JPS63178851A - Production of noble metal catalyst carried on ion-exchange resin - Google Patents
Production of noble metal catalyst carried on ion-exchange resinInfo
- Publication number
- JPS63178851A JPS63178851A JP31825787A JP31825787A JPS63178851A JP S63178851 A JPS63178851 A JP S63178851A JP 31825787 A JP31825787 A JP 31825787A JP 31825787 A JP31825787 A JP 31825787A JP S63178851 A JPS63178851 A JP S63178851A
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- exchange resin
- catalyst
- hydrosol
- resin
- 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
Links
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title description 4
- 239000003456 ion exchange resin Substances 0.000 title description 4
- 229920003303 ion-exchange polymer Polymers 0.000 title description 4
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 5
- 239000000084 colloidal system Substances 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011949 solid catalyst Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000010574 gas phase reaction Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- 229910052703 rhodium Inorganic materials 0.000 description 8
- 239000010948 rhodium Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- BLGXFZZNTVWLAY-SCYLSFHTSA-N yohimbine Chemical compound C1=CC=C2C(CCN3C[C@@H]4CC[C@H](O)[C@@H]([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 BLGXFZZNTVWLAY-SCYLSFHTSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、高い触媒活性を示す新規な担持型貴金属触媒
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a novel supported noble metal catalyst exhibiting high catalytic activity.
従来の技術
担持型貴金属触媒は、これに含まれる金属表面積が大き
く、また回収や取扱いが簡単なので最も多用されている
ものである。ところで、このような形態の金属触媒を製
造するには、活性炭やシリカゲル、ケイソウ土のような
比表面積の比較的大きい固体に触媒となる金属の塩を含
浸ないし吸着させ、次いでこれに分子状水素または適当
な還元剤を作用させて該金属塩を還元して金属微粒子を
生成させる方法が一般に行われている６しかしながら、
このような方法は、製造過程における温度や操作手順等
の微妙な条件の相違が、得られる担持型触媒の活性に大
きく影響し、触媒活性の制御が困難であるという欠点を
有している。Conventional technology-supported precious metal catalysts are the most widely used catalysts because they contain a large metal surface area and are easy to recover and handle. By the way, in order to produce this type of metal catalyst, a solid with a relatively large specific surface area, such as activated carbon, silica gel, or diatomaceous earth, is impregnated with or adsorbed with a metal salt that will serve as a catalyst, and then molecular hydrogen is added to this solid. Alternatively, a method of reducing the metal salt by applying an appropriate reducing agent to produce metal fine particles is commonly used.6 However,
Such methods have the disadvantage that subtle differences in conditions such as temperature and operating procedures during the production process greatly affect the activity of the obtained supported catalyst, making it difficult to control the catalyst activity.
一方、微細な金属コロイド粒子を含む金属ゾルは、再現
性がよく、調製が容易であるという長所があるが、これ
は外見上完全に透明な液体であるため、触媒金属の反応
後の回収が困難である上に、その使用する反応系が金属
ゾルの状態を安定に保持しうるちのに限られるし、また
高温下では金属コロイド粒子が非可逆的に凝集して触媒
活性が著しく低下するという欠点をもっている。On the other hand, metal sol containing fine metal colloid particles has the advantage of good reproducibility and easy preparation, but since it is a completely transparent liquid in appearance, it is difficult to recover the catalytic metal after the reaction. In addition to being difficult, the reaction system used is limited to being able to maintain the metal sol state stably, and metal colloid particles will irreversibly aggregate at high temperatures, resulting in a significant decrease in catalytic activity. It has shortcomings.
発明が解決しようとする問題点
本発明は、従来の貴金属触媒における、製造過程での条
件の相違の触媒活性への多大の影響、触媒金属の回収難
、金属粒子の凝集による活性低下等の欠点を克服し、活
性が高く、しかも再現性のめになされたものである。Problems to be Solved by the Invention The present invention solves the drawbacks of conventional precious metal catalysts, such as the large influence of differences in conditions during the manufacturing process on catalytic activity, difficulty in recovering the catalytic metal, and decreased activity due to agglomeration of metal particles. It was developed to overcome this problem, have high activity, and be reproducible.
問題点を解決するための手段
本発明者らは、金属コロイド粒子を固体に担持させるこ
とができれば、活性が高く、しかも再現性の良好な固体
触媒が得られると考え、その製造方法を開発するために
鋭意研究を重ねた結果、陰イオン交換樹脂を担体として
用いることにより、保護コロイドを添加しない貴金属ヒ
ドロゾル中の貴金属コロイド粒子を十分にしかも容易に
担持させ得ることを見出し、この知見に基づいて本発明
をなすに至った。Means for Solving the Problems The present inventors believe that if metal colloid particles can be supported on a solid, a solid catalyst with high activity and good reproducibility can be obtained, and have developed a method for producing the same. As a result of intensive research, it was discovered that by using an anion exchange resin as a carrier, noble metal colloid particles in a noble metal hydrosol without the addition of a protective colloid could be sufficiently and easily supported.Based on this knowledge, The present invention has been accomplished.
すなわち、本発明の方法は、貴金属ヒドロゾルを第四級
アンモニウム基を有する陰イオン交換樹脂と接触させる
ことによｌ）、貴金属コロイド粒子を樹脂表面上に担持
させて、担持型貴金属触媒製造することからなっている
。ここで、貴金属ヒドロゾルとは、水を分散媒とする、
ロジウム、パラジウム、白金、金、銀のような貴金属コ
ロイド粒子より成るゾルを意味する。That is, the method of the present invention involves producing a supported noble metal catalyst by bringing a noble metal hydrosol into contact with an anion exchange resin having a quaternary ammonium group, thereby supporting noble metal colloid particles on the resin surface. It consists of Here, noble metal hydrosol refers to a compound that uses water as a dispersion medium.
A sol consisting of colloidal particles of noble metals such as rhodium, palladium, platinum, gold, and silver.
本発明において用いられる貴金属ヒドロゾルの形成は、
対応する貴金属塩の水溶液に還元剤を作用させる公知の
方法に従って行うことができる。The formation of the noble metal hydrosol used in the present invention is
This can be carried out according to a known method in which a reducing agent is allowed to act on an aqueous solution of the corresponding noble metal salt.
貴金属塩としては、塩化ロジウム（ｌＩ［）、塩化パラ
ジウム（ｎ）、塩化白金酸、塩化金酸、硝酸銀などが用
いられ、還元剤としてはホルムアルデヒド、ヒドラジン
、水素化ホウ素塩などが用いられる。As the noble metal salt, rhodium chloride (lI[), palladium (n) chloride, chloroplatinic acid, chloroauric acid, silver nitrate, etc. are used, and as the reducing agent, formaldehyde, hydrazine, borohydride salt, etc. are used.
貴金属など疎水性のヒドロゾルには、通常分散状態を安
定化するための保護コロイドとして、ポリビニルアルコ
ールなどの水溶性ポリマーを加えることが多い。しかし
、本発明方法においてはこのような保護コロイドを含ま
ない貴金属ヒドロゾルを用いることが必要である。保護
コロイドを添加した貴金属ヒドロゾルを用いた場合は、
貴金属の担持率が著しく低下し、十分な触媒活性を示す
担持型触媒を得ることができない。本発明方法では、貴
金属ヒドロゾルが長期間安定である必要はなく、数十分
間程度均一透明なゾル状態が保持されればこの間に担持
が完了し、十分に目的を達することができる。A water-soluble polymer such as polyvinyl alcohol is often added to a hydrophobic hydrosol such as a noble metal as a protective colloid to stabilize the dispersion state. However, the method of the present invention requires the use of a noble metal hydrosol that does not contain such protective colloids. When using a noble metal hydrosol with added protective colloid,
The supporting rate of the noble metal decreases significantly, making it impossible to obtain a supported catalyst that exhibits sufficient catalytic activity. In the method of the present invention, it is not necessary for the noble metal hydrosol to be stable for a long period of time, and if a uniform and transparent sol state is maintained for about several tens of minutes, the support will be completed during this period, and the purpose can be fully achieved.
＝３−
モニウム基を有する陰イオン交換樹脂が用いられる。こ
の陰イオン交換樹脂に貴金属コロイド粒子を担持させる
のは、貴金属ヒドロゾルに陰イオン交換樹脂を加えてか
きまぜることにより行われる。=3- An anion exchange resin having a monium group is used. The anion exchange resin supports the noble metal colloid particles by adding the anion exchange resin to the noble metal hydrosol and stirring the mixture.
この際、貴金属ヒドロゾルの黒かっ色が退色して無色と
なることにより担持の完了したことが確認できる。これ
に伴いイオン交換樹脂は、当初の白色ないし淡黄色から
黒色ないし灰色に変化する。At this time, completion of the support can be confirmed by fading the brownish color of the noble metal hydrosol and becoming colorless. Along with this, the ion exchange resin changes from its initial white or pale yellow color to black or gray.
この過程に要する時間は通常１時間以内である。This process usually takes less than 1 hour.
こうして貴金属コロイド粒子を担持した固体触媒が得ら
れる。In this way, a solid catalyst supporting noble metal colloid particles is obtained.
担体として用いられるイオン交換樹脂は第四級アンモニ
ウム基を有する陰イオン交換樹脂であればよく、例えば
市販品では粉末又は粒状のアンバーライトＩＲＡ−９３
８、アンバーライトＣＧ−４００、アンバーライトＡ−
２６、アンバーライ）ＩＲＡ−９０４などが挙げられる
。担持率を高くするには表面積のより大きな粉末状の樹
脂を用いるのが有利である。ただし、市販の陰イオン交
換樹脂には、多くの場合不純物として、貴金属ヒドロゾ
ルに対して強い保護コロイド作用を示す物質が含まれて
いて担持の障害となるので、使用に先立って水洗などに
より、これを除いておくことが必要である。市販の陰イ
オン交換樹脂は大部分が塩素イオン型であるが、これを
水酸化ナトリウム、硫酸ナトリウムなどの水溶液で処理
して各々、水酸イオン型、硫酸イオン型などに変えたも
のも担体として用いられる。イオン交換樹脂の使用量は
担持される貴金属の総量の２０〜１０００倍重量、好ま
しくは５０〜５００倍重量程度である。貴金属ヒドロゾ
ルの調製にあたっては０．０１〜１ｍｍｏｌ／βの範囲
の濃度の原料貴金属塩水溶液に、その０．５〜１０倍モ
ル量の還元剤を加える。貴金属ヒドロゾルの調製及びこ
れを担持する操作は０〜５０℃の範囲でなされるが、通
常は室温付近でよい。The ion exchange resin used as a carrier may be any anion exchange resin having a quaternary ammonium group. For example, a commercially available product is Amberlite IRA-93 in powder or granular form.
8. Amberlight CG-400, Amberlight A-
26, Amber Rai) IRA-904, etc. In order to increase the loading rate, it is advantageous to use a powdered resin with a larger surface area. However, commercially available anion exchange resins often contain substances as impurities that have a strong protective colloid effect on noble metal hydrosols, which hinders their loading, so please wash them with water before use. It is necessary to exclude. Most commercially available anion exchange resins are of the chloride ion type, but they can also be treated with an aqueous solution of sodium hydroxide, sodium sulfate, etc. to change them to the hydroxide ion type, sulfate ion type, etc. as carriers. used. The amount of ion exchange resin used is about 20 to 1000 times, preferably about 50 to 500 times, the total amount of supported noble metals. In preparing a noble metal hydrosol, a reducing agent in a molar amount 0.5 to 10 times that amount is added to a raw material noble metal salt aqueous solution having a concentration in the range of 0.01 to 1 mmol/β. Preparation of the noble metal hydrosol and operations for supporting the same are carried out at a temperature in the range of 0 to 50°C, but usually around room temperature.
得られた担持型貴金属触媒を含む懸濁液はそのままで液
相反応に供することもできるが、通常はろ過又は遠心沈
降により該固体触媒を分取し、水又はアルコールなどで
洗浄した後、乾燥させ又は（ｌ−状態で保存して実用に
供される。The resulting suspension containing the supported noble metal catalyst can be directly subjected to the liquid phase reaction, but usually the solid catalyst is collected by filtration or centrifugal sedimentation, washed with water or alcohol, and then dried. It is used for practical purposes by being stored in the (L-state).
発明の効果
本発明によれば、極めて微細な貴金属コロイド粒子を担
持した固体触媒を容易かつ能率的に得ることができ、得
られた固体触媒は、その触媒表面積が大ぎく液相反応や
気相反応など広い範囲の触媒反応に使用できると同時に
、その回収も容易で゛触媒活性の再現性も良好である。Effects of the Invention According to the present invention, it is possible to easily and efficiently obtain a solid catalyst supporting extremely fine noble metal colloid particles, and the obtained solid catalyst has a large catalytic surface area for liquid-phase reactions and gas-phase reactions. It can be used in a wide range of catalytic reactions such as reactions, and at the same time, it is easy to recover and has good reproducibility of catalytic activity.
実施例 次に実施例によって本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
塩素イオン型陰イオン交換樹脂（ローム・アンド・ハー
ス社製、アンバーライトＣＧ−４００１１゜２００−４
００ ｍｅｓｈ）に８０倍重量の１０％水酸化ナトリウ
ム水溶液を加え約３０分間か鰺まぜ、水洗後ろ過、風乾
して水酸イオン型の陰イオン交換樹脂とした。別途、塩
化ロジウム（ｌｌＩＩ ）（ＲｈＣ１，・３ ）１２０
） ５０１１ ｍｏｌを純水９５社に溶解し、これに水
素化ホウ素ナトリウム２００μｍｏｌの水溶液５ｄを室
温でかきまぜながら滴下して黒かっ色で透明なロジウム
ヒドロゾルを得た。このゾルは数時間以上にわたって均
一透明な状態を保つ。このロジウムヒドロゾルに室温下
で、先の水酸イオン型の陰イオン交換樹脂０．５１５ｇ
を加え、１５分間がきまぜると、樹脂は黒灰色に変化し
、同時に溶液は無色となった。この樹脂を水洗後ろ過、
風乾して黒灰色微粒状の担持型ロジウム触媒が得られた
。Example 1 Chlorine ion type anion exchange resin (manufactured by Rohm and Haas, Amberlite CG-40011゜200-4
00 mesh) was added with 80 times the weight of a 10% aqueous sodium hydroxide solution, mixed for about 30 minutes, washed with water, filtered, and air-dried to obtain a hydroxide ion type anion exchange resin. Separately, rhodium chloride (llII) (RhC1,.3) 120
) 5011 mol was dissolved in pure water 95, and 5 d of an aqueous solution of 200 μmol of sodium borohydride was added dropwise thereto with stirring at room temperature to obtain a brownish and transparent rhodium hydrosol. This sol remains uniformly transparent for several hours or more. Add 0.515 g of the above hydroxyl ion type anion exchange resin to this rhodium hydrosol at room temperature.
was added and stirred for 15 minutes, the resin turned black-gray and at the same time the solution became colorless. After washing this resin with water, filter it.
After air drying, a supported rhodium catalyst in the form of black-gray fine particles was obtained.
この相持型ロジウム触媒１０ｚｙ（ロジウム１μｇ−原
子含有）を５０ａ＋Ｎ容ナス型フラスコに入れ、内部を
水素ガスで置換した後、溶存酸素を除いたエタノール２
０ｚβを加えて３０℃、１気圧の水素下で約１０分間か
きまぜて水素で飽和させた。これにシクロヘキセン０．
２５ｍｍｏｌを滴下したところ、直ちに水素の吸収が始
まった。約３０分でシクロヘキセンと等モルの水素を吸
収し、生成物としてシクロヘキサンが得られた。このと
きの水素化初速度はロジウム１ｇ−原子あたりに換算し
て０．４０ ｍｏｌ／ｓｅｅであった。10zy of this supported rhodium catalyst (containing 1 μg of rhodium atoms) was placed in a 50a+N eggplant flask, and after replacing the inside with hydrogen gas, ethanol 2 containing dissolved oxygen was added.
0zβ was added, and the mixture was stirred at 30° C. under 1 atm of hydrogen for about 10 minutes to saturate it with hydrogen. Add 0.0% cyclohexene to this.
When 25 mmol was added dropwise, hydrogen absorption started immediately. Equimolar amounts of hydrogen and cyclohexene were absorbed in about 30 minutes, and cyclohexane was obtained as a product. The initial hydrogenation rate at this time was 0.40 mol/see per 1 g of rhodium.
実施例２
担体の樹脂を変えて、担持型ロジウム、パラジウム及び
白金触媒を調製した。このようにして得られた担持型触
媒による３０℃、１気圧水素下におけるシクロヘキセン
の水素化初速度を次表に示す。Example 2 Supported rhodium, palladium and platinum catalysts were prepared by changing the carrier resin. The initial rate of hydrogenation of cyclohexene using the supported catalyst thus obtained at 30° C. and under 1 atm of hydrogen is shown in the following table.
シクロヘキセンの
Ｐｃ１Ｃ１２・２■２０ アンバーライトＣＧ−４０
０１１０，１６（水酸イオン型）
Ｈ３ＰｔＣｌｓ・６Ｈ２０アンバーライトＣＧ−４００
１１０，０５（水酸イオン型）
ＲｈＣＩ＋・３＋１．０ アンバーライトＩＲへ−９
３８０，３８（水酸イオン型）
ＲｈＣ１，・３１１２０ アンバーライトＣＧ−４０
０１１０，３６（塩素イオン型）
ＲｈＣ１ｓ・３Ｈ２０アンバーライトＣＧ−４００■
０．２３（硫酸イオン型）Cyclohexene Pc1C12・2■20 Amberlite CG-40
0110,16 (hydroxide ion type) H3PtCls・6H20 Amberlite CG-400
110,05 (hydroxide ion type) RhCI+・3+1.0 To Amberlight IR-9
380,38 (hydroxide ion type) RhC1, 31120 Amberlite CG-40
0110,36 (chloride ion type) RhC1s・3H20 Amberlight CG-400■
0.23 (sulfate ion type)
Claims (1)
陰イオン交換樹脂と接触させることにより、貴金属コロ
イド粒子を樹脂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。1. A method for producing a supported noble metal catalyst, which comprises bringing noble metal hydrosol into contact with an anion exchange resin having a quaternary ammonium group to support noble metal colloid particles on the resin surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31825787A JPS63178851A (en) | 1987-12-16 | 1987-12-16 | Production of noble metal catalyst carried on ion-exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31825787A JPS63178851A (en) | 1987-12-16 | 1987-12-16 | Production of noble metal catalyst carried on ion-exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63178851A true JPS63178851A (en) | 1988-07-22 |
| JPS6358621B2 JPS6358621B2 (en) | 1988-11-16 |
Family
ID=18097187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31825787A Granted JPS63178851A (en) | 1987-12-16 | 1987-12-16 | Production of noble metal catalyst carried on ion-exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63178851A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006198491A (en) * | 2005-01-19 | 2006-08-03 | Japan Science & Technology Agency | Polymer immobilized platinum catalyst and its use |
| JP2010214373A (en) * | 2003-02-14 | 2010-09-30 | Wako Pure Chem Ind Ltd | Platinum catalyst fixed on ion exchange resin |
-
1987
- 1987-12-16 JP JP31825787A patent/JPS63178851A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010214373A (en) * | 2003-02-14 | 2010-09-30 | Wako Pure Chem Ind Ltd | Platinum catalyst fixed on ion exchange resin |
| JP2006198491A (en) * | 2005-01-19 | 2006-08-03 | Japan Science & Technology Agency | Polymer immobilized platinum catalyst and its use |
| JP4568802B2 (en) * | 2005-01-19 | 2010-10-27 | 独立行政法人科学技術振興機構 | Polymer-immobilized platinum catalyst and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6358621B2 (en) | 1988-11-16 |
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