JP2851459B2 - Metal-based catalyst and method for producing the same - Google Patents
Metal-based catalyst and method for producing the sameInfo
- Publication number
- JP2851459B2 JP2851459B2 JP3204127A JP20412791A JP2851459B2 JP 2851459 B2 JP2851459 B2 JP 2851459B2 JP 3204127 A JP3204127 A JP 3204127A JP 20412791 A JP20412791 A JP 20412791A JP 2851459 B2 JP2851459 B2 JP 2851459B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- catalyst
- metal
- aluminum
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 72
- 229910052751 metal Inorganic materials 0.000 title claims description 49
- 239000002184 metal Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 53
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052703 rhodium Inorganic materials 0.000 claims description 24
- 239000010948 rhodium Substances 0.000 claims description 24
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 10
- 238000007772 electroless plating Methods 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 4
- 229940075630 samarium oxide Drugs 0.000 claims description 4
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 239000007789 gas Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- -1 and specifically Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 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 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
- 238000010981 drying operation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は一般的な酸化触媒、酸化
還元触媒のほか、アルコールの分解触媒、有機化合物の
合成触媒、各種燃料の燃焼排ガスの処理用触媒、有機溶
剤排ガス処理用触媒等に適用することのできる金属基触
媒及びその製造方法に関する。The present invention relates to a general oxidation catalyst, a redox catalyst, a catalyst for decomposing alcohol, a synthesis catalyst for organic compounds, a catalyst for treating combustion exhaust gas of various fuels, a catalyst for treating organic solvent exhaust gas, etc. The present invention relates to a metal-based catalyst that can be applied to a catalyst and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、排ガス処理用触媒として、一般に
はアルミナ、シリカ・アルミナ、コージライト、ムライ
ト、ジルコニア等の無機材料を基材としたペレットタイ
プ、多孔質マット及びハニカムタイプ等の担体に白金、
パラジウム、ロジウム、ルテニウム等の触媒活性成分を
担持したものが使用されてきた。また、耐熱性シリカ繊
維を基材としたものや、ＳＵＳ材等の金属薄板を基材と
したものも使用されてきた。2. Description of the Related Art Conventionally, as a catalyst for exhaust gas treatment, platinum, a carrier such as a pellet type, a porous mat and a honeycomb type based on an inorganic material such as alumina, silica / alumina, cordierite, mullite, and zirconia are generally used.
Those supporting a catalytically active component such as palladium, rhodium and ruthenium have been used. Further, those using a heat-resistant silica fiber as a base material and those using a thin metal plate such as a SUS material as a base material have been used.
【０００３】図２は数１０〜数１００μｍ厚さの金属薄
板を基材としたハニカム状触媒の断面図であり、薄板１
２を波型に成形し、平板１１と組み合わせて螺旋状に巻
き付けたもので、薄板表面に例えばγ−アルミナをウォ
ッシュ・コートし、その上に上記の触媒成分を担持した
ものである。FIG. 2 is a cross-sectional view of a honeycomb catalyst based on a thin metal plate having a thickness of several tens to several hundreds μm.
2 is formed into a corrugated shape and spirally wound in combination with the flat plate 11. The thin plate surface is wash-coated with, for example, γ-alumina, and the above catalyst component is carried thereon.
【０００４】[0004]
【発明が解決しようとする課題】上記のハニカム状触媒
は、図３に示すように、基材表面にウォッシュ・コート
されているため、ハニカムの目の各コーナに特に厚く触
媒層１３がコーティングされ（数１０〜数１００μｍ厚
さ）、触媒の付着が不均一であるばかりでなく、ハニカ
ムの開孔率が低下して排ガスが流れる際の通気抵抗を大
きくする傾向がある。そして、触媒を多量に付着するた
めコスト高になるという問題もある。As shown in FIG. 3, the above-mentioned honeycomb catalyst is wash-coated on the surface of the substrate, so that the catalyst layer 13 is particularly thickly coated on each corner of the honeycomb eyes. (Thickness of several tens to several hundreds of μm), not only the adhesion of the catalyst is non-uniform, but also the opening ratio of the honeycomb is reduced, and the ventilation resistance when exhaust gas flows tends to be increased. In addition, there is also a problem that the cost increases because a large amount of the catalyst is attached.
【０００５】そこで、本発明者らは上記の欠点を解消
し、金属薄板上に薄く、かつ、均一に触媒を担持するこ
とができ、通気抵抗の小さなハニカムタイプの触媒に適
した金属基触媒を提供するため、これまでに種々の提案
を行なってきた。（特願平０２−２４２８０８号、同平
０２−２３３３６３号及び同平０２−２４１１９７号）Therefore, the present inventors have solved the above-mentioned drawbacks and have developed a metal-based catalyst suitable for a honeycomb type catalyst having a small airflow resistance, which can support the catalyst thinly and uniformly on a thin metal plate. Various proposals have been made so far to provide. (Japanese Patent Application Nos. 02-242808, 02-233363 and 02-241197)
【０００６】ところが実際上の使用条件下では、より一
層の耐熱性や耐久性が強く要求され、長期間に亘って安
定した性能を発揮することができる触媒が求められてい
るのが現状である。However, under actual conditions of use, further heat resistance and durability are strongly required, and at present, there is a demand for a catalyst that can exhibit stable performance over a long period of time. .
【０００７】本発明は上記技術水準に鑑み、上記要望に
応じ、通気抵抗が小さく、また耐熱及び耐久性に優れた
ハニカムタイプの触媒及びその製造方法を提供しようと
するものである。The present invention has been made in view of the above technical level, and has as its object to provide a honeycomb-type catalyst having a small airflow resistance, excellent heat resistance and excellent durability, and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明は、 （１）アルミウニムを含む金属薄板を、空気中で８７
０〜９７０℃で加熱するか、空気中で１０２０〜１２
００℃で加熱するか、又は空気中で８７０〜９７０℃
で加熱した後、さらに空気中で１０２０〜１２００℃で
加熱することによって表面に針状または球状酸化アルミ
ニウムを析出させてなるアルミニウムを含む金属薄板表
面に、先ず酸化セリウム、酸化アルミニウム、酸化バリ
ウム、酸化ストロンチウム、酸化ジルコニウム、酸化ラ
ンタン及び酸化サマリウムよりなる群から選ばれた１種
または２種以上の助触媒が担持され、その上に白金、ロ
ジウム及びパラジウムよりなる群から選ばれた２種以上
の触媒を層状に担持されてなることを特徴とする金属基
触媒。According to the present invention, there is provided (1) a method of forming a thin metal sheet containing aluminum umni in an air atmosphere.
Heat at 0-970 ° C. or in air at 1020-12
Heat at 00 ° C or 870-970 ° C in air
After heating at 1024 to 1200 ° C. in the air, a cerium oxide, aluminum oxide, barium oxide, oxidized One or more cocatalysts selected from the group consisting of strontium, zirconium oxide, lanthanum oxide and samarium oxide are supported, and two or more catalysts selected from the group consisting of platinum, rhodium and palladium are supported thereon Is supported in a layered form.
【０００９】（２）上記１記載の金属基触媒の表面に、
さらに先ず上記１記載の助触媒、次に上記１記載の層状
触媒を担持されてなることを特徴とする金属基触媒。(2) On the surface of the metal-based catalyst described in (1),
Further, a metal-based catalyst comprising the cocatalyst described in the above item 1 and the layered catalyst described in the above item 1 supported thereon.
【００１０】（３）助触媒が構成元素を含有する水溶液
を塗布、焼成することによって形成され、触媒が構成元
素を含有する水溶液より無電解めっきにより形成される
ことを特徴とする上記１または２記載の金属基触媒の製
造方法。である。(3) The co-catalyst is formed by applying and baking an aqueous solution containing the constituent elements, and the catalyst is formed by electroless plating from the aqueous solution containing the constituent elements. A method for producing the metal-based catalyst according to the above. It is.
【００１１】[0011]
【作用】本発明の金属基触媒の製造過程を先ず図１によ
って説明し、次いで作用につき説明する。図１中、Ａは
白金、ロジウム、パラジウム等の出発原料であり、これ
ら出発原料は塩素を含有しない水溶性塩が好ましく、具
体的には硝酸塩、ジニトロジアミン塩等を使用するのが
好ましい。Ｂはナトリウム、カリウム、ホウ素、イオ
ウ、燐等の元素を含まない還元剤であり、具体的にはヒ
ドラジン、ホルムアルデヒド等が好適である。Ｃはアル
ミニウムを含有するステンレス等の金属薄板である。The production process of the metal-based catalyst of the present invention will be described first with reference to FIG. 1, and then the operation will be described. In FIG. 1, A is a starting material such as platinum, rhodium, or palladium, and the starting material is preferably a chlorine-free water-soluble salt, and specifically, a nitrate, a dinitrodiamine salt, or the like is preferably used. B is a reducing agent that does not contain elements such as sodium, potassium, boron, sulfur, and phosphorus, and specifically, hydrazine, formaldehyde, and the like are preferable. C is a thin metal plate such as stainless steel containing aluminum.
【００１２】白金、ロジウム、パラジウム等の出発原料
Ａはイオン交換水に溶解して原料還元剤調整槽１に送ら
れ、還元剤Ｂを加えて白金、ロジウム、パラジウム等の
微粒子化を図りメッキ槽２に送る。A starting material A such as platinum, rhodium, palladium or the like is dissolved in ion-exchanged water and sent to a raw material reducing agent adjusting tank 1, where a reducing agent B is added to make fine particles of platinum, rhodium, palladium or the like to form fine particles. Send to 2.
【００１３】触媒担体となる金属薄板Ｃは空気雰囲気中
の加熱処理工程３で、８７０〜９７０℃での加熱処
理、１０２０〜１２００℃での加熱処理または８７
０〜９７０℃で加熱した後さらに空気中で１０２０〜１
２００℃での加熱処理される。The metal sheet C serving as the catalyst carrier is subjected to a heat treatment at 870 to 970 ° C., a heat treatment at 102 to 1200 ° C.
After heating at 0 to 970 ° C, it is further heated to 1020 to 1 in air.
Heat treatment at 200 ° C.
【００１４】次に加熱して酸化アルミニウム層を形成し
た後、酸化物塗布工程４でセリウム、アルミニウム、バ
リウム、ストロンチウム、ジルコニウム、ランタン、サ
マリウム等の水溶性塩をイオン交換水に溶解し、必要に
応じてアルミニウムヒドロゾルを加えた水溶液中に浸漬
して塗布した後、焼成して金属薄板表面に上記元素の酸
化物を塗布する。Next, after heating to form an aluminum oxide layer, a water-soluble salt such as cerium, aluminum, barium, strontium, zirconium, lanthanum, and samarium is dissolved in ion-exchanged water in an oxide coating step 4, and Accordingly, after immersion in an aqueous solution to which an aluminum hydrosol is added and application, calcination is performed to apply an oxide of the above element to the surface of the metal sheet.
【００１５】酸化物を塗布された金属薄板をメッキ槽２
に浸漬して無電解メッキ法で触媒成分をメッキし、乾燥
工程５及び焼成工程６を経て金属薄板上に触媒層を形成
する。The metal sheet coated with the oxide is plated in a plating tank 2
And a catalyst component is plated by an electroless plating method, and a drying step 5 and a firing step 6 are performed to form a catalyst layer on the metal thin plate.
【００１６】以上の工程によって、本発明の金属基触媒
が得られるが更に上記工程によって得られた金属基触媒
上に、上記セリウム、アルミニウム、バリウム、ストロ
ンチウム、ジルコニウム、ランタン、サマリウム等の水
溶性塩をイオン交換水に溶解し、必要に応じてアルミニ
ウムヒドロゾルを加えた水溶液中に再度浸漬して塗布し
た後、再び白金、ロジウム及びパラジウムの各元素を各
元素ごとにメッキ操作と乾燥、焼付けを行なって各元素
を層状になるように担持してもよい。According to the above steps, the metal-based catalyst of the present invention can be obtained. Further, a water-soluble salt such as cerium, aluminum, barium, strontium, zirconium, lanthanum, samarium, etc. Is dissolved in ion-exchanged water, and if necessary, dipped again in an aqueous solution to which aluminum hydrosol is added, followed by application. Then, the respective elements of platinum, rhodium and palladium are again subjected to a plating operation, drying and baking for each element. Each element may be loaded so as to form a layer.
【００１７】触媒層を形成するとき、白金、ロジウム及
びパラジウムの各元素は一元素ごとに無電解メッキ操作
と乾燥、焼付けを行なって少なくとも２種の元素が層状
になるように担持するのがよい。When forming the catalyst layer, it is preferable that each of platinum, rhodium and palladium be subjected to an electroless plating operation, drying and baking for each element so that at least two kinds of elements are layered. .
【００１８】無電解メッキ操作は各元素ごとに単独メッ
キし、各元素を層状に担持する。層の構成は酸化アルミ
ニウム上の助触媒層から数えて、白金→ロジウム→白金
→ロジウム（計４層以上が好ましく、最上層はロジウム
元素であることが好ましい）に層状とすると効果的であ
る。In the electroless plating operation, each element is plated independently and each element is supported in a layer. It is effective to form a layer of platinum → rhodium → platin → rhodium (preferably at least 4 layers, and the uppermost layer is preferably a rhodium element), counting from the promoter layer on aluminum oxide.
【００１９】メッキ槽を出た金属薄板は乾燥工程５、焼
成工程６を経て仕上げとするが、必要に応じて、焼成後
に活性化処理を行うこともできる。乾燥操作は１０５℃
で０．５〜１時間あれば十分であり、焼成操作は５００
〜７００℃で０．５〜３時間を要する。焼成後の活性化
処理は水素雰囲気で４００〜５００℃で５分〜１時間行
うのがよい。The metal sheet that has exited the plating tank is finished through a drying step 5 and a firing step 6, but may be activated after firing, if necessary. Drying operation is 105 ° C
0.5 to 1 hour is sufficient, and the firing operation is 500 hours.
It takes 0.5 to 3 hours at ~ 700 ° C. The activation treatment after firing is preferably performed in a hydrogen atmosphere at 400 to 500 ° C. for 5 minutes to 1 hour.
【００２０】無電解メッキに際し、白金、ロジウム及び
パラジウムの濃度は０．１〜５００ｍｍｏｌ／ｌの範
囲、特に１０〜１５０ｍｍｏｌ／ｌの範囲が好適であ
る。In the electroless plating, the concentration of platinum, rhodium and palladium is preferably in the range of 0.1 to 500 mmol / l, particularly preferably in the range of 10 to 150 mmol / l.
【００２１】原料還元剤調整槽１中の還元剤濃度は０．
００１〜１０ｖｏｌ／ｖｏｌ％の範囲、特に０．００２
〜１ｖｏｌ／ｖｏｌ％の範囲が好適である。該調整槽１
における液の攪拌時間は１０〜２０分間で十分である。
調整後は速やかにメッキ槽に移して使用するのがよい。The concentration of the reducing agent in the raw material reducing agent adjusting tank 1 is 0.1.
001 to 10 vol / vol%, particularly 0.002
A range of １1 vol / vol% is preferred. Adjustment tank 1
In the above, the stirring time of the liquid is sufficient for 10 to 20 minutes.
After the adjustment, it is preferable to immediately transfer to the plating tank for use.
【００２２】金属薄板Ｃはアルミニウムを１〜８ｗｔ％
含有するフェライト系ステンレス鋼で、厚さが２５〜７
５μｍのものが好適である。The metal sheet C contains 1 to 8% by weight of aluminum.
Ferrite stainless steel containing 25 to 7 thickness
Those having a size of 5 μm are preferred.
【００２３】金属薄板Ｃの加熱処理工程の条件は下記の
いずれかの条件を採用すべきである。 ８７０〜９７０℃で空気雰囲気の加熱炉で１〜３０
時間、好ましくは５〜２０時間静置する。この加熱処理
により金属薄板表面に針状酸化アルミニウム層が形成さ
れ、比表面積の大きな触媒担体表面として有効に働く。Any of the following conditions should be adopted as the conditions for the heat treatment step of the metal sheet C. 1 to 30 in a heating furnace at 870 to 970 ° C. in an air atmosphere
Let stand for a time, preferably 5 to 20 hours. By this heat treatment, an acicular aluminum oxide layer is formed on the surface of the thin metal plate, which effectively functions as a catalyst support surface having a large specific surface area.
【００２４】 １０２０〜１２００℃で空気雰囲気の
加熱炉で１〜５時間静置する。この加熱処理により金属
薄板表面に球状酸化アルミニウム層が形成され、耐酸化
性に優れた触媒担体表面として有効に働く。It is left still for 1 to 5 hours in a heating furnace in an air atmosphere at 1,200 to 1,200 ° C. By this heat treatment, a spherical aluminum oxide layer is formed on the surface of the thin metal plate, and effectively works as a surface of the catalyst carrier having excellent oxidation resistance.
【００２５】 ８７０〜９７０℃で空気雰囲気の加熱
炉で１〜３０時間、好ましくは５〜２０時間静置して金
属薄板表面に針状酸化アルミニウム層を形成し、さら
に、１０２０〜１２００℃で空気雰囲気中に０．５〜３
０時間、好ましくは０．５〜５時間静置して、前記の針
状酸化アルミニウム層の下に堅牢な酸化アルミニウム層
を形成する。この加熱処理によりステンレス鋼等の金属
薄板の耐熱性を向上させるとともに、針状酸化アルミニ
ウム層を金属薄板に強く固定することができる。The needle-shaped aluminum oxide layer is formed on the surface of the thin metal plate by leaving it at 870 to 970 ° C. in a heating furnace in an air atmosphere for 1 to 30 hours, preferably 5 to 20 hours. 0.5-3 in the atmosphere
After standing for 0 hour, preferably 0.5 to 5 hours, a robust aluminum oxide layer is formed under the acicular aluminum oxide layer. By this heat treatment, the heat resistance of a thin metal plate such as stainless steel can be improved, and the acicular aluminum oxide layer can be strongly fixed to the thin metal plate.
【００２６】必要に応じてバインダとしてアルミニウム
ヒドロゾルを添加した酸化セリウム、酸化アルミニウ
ム、酸化バリウム、酸化ストロンチウム、酸化ジルコニ
ウム、酸化ランタン及び酸化サマリウムの群から選ばれ
た１種又は２種以上の酸化物を塗布する工程では、塩素
などのハロゲン元素を含まない水溶性の塩の濃度を０．
１〜２０００ｍｍｏｌ／ｌの範囲、好ましくは、０．５
〜１０００ｍｍｏｌ／ｌの範囲に調整した溶液中に、上
記加熱処理工程を経た金属薄板を浸漬して該溶液を塗布
し、次いで、乾燥し、焼成して上記酸化物を付着させ
る。One or more oxides selected from the group consisting of cerium oxide, aluminum oxide, barium oxide, strontium oxide, zirconium oxide, lanthanum oxide and samarium oxide, to which aluminum hydrosol is added as a binder if necessary. In the step of applying a water-soluble salt, the concentration of a water-soluble salt not containing a halogen element such as chlorine is adjusted to 0.1.
In the range of 1 to 2000 mmol / l, preferably 0.5
The thin metal plate subjected to the heat treatment step is immersed in a solution adjusted to a range of ~ 1000 mmol / l to apply the solution, and then dried and fired to adhere the oxide.
【００２７】無電解メッキ液の各濃度は０．１〜５００
ｍｍｏｌ／ｌの範囲、好ましくは、１０〜１５０ｍｍｏ
ｌ／ｌの範囲に調整する。メッキ時間は１〜５分であ
り、３〜１分でも十分である。このようにして得たメッ
キ量は０．０１〜２ｇ／ｍ2 （金属表面積）の範囲にあ
る。Each concentration of the electroless plating solution is 0.1 to 500.
mmol / l, preferably 10-150 mmol
Adjust to the range of l / l. The plating time is 1 to 5 minutes, and 3 to 1 minute is sufficient. The plating amount thus obtained is in the range of 0.01 to 2 g / m 2 (metal surface area).
【００２８】本発明の金属基触媒は、金属薄板上に析
出した酸化アルミニウム層により、大きな比表面積を有
する触媒担体表面を提供することができ、該針状酸化
アルミニウム層上に塗布された酸化セリウム、酸化アル
ミニウム、酸化バリウム、酸化ストロンチウム、酸化ジ
ルコニウム、酸化ランタン等の酸化物は、触媒の耐熱
性、耐久性を著しく向上させるとともに、白金、ロジウ
ム、パラジウム等の触媒機能をも著しく向上させる。ま
た、白金、ロジウム、パラジウム等の触媒元素の水溶
液中に還元剤を添加して、触媒元素の極微粒子を金属薄
板表面にメッキするので、強固な結合を確保することが
できる。更に、白金、ロジウム、パラジウム等の触媒
元素を層状に担持しているので、同一元素間の接触頻度
が少なくなり、シンタリング（半融）現象が防止できる
ので耐熱性が向上し、更に層状に担持された触媒元素
の間に助触媒層を介在させることにより、活性及び耐熱
・耐久性を増大させることができ、無電解メッキ液中
に触媒活性を低下させる物質の混入を防止することがで
きるので、触媒機能の低下を回避することができる。The metal-based catalyst of the present invention can provide a catalyst support surface having a large specific surface area by the aluminum oxide layer deposited on the metal sheet, and the cerium oxide coated on the acicular aluminum oxide layer Oxides such as aluminum oxide, barium oxide, strontium oxide, zirconium oxide and lanthanum oxide remarkably improve the heat resistance and durability of the catalyst, and also remarkably improve the catalytic function of platinum, rhodium, palladium and the like. Further, since a reducing agent is added to an aqueous solution of a catalytic element such as platinum, rhodium, palladium or the like, and ultrafine particles of the catalytic element are plated on the surface of the metal sheet, a strong bond can be secured. Furthermore, since catalytic elements such as platinum, rhodium, and palladium are supported in a layer, the frequency of contact between the same elements is reduced, and the sintering (semi-fusing) phenomenon can be prevented, so that the heat resistance is improved and the layer is formed. By interposing a co-catalyst layer between the supported catalyst elements, the activity, heat resistance and durability can be increased, and the incorporation of a substance that reduces the catalytic activity into the electroless plating solution can be prevented. Therefore, a decrease in the catalytic function can be avoided.
【００２９】[0029]
（実施例１）５ｗｔ％アルミニウムを含む厚さ５０μｍ
のステンレス鋼薄板を歯車加工によって波型に成形し、
平板と併せてコルゲート化して６０セル／ｃｍ2 のハニ
カム状とした。これを有機溶剤でよく洗浄して脱脂した
後、空気中で９６０℃で１６時間加熱処理し、次いで、
１０５０℃で１時間加熱処理したのち冷却した。(Example 1) 50 μm thickness containing 5 wt% aluminum
Of stainless steel sheet into a corrugated shape by gear processing,
It was corrugated together with the flat plate to form a honeycomb shape of 60 cells / cm 2 . This was thoroughly washed with an organic solvent and degreased, and then heat-treated at 960 ° C. for 16 hours in the air.
After a heat treatment at 1050 ° C. for 1 hour, the mixture was cooled.
【００３０】次に、アルミニウムヒドロゾルをバインダ
として硝酸セリウム１ｍｏｌ／ｌ、水酸化アルミニウム
０．１ｍｏｌ／ｌ（アルミニウムヒドロゾルから由来す
るものも含む）、及び硝酸バリウム０．００５ｍｏｌ／
ｌを含む水溶液中に、上記加熱処理後の金属薄板を２分
間浸漬してから取り出して１０５℃で３０分間乾燥し、
さらに、７００℃で１時間空気中で加熱して酸化物を塗
布した。Next, 1 mol / l of cerium nitrate, 0.1 mol / l of aluminum hydroxide (including those derived from aluminum hydrosol), and 0.005 mol / l of barium nitrate, using aluminum hydrosol as a binder.
The metal sheet after the heat treatment is immersed for 2 minutes in an aqueous solution containing
Further, the oxide was applied by heating at 700 ° C. for 1 hour in the air.
【００３１】この酸化物を塗布した金属薄板をジニトロ
ジアミン白金０．０２５ｍｏｌ／ｌ、ヒドラジン０．０
２ｖｏｌ／ｖｏｌ％含む液中に３分浸漬させた後、これ
を取出して１０５℃で３０分間乾燥し、６００℃で３０
分間焼付けした。The metal sheet coated with this oxide was treated with 0.025 mol / l of dinitrodiamine platinum and 0.025 mol / l of hydrazine.
After being immersed in a liquid containing 2 vol / vol% for 3 minutes, this was taken out, dried at 105 ° C. for 30 minutes, and dried at 600 ° C. for 30 minutes.
Bake for a minute.
【００３２】次に、硝酸ロジウム０．００５ｍｏｌ／
ｌ、ヒドラジン０．０２ｖｏｌ／ｖｏｌ％添加した液中
に３分間浸漬させた後、これを取り出して１０５℃で３
０分間乾燥し、６００℃で３０分間焼付けした。次に、
再び上記白金液に浸漬し、同様にして乾燥、焼付けをし
た後、同様にして再び上記ロジウム液に浸漬し、同様に
して乾燥、焼成した。Next, rhodium nitrate 0.005 mol /
l, immersed in a solution containing 0.02 vol / vol% hydrazine for 3 minutes, taken out, and then taken out at 105 ° C. for 3 minutes.
Dried for 0 minutes and baked at 600 ° C. for 30 minutes. next,
After being immersed again in the above-mentioned platinum solution, dried and baked in the same manner, it was immersed again in the above-mentioned rhodium solution, dried and baked in the same manner.
【００３３】さらに、２％水素雰囲気（窒素ベース）中
で４５０℃で１５分間活性化処理して、白金及びロジウ
ムが交互に積層した厚さ２〜３μｍ以下の薄い触媒層を
仕上げた。得られた触媒断面の開孔率は９０％以上であ
った。Further, an activation treatment was performed at 450 ° C. for 15 minutes in a 2% hydrogen atmosphere (nitrogen base) to obtain a thin catalyst layer having a thickness of 2 to 3 μm or less in which platinum and rhodium were alternately laminated. The porosity of the obtained catalyst cross section was 90% or more.
【００３４】この触媒を用いて、ＳＶ＝５００００／ｈ
ｒの条件下で、ＣＯ：２０００ｐｐｍ、プロパン：５０
００ｐｐｍ、ＮＯ：１０００ｐｐｍ、Ｏ2 ：２．６％を
含む燃焼排ガスを３５０℃で通したところ、ＣＯ、プロ
パン及びＮＯの浄化率はいずれも９５％以上であった。Using this catalyst, SV = 50,000 / h
Under the conditions of r, CO: 2000 ppm, propane: 50
When a combustion exhaust gas containing 00 ppm, NO: 1000 ppm, and O 2 : 2.6% was passed at 350 ° C., the purification rates of CO, propane, and NO were all 95% or more.
【００３５】（実施例２）５ｗｔ％アルミニウムを含む
厚さ５０μｍのステンレス鋼薄板を歯車加工によって波
型に成形し、平板と併せてコルゲート化して６０セル／
ｃｍ2 のハニカム状とした。これを有機溶剤でよく洗浄
して脱脂した後、空気中で１０５０℃で１時間加熱処理
して冷却した。Example 2 A 50 μm-thick stainless steel sheet containing 5 wt% aluminum was formed into a corrugated shape by gear processing, and formed into a corrugated shape together with a flat plate to form 60 cells / sheet.
cm 2 honeycomb shape. This was thoroughly washed with an organic solvent and degreased, and then heat-treated at 1050 ° C. for 1 hour in air to cool.
【００３６】次いで、アルミニウムヒドロゾルをバイン
ダとして硝酸セリウム１ｍｏｌ／ｌ、水酸化アルミニウ
ム０．１ｍｏｌ／ｌ（アルミニウムヒドロゾルから由来
するものも含む）及び硝酸バリウム０．００５ｍｏｌ／
ｌを含む水溶液中に、上記加熱処理後の金属薄板を２分
間浸漬してから取り出して１０５℃で３０分間乾燥し、
さらに、７００℃で１時間空気中で加熱して酸化物を形
成した。Next, using aluminum hydrosol as a binder, 1 mol / l of cerium nitrate, 0.1 mol / l of aluminum hydroxide (including those derived from aluminum hydrosol) and 0.005 mol / l of barium nitrate
The metal sheet after the heat treatment is immersed for 2 minutes in an aqueous solution containing
Further, heating was performed in air at 700 ° C. for 1 hour to form an oxide.
【００３７】この酸化物を塗布した金属薄板をジニトロ
ジアミン白金０．０２５ｍｏｌ／ｌ、ヒドラジン０．０
２ｖｏｌ／ｖｏｌ％含む液中に３分浸漬させた後、これ
を取出して１０５℃で３０分間乾燥し、６００℃で３０
分間焼付けした。次に、硝酸ロジウム０．００５ｍｏｌ
／ｌ、ヒドラジン０．０２ｖｏｌ／ｖｏｌ％添加した液
中に３分間浸漬させた後、これを取り出して１０５℃で
３０分間乾燥し、６００℃で３０分間焼付けした。次
に、再び上記白金液に浸漬し、同様にして乾燥、焼付け
をした後、同様にして再び上記ロジウム液に浸漬し、同
様にして乾燥、焼成した。The metal sheet coated with this oxide was treated with 0.025 mol / l of dinitrodiamine platinum and 0.025 mol / l of hydrazine.
After being immersed in a liquid containing 2 vol / vol% for 3 minutes, this was taken out, dried at 105 ° C. for 30 minutes, and dried at 600 ° C. for 30 minutes.
Bake for a minute. Next, rhodium nitrate 0.005mol
/ L, immersed in a solution containing 0.02 vol / vol% hydrazine for 3 minutes, taken out, dried at 105 ° C for 30 minutes, and baked at 600 ° C for 30 minutes. Next, it was immersed again in the above-mentioned platinum solution, dried and baked in the same manner, then immersed again in the above-mentioned rhodium solution, dried and baked in the same manner.
【００３８】さらに、２％水素雰囲気（窒素ベース）中
で４５０℃で１５分間活性化処理して、白金及びロジウ
ムが交互に積層した厚さ２〜３μｍ以下の薄い触媒層を
仕上げた。得られた触媒断面の開孔率は９０％以上であ
った。Further, an activation treatment was performed at 450 ° C. for 15 minutes in a 2% hydrogen atmosphere (nitrogen base) to complete a thin catalyst layer having a thickness of 2 to 3 μm or less in which platinum and rhodium were alternately laminated. The porosity of the obtained catalyst cross section was 90% or more.
【００３９】この触媒を用いて、ＳＶ＝５００００／ｈ
ｒの条件下で、ＣＯ：２０００ｐｐｍ、プロパン：５０
００ｐｐｍ、ＮＯ：１０００ｐｐｍ、Ｏ2 ：２．６％を
含む燃焼排ガスを３５０℃で通したところ、ＣＯ、プロ
パン及びＮＯの浄化率はいずれも９５％以上であった。Using this catalyst, SV = 50,000 / h
Under the conditions of r, CO: 2000 ppm, propane: 50
When a combustion exhaust gas containing 00 ppm, NO: 1000 ppm, and O 2 : 2.6% was passed at 350 ° C., the purification rates of CO, propane, and NO were all 95% or more.
【００４０】（実施例３）５ｗｔ％アルミニウムを含む
厚さ５０μｍのステンレス鋼薄板を歯車加工によって波
型に成形し、平板と併せてコルゲート化して６０セル／
ｃｍ2 のハニカム状とした。これを有機溶剤でよく洗浄
して脱脂した後、空気中で９６０℃で１６時間加熱処理
して冷却した。Example 3 A 50 μm-thick stainless steel thin plate containing 5 wt% aluminum was formed into a corrugated shape by gear processing, and formed into a corrugated shape together with a flat plate to form 60 cells / sheet.
cm 2 honeycomb shape. This was thoroughly washed with an organic solvent and degreased, and then heated in air at 960 ° C. for 16 hours and cooled.
【００４１】次いで、アルミニウムヒドロゾルをバイン
ダとして硝酸セリウム１ｍｏｌ／ｌ、水酸化アルミニウ
ム０．１ｍｏｌ／ｌ（アルミニウムヒドロゾルから由来
するものも含む）及び硝酸バリウム０．００５ｍｏｌ／
ｌを含む水溶液中に、上記加熱処理後の金属薄板を２分
間浸漬してから取り出して１０５℃で３０分間乾燥し、
さらに、７００℃で１時間空気中で加熱して酸化物を形
成した。Then, using aluminum hydrosol as a binder, cerium nitrate 1 mol / l, aluminum hydroxide 0.1 mol / l (including those derived from aluminum hydrosol) and barium nitrate 0.005 mol / l
The metal sheet after the heat treatment is immersed for 2 minutes in an aqueous solution containing
Further, heating was performed in air at 700 ° C. for 1 hour to form an oxide.
【００４２】この酸化物を塗布した金属薄板をジニトロ
ジアミン白金０．０２５ｍｏｌ／ｌ、ヒドラジン０．０
２ｖｏｌ／ｖｏｌ％含む液中に３分浸漬させた後、これ
を取出して１０５℃で３０分間乾燥し、６００℃で３０
分間焼付けした。次に、硝酸ロジウム０．００５ｍｏｌ
／ｌ、ヒドラジン０．０２ｖｏｌ／ｖｏｌ％添加した液
中に３分間浸漬させた後、これを取り出して１０５℃で
３０分間乾燥し、６００℃で３０分間焼付けした。次
に、再び上記白金液に浸漬し、同様にして乾燥、焼付け
をした後、同様にして再び上記ロジウム液に浸漬し、同
様にして乾燥、焼成した。A metal sheet coated with this oxide was treated with 0.025 mol / l of dinitrodiamine platinum and 0.025 mol / l of hydrazine.
After being immersed in a liquid containing 2 vol / vol% for 3 minutes, this was taken out, dried at 105 ° C. for 30 minutes, and dried at 600 ° C. for 30 minutes.
Bake for a minute. Next, rhodium nitrate 0.005mol
/ L, immersed in a solution containing 0.02 vol / vol% hydrazine for 3 minutes, taken out, dried at 105 ° C for 30 minutes, and baked at 600 ° C for 30 minutes. Next, it was immersed again in the above-mentioned platinum solution, dried and baked in the same manner, then immersed again in the above-mentioned rhodium solution, dried and baked in the same manner.
【００４３】さらに、２％水素雰囲気（窒素ベース）中
で４５０℃で１５分間活性化処理して、白金及びロジウ
ムが交互に積層した厚さ２〜３μｍ以下の薄い触媒層を
仕上げた。得られた触媒断面の開孔率は９０％以上であ
った。Further, an activation treatment was performed at 450 ° C. for 15 minutes in a 2% hydrogen atmosphere (nitrogen base) to complete a thin catalyst layer having a thickness of 2 to 3 μm or less in which platinum and rhodium were alternately laminated. The porosity of the obtained catalyst cross section was 90% or more.
【００４４】この触媒を用いて、ＳＶ＝５００００／ｈ
ｒの条件下で、ＣＯ：２０００ｐｐｍ、プロパン：５０
００ｐｐｍ、ＮＯ：１０００ｐｐｍ、Ｏ2 ：２．６％を
含む燃焼排ガスを３５０℃で通したところ、ＣＯ、プロ
パン及びＮＯの浄化率はいずれも９５％以上であった。Using this catalyst, SV = 50,000 / h
Under the conditions of r, CO: 2000 ppm, propane: 50
When a combustion exhaust gas containing 00 ppm, NO: 1000 ppm, and O 2 : 2.6% was passed at 350 ° C., the purification rates of CO, propane, and NO were all 95% or more.
【００４５】（実施例４）５ｗｔ％アルミニウムを含む
厚さ５０μｍのステンレス鋼薄板を歯車加工によって波
型に成形し、平板と併せてコルゲート化して６０セル／
ｃｍ2 のハニカム状とした。これを有機溶剤でよく洗浄
して脱脂した後、空気中で９６０℃で１６時間加熱処理
し、次いで、１０５０℃で１時間加熱処理したのち冷却
した。Example 4 A 50 μm-thick stainless steel sheet containing 5 wt% aluminum was formed into a corrugated shape by gear processing and corrugated together with the flat plate to form a corrugated sheet of 60 cells / cell.
cm 2 honeycomb shape. This was thoroughly washed with an organic solvent and degreased, and then heat-treated at 960 ° C. for 16 hours in air, then heat-treated at 1050 ° C. for 1 hour, and then cooled.
【００４６】次いで、アルミニウムヒドロゾルをバイン
ダとして硝酸セリウム１ｍｏｌ／ｌ、水酸化アルミニウ
ム０．１ｍｏｌ／ｌ（アルミニウムヒドロゾルから由来
するものも含む）及び硝酸バリウム０．００５ｍｏｌ／
ｌを含む水溶液中に、上記加熱処理後の金属薄板を２分
間浸漬してから取り出して１０５℃で３０分間乾燥し、
さらに、７００℃で１時間空気中で加熱して酸化物を塗
布した。Next, 1 mol / l of cerium nitrate, 0.1 mol / l of aluminum hydroxide (including those derived from aluminum hydrosol), and 0.005 mol / l of barium nitrate, using aluminum hydrosol as a binder.
The metal sheet after the heat treatment is immersed for 2 minutes in an aqueous solution containing
Further, the oxide was applied by heating at 700 ° C. for 1 hour in the air.
【００４７】この酸化物を塗布した金属薄板をジニトロ
ジアミン白金０．０２５ｍｏｌ／ｌ、ヒドラジン０．０
２ｖｏｌ／ｖｏｌ％含む液中に３分浸漬させた後、これ
を取出して１０５℃で３０分間乾燥し、６００℃で３０
分間焼付けした。次に、硝酸ロジウム０．００５ｍｏｌ
／ｌ、ヒドラジン０．０２ｖｏｌ／ｖｏｌ％添加した液
中に３分間浸漬させた後、これを取り出して１０５℃で
３０分間乾燥し、６００℃で３０分間焼付けした。The metal sheet coated with this oxide was treated with 0.025 mol / l of dinitrodiamine platinum and 0.025 mol / l of hydrazine.
After being immersed in a liquid containing 2 vol / vol% for 3 minutes, this was taken out, dried at 105 ° C. for 30 minutes, and dried at 600 ° C. for 30 minutes.
Bake for a minute. Next, rhodium nitrate 0.005mol
/ L, immersed in a solution containing 0.02 vol / vol% hydrazine for 3 minutes, taken out, dried at 105 ° C for 30 minutes, and baked at 600 ° C for 30 minutes.
【００４８】次に、アルミニウムヒドロゾルをバインダ
として上記硝酸セリウム１ｍｏｌ／ｌ、水酸化アルミニ
ウム０．１ｍｏｌ／ｌ（アルミニウムヒドロゾルから由
来するものも含む）及び硝酸バリウム０．００５ｍｏｌ
／ｌを含む水溶液に２分間浸漬してから取り出して１０
５℃で３０分間乾燥し、さらに、７００℃で１時間空気
中で加熱して酸化物を塗布した。そして、さらにこの上
に、上記と同様にして、再び白金液に浸漬し、同様にし
て乾燥、焼付けをした後、再び上記ロジウム液に浸漬
し、乾燥、焼成した。Next, using the aluminum hydrosol as a binder, the above-mentioned cerium nitrate 1 mol / l, aluminum hydroxide 0.1 mol / l (including those derived from aluminum hydrosol) and barium nitrate 0.005 mol
2 minutes in an aqueous solution containing
The coating was dried at 5 ° C. for 30 minutes and heated in air at 700 ° C. for 1 hour to apply the oxide. Then, it was immersed in a platinum solution again, dried and baked in the same manner as above, and then immersed again in the rhodium solution, dried and fired.
【００４９】さらに、２％水素雰囲気（窒素ベース）中
で４５０℃で１５分間活性化処理して、白金及びロジウ
ムが交互に積層した厚さ２〜５μｍ以下の薄い触媒層を
仕上げた。得られた触媒断面の開孔率は９０％以上であ
った。Further, an activation treatment was performed at 450 ° C. for 15 minutes in a 2% hydrogen atmosphere (nitrogen base) to complete a thin catalyst layer having a thickness of 2 to 5 μm or less in which platinum and rhodium were alternately laminated. The porosity of the obtained catalyst cross section was 90% or more.
【００５０】この触媒を用いて、ＳＶ＝５００００／ｈ
ｒの条件下で、ＣＯ：２０００ｐｐｍ、プロパン：５０
００ｐｐｍ、ＮＯ：１０００ｐｐｍ、Ｏ2 ：２．６％を
含む燃焼排ガスを３５０℃で通したところ、ＣＯ、プロ
パン及びＮＯの浄化率はいずれも９５％以上であった。Using this catalyst, SV = 50,000 / h
Under the conditions of r, CO: 2000 ppm, propane: 50
When a combustion exhaust gas containing 00 ppm, NO: 1000 ppm, and O 2 : 2.6% was passed at 350 ° C., the purification rates of CO, propane, and NO were all 95% or more.
【００５１】（実施例５）実施例４と同様にコルゲート
化したハニカム状の５％アルミニウムを含むステンレス
鋼薄板の加熱を、空気中で１０２０〜１２００℃で加
熱、空気中で８７０〜９７０℃で加熱した後、さらに
空気中で１０２０〜１２００℃に加熱した場合について
も、実施例４と同様の触媒調製によって、同等の触媒活
性が発現した。(Example 5) As in Example 4, a stainless steel sheet containing 5% aluminum, which was corrugated and formed into a honeycomb shape, was heated at 1,200 to 1,200 ° C in air and at 870 to 970 ° C in air. After heating, the same catalyst activity was exhibited by the same catalyst preparation as in Example 4 in the case of further heating in the air to 1024 to 1200 ° C.
【００５２】以上、本発明の金属基触媒及びその製造方
法について、特殊な実施例をあげて詳述したが、助触媒
として酸化セリウム、酸化アルミニウム、酸化バリウム
以外の酸化ストロンチウム、酸化ジルコニウム、酸化ラ
ンタン、酸化サマリウムを用いても、又触媒として白
金、ロジウム以外のパラジウムを使用しても、ほゞ同様
の効果が得られた。The metal-based catalyst of the present invention and the method for producing the same have been described in detail with reference to specific examples. However, strontium oxide, zirconium oxide, lanthanum oxide other than cerium oxide, aluminum oxide and barium oxide are used as promoters. Even when samarium oxide was used, or when palladium other than platinum and rhodium was used as a catalyst, almost the same effect was obtained.
【００５３】[0053]
【発明の効果】本発明は上記の構成を採用することによ
り、従来のウォッシュ・コート法で形成した触媒層の厚
さ５０〜１００μｍに比較して２〜３μｍ以下の極めて
薄い触媒層を形成することができるため、通気抵抗の小
さなハニカム状等の触媒形成に適し、特に、エンジン出
力の向上の観点から圧力損失の増大を抑えることが要請
される自動車排ガス処理用触媒等に適したものである。
また、触媒活性成分を担持するときのメッキ液には触媒
活性を阻害するような被毒成分を全く含まれておらず、
基板薄板上の針状酸化アルミニウム及び／又は球状酸化
アルミウニム皮膜と助触媒と触媒成分との組み合わせに
より、更には、触媒活性成分を層状に担持することによ
り高い触媒活性と耐熱・耐久性に優れた金属薄板触媒を
得ることができるようになった。According to the present invention, by employing the above structure, an extremely thin catalyst layer having a thickness of 2 to 3 μm or less as compared with a thickness of 50 to 100 μm of the catalyst layer formed by the conventional wash coat method is formed. Therefore, it is suitable for forming a honeycomb-shaped catalyst or the like having a small airflow resistance, and is particularly suitable for a vehicle exhaust gas treatment catalyst or the like which is required to suppress an increase in pressure loss from the viewpoint of improving engine output. .
In addition, the plating solution when carrying the catalytically active component does not contain any poisoning component that inhibits the catalytic activity,
The combination of the acicular aluminum oxide and / or spherical aluminum oxide oxide film on the substrate thin plate, the co-catalyst, and the catalyst component, and further, the catalyst active component is supported in a layered form, so that high catalytic activity and excellent heat resistance and durability are achieved. It has become possible to obtain a sheet metal catalyst.
【図１】本発明の金属基触媒の製造工程の説明図FIG. 1 is an explanatory view of a production process of a metal-based catalyst of the present invention.
【図２】一般的な金属薄板を基材としたハニカム状触媒
の断面図FIG. 2 is a cross-sectional view of a general honeycomb catalyst based on a thin metal plate.
【図３】従来の金属薄板ハニカム状触媒の欠点の説明図FIG. 3 is an explanatory view of a drawback of a conventional sheet metal honeycomb catalyst.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 23/63 Ｂ０１Ｊ 23/56 ３０１Ａ (72)発明者 鹿納 栄 横浜市中区錦町12番地 三菱重工業株式 会社 横浜研究所内 (72)発明者 井上 保夫 横浜市中区錦町12番地 菱日エンジニア リング株式会社 本牧事業所内 (56)参考文献 特開 昭63−7839（ＪＰ，Ａ) 特開 平４−114743（ＪＰ，Ａ) 特開 平４−122440（ＪＰ，Ａ) 実開 平４−122442（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.6，ＤＢ名) B01J 21/00 - 38/74──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 6 Identification code FI B01J 23/63 B01J 23/56 301A (72) Inventor Sakae Kanou 12 Nishikicho, Naka-ku, Yokohama-shi Yokohama Heavy Industries Ltd. 72) Inventor Yasuo Inoue 12 Nishiki-cho, Naka-ku, Yokohama-shi Honichi Engineering Co., Ltd. Honmoku Office (56) References JP-A-63-7839 (JP, A) JP-A-4-114743 (JP, A) Kaihei 4-122440 (JP, A) JP-A 4-122442 (JP, U) (58) Fields investigated (Int. Cl. 6 , DB name) B01J 21/00-38/74
Claims (3)
中で８７０〜９７０℃で加熱するか、空気中で１０２
０〜１２００℃で加熱するか、または空気中で８７０
〜９７０℃で加熱した後、さらに空気中で１０２０〜１
２００℃で加熱することによって表面に針状または球状
酸化アルミニウムを析出させてなるアルミニウムを含む
金属薄板表面に、先ず酸化セリウム、酸化アルミニウ
ム、酸化バリウム、酸化ストロンチウム、酸化ジルコニ
ウム、酸化ランタン及び酸化サマリウムよりなる群から
選ばれた１種または２種以上の助触媒が担持され、その
上に白金、ロジウム及びパラジウムよりなる群から選ば
れた２種以上の触媒を層状に担持されてなることを特徴
とする金属基触媒。1. A sheet metal containing aluminum is heated in air at 870-970 ° C. or in air.
Heat at 0-1200 ° C or 870 in air
After heating at ９970 ° C., it was further heated in air to
First, cerium oxide, aluminum oxide, barium oxide, strontium oxide, zirconium oxide, lanthanum oxide, and samarium oxide are formed on the surface of a thin metal sheet containing aluminum obtained by depositing acicular or spherical aluminum oxide on the surface by heating at 200 ° C. One or more co-catalysts selected from the group consisting of platinum, rhodium and palladium, and two or more catalysts selected from the group consisting of palladium supported thereon in a layered manner. Metal-based catalyst.
らに先ず請求項１記載の助触媒、次に請求項１記載の層
状触媒を担持されてなることを特徴とする金属基触媒。2. A metal-based catalyst comprising a metal-based catalyst according to claim 1 and a co-catalyst according to claim 1 and then a layered catalyst according to claim 1.
布、焼成することによって形成され、触媒が構成元素を
含有する水溶液より無電解めっきにより形成されること
を特徴とする請求項１または２記載の金属基触媒の製造
方法。3. The cocatalyst is formed by applying and baking an aqueous solution containing a constituent element, and the catalyst is formed by electroless plating from an aqueous solution containing a constituent element. A method for producing the metal-based catalyst according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3204127A JP2851459B2 (en) | 1991-08-14 | 1991-08-14 | Metal-based catalyst and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3204127A JP2851459B2 (en) | 1991-08-14 | 1991-08-14 | Metal-based catalyst and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0549945A JPH0549945A (en) | 1993-03-02 |
| JP2851459B2 true JP2851459B2 (en) | 1999-01-27 |
Family
ID=16485278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3204127A Expired - Lifetime JP2851459B2 (en) | 1991-08-14 | 1991-08-14 | Metal-based catalyst and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP2851459B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3227074B2 (en) * | 1995-05-01 | 2001-11-12 | 株式会社日立製作所 | Exhaust gas purification catalyst and exhaust gas purification method for lean burn and stoichiometric internal combustion engines |
| JP3327164B2 (en) * | 1996-08-06 | 2002-09-24 | 松下電器産業株式会社 | Catalyst body and method for producing the same |
| JP3826522B2 (en) * | 1997-11-27 | 2006-09-27 | 松下電器産業株式会社 | Air purification catalyst |
| JP4524142B2 (en) * | 2004-05-28 | 2010-08-11 | 三井金属鉱業株式会社 | Composite element |
| JP6789491B2 (en) * | 2015-08-25 | 2020-11-25 | 国立大学法人 熊本大学 | Metal foil catalyst and its manufacturing method, and catalyst converter |
-
1991
- 1991-08-14 JP JP3204127A patent/JP2851459B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0549945A (en) | 1993-03-02 |
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