JPS59120249A - Preparation of noble metal catalyst - Google Patents

Preparation of noble metal catalyst

Info

Publication number
JPS59120249A
JPS59120249A JP57228546A JP22854682A JPS59120249A JP S59120249 A JPS59120249 A JP S59120249A JP 57228546 A JP57228546 A JP 57228546A JP 22854682 A JP22854682 A JP 22854682A JP S59120249 A JPS59120249 A JP S59120249A
Authority
JP
Japan
Prior art keywords
noble metal
metal
hydrosol
aqueous solution
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP57228546A
Other languages
Japanese (ja)
Other versions
JPS6319217B2 (en
Inventor
Yukimichi Nakao
幸道 中尾
Kyoji Kaeriyama
帰山　享二
Masao Suda
須田　昌男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
Agency of Industrial Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agency of Industrial Science and Technology filed Critical Agency of Industrial Science and Technology
Priority to JP57228546A priority Critical patent/JPS59120249A/en
Publication of JPS59120249A publication Critical patent/JPS59120249A/en
Publication of JPS6319217B2 publication Critical patent/JPS6319217B2/ja
Granted legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

PURPOSE:To easily prepare a highly activated stable noble metal catalyt with excellent reproducibility, by reducing the aqueous solution of a salt such as one containing Rh, Pd, Pt, Ru, Au or Ag in the presence of a surfactant to form hydrosol. CONSTITUTION:The aqueous solution of a salt such as the chloride of a noble metal selected from Rh, Pd, Pt, Ru, Au and Ag is reductively treated by adding a water-soluble reducing agent, e.g. sodium borohydride, in the presence of a cationic, anionic or nonionic surfactant as protective substance for hydrosol. Thus, the obtd. noble metal hydrosol can be used as a uniform and stable liquid- phase catalyt. Carrier substance, e.g. metal hydroxide, difficulty soluble or insoluble to water may be agitatively suspended in said noble metal hydrosol at need. Hence, noble metal colloidal particles in the hydrosol are supported on the surface of said carrier to obtain a solid catalyst supporting the noble metal.

Description

【発明の詳細な説明】 本発明は、高い触媒活性をフ】りず新規な貴金属ヒドロ
シル触媒の製造方法及び担持型貴金属触媒の製造方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a noble metal hydrosyl catalyst without high catalytic activity, and a method for producing a supported noble metal catalyst.

金属触媒として、これまでに多くの形態が考え出されて
いるが、そのうちでも金属微粒子を含む担持型触媒は９
反応後の回収が容易であると同時に、金属比表面積が大
きく、触媒となる金属の使用量を大中１４に低減できる
ことから２価格の高い貴金属触媒に特に適している。担
持型貴金属触媒については、従来からの製法として、活
性炭やシリカゲル、ケイソウ土といった比表面積の比較
的大きな不活性固体に、触媒となる貴金属の塩を含浸な
いし吸着させ１次いで、これを分子状水素などの適当な
還元剤で処理することにより貴金属塩を還元して担体表
面上で貴金属微粒子を形成させる方法が知られている。Many forms of metal catalysts have been devised so far, but among them, supported catalysts containing fine metal particles are 9 types.
It is particularly suitable for expensive noble metal catalysts because it is easy to recover after the reaction, has a large metal specific surface area, and can reduce the amount of metal used as a catalyst to 14%. The conventional manufacturing method for supported noble metal catalysts is to impregnate or adsorb a noble metal salt to serve as a catalyst into an inert solid with a relatively large specific surface area, such as activated carbon, silica gel, or diatomaceous earth. A method is known in which noble metal salts are reduced by treatment with a suitable reducing agent such as eg, to form noble metal fine particles on the surface of a carrier.

しかし、この方法では、担体上の貴金属塩を全て貴金属
微粒子に変換するために、相当高温卜゛で還元反応を１
」う必要かあり。However, in this method, in order to convert all the noble metal salts on the carrier into noble metal fine particles, the reduction reaction is carried out at a considerably high temperature.
”Is it necessary?

その場合、貴金属微粒子の二次的な成長が起こるため、
その粒反分布か広がりかもで１触媒７＋’ｉ　’ｌｊ１
ｇの［１）税性についても、しはしは問題が生じる。ま
た。In that case, secondary growth of precious metal particles occurs, so
The particle anti-distribution or spread may be 1 catalyst 7+'i 'lj1
Questions also arise regarding the tax nature of item (1) in g. Also.

担体表向上の貴金属塩の密度か低い場合、一般に還元が
困Ａｉｍとなり、貴金属の稲５ｊｌによっては低担持率
の担持触媒か実除」ニ調製できないこともある。If the density of the noble metal salt that improves the carrier surface is low, reduction will generally be difficult, and depending on the precious metal, it may not be possible to prepare a supported catalyst with a low loading rate.

この他の金属触媒の形態として、液体中に、コ【Ｊイド
粒子と呼ばれる数Ｌｏ＋）オングストローム又はこれ以
下の粒径の金属微粒子が均一に分１１スした金属ゾルか
あり、特に貴金属について多くの神〕、１４が知られて
いる。これは、調製が容易であるうん２金属塩の還フし
反応が浴数中で穏和な条件下にイＪゎれるため２粒度分
布の狭い金属微粒子が？４７−られ。Another form of metal catalyst is a metal sol in which fine metal particles called co(J-ide particles) having a particle diameter of several Lo+ angstroms or smaller are uniformly distributed in a liquid. God], 14 are known. This is because the reflux reaction of metal salts, which are easy to prepare, is carried out under mild conditions in a bath, so fine metal particles with a narrow particle size distribution are produced. 47-Rare.

その触媒活性の再現性か良好である点て優れている３、
金属ツルは外見上元金に逍明なｄｋ体であり。It is excellent in that the reproducibility of its catalytic activity is good3.
The metal vine has a dk font that looks like the original metal.

通′７ｊ４’　＋液相反応の触媒として用いられるが２
反応後に触媒と生成物を分？ａする時、固体触媒のよう
なろ過による方法は通用できない。それで例えは。'7j4' + Used as a catalyst for liquid phase reactions, but 2
Separate the catalyst and products after the reaction? When using a, filtration methods such as those using solid catalysts cannot be used. So here's an example.

生成物を渭出させて分離することを４えると、金属ツル
かこのｌＩ！１凝集沈殿を起さないこと、すなわち７高
温下での分散の安定性が要求されることになる。金属ゾ
ルには、その分散状態を安定化させるため保護コロイド
と呼ばれるｔｉＪ落性品性高分子加されることか多いか
、水を分散媒とする金属ヒドロツルの場合、その分散状
態を高７，５１目−′でも安定に保つには、かなり多量
の保護コロイ１−′市分子の添加か必要であり、この高
分子か、今度は触媒反応に対し抑制剤として働くことに
なる。この他の解決法として、金属ゾル中の金１．．＋
４コ【」イド粒子を適当な不溶性固体」−に担持するこ
とかできれは。4. Letting the product flow out and separate it is a metal vine or this lI! 1) No coagulation and precipitation, 7) Stability of dispersion at high temperatures is required. In order to stabilize the dispersion state of the metal sol, a tiJ-resistant polymer called a protective colloid is often added, or in the case of metal hydrosols using water as the dispersion medium, the dispersion state is In order to maintain stability even with 51-', it is necessary to add a fairly large amount of protective colloid 1-', and this polymer, in turn, acts as an inhibitor for the catalytic reaction. Another solution is gold in metal sol. ．． +
It would be possible to support the 4 coid particles on a suitable insoluble solid.

金属ツル触媒同様調画フ容易てｆ・ａ：媒１１！：性の
］↑ｊ現性か良く、同時にろ過なとのｆｉｊ隼な操作て
容易に回収し得る１憂れた担持型金属触媒か得られると
期待される。このような観点から考え出された。金属ツ
ルからの１．］↓持型ブ独媒の調製法力）い（つかある
か。Like the metal vine catalyst, it is easy to adjust f・a: Medium 11! It is expected that a supported metal catalyst will be obtained which has good resiliency and can be easily recovered by careful operations such as filtration. It was conceived from this perspective. 1. From metal vines. ] ↓ Is there any way to prepare a long-lasting solvent?

この場合、保護コロイド品分ｊ−にＪ、って保護された
金属ゾルはこの用途に通さず、ｌＸ１ｉｎ剤を用いない
で、その代り金属含有率を極めて低く抑えた金属ヒドロ
シルを使用せざるを得ない。このゾルは準安定とてもい
うべき状態で、比較的低温又も徐々に凝集が進むことと
、扱う金属ヒドロシルが大量となることなどが、この方
法の難点である。また、保漁コロイド不在下では低濃度
でもヒドロシルを形成し得ない金属１例えば、ルテニウ
ムの担持型触媒の調製には通用できない。In this case, a metal sol protected by the protective colloid component j-to J cannot be used for this purpose, and instead, a metal hydrosil with an extremely low metal content must be used without using the lX1in agent. I don't get it. This sol is in a metastable state, and the disadvantages of this method are that the aggregation progresses gradually even at relatively low temperatures, and that a large amount of metal hydrosil must be handled. Furthermore, it cannot be used to prepare supported catalysts for metals such as ruthenium, which cannot form hydrosils even at low concentrations in the absence of colloids.

本発明者らは、従来触媒のこのような難点を克服し、よ
り優れた性能の貴金属触媒を容易にｄ、１製できる方法
を確立すべく鋭意検討を重ねた結果。The present inventors have conducted intensive studies to overcome these difficulties of conventional catalysts and to establish a method for easily producing noble metal catalysts with superior performance.

界ａＩ」活性剤により保護された貴金属ヒドロシルか。Noble metal hydrosyl protected by a tertiary aI activator.

高い触媒活１生を示すと同時に、貴金属含有率か高い場
合もその分散状態が安定で、高温下においても全（凝集
を起こさないこと、及び、これに包まれる貴金属コロイ
ド粒子か特定の担体ｑｌＪＪ’Ａの表面に効率よく吸宥
され、その結果得られる担持型貴金属触媒もまた高い触
媒活性を示すことを見出した。本発明は、これらの知見
に基づいて成すにｊ−うったものである。At the same time, it exhibits high catalytic activity, and its dispersion state is stable even when the precious metal content is high, and it does not aggregate even at high temperatures, and the precious metal colloidal particles enclosed therein are stable and the dispersion state is stable even when the precious metal content is high. It has been found that the supported noble metal catalysts obtained as a result of efficient adsorption on the surface of 'A' also exhibit high catalytic activity.The present invention is based on these findings. .

すなわち、不発］すｊは、ロジウム、パラジウム。That is, unexploded] is rhodium, palladium.

白金、ルテニウム、金、銀の中から選ばれた貴金属の塩
を水溶液とし、さらに、陽イオンｉ’＋−，，Ｖ＝’：
、イオン性又は非イオン性界面活１１．剤を溶解した蚊
に。A salt of a noble metal selected from platinum, ruthenium, gold, and silver is made into an aqueous solution, and cations i'+-,,V=':
, ionic or nonionic surfactant 11. To mosquitoes with dissolved agent.

地元処理することを特徴とする賃金ｋ」＝ヒドロシル触
媒の製造方法及び、この貴金属ヒドロツルを延溶性又は
不溶性の担体物貿と接触させて、これに含まれる貴金属
コロイド粒子を担体表面上に担持させることを特徴とす
る担持型貴金属触媒の製造方法を提供するものである。A method for producing a hydrosil catalyst characterized by local processing, and contacting the noble metal hydrosil with a soluble or insoluble carrier to support the noble metal colloid particles contained therein on the surface of the carrier. The present invention provides a method for manufacturing a supported noble metal catalyst characterized by the following.

本発明力ｌ去においてｔｊｅ、＜　＄；）として用いら
れる貴金属塩は、当該賃金１両の水溶性の塩化物＋　Ｉ
ｒｉ′ノ酸塩八とでへり２例えば、塩化ロジウム（ＩＩ
ｌ、）　、塩化パラジウム（Ｉｌ、）、塩化白金酸、塩
化ルテニウＪ・（１１１）、塩化金酸、硝ｒ１ν銀なと
が好ｊ〜である。The noble metal salt used as tje, <$;) in the present invention is the water-soluble chloride + I
For example, rhodium(II) chloride
Preferred examples include palladium chloride (Il,), chloroplatinic acid, ruthenium chloride J.(111), chloroauric acid, and silver nitrate.

本発明方法においては、￥ｉ金成ヒトｔＪツルの保疎物
貿として界面活性剤を用いることか必要であるか、この
界面活性剤としては２例えは、ステアリルトリメチルア
ンモニウムクロリド、ヘキザデシルトリメチルアンモニ
ウムブロミト、ヘキザデシルビリシニウムクロリトなと
の陽イオン性界面活比剤、ドデシル硫酸ナトリウム、ト
デシルベンセンスルポンｊ゛↓麦すトリウムなどの１収
イオン′ｌηＬ界１川活性剤、ポリエチレンクリコール
モノ−ｐ−ノニルフェニルエーテルなどの非イオン性界
曲活性剤をあげることができる。In the method of the present invention, is it necessary to use a surfactant to preserve the cranes? Two examples of this surfactant include stearyltrimethylammonium chloride and hexadecyltrimethylammonium chloride. Cationic surfactants such as bromite, hexadecylbiricinium chloride, 1-ion ion 'lηL' active agents such as sodium dodecyl sulfate, todecylbenzene sulfone and barley, polyethylene Mention may be made of nonionic surfactants such as glycol mono-p-nonylphenyl ether.

また、逗元処理の方法としては、水素化ホウメミナトリ
ウム、水素化ボウ素カリウムなとのアルカリ金属水素化
ホウ素塩の他、ヒドラジン、ホルムアルデヒドなどの水
溶性速元性物買を用いる貴金属塩の２１．元について公
知の方法かとられる。In addition, as a treatment method, in addition to alkali metal borohydride salts such as sodium borohydride and potassium borohydride, precious metal salts using water-soluble fast-acting chemicals such as hydrazine and formaldehyde are also available. 21. The original method can be used in a known manner.

本発明方法を実施するには、　ｊ’Ｊ＋定の貴金属塩及
び界面活１にｌ、斉ｉｊを水に溶解し、か（はん下に、
０”Ｃ：ないし１０００Ｃ，，１ＩＩＩ乱は室温におい
て還元剤又は６１元剤の水溶欣を加える。こうして、貴
金属ヒドロツルが２強（着色した透明な液体として得ら
れる。To carry out the method of the present invention, dissolve the noble metal salt of j'J + constant and surfactant 1 in water,
0"C: to 1000C, 1III. Add a reducing agent or an aqueous solution of the 61 base agent at room temperature. In this way, a precious metal hydrovine is obtained as a colored transparent liquid.

この際、原料となる貴金属塩は、水溶液中での濃度が０
０１〜３０ｔ１甫Ｉψ、／ｌ　の範囲になるように用い
られ、界面活性剤は、水溶液中の濃度か０．００１〜５
％の範囲になるように用いられる。また、還元剤は、原
料の貴金属塩に対し２等モル以」−用いられるのが望ま
しい。得られた貴金属ヒドロシルは。At this time, the raw material noble metal salt has a concentration of 0 in the aqueous solution.
The concentration of the surfactant in the aqueous solution is 0.001 to 5.
% range. Further, the reducing agent is desirably used in an amount of 2 equimole or more based on the noble metal salt of the raw material. The noble metal hydrosil obtained is.

そのまま均−ｌ（文相触媒として、水ン容赦反応に供す
ることかできる。It can be used as it is in a water-tolerant reaction as a catalyst.

本発明方法においては、さらに、担体としでう）１［溶
性又は不治性の物費が用いられる。担持処理は。In the method of the present invention, a soluble or incurable substance is further used as a carrier. What is the loading process?

貴金属ヒト１コゾル中に、担体となる物質を懸濁させて
かくはんすることにより行われる。この峙。This is carried out by suspending a carrier material in a noble metal cosol and stirring the suspension. This confrontation.

担体表向が着色するに従ってｊｔ金属フルの色は退色し
、これが無色になることで担持か完了したことを偉１．
忍できる。１−金属コロイドｊ立了−のヒト１」ゾルか
ら担体・＼の移行か遅い場合には、適宜温良を−Ｌ昇さ
せてこれをｌＩＬめることかてきる。担持処理に要する
時間は、大部分の場合数分以内であり。As the surface of the carrier becomes colored, the color of the jt metal color fades, and when it becomes colorless, it is known that the supporting process has been completed.
I can endure it. If the transfer of the carrier from the sol to the human 1-metal colloid is slow, the temperature can be increased as appropriate to slow this down. The time required for the loading process is within a few minutes in most cases.

最も遅い場合でも、１時間以内に完了する。このように
して青金１ｊ４コロイド粒子を担持した固体触媒か得、
られる。At its slowest, it can be completed within an hour. In this way, a solid catalyst supporting blue gold 1j4 colloidal particles was obtained,
It will be done.

担体として用いられる物質としては、まず、水ｌこ対し
離俗又は不溶である。金属の水Ｍ化物、酸化物、フッ化
物、炭廉塩、硫酸塩、リン酸塩をあげることかでき、具
体的には、水酸化マク不シウム、ｅ化マグネシウム、フ
ッ化マグネシウム、炭酸マクネジウド、水酸化カルシウ
ム、フッ化カルシウム、炭酸カルシウム、（〆し酸カル
シウム、リン酸カルシウム、炭酸バリウム、硫酸バリウ
ムなとのアルカリ土類金属塩の他、水酸化アルミニウム
。First, substances used as carriers are insoluble or insoluble in water. Examples include hydroxides, oxides, fluorides, carbonates, sulfates, and phosphates of metals, specifically, hydroxide, magnesium e-chloride, magnesium fluoride, carbonate, Calcium hydroxide, calcium fluoride, calcium carbonate, alkaline earth metal salts such as calcium phosphate, calcium phosphate, barium carbonate, and barium sulfate, as well as aluminum hydroxide.

酸化チタン、「賓化鉄（Ｈｌ）　、四三酸化鉄、ｌ俊化
銅（１１）、水酸化鉛Ｎ（１１）、酸化ｎｕ　ｆＯ、炭
酸亜鉛。Titanium oxide, iron oxide (Hl), triiron tetroxide, copper chloride (11), lead hydroxide N (11), nufO oxide, zinc carbonate.

酸化ジルコニウムなどをあげることができる。この池、
イオン交換＋１１ｊＩＩｉｌ＋　＋活性炭、粉砕した石
炭。Examples include zirconium oxide. This pond,
Ion exchange +11jIIIil+ + activated carbon, crushed coal.

活性白土なども担体として用Ｇ、られる。なお、そのＩ
「態は１００　ｍｅ　ｓ　ｈより細かい粉末状が好まし
いが、貴金属の担持率か低い場合には、これ以外の例え
は１粒状のものや成形品を用いることもｉｉＪ能である
。担体物質は、形成される貴金属コロイド粒子の２０〜
１００００倍重ふえ、好ましくは５０〜５００倍車量が
用いられる。Activated clay and the like can also be used as carriers. In addition, that I
It is preferable that the carrier material be in the form of a powder finer than 100 mes h, but if the loading rate of the precious metal is low, it is also possible to use a single granule or a molded product. 20 ~ of the noble metal colloid particles formed
The weight is 10,000 times heavier, preferably 50 to 500 times heavier.

彷、られた担持型１′ｊ金机）甥媒を含む）Ｖ、ｒ蜀７
ｆｋは、そのままで水溶液のｒｌに札反応に供すること
もできるか、、ｉ＋ｎ′畠は静置又は遠心分離により沈
降させ、又はろ過して該固体触媒を分散し、水又はアル
コールなどで洗浄後、乾燥させて使用する。Wandering, carrying type 1'j golden desk) including nephew medium) V, r Shu 7
fk can be directly subjected to the tag reaction in an aqueous solution of rl, or i + n' can be left standing or sedimented by centrifugation, or the solid catalyst can be dispersed by filtration, and after washing with water or alcohol, etc. , dry and use.

本発明方法により得られる貝金ＩＢ、＋４ヒト゛ロゾル
の第一のｑ、′Ｊ似は、これか非７！’に向い触媒活１
コ（ユを有することである。−例として、オレフィンの
水素化触媒として用いた場合の弔位貴金属あたりの比較
では１本発明方法によるｔｆｆシウムヒトｒ１ゾルは。The first q, 'J similarity of Kaikin IB, +4 hydrosol obtained by the method of the present invention is this or non-7! towards 'catalytic activity 1
As an example, when used as an olefin hydrogenation catalyst, the tff sium hydroxide sol according to the method of the present invention is compared with respect to the noble metal.

市販の活′１１−炭担持ロシウム触媒の５侶以」二の４
！□性を示す。第二の特徴は９分散状態の高い安定性に
あり１例えは常圧下で長時間Ｑｂｋさせた俊でも。Five components of commercially available activated 11-charcoal supported rosium catalysts" 2-4
! □Shows gender. The second feature is the high stability of the 9-dispersion state, even when Qbk is maintained for a long time under normal pressure.

濁り又は沈殿は全（認められず、完全に透明な状１１県
を保ち触媒活性も低下しない。これに対し１例えばポリ
ヒニルピロリドンを保護物質として使用した貴金属ヒド
ロシルは、調製直後に既に少量の１蜀りが認められるう
え、　＆ｔｉ１Ｍ＊なとの加熱処理により徐々に濁りが
増加し触媒活性も低下する。No turbidity or precipitation was observed, and the catalyst remained completely transparent with no decrease in catalytic activity. In contrast, precious metal hydrosils using polyhinylpyrrolidone as a protective substance, for example, already contain a small amount of water immediately after preparation. In addition to this, the heat treatment with &ti1M* gradually increased the turbidity and decreased the catalytic activity.

本発明方法により得られる担長型貴金ｊ萬触媒もまた。There is also a supported precious metal catalyst obtained by the method of the present invention.

高い触媒活性を示す点に特徴があり、担動型ロジウム触
媒の例でいえば、　ｊｉｉ位ロジウム当りの比較で、界
面活性剤を用いないロジウムヒドロシルから得られる担
持触媒の２倍以上の触媒活性を示す。この他、貴金属ヒ
ドロシルに対し、これと接触さぜる担体の使用届６をＪ
ｌ・＾加させることにより、容易に低い担持率の責、ｉ
ｚ属触媒か得られることも本発明方法の腸（奴である。It is characterized by high catalytic activity, and in the case of supported rhodium catalysts, in terms of rhodium in the jii position, it has more than twice as much catalyst as the supported catalyst obtained from rhodium hydrosil without using a surfactant. Shows activity. In addition, for precious metal hydrosil, J.
By adding l・^, it is easy to take responsibility for low loading rate, i
It is also possible to obtain catalysts of the Z group using the method of the present invention.

奉・究明によれは、極めてｊ敢細な貴金属コロイド粒子
を含む貴金属ヒドロシル触媒及び貴金属コロイド゛拉子
を担持した固体触媒か容易に再現゛Ｉｉ１．よくイＩＩ
ら、！ｌ、これら貴金属触媒はいずれも１’：：＋い触
媒病１−１．を小し、液相又は気相の広い範囲の触媒反
応に使用できる。Through research and investigation, it was found that a noble metal hydrosil catalyst containing extremely fine noble metal colloid particles and a solid catalyst supporting noble metal colloid particles could be easily reproduced.Ii1. Well II
and others,! Both of these noble metal catalysts have 1'::+catalytic disease 1-1. It can be used for a wide range of catalytic reactions in the liquid or gas phase.

次に、実施例により本発明をさらに）ｊ１′、１４１１
に説明する。Next, the present invention is further explained by examples) j1', 1411
Explain.

実施例１ 塩化ロジウム（ＩＩＩ）　（Ｒｈ（７，・３Ｈ２０）　
５０μｍ丁１０７７及びポリエチレンクリコールモノ−
ｐ−ノニルフェニル」―−チル（ポリエチレンクリコー
ル部分の重合度−１０）１０１ｎｇを純水９５ｍ１に溶
解し、これに、かくばん下、水素化ホウ素ナトリウム（
ＮａＢＨ，）２００　Ｉｔ　ｍｏ　ｌの水溶液５１ｎＪ
＆を滴下した。淡橙色の水溶液は、　５＝−Ｆの途中に
黒かっ色に急変し、目的のＬ１ジ１ンムヒトロソ゛ルが
得られた。このロジウムヒドロシル０．４　ｎ１１　（
ロジウムを０２μｇ−ａｔｏｍ汀む）を水素４１７ｎ気
中て、あらかしめアルコ／Ｉ゛′で還流して酸素をしＪ
′：、いた純水２Ｑｍ７中に、　ヒトロソル調製に用い
た界面活′ＩＩ　ｊＦｌｊ、ずなわらポリエチレンクリ
コールモノ−ｐ−ノニルフェニル：Ｊ−−デル２ＩＩ１
ｇを１２”ｉ解した溶成で布状し、さらに３０”Ｃ，１
気圧の水素下でかくはんしながらアクリルアミド０．２
５　ｍ　ｍｏｌの水溶液１ｎｌｌをｌｌｌ上下ると水素
の吸収か始まり。Example 1 Rhodium(III) chloride (Rh(7,.3H20)
50μm 1077 and polyethylene glycol mono-
Dissolve 101 ng of p-nonylphenyl (polymerization degree of polyethylene glycol moiety - 10) in 95 ml of pure water, and add sodium borohydride (
NaBH,) 200 It mol aqueous solution 51 nJ
& was dropped. The light orange aqueous solution suddenly turned blackish-brown in the middle of the 5=-F reaction, and the desired L1 dimer hydrosol was obtained. This rhodium hydrosil 0.4 n11 (
Rhodium (02 μg-atom) was placed in 417 n of hydrogen and refluxed with Alco/I' to remove oxygen.
': In pure water 2Qm7, surfactant 'II jFlj, Zunawara polyethylene glycol mono-p-nonylphenyl: J--Dell 2II1
g was melted to form a cloth by melting 12"I, and further 30"C, 1
Acrylamide 0.2 while stirring under atmospheric pressure of hydrogen.
When 1nll of a 5 mmol aqueous solution is raised and lowered, hydrogen absorption begins.

プＬ」ピオンアミド゛か生成した。Produced L-pionamide.

水素吸収初連反は１．３６ｍｏＩ！、／ｓｅｃ　−ｇ　
−ａｔｏｍＲｈであり２反応は約２０分で完了した。The initial hydrogen absorption reaction is 1.36 moI! , /sec -g
-atomRh, and the two reactions were completed in about 20 minutes.

実施例２ 実施例１と同様の操作により、ハ；Ｌ料となるＳｉ金属
塩、界面活性剤及び還元剤を変えて貴金属ヒト′ロゾル
を調製した。こうして得らイした貴金執ヒト゛ロゾルに
よる。水溶ｆ伎中、３０″（ハ１気圧水素−トにおける
アクリルアミドの水素化初速ｊ斐を次表に）」〈ず。Example 2 In the same manner as in Example 1, noble metal human rosol was prepared by changing the Si metal salt, surfactant, and reducing agent used as the L material. Due to the precious metals obtained in this way. In an aqueous solution, 30'' (the initial hydrogenation rate of acrylamide in a hydrogen atmosphere of 1 atm is shown in the table below).

ａｔｏｍ金属） ＰｄＣ１，ｆ５七ル倍　　　ドデシ＋レベンゼン　　Ｎ
ａ３１（、２，２６，４−Ｂ＋ｒｌｌＣｒ′Ｃ溶解）　
　　ｘ　＋しＩＮ　＞酸すトリウム ステアリルトリメ　　抱水ヒト　１２５ヂノ１アンセニ
ウム　　ラジン クＯ’Ｊ　ｔ’　　　　　　　（５００７ｔｒｌｌＯ／
！使用） ＲｕＣｇ、　・３Ｈ＋ＯＮａＢＨ，０，０４Ｈ＋ＰＬＣ
ｌ：ｉ・６ＲＯドデンル硫酸ナト　　　　ノ１０３３リ
ウム 実施例３ 塩化ロジウｌ、（１１１）　　（ＲｈＣ／’、・３）Ｌ
Ｏ）　５０ｚ＋ｍＯＩ！及ヒヘキサデシルトリメチルア
ンモニウムヒドロキシド１０　ｍｇを純水９５　ｍｌに
溶解し、これにかくはん下で、　ＮａＢＨ＋２００μｍ
ｏｚの水溶液５　ｍ／を滴下して黒かっ色て６明なロジ
ウムヒドロシルを得た。atom metal) PdC1, f5 7 times dodecyl + lebenzene N
a31 (2,26,4-B+rllCr′C dissolution)
X
! Use) RuCg, 3H+ONaBH, 0,04H+PLC
l:i・6ROdodenylsulfate sodium 1033ium Example 3 Rhodium chloride l, (111) (RhC/',・3)L
O) 50z+mOI! 10 mg of hexadecyltrimethylammonium hydroxide were dissolved in 95 ml of pure water, and while stirring, NaBH + 200 μm was added.
A 5 m/oz aqueous solution was added dropwise to obtain brownish black rhodium hydrosil.

別逆、水酸化マク不シウム０．５０ｇを純水５０１ＴＩ
　Ｂ中にｌｉ蜀させておき、かくはん下（こロシウノ、
ヒドロツルを江ぎ込み、５分間か（はんした後、静置し
。Separately, add 0.50g of Macunium hydroxide to 501TI of pure water.
Leave it in the middle of B and stir it.
Pour in the hydrovine and let it stand for 5 minutes.

」−パｉ液を除いた。−夜風乾して大ｒｊｌｉ分の水分
をＩ’ｊ？いた後、減圧下で乾燥し、灰色粉末状の担持
型ロジウム触媒を得た。” - omitted the liquid. - Dry in the air at night and remove a large amount of water from I'j? After that, it was dried under reduced pressure to obtain a supported rhodium catalyst in the form of a gray powder.

この担１！■型ロジウムｊ性媒］、Ｏｒｎｇ　（ロジウ
ム１μｇ−ａｔｏ　ｍ　含有）を５Ｑｒｎｌ容ナス型フ
ラスコに入れ。This person is 1! Type (1) rhodium j-type medium] and Orng (containing 1 μg-atom of rhodium) were placed in a 5Qrnl eggplant-shaped flask.

内部を水素カスで置換した後、浴存取索をＩ’ｚｔ″Ｏ
いたエタノール２Ｑ　ｒｎ　ｌを加えて３０”Ｃ，１気
圧の水素下で約１１；ｕ間か（はんして水素で飽和させ
た。これにンクロヘキセン０，２５ｒｎ　１１１０　ｉ
を、゛画工すると水素の吸収が奸ｉまり、シクロヘギザ
ンか生成した。水素吸収初速反は１．０３ｍｏｌ／’ｓ
ｅｃ　−ｇ−ａｔｏｍ　Ｒｈであり。After replacing the inside with hydrogen scum, I'zt''O
2 Q rn l of ethanol was added and saturated with hydrogen at 30"C and 1 atm hydrogen for about 11 hours. To this was added 0.25 rn 1110 i
When it was painted, hydrogen absorption increased and cyclohexane was formed. Hydrogen absorption initial velocity reaction is 1.03 mol/'s
ec-g-atom Rh.

反応は約１５分で完了した。The reaction was completed in about 15 minutes.

実施例４ 実施例３と同様の操作により、　１３；！料となる貴金
属塩、界［Ｉ′ｉ］活性剤、還元剤及び担体を変えて担
持型置り１萬触媒を６υ１！１袋した。こうし、てイも
“られた担持型触媒による。エタノールン行液中、　　
３０−Ｇ　、　　１　’ｙ＜Ｃバーの水素下におけるン
クロヘキセンの水系化初速度を次表に小す。Example 4 By the same operation as in Example 3, 13;! The noble metal salt, the [I'i] activator, the reducing agent, and the carrier were changed, and 6υ1!1 bags of 10,000 supported catalysts were prepared. In this way, it is also possible to use a supported catalyst.
30-G, the initial rate of conversion of nclohexene into an aqueous system under hydrogen with 1'y<C bar is summarized in the following table.

（ｍｏｌ／ｓｅｃ−ｇ−ａｔｏｍ 金属） ３Ｈ２０−ｐ−ノニルフェニルＪ −チル イオン交換相　　　　１８０ 脂（アンバー ライトＣＧ− ４００１１型） ｔｌ！　　　　ヘキサデシルトリメチ　　Ｍｇ（ＯＨ）
２　　　　０．３　］ルアンモニウムクロリド ＲｕＣ１ｙ　・　　　ヘキサデシルトリメチ　　　　　
　　　　　　　０．１０３　Ｈ２０ルアンモニウムヒド
ロ キシド Ｈ２ＰｔＣ６，・　　ドデンル硫酸ナトリウ　　　　　
　　　　　　　　０．１９６Ｈ，，０ム 活性炭　　０１０ ＋ｌ抱水ヒドラジン（５００ｊ１ｍｏ１月（＝よりん〕
し。(mol/sec-g-atom metal) 3H20-p-nonylphenyl J-thyl ion exchange phase 180 Fat (Amberlite CG-40011 type) tl! Hexadecyl trimethy Mg(OH)
2 0.3] Ruammonium chloride RuC1y/hexadecyl trimethy
0.103 H20 ammonium hydroxide H2PtC6, Sodium sulfate
0.196H,,0m activated carbon 010 +l hydrazine hydrate (500j1mo1 month (=Yorin)
death.

Ｃ（Ｄ　他ハ全テＮｉ１ＢＨ＋　（２００１１ｍｏｄ）
により、ｌ’＋ｆｆｉ几。C (D and others) Ni1BH+ (20011mod)
Therefore, l'+ffi 几.

Claims (1)

【特許請求の範囲】[Claims] （１）ロジウム、パラジウム、白金、ルテニウム。 金、銀の中から選はれた青金ｊ高の塩の水溶液を。 陽イオン性２隘イオン性又は非イオン性の界面活’ｌｉ
ｔ　ｆｉｌＪの存在下に還元処理して貴金属ヒトロソル
を形成させることを４〕徴とする貴金属触媒の製造方法
。 （２１ロジウム、パラジウム＋　白金、ルテニウム。 金、銀の中からＪムはれた貴金属の塩の水溶液を。 陽イオン性、呟イオン性又は非イオン性の界（口ｌｒｔ
！ｉ　ｉ９ｇ　Ｗ’ｊの存在ドに趣〕じ処理して貰金城
ヒドロシルを形成させ１次いで、これを軸沿性又は不溶
性の担体物質に接触させて、これに含まれる貴金属コロ
イド粒子を担体表面」二に担Ｊ１させることを特徴とす
る貴金属触媒の製造方法。(1) Rhodium, palladium, platinum, ruthenium. An aqueous solution of blue and gold salts selected from gold and silver. Cationic 2nd ionic or nonionic surfactant'li
4) A method for producing a noble metal catalyst, comprising forming a noble metal hydrosol through reduction treatment in the presence of t filJ. (21 rhodium, palladium + platinum, ruthenium. An aqueous solution of salts of precious metals extracted from gold and silver.
! i9g W'j is treated in the same manner as above to form Kinjo hydrosil, which is then brought into contact with an axial or insoluble carrier material, and the noble metal colloidal particles contained therein are transferred to the surface of the carrier. A method for producing a precious metal catalyst, which comprises secondly supporting J1.
JP57228546A 1982-12-27 1982-12-27 Preparation of noble metal catalyst Granted JPS59120249A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP57228546A JPS59120249A (en) 1982-12-27 1982-12-27 Preparation of noble metal catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57228546A JPS59120249A (en) 1982-12-27 1982-12-27 Preparation of noble metal catalyst

Publications (2)

Publication Number Publication Date
JPS59120249A true JPS59120249A (en) 1984-07-11
JPS6319217B2 JPS6319217B2 (en) 1988-04-21

Family

ID=16878076

Family Applications (1)

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Country Link
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Cited By (15)

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JPS6163780A (en) * 1984-09-03 1986-04-01 工業技術院長 Conductive fiber molded article and its production
JPS61107937A (en) * 1984-11-01 1986-05-26 Agency Of Ind Science & Technol Preparation of noble metal organosol
JPS6468478A (en) * 1987-09-07 1989-03-14 Agency Ind Science Techn Metal plating method using silver hydrosol
GB2286197A (en) * 1994-02-02 1995-08-09 Hitachi Chemical Co Ltd Chemical reducing solution for copper oxide
JPH09948A (en) * 1995-06-20 1997-01-07 Ishihara Sangyo Kaisha Ltd Method for carrying particles of inorganic material
JP2001079382A (en) * 1999-09-13 2001-03-27 I Betsukusu:Kk Method of producing metal colloid and metal colloid produced by the method
US6569358B1 (en) * 2001-12-07 2003-05-27 National Institute Of Advanced Industrial Science And Technology Method for incorporating metal nanoparticles in porous materials
JP2005230699A (en) * 2004-02-19 2005-09-02 Toyota Motor Corp Production method for gold catalyst and its usage
WO2007074749A1 (en) 2005-12-27 2007-07-05 Apt Co., Ltd. Prophylactic and/or therapeutic agent for chronic obstructive pulmonary disease
JP2008055425A (en) * 2007-10-29 2008-03-13 Toyota Central R&D Labs Inc Decomposition/removal method of aldehydes
JP2009214099A (en) * 2008-02-14 2009-09-24 Okayama Univ Method for producing amide compound and catalyst to be used therein
US7838043B2 (en) 2003-02-20 2010-11-23 Apt Co., Ltd Superoxide anion decomposing agent
KR101204341B1 (en) 2010-09-30 2012-11-23 성일하이텍(주) Methods of Synthesis of ruthenium metal powder using reductants in liquid phase
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6163780A (en) * 1984-09-03 1986-04-01 工業技術院長 Conductive fiber molded article and its production
JPS61107937A (en) * 1984-11-01 1986-05-26 Agency Of Ind Science & Technol Preparation of noble metal organosol
JPH0249365B2 (en) * 1984-11-01 1990-10-30 Kogyo Gijutsuin
JPS6468478A (en) * 1987-09-07 1989-03-14 Agency Ind Science Techn Metal plating method using silver hydrosol
JPH0553873B2 (en) * 1987-09-07 1993-08-11 Kogyo Gijutsuin
GB2286197A (en) * 1994-02-02 1995-08-09 Hitachi Chemical Co Ltd Chemical reducing solution for copper oxide
GB2286197B (en) * 1994-02-02 1997-06-04 Hitachi Chemical Co Ltd Chemical reducing solution for copper oxide
JPH09948A (en) * 1995-06-20 1997-01-07 Ishihara Sangyo Kaisha Ltd Method for carrying particles of inorganic material
JP2001079382A (en) * 1999-09-13 2001-03-27 I Betsukusu:Kk Method of producing metal colloid and metal colloid produced by the method
US6569358B1 (en) * 2001-12-07 2003-05-27 National Institute Of Advanced Industrial Science And Technology Method for incorporating metal nanoparticles in porous materials
US7838043B2 (en) 2003-02-20 2010-11-23 Apt Co., Ltd Superoxide anion decomposing agent
JP4578820B2 (en) * 2004-02-19 2010-11-10 トヨタ自動車株式会社 Method for producing gold catalyst and method for using the same
JP2005230699A (en) * 2004-02-19 2005-09-02 Toyota Motor Corp Production method for gold catalyst and its usage
WO2007074749A1 (en) 2005-12-27 2007-07-05 Apt Co., Ltd. Prophylactic and/or therapeutic agent for chronic obstructive pulmonary disease
JP2008055425A (en) * 2007-10-29 2008-03-13 Toyota Central R&D Labs Inc Decomposition/removal method of aldehydes
JP2009214099A (en) * 2008-02-14 2009-09-24 Okayama Univ Method for producing amide compound and catalyst to be used therein
KR101204341B1 (en) 2010-09-30 2012-11-23 성일하이텍(주) Methods of Synthesis of ruthenium metal powder using reductants in liquid phase
JP2014534332A (en) * 2012-05-11 2014-12-18 エルジー・ケム・リミテッド Method for producing hollow metal nanoparticles and hollow metal nanoparticles produced thereby
JP2015501387A (en) * 2012-05-11 2015-01-15 エルジー・ケム・リミテッド Hollow metal nanoparticles
WO2021033590A1 (en) 2019-08-20 2021-02-25 有正 宮本 Agent for reducing malodor of flatulence and/or stool

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