilized alumina layer on the surface of the catalyst carrier base material.
本発明において、前記安定化アルミナ粉末とは。In the present invention, what is the stabilized alumina powder?
アルミナに予めランタン、セリウム、ネオジムなどの希
土類元素、或いはバリウム、ストロンチウムなどのアル
カリ土類元素の一種以上を含有させたものをいう、水溶
性アルミニウム塩としては。The water-soluble aluminum salt refers to alumina containing one or more of rare earth elements such as lanthanum, cerium, and neodymium, or alkaline earth elements such as barium and strontium.
硝酸アルミニウム、塩化アルミニウム、塩基性アルミニ
ウム等を用いる。また、アルミナゾル或いは無定形アル
ミナゾルも、スラリーがゲル化しない範囲であれば、使
用することもできる。この場合、アルミナゾル中のアル
ミナのモル置は、水溶性アルミニウム塩のモル数に加え
ればよい、 酸としては硝酸、酢酸等を用いる。また、
水溶性希土類塩としては、硝酸ランタン、塩化ランタン
。Aluminum nitrate, aluminum chloride, basic aluminum, etc. are used. Furthermore, alumina sol or amorphous alumina sol can also be used as long as the slurry does not gel. In this case, the mole amount of alumina in the alumina sol can be determined by adding it to the mole number of the water-soluble aluminum salt. As the acid, nitric acid, acetic acid, etc. are used. Also,
Examples of water-soluble rare earth salts include lanthanum nitrate and lanthanum chloride.
硝酸ネオジムなどを用いる。Use neodymium nitrate, etc.
触媒担体基材としては、コーディエライトムライト、ス
ポジュメンなどを用いる。As the catalyst carrier base material, cordierite mullite, spodumene, etc. are used.
担体基材表面へ、上記安定化アルミナ粉末、水溶性希土
類塩等の混合スラリー（泥漿）を付着させる方法として
は、該スラリー中へ担体基材を浸漬すること、担体基材
表面にスラリーを噴きつけること、塗布することなどが
ある。スラリーの形成は、安定化アルミナ粉末に対して
、水溶性アルミニウム塩２〜ｌ Ｑｗｔ％、酸ｌ〜ｌ
Ｑｗｔ％。Methods for attaching the mixed slurry (slurry) of the above-mentioned stabilized alumina powder, water-soluble rare earth salt, etc. to the surface of the carrier substrate include immersing the carrier substrate in the slurry, and spraying the slurry onto the surface of the carrier substrate. It can be applied, applied, etc. Formation of the slurry consists of 2 to 1 Qwt% of water-soluble aluminum salt, 1 to 1 of acid to stabilized alumina powder.
Qwt%.
水溶性希土類塩２〜ｌ Ｑｗｔ％、水１０〜５０ｗｔ％
を加えることにより行う、また、スラリーを形成する場
合、水溶性アルミニウム塩、酸の一方又は双方に対する
水溶性希土類塩の添加割合は０゜１〜２．０モル倍とす
ることが好ましい、この範囲を越えると製造した担体の
高温耐久性が低下するおそれがある。Water-soluble rare earth salt 2-l Qwt%, water 10-50wt%
In addition, when forming a slurry, the addition ratio of the water-soluble rare earth salt to one or both of the water-soluble aluminum salt and the acid is preferably 0.1 to 2.0 times by mole, within this range. If it exceeds this, there is a risk that the high temperature durability of the produced carrier will deteriorate.
本発明によれば、担体の製造過程において、安定化アル
ミナ粉末中の希土類、アルカリ土類が溶出することがな
いので、確実に安定化アルミナ層を担体基材の表面に形
成することができる。そのため、高温においても高い表
面積を維持し、耐久性に優れた触媒担体を製造すること
ができる。According to the present invention, rare earth elements and alkaline earth elements in the stabilized alumina powder are not eluted during the manufacturing process of the carrier, so that a stabilized alumina layer can be reliably formed on the surface of the carrier base material. Therefore, it is possible to produce a catalyst carrier that maintains a high surface area even at high temperatures and has excellent durability.
このような、優れた効果が得られるのは９次のような理
由によるものと考えられる。The reason why such excellent effects can be obtained is considered to be due to the following reasons.
即ち１本発明においては、希土類元素などを固溶させた
前記安定化アルミナ粉末は、適量の水溶性希土類塩が存
在する状態の下で、水溶性アルミニウム塩並びに酸の一
方又は双方と撹拌混合されている。That is, in the present invention, the stabilized alumina powder containing a rare earth element or the like is stirred and mixed with one or both of a water-soluble aluminum salt and an acid in the presence of an appropriate amount of a water-soluble rare earth salt. ing.
このため、安定化アルミナ粉末中の希土類あるいはアル
カリ土類が溶出することがない、即ち乾燥・焼成過程中
において、スラリー中の水溶性希土類塩が水溶性アルミ
ニウム塩中に固溶するため。For this reason, the rare earth or alkaline earth in the stabilized alumina powder does not elute; that is, the water-soluble rare earth salt in the slurry dissolves in the water-soluble aluminum salt during the drying and firing process.
安定化アルミナ粉末からは希土類あるいはアルカリ土類
の溶出は無く、高温においても高い表面積が保たれる。There is no elution of rare earth or alkaline earth elements from the stabilized alumina powder, and a high surface area is maintained even at high temperatures.
また、添加した水溶性アルミニウム塩又は添加した酸に
溶解した水溶性アルミニウム塩は添加した水溶性希土類
塩と高温において反応し、希土類元素は活性アルミナ格
子中に含有される。Further, the added water-soluble aluminum salt or the water-soluble aluminum salt dissolved in the added acid reacts with the added water-soluble rare earth salt at high temperature, and the rare earth element is contained in the activated alumina lattice.
実施例１
硝酸ランタンの水溶液を１表面積が１６０ｍ”７ｇであ
るアルミナに、該アルミナに対し１モル％のランタン含
有量となるような割合において。Example 1 An aqueous solution of lanthanum nitrate was applied to alumina having a surface area of 160 m''7 g in proportions such that the lanthanum content was 1 mol % with respect to the alumina.
含浸させた。その後、上記アルミナを乾燥させ。Impregnated. Then, dry the alumina.
水分を取り除いた後、６００℃、空気中、３時間にて焼
成し、アルミナにランタンを含有させた。After removing moisture, it was fired at 600° C. in air for 3 hours to make the alumina contain lanthanum.
次に、硝酸バリウムの水溶液を用い、上記アルミナに対
し１モル％のバリウム含有量となるような割合にて、上
記と同様にしてバリウムを含有させた。これにより、ラ
ンタンとバリウムとを含有してなるＴ−アルミナを調製
した。更に該アルミナを８７０℃、空気中、３時間に−
て焼成して安定化されたアルミナを調製した。そして該
安定化アルミナを振動ミルにより粉砕して平均粒径１０
μｍの粉末にした。Next, using an aqueous solution of barium nitrate, barium was added in the same manner as above at a ratio such that the barium content was 1 mol % relative to the alumina. In this way, T-alumina containing lanthanum and barium was prepared. Furthermore, the alumina was heated at 870°C in air for 3 hours.
Stabilized alumina was prepared by firing. Then, the stabilized alumina was pulverized using a vibrating mill, with an average particle size of 10
It was made into a μm-sized powder.
次に、該安定化アルミナ４Ｋｇと硝酸アルミニウム（Ａ
Ｉ（Ｎｏ３）２ ９Ｈｚ Ｏ）２４０ｇと硝酸ランタン
（Ｌａ （ＮＯ３） ３ ・６Ｈｚ ０）１３８〜５
６０ｇ （硝酸アルミニウムに対して０゜５〜２モル倍
）とを水と共にボールミリングした。Next, 4 kg of the stabilized alumina and aluminum nitrate (A
I (No3)2 9Hz O) 240g and lanthanum nitrate (La (NO3)3 ・6Hz 0) 138~5
60 g (0.5 to 2 moles of aluminum nitrate) was ball milled together with water.
これによりウォソシェコートスラリーを生成させた。そ
して断面積１ｉｎ”当たり約４００の流路を含むコーデ
ィエライトの一体性担体を上記スラリー中に浸漬した。This produced a Wososhekote slurry. A monolithic support of cordierite containing approximately 400 channels per inch of cross-sectional area was then immersed in the slurry.
続いて圧縮空気で一体化物の過剰液を吹き去り、この一
体化物を乾燥して遊離の水を除去し、そして７００℃で
１時間焼成し。Subsequently, excess liquid of the monolith was blown away with compressed air, the monolith was dried to remove free water, and calcined at 700° C. for 1 hour.
一体性担体上に約５０μｍの安定化アルミナ層をコート
した。A stabilized alumina layer of approximately 50 μm was coated onto the monolithic support.
以上により、第１表に示すＮｏ、１〜５の触媒担体を製
造した。As described above, catalyst carriers Nos. 1 to 5 shown in Table 1 were manufactured.
次に、この触媒担体の耐久性を試験するため。Next, to test the durability of this catalyst carrier.
１２００℃、空気中、１０時間加熱し、安定化アルミナ
層のα転移量〔Ｘ線回折（Ｘ ＲＤ）で測定〕と比表面
積（Ｎ２吸着によるＢＥＴ法で測定）とを測定した。そ
の結果を第１表に示す。It was heated at 1200° C. in air for 10 hours, and the amount of α transition [measured by X-ray diffraction (XRD)] and specific surface area (measured by BET method using N2 adsorption) of the stabilized alumina layer were measured. The results are shown in Table 1.
比較のために、上記と同様にして、スラリー調製時、硝
酸ランタンを全く添加しない触媒担体Ｎｏ、Ｃ１，及び
硝酸ランタンを８４０ｇ （硝酸アルミニウムの３モル
倍）添加した触媒担体Ｎｏ。For comparison, in the same manner as above, catalyst carrier No. C1 was prepared without adding any lanthanum nitrate, and catalyst carrier No. was added with 840 g of lanthanum nitrate (3 times the mole of aluminum nitrate).
Ｃ２とを製造し、上記と同様な試験を行った。その結果
を第１表に示した。C2 was manufactured and tested in the same manner as above. The results are shown in Table 1.
第１表において「Ｌ／Ａモル倍」とは「硝酸ランタン／
硝酸アルミニウム」のモル比率を示す（以下同じ）。ま
た、「α化率」とは、安定化アルミナがα−アルミナに
転移した割合を示し、この値が低い程担体の耐久性が高
い。In Table 1, "L/A mole times" means "lanthanum nitrate/
The molar ratio of "aluminum nitrate" is shown (the same applies below). Furthermore, the term "gelatinization rate" refers to the rate at which stabilized alumina is transformed into α-alumina, and the lower this value is, the higher the durability of the carrier is.
第１表から明らかなように１本発明による触媒担体は、
高温においても比較担体よりα転移量が小さり、シかも
高比表面積を保っており、優れた担体であることが分か
る。As is clear from Table 1, the catalyst carrier according to the present invention is:
Even at high temperatures, the amount of α-transition is smaller than that of the comparative carrier, and the carrier maintains a high specific surface area, indicating that it is an excellent carrier.
実施例２
硝酸ランタンの水溶液を、実施例１と同様のアルミナに
対し１．３モル％のランタン含有量となるような割合に
おいて、含浸させた。その後、実施例１と同様にして、
アルミナにランタンを含有せた。更に該アルミナを１０
００℃、空気中、３時間にて焼成し、粉砕して、平均粒
径１０μｍの安定化アルミナ粉末を調製した。Example 2 Alumina similar to Example 1 was impregnated with an aqueous solution of lanthanum nitrate at a ratio such that the lanthanum content was 1.3 mol %. After that, in the same manner as in Example 1,
Alumina contains lanthanum. Furthermore, 10 of the alumina
The mixture was calcined at 00° C. in air for 3 hours and pulverized to prepare stabilized alumina powder with an average particle size of 10 μm.
次に、該安定化アルミナ４Ｋｇと硝酸アルミニウム２４
０ｇと硝酸ランタン２８０ｇ （硝酸アルミニウムに対
して１．０モル倍）とを水と共にボールミリングするこ
とによりウォッシュコートスラリーを生成させた。その
後、実施例１と同様のコーディエライトの一体性担体を
上記スラリー中に浸漬し、実施例１と同様にして上記一
体性担体上に約５０μｍの安定化アルミナ層をコートし
た。Next, 4 kg of the stabilized alumina and 24 kg of aluminum nitrate were added.
A washcoat slurry was produced by ball milling 0 g of lanthanum nitrate and 280 g of lanthanum nitrate (1.0 molar amount relative to aluminum nitrate) together with water. Thereafter, a monolithic cordierite support as in Example 1 was immersed in the slurry, and a stabilized alumina layer of about 50 μm was coated on the monolithic support in the same manner as in Example 1.
この担体をＮｏ、６とする。This carrier is designated as No. 6.
比較のために、スラリー調製時、硝酸ランタンを全く添
加せず、他は上記と同様にして担体Ｎｏ。For comparison, carrier No. was prepared in the same manner as above except that no lanthanum nitrate was added during slurry preparation.
Ｃ３を製造した。C3 was produced.
上記の各担体について、実施例１と同様な試験を行った
。その結果を第２表に示した。The same tests as in Example 1 were conducted for each of the above carriers. The results are shown in Table 2.
第２表
第２表から明らかなように１本発明による触媒担体は、
高温においても比較触媒担体よりα転移量が小さく、シ
かも高比表面積を保っており、優れた担体である。As is clear from Table 2, the catalyst carrier according to the present invention is:
Even at high temperatures, the amount of alpha transition is smaller than that of comparative catalyst carriers, and it maintains a high specific surface area, making it an excellent carrier.
実施例３
実施例２と同様の硝酸ランタン含浸アルミナを調製し、
同様に乾燥、焼成してアルミナにランタンを含有させた
。更に、実施例１と同様に、平均粒径ＩＱｐｍの安定化
アルミナ粉末を調製した。Example 3 Lanthanum nitrate impregnated alumina similar to Example 2 was prepared,
The alumina was similarly dried and fired to contain lanthanum. Furthermore, in the same manner as in Example 1, stabilized alumina powder having an average particle size of IQpm was prepared.
次に該アルミナ４Ｋｇと硝酸アルミニウム２４０ｇと無
定形繊維状アルミナゾル（有機酸安定型）８００ｇ （
ＡＪｔ Ｏｘ換算で８０ｇ）と硝酸ランタン９７３ｇ
＜Ｌａ／Ａｌ−１，０−ｔル）とを水と共にボールミリ
ングすることによりウォッシュコートスラリーを生成さ
せた。そして実施例１と同様のコーディエライトの一体
性担体を上記スラリー中に浸漬し、実施例１と同様にし
て上記一体性担体上に約５０μｍの安定化アルミナ層を
コートした。この担体をＮ００７とする。Next, 4 kg of the alumina, 240 g of aluminum nitrate, and 800 g of amorphous fibrous alumina sol (organic acid stable type) (
80g (converted to AJt Ox) and 973g of lanthanum nitrate
A washcoat slurry was produced by ball milling <La/Al-1,0-tL) with water. A monolithic cordierite support similar to that in Example 1 was then immersed in the slurry, and a stabilized alumina layer of about 50 μm was coated on the monolithic support in the same manner as in Example 1. This carrier is designated as N007.
比較のために、スラリー調製時、硝酸ランタンを全く添
加せず、他は上記と同様にして担体Ｎｏ、Ｃ４を製造し
た。For comparison, carrier No. C4 was produced in the same manner as above except that lanthanum nitrate was not added at all when preparing the slurry.
上記の各担体について、実施例１と同様な試験を行った
。その結果を第３表に示した。なお、第３表におけるｒ
Ｌｇ／Ａｇモル倍」とは、スラリー作成時に添加した「
アルミニウムのダラム原子」に対する「ランタンのダラ
ム原子」のモル比を示す（以下。The same tests as in Example 1 were conducted for each of the above carriers. The results are shown in Table 3. In addition, r in Table 3
"Lg/Ag mole times" means "Lg/Ag mole times"
The molar ratio of ``dulam atoms of lanthanum'' to ``dulam atoms of aluminum'' is shown below (below).
同じ）。same).
第３表から明らかなように１本発明による触媒担体は、
高温においても比較触媒担体よりα転移量が小さく、シ
かも高比表面積を保っており、優れた担体である。As is clear from Table 3, the catalyst carrier according to the present invention is:
Even at high temperatures, the amount of alpha transition is smaller than that of comparative catalyst carriers, and it maintains a high specific surface area, making it an excellent carrier.
実施例４
実施例１と同様の硝酸ランタン含浸アルミナを調製し、
同様に乾燥、焼成してアルミナにランタンを含有させた
。更に、実施例１と同様にして、平均粒径ｌＯμｍの安
定化アルミナ粉末を調製した。次に該アルミナ４Ｋｇと
硝酸アルミニウム２４０ｇと擬ベーマイト形アルミナを
アルミナ換算で８０ｇと硝酸ランク７９７３ｇ （Ｌａ
／ＡＩ＝１．０モル）とを水と共にボールミリングする
ことによりウォッシュコートスラリーを生成させた。そ
して実施例１と同様のコーディエライトの一体性担体を
スラリー中に浸漬した。Example 4 Lanthanum nitrate-impregnated alumina similar to Example 1 was prepared,
The alumina was similarly dried and fired to contain lanthanum. Furthermore, in the same manner as in Example 1, stabilized alumina powder having an average particle size of 10 μm was prepared. Next, add 4 kg of the alumina, 240 g of aluminum nitrate, and pseudo-boehmite alumina to 80 g in terms of alumina and 7973 g of nitric acid rank (La
/AI=1.0 mol) was ball milled with water to produce a washcoat slurry. A monolithic cordierite support similar to that in Example 1 was then immersed in the slurry.
続いて、実施例１と同様に乾燥、焼成し、上記一体性担
体上に約５０μｍの安定化アルミナ層をコートした。Subsequently, it was dried and fired in the same manner as in Example 1, and a stabilized alumina layer of about 50 μm was coated on the above-mentioned monolithic support.
この担体をＮｏ、８とする。This carrier is designated as No. 8.
比較のために、スラリー調製時、硝酸ランタンを全く添
加せず、他は上記と同様にして担体Ｎｏ、Ｃ５を製造し
た。For comparison, carrier No. C5 was produced in the same manner as above except that lanthanum nitrate was not added at all when preparing the slurry.
上記の各担体について実施例１と同様な試験を行った。The same tests as in Example 1 were conducted for each of the above carriers.
その結果を第４表に示した。The results are shown in Table 4.
第４表から明らかなように２本発明による触媒担体は、
高温においても比較触媒担体よりα転移量が小さく、シ
かも高比表面積を保っており、優れた担体である。As is clear from Table 4, the two catalyst supports according to the present invention are:
Even at high temperatures, the amount of alpha transition is smaller than that of comparative catalyst carriers, and it maintains a high specific surface area, making it an excellent carrier.
実施例５
硝酸ネオジムの水溶液を表面積が１６０ｍ”／ｇである
アルミナに、アルミナに対し１モルのネオジム含有量と
なるような割合において、含浸させた。その後、実施例
１と同様にしてアルミナにネオジムを含有させた。Example 5 Alumina having a surface area of 160 m''/g was impregnated with an aqueous solution of neodymium nitrate in a ratio such that the neodymium content was 1 mole per alumina. Thereafter, the alumina was impregnated in the same manner as in Example 1. Contains neodymium.
次に、硝酸バリウムの水溶液を用い、上記アルミナに対
し１モル％のバリウム含有量となるような割合にて、上
記と同様にしてバリウムを含有させた。Next, using an aqueous solution of barium nitrate, barium was added in the same manner as above at a ratio such that the barium content was 1 mol % relative to the alumina.
これにより、ネオジムとバリウムとが含有してなるγ−
アルミナをＩＡ整した。更に８亥アルミナを８７０℃、
空気中、３時間にて焼成して安定化されたアルミナを調
整し、粉砕して、平均粒径１０μｍの安定化アルミナ粉
末を調整した。As a result, γ- containing neodymium and barium
IA conditioned alumina. Furthermore, 800 alumina was heated to 870℃,
Stabilized alumina was prepared by firing in air for 3 hours, and pulverized to prepare stabilized alumina powder with an average particle size of 10 μm.
次に該アルミナ４ｋｇと硝酸アルミニウム２４０ｇと硝
酸ランタン２８０ｇ （硝酸アルミニウムに対して１．
０モル倍）とを水と共にボールミリングすることにより
ウォフシュコートスラＩＪ−を生成させた。Next, 4 kg of the alumina, 240 g of aluminum nitrate, and 280 g of lanthanum nitrate (1.
0 mole) was ball-milled with water to produce Wofshcote slather IJ-.
そして、実施例１と同様のコーディエライトの一体性担
体を該スラリー中に浸漬し、実施例１と同様にして上記
一体性担体上に約５０μｍの安定化アルミナ層をコート
した。この担体をＮｏ、９とする。Then, a monolithic cordierite support similar to that in Example 1 was immersed in the slurry, and a stabilized alumina layer of about 50 μm was coated on the monolithic support in the same manner as in Example 1. This carrier is designated as No. 9.
比較のために、スラリー調製時、硝酸ランタンを全く添
加せず、他は同様にして担体Ｎｏ、Ｃ６を製造した。上
記の各担体について、実施例１と同様な試験を行った。For comparison, carrier No. C6 was produced in the same manner except that lanthanum nitrate was not added at all when preparing the slurry. The same tests as in Example 1 were conducted for each of the above carriers.
その結果を第５表に示した。The results are shown in Table 5.
第５表
第５表から明らかなように２本発明による触媒担体は、
高温においても比較触媒担体よりα転移量が小さり、シ
かも高比表面積を保っており、優れた担体である。Table 5 As is clear from Table 5, the catalyst carrier according to the present invention is
Even at high temperatures, the amount of alpha transition is smaller than that of comparative catalyst carriers, and it maintains a high specific surface area, making it an excellent carrier.
実施例６
硝酸セリウムの水溶液を９表面積が１６０ ｍ”／ｇで
あるアルミナに、該アルミナに対し１モル％のセリウム
含有量となるような割合において、含浸させ。Example 6 Alumina having a surface area of 160 m''/g was impregnated with an aqueous solution of cerium nitrate in a proportion giving a cerium content of 1 mol % to the alumina.
更に実施例１と同様にして、アルミナにセリウムを含有
させた。Furthermore, in the same manner as in Example 1, cerium was added to alumina.
次に、硝酸ランタンの水溶液を用い、上記アルミナに対
し０．５モル％のランタン含有量となるような割合にて
、上記と同様にしてランタンを含有させた。 これによ
り、セリウムとランタンとが含有してなるγ−アルミナ
を調製した。更に該アルミナを８７０℃、空気中、３時
間にて焼成して安定化されたアルミナを調製した。そし
て実施例１と同様にして、平均粒径１０μｍの安定化ア
ルミナ粉末を調整した。Next, using an aqueous solution of lanthanum nitrate, lanthanum was incorporated in the same manner as above at a ratio such that the lanthanum content was 0.5 mol % with respect to the alumina. In this way, γ-alumina containing cerium and lanthanum was prepared. Further, the alumina was fired at 870° C. in air for 3 hours to prepare stabilized alumina. Then, in the same manner as in Example 1, stabilized alumina powder having an average particle size of 10 μm was prepared.
次に、該アルミナ４ｋｇと硝酸アルミニウム２４０ｇと
硝酸ランタン２８０ｇ （硝酸アルミニウムに対して１
．０モル倍）とを水と共にボールミリングすることによ
りウォッシュコートスラリーを生成させた。そして、実
施例１と同様のコーディエライトの一体性担体をスラリ
ー中に浸漬し、実施例１と同様にして、一体性担体上に
約５０μｍの安定化アルミナ層をコートした。この担体
をＮｌｌ０とする。Next, 4 kg of the alumina, 240 g of aluminum nitrate, and 280 g of lanthanum nitrate (1 kg for aluminum nitrate)
．． A washcoat slurry was produced by ball milling 0 mole times) with water. Then, a monolithic cordierite support similar to that in Example 1 was immersed in the slurry, and a stabilized alumina layer of about 50 μm was coated on the monolithic support in the same manner as in Example 1. This carrier is designated as Nll0.
比較のために、スラリー調整時、硝酸ランタンは全く添
加しない担体−７，並びに硝酸ランタンの代わりに炭酸
ランタン（Ｌ ａｘ（Ｇｏ） ｓ ・８ Ｈｚ Ｏ）
３８９ｇ （硝酸アルミニウムに対して１．０モル倍）
を使用した担体１ｌｌａＣ８とを製造した。For comparison, when preparing the slurry, carrier-7 was prepared in which no lanthanum nitrate was added, and lanthanum carbonate (L ax (Go) s 8 Hz O) was used instead of lanthanum nitrate.
389g (1.0 mole times that of aluminum nitrate)
A carrier 1llaC8 was manufactured using the following.
上記の各担体につき、実施例１と同様な試験を行第６表 第６表から明らかに１本発明による触媒担体は。For each of the above carriers, tests similar to those in Example 1 were conducted.Table 6 It is clear from Table 6 that the catalyst support according to the invention is:
高温においても比較触媒担体よりα転移量が小さく。Even at high temperatures, the amount of alpha transition is smaller than that of comparative catalyst carriers.
しかも高比面積を保っており、優れた担体である。Moreover, it maintains a high specific area and is an excellent carrier.
実施例７
硝酸ランタンの水溶液を実施例１と同様のアルミナに、
該アルミナに対し１．３モル％のランタン含有量となる
ような割合において、含浸させた。その後、実施例１と
同様にしてアルミナにランタンを含有させた。更に該ア
ルミナを１０００℃、空気中。Example 7 An aqueous solution of lanthanum nitrate was added to the same alumina as in Example 1.
The impregnation was carried out in such a proportion that the lanthanum content was 1.3 mol % based on the alumina. Thereafter, lanthanum was added to alumina in the same manner as in Example 1. Furthermore, the alumina was heated to 1000°C in air.
３時間にて焼成し、粉砕して平均粒径１０μｍの安定化
アルミナ粉末を調製した。It was fired for 3 hours and pulverized to prepare stabilized alumina powder with an average particle size of 10 μm.
次に、該アルミナ４Ｋｇと硝酸アルミニウム２４０ｇと
硝酸ランタン２８０ｇ （硝酸アルミニウムに対して１
．０モル倍）とを水及び酸化セリウム（０８０り１．１
５Ｋｇと共にボールミリングすることによりウォッシュ
コートスラリーを生成させた。Next, 4 kg of the alumina, 240 g of aluminum nitrate, and 280 g of lanthanum nitrate (1 kg for aluminum nitrate)
．． 0 mol) and water and cerium oxide (080 mol 1.1
A washcoat slurry was produced by ball milling with 5Kg.
そして、実施例１と同様のコーディエライトの一体性担
体を上記スラリー中に浸漬し、実施例１と同様にして上
記一体性担体上に約５０．ｃｒｍの安定化アルミナ層を
コートし、セリウムを０．３モル／１含有する本発明に
よる担体Ｎａ１ｌを製造した。Then, a monolithic cordierite support similar to that in Example 1 is immersed in the slurry, and the same procedure as in Example 1 is applied onto the monolithic support for about 50%. A support Na1l according to the invention was prepared, coated with a stabilized alumina layer of crm and containing 0.3 mol/1 cerium.
また、上記と同様にして、酸化セリウムに変えて炭酸セ
リウム（Ｇｅｔ（ＣＯｓ）ｚ Ｈ５Ｈｚ Ｏ） ３．
６８Ｋｇを添加し、担体Ｎｏ、１１と同様にして、セ
リウムを０．３モル／１含有する本発明にがかる担体Ｎ
ｏ、１２も製造した。Also, in the same manner as above, cerium carbonate (Get(COs)z H5Hz O) was used instead of cerium oxide.
A carrier N according to the present invention containing 0.3 mol/1 cerium was added in the same manner as carrier No. 11.
o, 12 were also produced.
比較のために、スラリー調製時、硝酸ランタンを全く添
加せず他は上記と同様にして、担体Ｎｏ、Ｃ９を製造し
た。上記の各担体について、実施例１と第７表
゛ 第７表から明らかなように１本発明による触媒担
体は高温においても比較触媒担体よりα転移量が小さり
、シかも高比表面積を保っており、優れた担体であるこ
とが分かる。For comparison, carrier No. C9 was produced in the same manner as above except that lanthanum nitrate was not added at all during slurry preparation. Regarding each of the above-mentioned supports, Example 1 and Table 7 As is clear from Table 7, the catalyst support according to the present invention has a smaller α-transfer amount than the comparative catalyst support even at high temperatures, and also maintains a high specific surface area. It can be seen that it is an excellent carrier.
実施例８
実施例７と同様にして調製した安定化アルミナ４Ｋｇと
硝酸（ＨＮ○ｓ）４０ｇと硝酸ランタン２８０ｇ（硝酸
に対して１．０モル倍）とを水と共にボールミリングす
ることによりウォッシュコートスラリーを生成させた。Example 8 A wash coat was prepared by ball milling 4 kg of stabilized alumina prepared in the same manner as in Example 7, 40 g of nitric acid (HN○s), and 280 g of lanthanum nitrate (1.0 times the mole of nitric acid) together with water. A slurry was generated.
そして実施例１と同様のコーディエライトの一体性担体
を上記スラリー中に浸漬し。Then, a monolithic cordierite support similar to that in Example 1 was immersed in the slurry.
実施例１と同様にして上記一体性担体上に約５０μｍの
安定化アルミナ層をコートした。この担体をＮ０１１３
とする。A stabilized alumina layer of approximately 50 μm was coated onto the monolithic support as in Example 1. This carrier is N0113
shall be.
比較のために、スラリー調製時、硝酸ランタンを全く添
加せず、他は上記と同様にして担体Ｎｏ、Ｃ１０を製造
した。上記の各担体について実施例１と同様な試験をお
こなった。その結果を第８表に示した。第８表において
、ｒＬ／Ｎモル倍」とは５ 「硝酸ランタン／硝酸」の
モル比率をしめす。For comparison, carrier No. C10 was produced in the same manner as above except that lanthanum nitrate was not added at all when preparing the slurry. The same tests as in Example 1 were conducted for each of the above carriers. The results are shown in Table 8. In Table 8, "rL/N mole times" indicates the molar ratio of "lanthanum nitrate/nitric acid".
第８表から明らかなように１本発明による触媒担体は高
温においても比較触媒担体よりα転移量が小さり、シか
も高比表面積を保っており、優れた担体であることが分
かる。As is clear from Table 8, the catalyst carrier according to the present invention has a smaller α-transfer amount than the comparative catalyst carrier even at high temperatures, and also maintains a high specific surface area, indicating that it is an excellent carrier.
実験例
実施例４の触媒担体Ｎ０９８と比較触媒担体Ｎｏ、Ｃ５
とに触媒成分を担持し、触媒活性を試験した。Experimental Example Catalyst carrier No. 098 of Example 4 and comparative catalyst carrier No. C5
A catalyst component was supported on the catalyst and the catalyst activity was tested.
所定濃度の硝酸セリウム（Ｃｅ （Ｎｏ）：＋ ）の
溶液に、上記担体を浸漬し、乾燥後６００℃で３時間、
空気中で焼成し、該担体１ａに対し酸化セリウム０．３
モルを担持した。次いで、これを所定濃度のジニトロジ
アンミン白金［Ｐｔ （ＮＨｓ）ｚ（ＮＯ□）２〕水
溶液に１時間浸漬し、引き上げて余分な水分を吹き払い
、２００℃で１時間乾燥した。更に所定濃度の塩化ロジ
ウムＣＲｈＣｌ３〕水溶液に１時間浸漬し、引き上げ、
余分な水分を吹き払い２００℃で乾燥した。このように
して、上記触媒担体１１に対してセリウムを４０ｇ、白
金を１．５ｇ、 ロジウムを０．３ｇ担持させた本発明
に係る触媒Ａと、比較例に係る触媒Ｂとを調整した。The above carrier was immersed in a solution of cerium nitrate (Ce(No):+) at a predetermined concentration, dried and then heated at 600°C for 3 hours.
Calcinate in air and add 0.3 cerium oxide to the carrier 1a.
It carried moles. Next, this was immersed in an aqueous solution of dinitrodiammine platinum [Pt(NHs)z(NO□)2] at a predetermined concentration for 1 hour, pulled out, excess water was blown off, and dried at 200°C for 1 hour. Furthermore, it was immersed in an aqueous solution of rhodium chloride CRhCl3 at a predetermined concentration for 1 hour, and then pulled out.
Excess water was blown off and dried at 200°C. In this way, catalyst A according to the present invention, in which 40 g of cerium, 1.5 g of platinum, and 0.3 g of rhodium were supported on the catalyst carrier 11, and catalyst B according to a comparative example were prepared.
上記２種の触媒Ａ及びＢの各々を、排気量２゜８１１の
エンジンの排気系に装着して２００時間の耐久試験を行
った。その際の触媒層の温度は約９５０℃であった。そ
の後、排気ガスの触媒層入口の温度を３００℃と３５０
℃の２通りに変えて各々の浄化率を測定した。この結果
を第９表に示した。Each of the above two types of catalysts A and B was installed in the exhaust system of an engine with a displacement of 2°811, and a 200 hour durability test was conducted. The temperature of the catalyst layer at that time was about 950°C. After that, the temperature at the entrance of the exhaust gas catalyst layer was adjusted to 300℃ and 350℃.
The purification rate was measured by changing the temperature in two ways. The results are shown in Table 9.
第９表
第９表からも明らかなように１本実施例により製造した
触媒Ａは、低温時２高温時の双方においても極めて高活
性であることがわかる。この原因は触媒担体の安定化ア
ルミナのコート層が変態しないためである。従って９本
発明に係る触媒担体を用いた触媒は、高温耐久性に優れ
たものであることが分かる。As is clear from Table 9, Catalyst A produced according to this example has extremely high activity both at low temperatures and at high temperatures. This is because the stabilized alumina coating layer of the catalyst carrier does not undergo transformation. Therefore, it can be seen that the catalyst using the catalyst carrier according to the present invention has excellent high-temperature durability.
Claims (3)
安定化アルミナ粉末、水溶性アルミニウム塩並びに酸の
一方又は双方と、水溶性希土類塩と水とを撹拌混合して
スラリーを形成し、該スラリーを、触媒担体基材表面に
付着させた後、乾燥、焼成して、前記触媒担体基材表面
に安定化アルミナ層を形成することを特徴とする触媒担
体の製造方法。(1) A slurry is formed by stirring and mixing one or both of a stabilized alumina powder, a water-soluble aluminum salt, and an acid containing one or more rare earths or alkaline earths, and the water-soluble rare earth salt and water. A method for producing a catalyst carrier, which comprises applying a slurry to the surface of a catalyst carrier base material, followed by drying and firing to form a stabilized alumina layer on the surface of the catalyst carrier base material.
化アルミニウム、塩基性アルミニウムであることを特徴
とする特許請求の範囲第１項記載の触媒担体の製造方法
。(2) The method for producing a catalyst carrier according to claim 1, wherein the water-soluble aluminum salt is aluminum nitrate, aluminum chloride, or basic aluminum.
であることを特徴とする特許請求の範囲第１項記載の触
媒担体の製造方法。(3) The method for producing a catalyst carrier according to claim 1, wherein the water-soluble rare earth salt is lanthanum nitrate or lanthanum chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5115087A JPS63218254A (en) | 1987-03-05 | 1987-03-05 | Production of catalyst carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5115087A JPS63218254A (en) | 1987-03-05 | 1987-03-05 | Production of catalyst carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63218254A true JPS63218254A (en) | 1988-09-12 |
Family
ID=12878786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5115087A Pending JPS63218254A (en) | 1987-03-05 | 1987-03-05 | Production of catalyst carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63218254A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036097A1 (en) * | 1999-11-16 | 2001-05-25 | Ibiden Co., Ltd. | Catalyst and method for preparation thereof |
| JP2003531716A (en) * | 2000-03-17 | 2003-10-28 | エナジー・インターナショナル・コーポレーション | Highly active Fischer-Tropsch synthesis using doped thermally stable catalyst supports |
| US6764672B2 (en) | 2001-04-03 | 2004-07-20 | Alcoa Inc. | Thermally stable alumina particulates |
| KR100482426B1 (en) * | 1999-12-22 | 2005-04-14 | 주식회사 포스코 | Preparation of gamma-alumina for heat -resist |
| US6939825B1 (en) | 1999-06-23 | 2005-09-06 | Ibiden Co., Ltd. | Carrier for catalyst and method for preparing the same |
| US7625529B2 (en) | 2000-09-29 | 2009-12-01 | Ibiden Co., Ltd. | Catalyst-carrying filter |
| JP2015100787A (en) * | 2013-11-28 | 2015-06-04 | マツダ株式会社 | Production method of catalyst for exhaust gas purification |
-
1987
- 1987-03-05 JP JP5115087A patent/JPS63218254A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6939825B1 (en) | 1999-06-23 | 2005-09-06 | Ibiden Co., Ltd. | Carrier for catalyst and method for preparing the same |
| US7119046B2 (en) | 1999-06-23 | 2006-10-10 | Ibiden Co., Ltd. | Catalyst carrier and method of producing same |
| US7196037B2 (en) | 1999-06-23 | 2007-03-27 | Ibiden Co., Ltd. | Catalyst carrier and method of producing same |
| WO2001036097A1 (en) * | 1999-11-16 | 2001-05-25 | Ibiden Co., Ltd. | Catalyst and method for preparation thereof |
| US7250385B1 (en) | 1999-11-16 | 2007-07-31 | Ibiden Co., Ltd. | Catalyst and method for preparation thereof |
| KR100482426B1 (en) * | 1999-12-22 | 2005-04-14 | 주식회사 포스코 | Preparation of gamma-alumina for heat -resist |
| JP2003531716A (en) * | 2000-03-17 | 2003-10-28 | エナジー・インターナショナル・コーポレーション | Highly active Fischer-Tropsch synthesis using doped thermally stable catalyst supports |
| JP4933014B2 (en) * | 2000-03-17 | 2012-05-16 | サソル・テクノロジー（ユーケイ）リミテッド | Highly active Fischer-Tropsch synthesis using doped and thermally stable catalyst supports |
| US7625529B2 (en) | 2000-09-29 | 2009-12-01 | Ibiden Co., Ltd. | Catalyst-carrying filter |
| US6764672B2 (en) | 2001-04-03 | 2004-07-20 | Alcoa Inc. | Thermally stable alumina particulates |
| JP2015100787A (en) * | 2013-11-28 | 2015-06-04 | マツダ株式会社 | Production method of catalyst for exhaust gas purification |
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