JPS5944101B2 - Method for producing catalyst composition - Google Patents
Method for producing catalyst compositionInfo
- Publication number
- JPS5944101B2 JPS5944101B2 JP55180518A JP18051880A JPS5944101B2 JP S5944101 B2 JPS5944101 B2 JP S5944101B2 JP 55180518 A JP55180518 A JP 55180518A JP 18051880 A JP18051880 A JP 18051880A JP S5944101 B2 JPS5944101 B2 JP S5944101B2
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- carbon
- carrier
- catalyst composition
- present
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 229910000510 noble metal Inorganic materials 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 239000003870 refractory metal Substances 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 alkaline freerazine Chemical compound 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 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
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】
本発明は主として、可燃性ガスの酸化燃焼反応に使用さ
れる触媒組成物、特に自動車の排気ガスや工場排ガスの
浄化に適した触媒組成物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention primarily relates to a method for producing a catalyst composition suitable for use in oxidation combustion reactions of combustible gases, particularly for purifying automobile exhaust gas and factory exhaust gas.
詳しくは、無機耐火性物質から成る担体の表面に耐火性
金属酸化物及び触媒活性貴金属を微細かつ均一に分散分
布して担持させた触媒組成物の製造方法に関するもので
ある。Specifically, the present invention relates to a method for producing a catalyst composition in which a refractory metal oxide and a catalytically active noble metal are finely and uniformly dispersed and supported on the surface of a carrier made of an inorganic refractory substance.
従来、触媒活性成分を担体に担持させた触媒としては、
例えば、粒状活性アルミナ自体や活性アルミナを被覆付
着させたような担体に貴金属化合物溶液を含浸して付着
させ、還元し貴金属を析出させて得られる触媒が代表的
なものとして知られている。Conventionally, as a catalyst in which a catalytically active component is supported on a carrier,
For example, catalysts obtained by impregnating and adhering a precious metal compound solution to a carrier such as granular activated alumina itself or a carrier coated with activated alumina and reducing it to precipitate the precious metal are known as typical catalysts.
可燃性ガスの燃焼反応に使用される触媒では、添加され
た貴金属は、担体表面層の非常に薄い部分に存在するも
のが主に反応に関与する場合が多く、したがって、深層
に存在する貴金属は不必要であって、深層に反応して関
与しない貴金属が多（担持された触媒は不経済な上に、
使用された貴金属に対する、その触媒の効果は低いこと
になる。In catalysts used for combustion reactions of combustible gases, the added precious metals present in a very thin part of the surface layer of the carrier are often mainly involved in the reaction; therefore, the precious metals present in the deep layer are There are many precious metals that are unnecessary and do not participate in the deep reaction (supported catalysts are uneconomical,
The effect of the catalyst on the precious metal used will be low.
このような問題に対して、貴金属成分を担体表層部分に
付着させた触媒の製造方法として、貴金属化合物溶液に
酸又はアルカリを添加して微酸性にした溶液を担体を含
浸させる方法（特公昭５２２３９２０号）が知られてい
る。To solve this problem, as a method for manufacturing a catalyst in which a noble metal component is attached to the surface layer of a carrier, a method is proposed in which a carrier is impregnated with a solution made slightly acidic by adding acid or alkali to a precious metal compound solution (Japanese Patent Publication No. 5223920). No.) is known.
しかしながら、このような方法ではＰＨ以外に含浸温度
、時間、溶液中貴金属濃度等付着深度に影響する因子が
多く、付着深度を一定に調節することが難かしい。However, in such a method, there are many factors other than pH that affect the adhesion depth, such as impregnation temperature, time, and concentration of noble metal in the solution, and it is difficult to adjust the adhesion depth to a constant value.
本発明者らは、従来触媒のこれらの欠点を改良し、触媒
活性貴金属成分を主として担体表層部分に確実かつ容易
に付着担持させる触媒組成物の製造方法について鋭意検
討し、その結果、触媒活性貴金属を含有するカーボンと
耐火性金属酸化物を含む水性スラリーを無機耐火性担体
上に付着させ、焼成してカーボンを燃焼除去することに
より貴金属成分及び耐火性金属酸化物を担体上に微細か
つ均一に担持させ得ることを見出し、本発明の製造方法
を完成した。The present inventors have made extensive studies on a method for producing a catalyst composition that improves these drawbacks of conventional catalysts and allows catalytically active noble metal components to be deposited and supported mainly on the surface layer of the carrier. An aqueous slurry containing carbon and refractory metal oxides is deposited on an inorganic refractory carrier, and the carbon is burned off by firing, thereby finely and uniformly distributing the precious metal components and refractory metal oxides on the carrier. It was discovered that it could be supported, and the manufacturing method of the present invention was completed.
すなわち、本発明は貴金属及び／又は水不溶性貴金属化
合物を含有するカーボンと耐火性金属酸化物を含む水性
スラリーを無機耐火性担体上に付着させ、次いで焼成し
てカーボンを燃焼除去して得られる貴金属を含有する触
媒組成物の製造方法である。That is, the present invention provides a precious metal obtained by depositing an aqueous slurry containing carbon containing a noble metal and/or a water-insoluble noble metal compound and a refractory metal oxide on an inorganic refractory carrier, and then sintering to burn off the carbon. A method for producing a catalyst composition containing.
本発明の製造方法により得られる触媒組成物は、担体の
表層部分に触媒活性の貴金属成分が、確実かつ均一に分
散担持されたものであり、高価な貴金属を無駄に使用す
ることのない、工業的価値の高い、かつ高活性の触媒組
成物である。The catalyst composition obtained by the production method of the present invention has a catalytically active precious metal component reliably and uniformly dispersed and supported on the surface layer of the carrier, and is suitable for industrial use without wasting expensive precious metals. It is a highly active catalyst composition with high commercial value.
本発明の方法において、使用される担体は、機械的強度
を有する無機耐火性担体であって、例えば、アルミナ、
シリカ、マグネシア、酸化チタン酸化クロム、酸化ジル
コニウム等のｍ体もしくはそれらの混合物又はこれらの
化合物からなる多孔粒状もしくはスポンジ状担体、ある
いはこのような化合物を材料として造られたハニカム担
体等が使用される。In the method of the present invention, the carrier used is an inorganic refractory carrier having mechanical strength, such as alumina,
A porous granular or sponge-like carrier made of silica, magnesia, titanium oxide, chromium oxide, zirconium oxide, etc. or a mixture thereof, or a compound thereof, or a honeycomb carrier made of such a compound is used. .
また、貴金属及び／又は水不溶性貴金属化合物を含有す
るカーボンとは、触媒活性な貴金属、又は後で焼成する
ことによって分解し、触媒活性な貴金属を析出する貴金
属化合物がカーボンに含有されたものであり（以下貴金
属含有カーボンと略記する）貴金属及び貴金属化合物と
しては、例えば、ロジウム、パラジウム、イリジウム及
び白金、並びにこれらの硫化物等がある。In addition, carbon containing a noble metal and/or a water-insoluble noble metal compound refers to carbon containing a catalytically active noble metal or a noble metal compound that decomposes and precipitates a catalytically active noble metal when fired later. Examples of noble metals and noble metal compounds (hereinafter abbreviated as noble metal-containing carbon) include rhodium, palladium, iridium, platinum, and sulfides thereof.
上記の貴金属含有カーボンは次の方法で調製する。The above noble metal-containing carbon is prepared by the following method.
すなわち、貴金属化合物、例えば貴金属の塩酸塩、硫酸
塩、硝酸塩等の水溶液中にカーボンを浸漬し、カーボン
に貴金属化合物を含浸させる。That is, carbon is immersed in an aqueous solution of a noble metal compound, such as a hydrochloride, sulfate, or nitrate of a noble metal, to impregnate the carbon with the noble metal compound.
使用するカーボンとしては、触媒担体用としては勿論、
化学薬品の精製、ガス吸着、顔料、ゴム充填材等の用途
に市販されている粒状、粉状の活性炭やカーボンブラッ
クなどが広く使用でき、特に限定はないが含浸後のろ過
、洗浄の点からは粒状のカーボンが好ましい。The carbon used is of course for catalyst carriers,
Granular and powdered activated carbon and carbon black, which are commercially available for chemical refining, gas adsorption, pigments, rubber fillers, etc., can be widely used, and there are no particular limitations, but from the point of view of filtration and cleaning after impregnation. is preferably granular carbon.
カーボンに貴金属化合物の水溶液を含浸させた後乾燥す
る。Carbon is impregnated with an aqueous solution of a noble metal compound and then dried.
つぎにこのカーボンを還元剤、例えば、アルカリ性ホル
マリン、アルカリ性快ドラジン、水素化ホウ酸ナトリウ
ム又は水素ガス等によって還元して貴金属を金属状とし
て生成させるか、あるいは硫化水素処理により水不溶性
の貴金属化合物を生成させ、水で十分に洗浄し、乾燥後
、微粉砕して貴金属含有カーボンを得る。Next, this carbon is reduced with a reducing agent such as alkaline formalin, alkaline freerazine, sodium borate, hydrogen gas, etc. to produce a noble metal in the form of a metal, or a water-insoluble noble metal compound is produced by hydrogen sulfide treatment. It is produced, thoroughly washed with water, dried, and then pulverized to obtain noble metal-containing carbon.
この貴金属含有カーボンの貴金属含有率は、好ましくは
１゜〜５０％であり、１％以下では、カーボン量が多す
ぎて焼成後の触媒の強度が弱くなり、また５０％以上で
は、貴金属の分散が不充分となるおそれがあり好ましく
ない。The noble metal content of this noble metal-containing carbon is preferably 1° to 50%; if it is less than 1%, the carbon content is too large and the strength of the fired catalyst becomes weak, and if it is more than 50%, the noble metal is not dispersed. This is not preferable as it may result in insufficient performance.
本発明の方法において使用される耐火性金属酸化物は、
アルミナ、シリカ、マグネシア、セリア、チタニア、ク
ロミア等であって、これらは単独でも、２種以上の混合
物であってもよい。The refractory metal oxide used in the method of the invention is:
Alumina, silica, magnesia, ceria, titania, chromia, etc. may be used alone or in a mixture of two or more.
本発明の触媒組成物を製造するには、前記の耐火性金属
酸化物のゾル又は耐火性金属酸化物の微粉末を水中に懸
濁させ、必要に応じて硝酸、塩酸又は酢酸等で微酸性と
した水性スラリーに貴金属含有カーボンを添加混合し懸
濁させる。To produce the catalyst composition of the present invention, the sol of the refractory metal oxide or the fine powder of the refractory metal oxide described above is suspended in water, and if necessary, the mixture is slightly acidified with nitric acid, hydrochloric acid, acetic acid, etc. Precious metal-containing carbon is added to the aqueous slurry and suspended.
この水性スラリーにおいて、貴金属含有カーボンと耐火
性金属酸化物の量は、重量比で５：１００−１００ ：
１００が好ましく、液中の両者の合計量には特に限定は
ないが、通常、５〜５０重量％である。In this aqueous slurry, the amount of noble metal-containing carbon and refractory metal oxide is in a weight ratio of 5:100-100:
100 is preferable, and the total amount of both in the liquid is not particularly limited, but is usually 5 to 50% by weight.
この水性スラリーを無機耐火性担体に付着させる方法と
しては、各種の方法が適用可能であり、例えば、水性ス
ラリー液に担体を浸漬して含浸付着させる方法や、相体
に水性スラリー液を塗布付着させる方法等が適用できる
。Various methods can be applied to attach this aqueous slurry to the inorganic refractory carrier. For example, a method in which the carrier is immersed in an aqueous slurry liquid to impregnate it, or a method in which an aqueous slurry liquid is applied to the carrier to attach it. A method to do so can be applied.
水性スラリーを担体に含浸付着させ、過剰付着分を除去
した後、乾燥し、焼成処理を行なう。After impregnating and adhering the aqueous slurry to the carrier and removing the excess adhesion, it is dried and subjected to a firing treatment.
焼成処理は、水不溶性貴金属化合物を含有する場合は分
解して貴金属を析出し、又カーボンが燃焼除去し得る温
度、時間であればよく、特に限定されない。The firing treatment is not particularly limited, as long as it is at a temperature and time that can decompose the water-insoluble noble metal compound to precipitate the precious metal and burn off carbon.
通常、４００〜８００℃で１〜５時間焼成すれば十分で
ある。Usually, firing at 400 to 800°C for 1 to 5 hours is sufficient.
上記のように調製して得られる本発明の触媒組成物は、
水性スラリー液中の耐火性金属酸化物が微粉末の場合は
担体表面に留まり、微細なゾルの場合は担体表面のみな
らず、担体内部にまでも浸透して行くが、貴金属成分は
、貴金属塩類水溶液の含浸法と異なり、カーボン粉末に
含有された固体粒子であるために表層部に留まる。The catalyst composition of the present invention prepared as described above is
If the refractory metal oxide in the aqueous slurry is a fine powder, it remains on the surface of the carrier, and if it is a fine sol, it penetrates not only the surface of the carrier but also the inside of the carrier. Unlike the aqueous solution impregnation method, solid particles contained in carbon powder remain in the surface layer.
その結果、表面が粗く、かつ表層部に貴金属を含有する
多孔性耐火性金属酸化物の層を有する触媒組成物が得ら
れる。As a result, a catalyst composition having a rough surface and a layer of a porous refractory metal oxide containing a noble metal in the surface layer is obtained.
本発明の触媒組成物においては、貴金属を含むカーボン
微粉末の組成及びカーボン微粉末と耐火性金属酸化物と
の水性スラリーにおける両者の混合割合を適度に変える
ことにより、触媒表面の貴金属成分と耐火性金属酸化物
の混合層の厚さを調節することができる。In the catalyst composition of the present invention, by appropriately changing the composition of the noble metal-containing fine carbon powder and the mixing ratio of the fine carbon powder and the refractory metal oxide in the aqueous slurry, the precious metal component on the catalyst surface can be The thickness of the mixed metal oxide layer can be adjusted.
また、焼成後の貴金属の担持をより強固にするため、耐
火性金属酸化物、例えばアルミナゾルを含浸、乾燥、焼
成することもできる。Further, in order to more firmly support the noble metal after firing, it is also possible to impregnate with a refractory metal oxide, such as alumina sol, and then dry and fire.
以上のようにして得られる触媒組成物は、力一ボンの燃
焼除去により微細孔が生成し、その場所に存在する貴金
属成分がガスに対して有効に作用すること、また、貴金
属が表層部に含まれるため溶液含浸法によって貴金属が
表層部から深部にわたって広く分布含有されている従来
触媒よりも活性が高く、同一の浄化反応率を達成するた
めには、従来の触媒より少量の貴金属含有量でよいこと
、等の優れた特徴を有するものである。The catalyst composition obtained as described above is characterized by the fact that fine pores are generated by the combustion and removal of the force, and the precious metal component present in those places acts effectively on the gas, and that the precious metal is present in the surface layer. Because of this, the activity is higher than conventional catalysts in which precious metals are widely distributed from the surface layer to the deep layer by solution impregnation method, and in order to achieve the same purification reaction rate, a smaller amount of precious metals than conventional catalysts is required. It has excellent characteristics such as good things.
以下、実施例により、本発明をさらに説明する６実施例
１
塩化白金酸２．７０？を水２ｍｌに溶解した溶液に粒状
活性炭（東洋カルボッ製ＰＣＢ ）４１を添加し、溶液
を全量活性炭に吸収させる。Hereinafter, the present invention will be further explained with reference to six examples.Example 1 Chloroplatinic acid 2.70? Granular activated carbon (PCB manufactured by Toyo Calbo Co., Ltd.) 41 is added to a solution prepared by dissolving this in 2 ml of water, and the entire amount of the solution is absorbed into the activated carbon.
室温で３０分放置した後、アルカリ性１％ヒドラジン水
溶液３０ｍ１を除々に滴下し、１時間攪拌する。After standing at room temperature for 30 minutes, 30 ml of alkaline 1% hydrazine aqueous solution was gradually added dropwise, and the mixture was stirred for 1 hour.
次にろ液に塩素イオンのなくなるまで純水で洗浄ろ過す
る。Next, wash and filter with pure water until the filtrate is free of chlorine ions.
次にボールミルで１０ミクロン以下に微粉砕し、これに
７％アルミナゾル２２０グを加えて、よく混合し、白金
、活性炭、アルミナゾルからなるスラリーをつくる。Next, the powder is finely ground to 10 microns or less using a ball mill, and 220 g of 7% alumina sol is added thereto and mixed well to form a slurry consisting of platinum, activated carbon, and alumina sol.
セル形状上４角形、吸水率３０％のコージェライトハニ
カム２６０１を前記スラリー中に常温で約１０分間漬は
引き上げて予冷し、余分のスラリーは空気流で吹きとば
して除き、２００℃で乾燥する操作を３回繰り返し、最
後に８００℃で２時間焼成する。Cordierite honeycomb 2601, which is square in cell shape and has a water absorption rate of 30%, is soaked in the slurry at room temperature for about 10 minutes, then pulled out and precooled, the excess slurry is blown off with an air stream, and dried at 200°C. Repeat this three times, and finally bake at 800°C for 2 hours.
更に１５％アルミナゾルを含浸させ、乾燥し、４００℃
で１時間焼成した。Further impregnated with 15% alumina sol, dried and heated at 400°C.
Baked for 1 hour.
添加した白金は表面から約２０ミクロンの深さまでに存
在している。The added platinum is present at a depth of about 20 microns from the surface.
比較例 １
実施例１と同じコージェライトハニカム２６０１に７％
アルミナゾル２２０グを含浸させ、余分のゾルは空気流
で吹きとばして除き、２００℃で乾燥する操作を３回繰
り返し、最後に４００℃で２時間焼成する。Comparative example 1 Cordierite honeycomb 2601 same as Example 1 with 7%
The process of impregnating 220 g of alumina sol, blowing off the excess sol with an air stream, drying at 200°C three times, and finally firing at 400°C for 2 hours.
次に塩化白金酸２７０ノを水１５０ｍ１に溶解した溶液
を前記アルミナ付ノ・ニカムに含浸し１５０℃で乾燥す
ることを２回繰り返して全量をハニカムに吸収させる。Next, the alumina-coated honeycomb was impregnated with a solution of 270 parts of chloroplatinic acid dissolved in 150 ml of water and dried at 150°C twice, so that the entire amount was absorbed into the honeycomb.
乾燥後アルカリ性１％ヒドラジン水溶液に含浸して還元
し、白金黒を生成させ、純水で洗浄して塩素イオンを除
去し２００℃で乾燥し、８００℃、２時間焼成した。After drying, it was impregnated with an alkaline 1% hydrazine aqueous solution for reduction to produce platinum black, washed with pure water to remove chlorine ions, dried at 200°C, and fired at 800°C for 2 hours.
添加した白金は表面から５０〜１００ミクロンの深さま
でに存在している。The added platinum is present at a depth of 50 to 100 microns from the surface.
実施例 ２
実施例１と同様の方法で、粒状活性炭４′？と塩化パラ
ジウムナトリウム２．７６？、７％アルミナゾル２２（
ｌとからパラジウム、活性炭、アルミナゾルからなるス
ラリーを調製する。Example 2 In the same manner as in Example 1, granular activated carbon 4'? and sodium palladium chloride 2.76? , 7% alumina sol 22 (
A slurry consisting of palladium, activated carbon, and alumina sol is prepared from the following.
直径５ミリの活性アルミナゾルッ）５００ｍＪにこのス
ラリーを含浸付着させ、２００℃で乾燥する操作を３回
繰り返し、最後に８００℃で２時間焼成した。This slurry was impregnated onto 500 mJ of activated alumina sol having a diameter of 5 mm, dried at 200°C three times, and finally fired at 800°C for 2 hours.
添加したパラジウムは表面から約３０ミクロンの深さま
でに存在している。The added palladium is present at a depth of about 30 microns from the surface.
比較例 ２
実施例２と同じ活性アルミナペレット５００ｍ１に７％
アルミナゾルを含浸付着させ２００°Ｃで乾燥し、４０
０℃で焼成した。Comparative Example 2 7% in 500ml of activated alumina pellets same as Example 2
Impregnated with alumina sol, dried at 200°C,
It was fired at 0°C.
次に塩化パラジウムナトリウム２．７６１を水１５０ｍ
１に溶解した溶液をペレットに含浸付着させ、乾燥後ア
ルカリ性１％ヒドラジン溶液に含浸してパラジウム黒を
生成させ、純水で洗浄して塩素イオンを除去し、２００
℃で乾燥し、８００℃で２時間焼成した。Next, add 2.761 ml of sodium palladium chloride to 150 ml of water.
The pellets were impregnated with a solution dissolved in 1 and adhered to the pellets, and after drying, impregnated with an alkaline 1% hydrazine solution to produce palladium black, washed with pure water to remove chloride ions,
It was dried at 800°C for 2 hours.
添加パラジウムは表面から約２００ミクロンの深さまで
に存在している。The added palladium is present at a depth of about 200 microns from the surface.
参考例 １
前記各触媒の活性比較を次の条件で実施し、下表の結果
を得た。Reference Example 1 The activity of each of the catalysts was compared under the following conditions, and the results shown in the table below were obtained.
反応原料ガス組成（容積比）
プロピレン ６００ ｐｐｍ
ｃｏ ｉ、 ｏ ％０２
０．８５％
Ｈ２０１０，０％
Ｎ２ 残 部
空間速度 ３００００Ｈｒ ’
触媒層入口ガス温度 ３５０°ＣReaction raw material gas composition (volume ratio) Propylene 600 ppm co i, o %02
0.85% H2010,0% N2 Remaining space velocity 30000Hr' Catalyst layer inlet gas temperature 350°C
Claims (1)
カーボンと耐火性金属酸化物を含む水性スラリーを、無
機耐火性担体上に付着させ、次いで焼成してカーボンを
燃焼除去して得られる貴金属を含有する触媒組成物の製
造方法。1 Containing a noble metal obtained by depositing an aqueous slurry containing carbon containing a noble metal and/or a water-insoluble noble metal compound and a refractory metal oxide on an inorganic refractory carrier, and then sintering to burn off the carbon. Method for producing catalyst composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55180518A JPS5944101B2 (en) | 1980-12-22 | 1980-12-22 | Method for producing catalyst composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55180518A JPS5944101B2 (en) | 1980-12-22 | 1980-12-22 | Method for producing catalyst composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57105245A JPS57105245A (en) | 1982-06-30 |
| JPS5944101B2 true JPS5944101B2 (en) | 1984-10-26 |
Family
ID=16084656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55180518A Expired JPS5944101B2 (en) | 1980-12-22 | 1980-12-22 | Method for producing catalyst composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5944101B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6670300B2 (en) * | 2001-06-18 | 2003-12-30 | Battelle Memorial Institute | Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions |
| ES2277545B1 (en) * | 2005-11-18 | 2008-06-16 | Consejo Superior Investig. Cientificas | SIMPLIFIED PROCEDURE FOR THE PREPARATION OF METAL CATALYSTS OR METAL OXIDES SUPPORTED ON POROUS MATERIALS. |
| JP2008168278A (en) * | 2006-12-15 | 2008-07-24 | Nissan Motor Co Ltd | Catalyst for cleaning exhaust gas and its manufacturing method |
| JP5323582B2 (en) * | 2009-05-14 | 2013-10-23 | 国立大学法人北海道大学 | Method for producing photocatalyst body |
| JP6398917B2 (en) * | 2015-09-02 | 2018-10-03 | マツダ株式会社 | Exhaust gas purification catalyst material manufacturing method, exhaust gas purification catalyst material, and exhaust gas purification catalyst including the exhaust gas purification catalyst material |
-
1980
- 1980-12-22 JP JP55180518A patent/JPS5944101B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57105245A (en) | 1982-06-30 |
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