JPS63224738A - Production of ruthenium dioxide carring catalyst - Google Patents
Production of ruthenium dioxide carring catalystInfo
- Publication number
- JPS63224738A JPS63224738A JP62057914A JP5791487A JPS63224738A JP S63224738 A JPS63224738 A JP S63224738A JP 62057914 A JP62057914 A JP 62057914A JP 5791487 A JP5791487 A JP 5791487A JP S63224738 A JPS63224738 A JP S63224738A
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- carrier
- compd
- catalyst
- dioxide
- 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
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 2
- 150000003304 ruthenium compounds Chemical class 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 14
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 229910021603 Ruthenium iodide Inorganic materials 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 abstract description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- ZFBUHAMJIRQEOU-UHFFFAOYSA-N [Ce++].[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ce++].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZFBUHAMJIRQEOU-UHFFFAOYSA-N 0.000 abstract 1
- DAKKHQAZXRANTD-UHFFFAOYSA-O [NH4+].[Ce+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [NH4+].[Ce+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DAKKHQAZXRANTD-UHFFFAOYSA-O 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 12
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- -1 ruthenium dioxide compound Chemical class 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical group 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MABUCSPRFWKLAI-UHFFFAOYSA-N methanol;octadecanoic acid Chemical compound OC.CCCCCCCCCCCCCCCCCC(O)=O MABUCSPRFWKLAI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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、二酸化ルテニウム添着触媒の製造方法に関し
、更に詳しくは過酸化物の分解などの酸化還元反応の触
媒として有用な二酸化ルテニウム添着触媒の製法に関す
る。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a catalyst impregnated with ruthenium dioxide, and more specifically, a method for producing a catalyst impregnated with ruthenium dioxide, which is useful as a catalyst for redox reactions such as decomposition of peroxide. Regarding the manufacturing method.
二酸イζルテニウム（Ｒｕ０２）は、少なくとも室温で
は、酸、アルカリなどに侵されない安定な化合物であり
、過酸化物の分解などの酸化還元反応に対し強い触媒作
用を持っており、食塩電解の際の陽極（通常金属チタン
）表面につけて塩素の過電圧を低下せしめるのに極めて
有効に利用されている。Ruthenium dioxide (Ru02) is a stable compound that is not attacked by acids and alkalis at least at room temperature, and has a strong catalytic effect on redox reactions such as decomposition of peroxides, and is used in salt electrolysis. It is very effectively used to reduce the overvoltage of chlorine by attaching it to the surface of the anode (usually titanium metal).
しかし、有機化学反応では水添触媒としての僅かな報告
があるに過ぎない。これは、ＲｕＯ２を耐熱性に乏しく
或いは複雑な形状の担体に担持ぜしめて、実用的な触媒
を製造することが容易でないことに起因する。However, there are only a few reports on its use as a hydrogenation catalyst in organic chemical reactions. This is because it is not easy to manufacture a practical catalyst by supporting RuO2 on a carrier with poor heat resistance or a complicated shape.
本発明者らは、上述のような現状に鑑み鋭意検討した結
果、無機物並びに有機物の種々の形状の担体に容易な方
法でＲｕＯ□を添着することのできる、実用的なＲｕＯ
２添着触媒の製造方法を見出した。As a result of intensive studies in view of the above-mentioned current situation, the present inventors have discovered a practical RuO that can be attached to supports of various shapes of inorganic and organic materials by an easy method.
We have discovered a method for producing a 2-impregnated catalyst.
本発明によれば二酸化ルテニウム添着触媒の製造方法が
提供されるのであって、この方法は、ルテニウノ、化合
物の水溶液に酸化剤を添加し、四酸化ルテニウムとして
揮発させて担体上に付着ぜしく２）
め、担体上で四酸化ルテニウムを二酸化ルテニウムに還
元せしめることを特徴とする。According to the present invention, a method for producing a catalyst impregnated with ruthenium dioxide is provided, and this method involves adding an oxidizing agent to an aqueous solution of a ruthenium dioxide compound, volatilizing it as ruthenium tetroxide, and depositing it on a carrier. ) is characterized by reducing ruthenium tetroxide to ruthenium dioxide on a carrier.
ルテニウムの揮発性は古くから知られており、一般に揮
発性ルテニウムというのは殆どが四酸化物（ＲｕＯ＜）
である。この四酸化ルテニウム（ＲｕＯ４）は８００℃
以上では安定であるが、それ以下では不安定で還元性物
質上ではすぐに還元されて安定なＲｕＯ２になる。Ｒｕ
ｂ、は弱酸としての性質をもっているので強塩基性の液
からは揮発しないが、酸性の液からは揮発する。The volatility of ruthenium has been known for a long time, and volatile ruthenium is generally mostly tetroxide (RuO<).
It is. This ruthenium tetroxide (RuO4) is heated to 800℃
Above that, it is stable, but below that, it is unstable and is immediately reduced to stable RuO2 on a reducing substance. Ru
Since b has properties as a weak acid, it does not volatilize from strongly basic liquids, but it volatilizes from acidic liquids.
Ｒｕ化合物の水溶液にＣｅ （ＩＶ）などの酸化剤を添
加すると、Ｒｕは酸化されてＲｕｂ、を生じ、徐々に揮
発してくる。このものはオゾンに似た臭気をもち、かな
り有機物的な性質があり、例えば四塩化炭素、クロロホ
ルムあるいはベンゼン、トルエン、ヘキサン、オクタン
、ドデカンなどの各種の炭化水素に溶解し、殆どの有機
化合物によく付着する性質をもっている。ところが、Ｒ
ｕＯ４は強い酸化力を有するため、上記有機１ヒ合物に
溶解もしくは付着したＲｕｂ、は速やかに有機化合物を
酸化して、ｔｑ）
自らはＲｕＯ２となり、有機溶媒中にあるいは有機化合
物表面に析出してくる。一方、ＲｕＯ□はさきにも述べ
たように過酸化物分解の触媒作用をもっているので、一
旦析出しなＲｕＯ２によって周辺のＲｕＯ４はつぎつぎ
に分解してＲｕＯ２を生ずるいわゆる自己触媒反応が見
られる。かくして生じたＲｕＯ２は極めて微細であり、
固体有機物表面には極めて強固に付着する。When an oxidizing agent such as Ce (IV) is added to an aqueous solution of a Ru compound, Ru is oxidized to produce Rub, which gradually evaporates. This substance has an odor similar to ozone and is quite organic in nature; it is soluble in carbon tetrachloride, chloroform, and various hydrocarbons such as benzene, toluene, hexane, octane, and dodecane, and is compatible with most organic compounds. It has the property of adhering well. However, R
Since uO4 has a strong oxidizing power, Rub dissolved in or attached to the organic compound described above quickly oxidizes the organic compound, turning itself into RuO2 and precipitating in the organic solvent or on the surface of the organic compound. It's coming. On the other hand, as mentioned earlier, RuO□ has a catalytic effect on peroxide decomposition, so that once precipitated RuO2 decomposes surrounding RuO4 one after another to produce RuO2, a so-called autocatalytic reaction. The RuO2 thus produced is extremely fine;
It adheres extremely firmly to solid organic surfaces.
本発明に用いられるＲｕ化合物は水溶性化合物であれば
良く、Ｒｕ化合物としては種々の化合物があるが、硝酸
ルテニウム［Ｒｕ（ＮＯ３））、塩化ルテニウム［Ｒｕ
Ｃｌ３〕、ヨウ化ルテニウム［：ＲｕＴ、）等３価のＲ
ｕ化合物が良く、とりわけ硝酸ルテニウムが操作上好ま
しい。また、操作時の濃度としては数ｐｐｍから％オー
ターまでの広い範囲で使用可能である。The Ru compound used in the present invention may be any water-soluble compound, and there are various Ru compounds, including ruthenium nitrate [Ru(NO3)), ruthenium chloride [Ru
Cl3], ruthenium iodide [:RuT, ), etc., trivalent R
U compounds are preferred, and ruthenium nitrate is particularly preferred for operational reasons. Further, the concentration during operation can be used in a wide range from several ppm to 10%.
Ｒ，Ｌｌの酸化剤には硝酸第二セリウム（Ｃｅ（ＮＯ３
）Ｊ硝酸第二セリウムアンモニウムＣ（ＮＨ−＞２ｃｅ
（ＮＯ３）６）過ヨウ素酸カリウム〔Ｋ■０４〕、過マ
ンガン酸カリウムＣＫＭｎＯ４） 、重クロム酸カリウ
ムＣＫ２Ｃｒ２Ｏ７，：］（Ａｌ
硫酸第二セリウム〔Ｃｅ（ＳＯｌ）２〕、過硫酸アンモ
ニウムＣ（Ｎ１１４）２８２０ｇ ）或いは電気的手法
等種々あるが、とりわけ硝酸第二セリウムアンモニウム
もしくは硝酸第二セリウムが操作上好ましい。また、酸
化剤は固体状、粉体状でも使用出来るが、固体状、粉１
本状では均−性及び酸化剤としての効率が悪く、溶液状
で使用するのが好ましい。操作時の酸化剤濃度はＲｕ同
様広い範囲で可能であるが、Ｒｕ溶液中のＲｕの当量及
び添加量を考慮して適宜濃度を決定すれば良く、一般に
は０．１〜２．０モル濃度が適切である。The oxidizing agent for R and Ll is ceric nitrate (Ce(NO3
) J ceric ammonium nitrate C (NH->2ce
(NO3)6) Potassium periodate [K■04], Potassium permanganate CKMnO4), Potassium dichromate CK2Cr2O7, : ] (Al Ceric sulfate [Ce(SOl)2], Ammonium persulfate C (N114) There are various methods such as 2820g) or electrical methods, but ceric ammonium nitrate or ceric nitrate is particularly preferred in terms of operation. In addition, the oxidizing agent can be used in solid or powdered form;
In this form, the homogeneity and efficiency as an oxidizing agent are poor, so it is preferable to use it in the form of a solution. The concentration of the oxidizing agent during operation can be in a wide range as with Ru, but the concentration may be determined appropriately by taking into consideration the equivalent amount of Ru in the Ru solution and the amount added, and is generally 0.1 to 2.0 molar concentration. is appropriate.
担体の材買としては有機物または無機物のいずれである
かを問わない。ＲｕＯ４の性質」二還元性を有する有機
化合物を担体とする場合は操作上特に問題とならない。It does not matter whether the carrier material is organic or inorganic. "Properties of RuO4" When an organic compound having a direducing property is used as a carrier, there is no particular problem in operation.
しかし、有機化合物であっても化学的に安定なもの或い
は無機物の場合は、ＲｕＯ４とは反応せず、ＲｕＯ２が
析出し難い為、操作上以下のような工夫を要する。However, in the case of chemically stable organic compounds or inorganic compounds, they do not react with RuO4 and RuO2 is difficult to precipitate, so the following operational measures are required.
即ち、化学的に安定なものではその表面に極めて微量の
還元性有機物を付着せしめておくことにより微細なＲｕ
Ｏ２を析出させ、しかも強固に付着せしめることが出来
る。ＲｕＯ４に対し不活性な各種のセラミック、ガラス
、黒鉛、ポリフッ化エチレン（テフロン）等を担体とし
てＲｕＯ□を添着せしめようとする場合には、先ず表面
を微量の有機（化合）物など還元性物質で被っておき、
ＲｕＯ２の析出を助けなければならない。例えば、微量
の油脂膜をつくっておけば効果的であり、その皮膜をつ
くるにはベンゼン、アルコールなどの揮発性の溶媒で油
脂の希薄溶液をつくり、これを担体物質につけ、溶媒を
揮散させる方法とか、油脂を加熱して発生するガスに担
体物質をさらしてもよい。即ち、わずかに担体を有機物
で汚す程度が望ましい。有機物が多すぎ或いは担体への
付着性が弱いときは、析出しなＲｕＯ２は剥離してしま
う。In other words, if a chemically stable Ru
O2 can be precipitated and adhered firmly. When attempting to attach RuO□ using various types of ceramics, glass, graphite, polyfluorinated ethylene (Teflon), etc. as carriers that are inert to RuO4, first coat the surface with a trace amount of a reducing substance such as an organic (compound). Cover it with
The precipitation of RuO2 must be supported. For example, it is effective to create a small amount of oil film, and to create that film, you can create a dilute solution of oil with a volatile solvent such as benzene or alcohol, apply this to a carrier material, and evaporate the solvent. Alternatively, the carrier material may be exposed to gas generated by heating oil or fat. That is, it is desirable that the carrier be slightly contaminated with organic matter. If there is too much organic matter or if the adhesion to the carrier is weak, the precipitated RuO2 will peel off.
表面に酸化物皮膜を作って安定化している、例えばステ
ンレススチール、ジルコニウム合金などの場合は表面を
水素ガスなどでわずかに還元させておき、その後ＲｕＯ
４で処理するのが有効である。For example, in the case of stainless steel, zirconium alloy, etc., which are stabilized by forming an oxide film on their surfaces, the surface is slightly reduced with hydrogen gas, etc., and then RuO
4 is effective.
ＲｕＯ２析出後適当な温度で加熱することにより表面に
より強固なＲｕＯ２をつけることが出来る。By heating at an appropriate temperature after RuO2 precipitation, stronger RuO2 can be attached to the surface.
以下に、実施例を示し、本発明を具体的に説明する。 EXAMPLES Below, the present invention will be specifically explained with reference to Examples.
実施例１
１Ｌの共栓付三角フラスコにポリエヂレン粉末（１００
ｘ ２００メッシ、：Ｌ ）１００［？を入れ、これに
ＲｕＯ２として１ｍｇ／ｍｌを含む硝酸酸性硝酸ルテニ
ウム水溶液１１０ｍ１を加え、次いでＩＭ硝酸第二セリ
ウムアンモニウム水溶？７Ｍ８．３ｍｌを加える。栓を
した後３０分間ふりまぜる。その後、粉末を濾別し、メ
タノールで洗った後風乾さぜ、ＲｕＯ２０，１２６添着
ポリエチレン粉末を得た。Example 1 Polyethylene powder (100
x 200 Messi, :L) 100[? to this was added 110 ml of a nitric acidic ruthenium nitrate aqueous solution containing 1 mg/ml of RuO2, and then IM ceric ammonium nitrate aqueous solution? Add 8.3 ml of 7M. After capping, stir for 30 minutes. Thereafter, the powder was filtered, washed with methanol, and air-dried to obtain RuO20,126-impregnated polyethylene powder.
実施例２
１Ｌの共栓付三角フラスコにポリプロピレン粉末（１０
０ｘ ２００メツシユ） １００ｇを入れ、以下実施例
１と同様に操作し、Ｒｕ０２０．１％添着ポリプロピレ
ン粉末を得な。Example 2 Polypropylene powder (10
0x200 mesh) was added and the following procedure was carried out in the same manner as in Example 1 to obtain a polypropylene powder impregnated with 0.1% Ru0.
実施例３
ヤシ殻活性炭（２０Ｘ ４８メツシユ）１００１？を第
１図に示す装置の円筒状ステンレス製金ｉ１１Ｍ（容量
２５０ｍ ｌ ）に充填し、円筒状密閉容器内で３ｐｐ
ｍの速度で回転させておく。注入口より容器内にＲｕＯ
２として１ｍｇ／ｍｌを含む硝酸酸性硝酸ルテニウム水
溶液５５０＋ｎｌを加え、次いで同じ注入口より１Ｍ硝
酸第二セリウムアンモニウム水溶液４２．５＋１１１を
１５分かけて注加し、その後３０分間運転する。終了後
、ヤシ殻活性炭を円筒状ステンレス製金網から取り出し
、ＲｕＯ２０，５％添着ヤシ殻活性炭を得た。Example 3 Coconut shell activated carbon (20X 48 mesh) 1001? was filled into a cylindrical stainless steel gold i11M (capacity 250 ml) of the apparatus shown in Fig. 1, and 3 pp.
Let it rotate at a speed of m. RuO enters the container from the injection port.
As No. 2, 550+ nl of a nitric acidic ruthenium nitrate aqueous solution containing 1 mg/ml was added, and then a 1M ceric ammonium nitrate aqueous solution of 42.5+111 was injected from the same injection port over 15 minutes, followed by operation for 30 minutes. After completion, the coconut shell activated carbon was taken out from the cylindrical stainless steel wire gauze to obtain coconut shell activated carbon impregnated with 20.5% RuO.
実施例４
１０．６ｃｍＸ３０ｃｍ（表面積３１８ｃ＋ｎ勺の布状
活性炭を第１図に示す装置の円筒状ステンレス製金網２
の表面に張り付け、円筒状密閉容器１内でモータ４によ
り３ｒｐ＋ｎの速度で回転させておく。注入口３より容
器内にＲｕＯ２として０．１ ＋ｎｇ／ｍｌを含む硝酸
酸性硝酸ルテニウム水溶液３５ｍ１を加え、次いで同じ
注入口より０．１Ｍ硝酸第二セリウムアンモニウム水溶
液３ｍｌを５分かりて注加し、その後３０分間運転する
。終了後、布状活性炭を円筒状ステンレス製金網からは
がし、Ｒｕｂ２ｏ、 １ ｇ／ｍ２添着活性炭を得た。Example 4 Cloth-like activated carbon with a surface area of 318 cm x 30 cm (318 cm
is pasted on the surface of the cylindrical sealed container 1 and rotated by the motor 4 at a speed of 3rp+n. Add 35 ml of a nitric acidic ruthenium nitrate aqueous solution containing 0.1 + ng/ml as RuO2 into the container through the injection port 3, then pour 3 ml of a 0.1 M ceric ammonium nitrate aqueous solution in 5 minutes from the same injection port, and then Drive for 30 minutes. After completion, the cloth-like activated carbon was peeled off from the cylindrical stainless wire gauze to obtain Rub2o, 1 g/m2 impregnated activated carbon.
実施例５
１０．６ｃｍＸ３０ｃｍ（表面積３１８ｃ＋ｎ２）のポ
リエチレンフィルムを第１図に示す装置の円筒状ステン
レス製金網２の表面に張り付け、その後実施例４と同様
に操作し、ＲｕＯ２０，１ｇ／ｍ２添着ポリエチレンフ
ィルムを得た。Example 5 A polyethylene film of 10.6 cm x 30 cm (surface area 318 c + n2) was attached to the surface of the cylindrical stainless steel wire mesh 2 of the apparatus shown in FIG. I got it.
実施例６
１０．６ｃｍＸ３０ｃｍ（表面ｆｉｆ３１８ｃｍ２）の
テフロンフィルムを０．ＯＩＷ／Ｗ％ステアリン酸メタ
ノール溶液に一時間浸漬し、その後取り出し、風乾させ
る。次いで、第１図に示す装置の円筒状ステンレス製金
網２の表面に張り付け、次いで実施例４と同様に操作し
、ＲｕＯ２０、１ｇ／ ｍ２添着テフロンフィルムを得
た。Example 6 A Teflon film of 10.6 cm x 30 cm (surface fif 318 cm2) was coated with 0. Soak in OIW/W% stearic acid methanol solution for one hour, then remove and air dry. Next, it was pasted on the surface of the cylindrical stainless steel wire mesh 2 of the apparatus shown in FIG. 1, and then operated in the same manner as in Example 4 to obtain a Teflon film impregnated with RuO20 at 1 g/m2.
実施例７
布状活性炭５（２０ｃｍ幅Ｘ５ｍ長さ）を第２図に示ず
装置にセラ１へし、ＲｕＯ２として０．１＋ｎｇ／ｍｌ
を含む硝酸酸性硝酸ルテニウム水溶液４４０＋ｎｌ、０
．１Ｍ硝酸第二セリウムアンモニウム水溶液３８ｍ１を
１７０分かけてｎｕ注入口８およびＣｅ注入口９より注
入する。Ｒ，ｕ溶液およびＣｅ溶液注入開始直後に駆動
ローラ６を布状活性炭が１ｃｍ／ｍｉｎ、の速度で移動
するように回転させ、注入終了ｆ＆６０分間（操（’ｔ
Ｈ時間合計２３０分）運転し、終了とする。布状活性炭
をローラがｔ、はずし２、運転開始直後及び２００分目
のところで切り取り、ＲＬＩ０２０．１ ｇ／ ｍ２添
着布状活性炭２ｍ（２０ｃｒｎ幅×２【ｏ長さ一表面積
４．０００ｃｍ２）を得た。Example 7 Cloth-like activated carbon 5 (20 cm width x 5 m length) was placed in a cellar 1 in an apparatus not shown in Fig. 2, and 0.1+ng/ml of RuO2 was added.
Nitric acidic ruthenium nitrate aqueous solution containing 440+nl, 0
．． 38 ml of 1M ceric ammonium nitrate aqueous solution is injected from the nu injection port 8 and the Ce injection port 9 over 170 minutes. Immediately after starting the injection of the R, u solution and the Ce solution, the drive roller 6 was rotated so that the cloth-like activated carbon moved at a speed of 1 cm/min, and the injection was completed for f & 60 minutes (operation ('t).
H time total 230 minutes) operation and end. The cloth-like activated carbon was cut off when the roller was removed 2, immediately after the start of operation, and at the 200th minute to obtain RLI020.1 g/m2 impregnated cloth-like activated carbon 2 m (20 crn width x 2 [o length per surface area 4.000 cm2). Ta.
第１図は実施例で用いた、本発明方法の実施のための装
置の一態様を示す模式図であり、第２図は他の態様の装
置を示す模式図である。
１・・・密閉容器、 ２・・・スデンレス金網、３
・・・注入口、 ４・・・モーター、５・・・−
布状活性炭、 ６・・・駆動ローラ、７・・・支持ロー
ラ、 ８，９・・・溶液注入口、１０・・・じゃま板
。
１・・・密閉容器
２・・・ステンレス金鋼
３．８．９・・・溶液注入口
４・・・モータ
６・・駆動口−ラFIG. 1 is a schematic diagram showing one embodiment of the apparatus for carrying out the method of the present invention used in Examples, and FIG. 2 is a schematic diagram showing another embodiment of the apparatus. 1...Airtight container, 2...Sdenless wire mesh, 3
...Inlet, 4...Motor, 5...-
Cloth-like activated carbon, 6... Drive roller, 7... Support roller, 8, 9... Solution inlet, 10... Baffle plate. 1... Airtight container 2... Stainless steel 3.8.9... Solution inlet 4... Motor 6... Drive port-ra
Claims (1)
化ルテニウムとして揮発させて担体上に付着せしめ、担
体上で四酸化ルテニウムを二酸化ルテニウムに還元せし
めることを特徴とする、二酸化ルテニウム添着触媒の製
造方法。1. Production of a catalyst impregnated with ruthenium dioxide, which is characterized by adding an oxidizing agent to an aqueous solution of a ruthenium compound, volatilizing it as ruthenium tetroxide and depositing it on a carrier, and reducing the ruthenium tetroxide to ruthenium dioxide on the carrier. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62057914A JPS63224738A (en) | 1987-03-14 | 1987-03-14 | Production of ruthenium dioxide carring catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62057914A JPS63224738A (en) | 1987-03-14 | 1987-03-14 | Production of ruthenium dioxide carring catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63224738A true JPS63224738A (en) | 1988-09-19 |
| JPH0568302B2 JPH0568302B2 (en) | 1993-09-28 |
Family
ID=13069261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62057914A Granted JPS63224738A (en) | 1987-03-14 | 1987-03-14 | Production of ruthenium dioxide carring catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63224738A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004283774A (en) * | 2003-03-24 | 2004-10-14 | Kaken:Kk | Catalyst for fuel cell and its manufacturing method |
| JP2009533830A (en) * | 2006-04-14 | 2009-09-17 | アプライド マテリアルズ インコーポレイテッド | Reliable fuel cell electrode design |
| CN101862674A (en) * | 2010-05-24 | 2010-10-20 | 清华大学 | Monolithic catalyst for use in preparation of chloride by using hydrogen chloride and preparation method thereof |
| CN108097244A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of preparation of anti-sintering load ruthenium catalyst of high dispersive and catalyst and application |
| CN110453210A (en) * | 2019-09-06 | 2019-11-15 | 北京星航机电装备有限公司 | A kind of low chromium magnesium alloy chemical oxidation solution and chemical oxidation method |
| CN114121336A (en) * | 2022-01-27 | 2022-03-01 | 西安宏星电子浆料科技股份有限公司 | High-wear-resistance paste |
-
1987
- 1987-03-14 JP JP62057914A patent/JPS63224738A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004283774A (en) * | 2003-03-24 | 2004-10-14 | Kaken:Kk | Catalyst for fuel cell and its manufacturing method |
| JP2009533830A (en) * | 2006-04-14 | 2009-09-17 | アプライド マテリアルズ インコーポレイテッド | Reliable fuel cell electrode design |
| CN101862674A (en) * | 2010-05-24 | 2010-10-20 | 清华大学 | Monolithic catalyst for use in preparation of chloride by using hydrogen chloride and preparation method thereof |
| CN108097244A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of preparation of anti-sintering load ruthenium catalyst of high dispersive and catalyst and application |
| CN110453210A (en) * | 2019-09-06 | 2019-11-15 | 北京星航机电装备有限公司 | A kind of low chromium magnesium alloy chemical oxidation solution and chemical oxidation method |
| CN114121336A (en) * | 2022-01-27 | 2022-03-01 | 西安宏星电子浆料科技股份有限公司 | High-wear-resistance paste |
| CN114121336B (en) * | 2022-01-27 | 2022-04-19 | 西安宏星电子浆料科技股份有限公司 | High-wear-resistance paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0568302B2 (en) | 1993-09-28 |
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