JPH06269667A - Production of noble metal carried activated carbon catalyst - Google Patents
Production of noble metal carried activated carbon catalystInfo
- Publication number
- JPH06269667A JPH06269667A JP8547693A JP8547693A JPH06269667A JP H06269667 A JPH06269667 A JP H06269667A JP 8547693 A JP8547693 A JP 8547693A JP 8547693 A JP8547693 A JP 8547693A JP H06269667 A JPH06269667 A JP H06269667A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- ion exchange
- noble metal
- carbon catalyst
- 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.)
- Pending
Links
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- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機合成反応等に利用さ
れる、貴金属担持活性炭触媒の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a noble metal-supported activated carbon catalyst, which is used in organic synthesis reactions and the like.
【０００２】[0002]
【従来の技術】従来貴金属担持活性炭触媒の製造方法と
しては、含浸法、イオン交換法などがあった。含浸法は
貴金属塩の水溶液に活性炭を加えて貴金属塩を吸着させ
た後還元を行うものである。一方イオン交換法は活性炭
表面にイオン交換基をつけたあと、貴金属のイオンとイ
オン交換した後還元を行う方法である。2. Description of the Related Art Conventionally, as a method for producing a noble metal-supported activated carbon catalyst, there have been an impregnation method and an ion exchange method. In the impregnation method, activated carbon is added to an aqueous solution of a noble metal salt to adsorb the noble metal salt and then reduction is performed. On the other hand, the ion exchange method is a method of attaching an ion exchange group on the surface of activated carbon, and then performing ion exchange with ions of a noble metal and then performing reduction.
【０００３】一例としてパラジウム−活性炭触媒の製造
方法を説明すると、含浸法では塩化パラジウムと塩酸の
水溶液を活性炭に加えて塩化パラジウムを吸着させた後
還元を行いパラジウム粒子を活性炭上に担持させるもの
である。一方イオン交換法では、まず濃硝酸に活性炭を
加えて表面処理を行い、活性炭表面にカルボン酸基を生
じさせる。次にアンモニア水によってＮＨ4 型活性炭と
してからテトラアンミンパラジウム(II)クロライド水溶
液を加えイオン交換を行わせた後、乾燥後水素還元を行
って触媒を得る。なお、イオン交換法を用いると、含浸
法よりはるかに高分散な担持触媒を得ることができる。As an example, a method for producing a palladium-activated carbon catalyst will be explained. In the impregnation method, an aqueous solution of palladium chloride and hydrochloric acid is added to activated carbon to adsorb palladium chloride and then reduction is carried out to support palladium particles on the activated carbon. is there. On the other hand, in the ion exchange method, activated carbon is first added to concentrated nitric acid for surface treatment to generate carboxylic acid groups on the activated carbon surface. Next, NH 4 type activated carbon is prepared with aqueous ammonia and then a tetraamminepalladium (II) chloride aqueous solution is added for ion exchange, followed by drying and hydrogen reduction to obtain a catalyst. The ion exchange method can provide a supported catalyst having a much higher dispersion than the impregnation method.
【０００４】[0004]
【発明が解決しようとする課題】ところが、このような
イオン交換法を用いても、従来得られる貴金属担持活性
炭触媒はまだ満足のできる物とはいえないものであっ
た。その原因としては前処理で用いられ濃硝酸処理によ
り活性炭の表面が酸で侵され、凹凸が減少し表面積もそ
れに伴い減少してしまい貴金属が高分散されなくなって
しまっていた。またイオン交換の効率が悪く一度に高担
持（10重量％程度）の触媒が得られない、通常の水素還
元ではパラジウム粒子の核成長がおこり、粒径が大きく
なる等の問題があった。本発明は上記の問題を解決し、
イオン交換法により粒径の小さな貴金属が、高分散、高
担持された活性炭触媒の製造方法を提供することを目的
とする。However, even if such an ion exchange method is used, the noble metal-supported activated carbon catalyst obtained hitherto cannot be said to be a satisfactory one. The cause was that the surface of the activated carbon was used in the pre-treatment and was attacked by the acid by the concentrated nitric acid treatment, the unevenness was reduced and the surface area was also reduced accordingly, and the precious metal was not highly dispersed. In addition, there are problems that the efficiency of ion exchange is poor and a catalyst of high loading (about 10% by weight) cannot be obtained at a time, and the nucleus growth of palladium particles occurs in ordinary hydrogen reduction, and the particle size becomes large. The present invention solves the above problems,
It is an object of the present invention to provide a method for producing an activated carbon catalyst in which a noble metal having a small particle size is highly dispersed and highly supported by an ion exchange method.
【０００５】[0005]
【課題を解決するための手段】貴金属のアンミン塩を用
いてイオン交換法により貴金属が担持された活性炭触媒
を製造する際に、あらかじめ活性炭を空気中、 300〜 5
00℃の温度で熱処理し、イオン交換を行った活性炭を還
元するガスとして一酸化炭素を 0.1〜10容量％含有する
水素ガスを用い、該ガス中 100〜 300℃の温度で、イオ
ン交換を行った活性炭を還元した後、再度イオン交換、
還元を繰り返すことにより達成される。[Means for Solving the Problems] When an activated carbon catalyst carrying a precious metal is prepared by an ion exchange method using an ammine salt of a precious metal, the activated carbon is preliminarily heated to 300 to 5 in air.
A hydrogen gas containing 0.1 to 10% by volume of carbon monoxide was used as a gas for reducing the activated carbon that had been heat-treated and ion-exchanged at a temperature of 00 ° C., and the ion exchange was performed at a temperature of 100 to 300 ° C. Ion exchange after reducing the activated carbon
It is achieved by repeating the reduction.
【０００６】[0006]
【作用】活性炭をあらかじめ空気中で熱処理する理由
は、従来の濃硝酸処理では活性炭の表面が酸で侵され凹
凸が減少し、表面積も減少してしまうのに対し、空気中
にて 300〜 500℃、望ましくは 400〜 450℃の温度で熱
処理することにより、活性炭の表面積が増加するととも
にイオン交換能をもつカルボン酸基が増加するため、従
来より貴金属が高分散された触媒が得られるものであ
る。なお 300℃未満では活性炭と酸素の反応があまり起
こらず、表面積増加、カルボン酸基増加があまり期待で
きず、また 500℃を越えると、活性炭が反応しすぎて変
質してしまう恐れがある。[Function] The reason why activated carbon is preheated in air is that the surface of activated carbon is attacked by acid in the conventional concentrated nitric acid treatment to reduce unevenness and the surface area is also reduced. By heat treating at a temperature of ℃, preferably 400-450 ℃, the surface area of activated carbon increases and the number of carboxylic acid groups with ion exchange capacity increases. is there. If the temperature is lower than 300 ° C, the reaction between activated carbon and oxygen does not occur so much, and the increase in surface area and the increase in carboxylic acid groups cannot be expected. If the temperature exceeds 500 ° C, the activated carbon may react excessively and be deteriorated.
【０００７】またイオン交換を行った活性炭を還元する
とき、水素ガス中に 0.1〜10容量％の一酸化炭素を混合
させておくのは、水素のみの場合生成した貴金属粒子の
核成長を起こし粒径が大きくなるのに対し、一酸化炭素
を混合させておくと、一酸化炭素がパラジウム粒子に吸
着し、パラジウム粒子の成長を防止することができるた
めである。なお 0.1容量％未満では一酸化炭素の添加効
果があまり表れず、また10容量％を超えると還元が弱ま
るために望ましくない。When reducing the ion-exchanged activated carbon, it is necessary to mix 0.1 to 10% by volume of carbon monoxide in hydrogen gas in the case of hydrogen only, which causes nuclei growth of noble metal particles produced. This is because, while the diameter becomes large, when carbon monoxide is mixed, carbon monoxide is adsorbed on the palladium particles and the growth of the palladium particles can be prevented. If it is less than 0.1% by volume, the effect of adding carbon monoxide is not so remarkable, and if it exceeds 10% by volume, reduction is weakened, which is not desirable.
【０００８】さらに一回のイオン交換処理のみでは、イ
オン交換基がすべて貴金属をイオン交換されるわけでは
ないので、一度イオン交換された貴金属を還元して活性
炭上に担持した後、さらにイオン交換処理することによ
り、残っているイオン交換基が貴金属でイオン交換さ
れ、高担持の活性炭触媒が得られるものである。Further, since only one ion-exchange treatment does not completely ion-exchange the noble metal with the ion-exchange groups, the once-exchanged noble metal is reduced and supported on activated carbon, and then the ion-exchange treatment is further carried out. By doing so, the remaining ion exchange groups are ion-exchanged with the noble metal, and a highly supported activated carbon catalyst is obtained.
【０００９】[0009]
【実施例】以下に貴金属としてパラジウムを用いた場合
の実施例を記載するが、本発明を限定するものではな
い。EXAMPLES Examples in which palladium is used as a noble metal will be described below, but the present invention is not limited thereto.
【００１０】[0010]
【実施例１】武田薬品製活性炭（ＬＰＫ−４１８） 10.
00ｇをイメージ炉で 450℃、２時間、空気流量２ｌ／mi
n 、昇温速度20℃／min の条件設定のもと熱処理を行っ
たところ、表面改質された活性炭4.89ｇを得た。得られ
た活性炭4.00ｇに純水60mlを注ぎ、メカニカルスターラ
ー（150rpm) を用い95℃の湯浴上で１時間撹拌した。そ
の後温度を60℃とし濃アンモニア水 2.4mlを加え、テト
ラアンミンパラジウム(II)クロライド0.7364ｇを60mlの
純水に溶かした液を加え、30分後さらに濃アンモニア水
1.2mlを加えて１晩静置した。混合物を濾過水洗後、炉
液中のパラジウム含有量を分析し、計算よりパラジウム
を5.41重量％担持した活性炭が得られた。[Example 1] Takeda Pharmaceutical Activated Carbon (LPK-418) 10.
00g in an image furnace at 450 ° C for 2 hours, air flow 2l / mi
When heat treatment was performed under the conditions of n and temperature rising rate of 20 ° C./min, 4.89 g of surface-modified activated carbon was obtained. 60 ml of pure water was poured into 4.00 g of the obtained activated carbon, and the mixture was stirred for 1 hour on a water bath at 95 ° C using a mechanical stirrer (150 rpm). After that, adjust the temperature to 60 ° C, add 2.4 ml of concentrated ammonia water, add 0.7364 g of tetraamminepalladium (II) chloride in 60 ml of pure water, and after 30 minutes, add more concentrated ammonia water.
1.2 ml was added and left still overnight. After the mixture was filtered and washed with water, the palladium content in the furnace liquid was analyzed, and from the calculation, activated carbon carrying 5.41% by weight of palladium was obtained.
【００１１】[0011]
【実施例２】実施例１と同様にして得られた、パラジウ
ム5.21重量％を担持した活性炭を一酸化炭素１容量％含
む水素ガス中で 300℃にて１時間還元した後、再度実施
例１と同様の方法でイオン交換し、再度一酸化炭素−水
素ガス中にて還元したところ、パラジウムを 10.02重量
％担持した活性炭触媒が得られた。なおこのときのパラ
ジウム粒子の粒径は5.26Åであった。Example 2 Activated carbon supporting 5.21% by weight of palladium obtained in the same manner as in Example 1 was reduced in hydrogen gas containing 1% by volume of carbon monoxide at 300 ° C. for 1 hour, and then again in Example 1 Ion exchange was carried out in the same manner as in, and reduction was again carried out in carbon monoxide-hydrogen gas, and an activated carbon catalyst supporting 10.02% by weight of palladium was obtained. The particle size of the palladium particles at this time was 5.26Å.
【００１２】[0012]
【比較例１】実施例２において一酸化炭素−水素ガスを
水素ガスのみに変更して 300℃で２時間還元したとこ
ろ、パラジウムの粒径は6.47Åであった。Comparative Example 1 When the carbon monoxide-hydrogen gas was changed to only hydrogen gas and reduction was carried out at 300 ° C. for 2 hours in Example 2, the particle size of palladium was 6.47Å.
【００１３】[0013]
【実施例３】武田薬品製活性炭（ＬＰＫ−４１８）を空
気中、 400℃、１時間熱処理を行った後、その比表面積
を測定したところ、1240ｍ2 ／ｇであった。[Example 3] Activated carbon (LPK-418) manufactured by Takeda Pharmaceutical Co., Ltd. was heat treated in air at 400 ° C for 1 hour, and then its specific surface area was measured and found to be 1240 m 2 / g.
【００１４】[0014]
【比較例２】武田薬品製活性炭（ＬＰＫ−４１８）30ｇ
に濃硝酸 100mlを加えて沸点にて１時間処理した後、そ
の比表面積を測定したところ 930ｍ2 ／ｇであった。[Comparative Example 2] Takeda Pharmaceutical Activated Carbon (LPK-418) 30 g
After adding 100 ml of concentrated nitric acid to the solution and treating it at the boiling point for 1 hour, the specific surface area was measured and found to be 930 m 2 / g.
【００１５】[0015]
【発明の効果】上記述べてきたとおり、本発明の製造方
法によれば、イオン交換法により粒径の小さな貴金属が
高分散、高担持された貴金属担持活性炭触媒を得ること
かでき、高活性な触媒としてたいへん有用である。As described above, according to the production method of the present invention, it is possible to obtain a noble metal-supported activated carbon catalyst in which a noble metal having a small particle size is highly dispersed and highly supported by an ion exchange method, and thus a highly active catalyst can be obtained. Very useful as a catalyst.
Claims (1)
換法により貴金属が担持された活性炭触媒を製造する方
法において、あらかじめ活性炭を空気中 300〜 500℃の
温度で熱処理し、イオン交換を行った活性炭を還元する
ガスとして一酸化炭素を 0.1〜10容量％含む水素ガスを
用い、該ガス中 100〜 300℃の温度で、イオン交換を行
った活性炭を還元した後、再度イオン交換・還元を繰り
返すことを特徴とする貴金属担持活性炭触媒の製法。1. A method for producing an activated carbon catalyst supporting a noble metal by an ion exchange method using an ammine salt of a noble metal, in which the activated carbon is preliminarily heat-treated in air at a temperature of 300 to 500 ° C. for ion exchange. Hydrogen gas containing 0.1 to 10% by volume of carbon monoxide is used as a gas for reducing activated carbon, and the activated carbon that has undergone ion exchange is reduced at a temperature of 100 to 300 ° C. in the gas, and then ion exchange and reduction are repeated. A method for producing a noble metal-supported activated carbon catalyst, which is characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8547693A JPH06269667A (en) | 1993-03-19 | 1993-03-19 | Production of noble metal carried activated carbon catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8547693A JPH06269667A (en) | 1993-03-19 | 1993-03-19 | Production of noble metal carried activated carbon catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06269667A true JPH06269667A (en) | 1994-09-27 |
Family
ID=13859969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8547693A Pending JPH06269667A (en) | 1993-03-19 | 1993-03-19 | Production of noble metal carried activated carbon catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06269667A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019131270A1 (en) | 2017-12-25 | 2019-07-04 | 株式会社クラレ | Activated carbon, metal-carrying activated carbon using same and hydrogenation reaction catalyst |
-
1993
- 1993-03-19 JP JP8547693A patent/JPH06269667A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019131270A1 (en) | 2017-12-25 | 2019-07-04 | 株式会社クラレ | Activated carbon, metal-carrying activated carbon using same and hydrogenation reaction catalyst |
| KR20200100692A (en) | 2017-12-25 | 2020-08-26 | 주식회사 쿠라레 | Activated carbon, metal-supported activated carbon using the same, and hydrogenation catalyst |
| US10974224B2 (en) | 2017-12-25 | 2021-04-13 | Kuraray Co., Ltd | Activated carbon, metal-carrying activated carbon using same and hydrogenation reaction catalyst |
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