JP2005154834A - Ruthenium ultrafine powder and its production method - Google Patents
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- JP2005154834A JP2005154834A JP2003395152A JP2003395152A JP2005154834A JP 2005154834 A JP2005154834 A JP 2005154834A JP 2003395152 A JP2003395152 A JP 2003395152A JP 2003395152 A JP2003395152 A JP 2003395152A JP 2005154834 A JP2005154834 A JP 2005154834A
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- 239000000843 powder Substances 0.000 title claims abstract description 62
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 36
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000009832 plasma treatment Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- 230000002776 aggregation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000004663 powder metallurgy Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
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Abstract
Description
本発明は、触媒や粉末冶金原料などの用途に使用可能な、ルテニウム超微粉末およびその製造方法に関するものである。 The present invention relates to a ruthenium ultrafine powder that can be used for applications such as catalysts and powder metallurgical raw materials, and a method for producing the same.
従来、触媒用のルテニウム粉末は、例えば塩化物水溶液の液中還元による方法によって製造されていた（特許文献１参照）。また、粉末冶金用のルテニウム粉末としては、例えば金属塩の酸化還元による方法によって製造されていた（特許文献２参照）。 Conventionally, ruthenium powder for a catalyst has been produced by, for example, a method of reducing an aqueous chloride solution in a liquid (see Patent Document 1). Moreover, as ruthenium powder for powder metallurgy, it was manufactured, for example by the method by the oxidation reduction of a metal salt (refer patent document 2).
ルテニウムは、白金族元素のひとつであり、グラム単価が高価であるだけでなく、比重も大きいため、同じ体積当たりの価格が極めて高い。従って、使用される分野を問わず、低価格化のためには、用いるルテニウムの量を可能な限り少なくしたいという強い要求がある。例えば、触媒用途の場合には、反応の面積を多くするために、同じ重量であればなるべく多くの表面積を持った粉末が望ましく、このためには、粉末の粒径は、細かい方が良いとされている。 Ruthenium is one of the platinum group elements, and not only is the gram unit price expensive, but also has a large specific gravity, so the price per volume is extremely high. Therefore, regardless of the field of use, there is a strong demand to reduce the amount of ruthenium used as much as possible in order to reduce the price. For example, in the case of a catalyst application, in order to increase the reaction area, a powder having as much surface area as possible is desirable for the same weight, and for this purpose, a finer particle size is better. Has been.
また、ルテニウムは、融点が約２５００℃と高いために、非常に難焼結性の材料でもある。粉末冶金用途の場合には、焼結性の高さが重要な要素となる。このためにも、粉末の粒径は細かい方が良いとされている。
上述のような、従来のルテニウム粉末の製造方法は、有効な手法ではあるが、製造速度が遅く、量産性に欠けるという欠点があった。特許文献２の手法の場合には、得られる粉末の粒径は数μｍ以上であり、平均粒径が１μｍ以下のルテニウム超微粉末を安定して量産することは困難であった。特許文献１の手法の場合には、結晶性が悪く、粉末の表面の凹凸が大きく荒れているために、粉末の流動性が悪いという問題があった。
Although the conventional method for producing ruthenium powder as described above is an effective method, it has a drawback in that the production rate is slow and mass productivity is lacking. In the case of the technique of
本発明の目的は、平均粒径１μｍ以下という超微細なルテニウム超微粉末を安定して提供することである。 An object of the present invention is to stably provide an ultrafine ruthenium ultrafine powder having an average particle size of 1 μm or less.
直径１μｍ以下といった超微細な金属粉末が製造可能な方法は幾つかあるが、その中でも量産性と安定性の高い方法は、金属原料を蒸気化し、それを凝集させて回収する方法である。しかし、本発明が製造の対象とするルテニウム粉末においては、元素Ｒｕは融点が約２５００℃、沸点が約４９００℃という極めて難溶解、難蒸発性の材料であり、通常の加熱方法ではとても蒸発させることは困難な元素種である。 There are several methods that can produce an ultrafine metal powder having a diameter of 1 μm or less. Among them, a method with high mass productivity and stability is a method in which a metal raw material is vaporized and then aggregated and recovered. However, in the ruthenium powder to be manufactured by the present invention, the element Ru is an extremely difficult-to-dissolve and hardly-evaporable material having a melting point of about 2500 ° C. and a boiling point of about 4900 ° C. It is a difficult element species.
そこで、本発明者は、高いエネルギーの熱プラズマ処理に着目した。つまり、熱プラズマでは１万度を超えるような高温の発生が可能であり、この極めて高い温度を利用することによってルテニウムのような高融点、高沸点材料でも、溶融、気化できると考えた。そして、試行を繰り返した結果、熱プラズマを利用した手法によれば、超微細なルテニウム粉末、特には各種の触媒や粉末冶金原料に最適なルテニウム超微粉末とできることを知見し、本発明に到達した。 Therefore, the present inventor has focused on high energy thermal plasma processing. In other words, it was considered that thermal plasma can generate a high temperature exceeding 10,000 degrees, and by using this extremely high temperature, even a high melting point and high boiling point material such as ruthenium can be melted and vaporized. As a result of repeated trials, it was discovered that ultra-fine ruthenium powder, particularly ruthenium ultra-fine powder suitable for various catalysts and powder metallurgy raw materials, can be obtained by the method using thermal plasma, and the present invention has been achieved. did.
すなわち本発明は、（１）実質的にＲｕでなる微粉末であって、熱プラズマ処理により平均粒径が１μｍ以下に調整されていることを特徴とするルテニウム超微粉末である。 That is, the present invention is (1) a ruthenium ultrafine powder characterized in that it is a fine powder substantially made of Ru, and the average particle size is adjusted to 1 μm or less by thermal plasma treatment.
また、（２）Ｒｕを含む原料を熱プラズマ中に通して気化させ、凝集させることで、平均粒径が１μｍ以下に調整された実質的にＲｕでなる微粉末を得ることを特徴とするルテニウム超微粉末の製造方法、（３）あるいはさらに、凝集は、原料が気化された蒸気に不活性ガスを接触させて行なうことを特徴とするルテニウム超微粉末の製造方法、（４）あるいはさらに、原料は、実質的にＲｕでなる粉末であることを特徴とするルテニウム超微粉末の製造方法である。 (2) Ruthenium characterized by obtaining a fine powder substantially made of Ru having an average particle diameter adjusted to 1 μm or less by vaporizing and aggregating a raw material containing Ru through thermal plasma. A method for producing ultrafine powder, (3) or, further, agglomeration is carried out by bringing an inert gas into contact with the vaporized raw material, (4) or further, The raw material is a ruthenium ultrafine powder manufacturing method characterized in that the raw material is a powder substantially made of Ru.
本発明によれば、例えば触媒用、粉末冶金原料用に適したルテニウム超微粉末を安定して量産することが可能となる。 According to the present invention, it is possible to stably mass-produce ruthenium ultrafine powder suitable for, for example, a catalyst and a powder metallurgy raw material.
上述したように、本発明の重要な特徴は、ルテニウムという難溶融、難蒸発性の材料を気化させるにあたり、熱プラズマという強力な熱源を用いる点である。そして、その特別な熱源を用いたことで気化させた原料蒸気を凝集させることにより、１μｍ以下のルテニウム粉末を得るところに特徴を有する。ここで、本発明のルテニウム超微粉末とは、平均粒径で１μｍ以下の粉末を言い、１μｍ以下とするのは、先述の理由により、特に触媒や粉末冶金原料の用途に好ましいからである。 As described above, an important feature of the present invention is that a powerful heat source called thermal plasma is used to vaporize a hardly meltable and hardly vaporizable material called ruthenium. And, it is characterized in that ruthenium powder of 1 μm or less is obtained by agglomerating the raw material vapor evaporated by using the special heat source. Here, the ultrafine ruthenium powder of the present invention means a powder having an average particle diameter of 1 μm or less, and the reason why it is 1 μm or less is that it is particularly preferable for use as a catalyst or a powder metallurgical raw material for the reasons described above.
本発明のルテニウム超微粉末の製造方法について説明する。図１は、そのための装置構成の一例を示すものである。図１において、原料は、ガスに乗せた原料粉末４として原料供給管３を通って、高周波プラズマトーチ２により発生させた熱プラズマ５中に供給される。そして、その供給された原料粉末は、ほとんど瞬時に気化し、搬送ガス６に乗ってチャンバー１から回収容器７へと運ばれるうちに凝集し、超微粉末となる。ポンプ８によって差圧が与えられている回収容器７は内部にフィルタがセットされており、このフィルタで粉末が回収される。
The method for producing the ruthenium ultrafine powder of the present invention will be described. FIG. 1 shows an example of an apparatus configuration for that purpose. In FIG. 1, a raw material is supplied as a raw material powder 4 on gas through a raw
まず、熱プラズマ中に投入する原料としては、ルテニウムを含む原料であればよいが、製造するルテニウム超微粉末の高純度と均一かつ超微細な粒度分布を達成するためには、実質的にＲｕでなる原料粉末であることが好ましい。例えば従来の金属塩酸化還元法で得たルテニウム粉末などを用いることができる。 First, the raw material to be introduced into the thermal plasma may be a raw material containing ruthenium, but in order to achieve the high purity and uniform and ultrafine particle size distribution of the ruthenium ultrafine powder to be produced, it is substantially Ru. The raw material powder is preferably For example, ruthenium powder obtained by a conventional metal hydrochloride reduction method can be used.
次に、熱源としては、図１では高周波プラズマの例を示すが、直流プラズマにも適用可能である。但し、直流プラズマはプラズマの速度が速いために、原料（原料粉末）のプラズマ滞在時間が短く、蒸発を促進するためには高周波プラズマを使用することが好ましい。プラズマの動作ガスとしては、アルゴン、ヘリウムなどが用いられる。水素を用いることも可能であって、水素を用いた場合には得られる粉末の粒径が微細になる傾向があることから、好ましい。 Next, as an example of the heat source, FIG. 1 shows an example of high-frequency plasma, but it can also be applied to DC plasma. However, since direct current plasma has a high plasma speed, the plasma residence time of the raw material (raw material powder) is short, and it is preferable to use high frequency plasma in order to promote evaporation. Argon, helium, or the like is used as a plasma working gas. Hydrogen can also be used, and the use of hydrogen is preferable because the particle size of the resulting powder tends to be fine.
そして、搬送ガスとしては、アルゴンやヘリウムなどの不活性ガスを用いることが、酸化抑制の面で好ましい。搬送ガスは、気化したＲｕの蒸気を強制冷却する役割を兼ねており、凝集して得られる粉末の形状や粒径などに強い影響を与える。その影響は、容器形状や排気効率、ガス種などにも依存しているため、一概には説明しにくいが、流量が増えるに従って微粒子化、単粒子化する傾向にある。 And as carrier gas, it is preferable in terms of oxidation suppression to use inert gas, such as argon and helium. The carrier gas also serves to forcibly cool the vaporized Ru vapor, and has a strong influence on the shape and particle size of the powder obtained by agglomeration. The influence depends on the shape of the container, the exhaust efficiency, the gas type, and the like, and is difficult to explain in general. However, as the flow rate increases, it tends to become fine particles or single particles.
熱プラズマ処理に供する原料には、金属塩酸化還元法で得た、純度９９．９％Ｒｕの平均粒径１０μｍの粉末を用いた。そして、この原料粉末を、流量１ＮＬ／ｍｉｎのＡｒガスと混ざった状態で、毎分２０ｇづつプラズマ中に投入した。プラズマの発生には、出力１０ｋＷの小型高周波プラズマ発生装置を用いた。動作ガスにはＡｒガスを流量２０ＮＬ／ｍｉｎで用いた。搬送ガスにはＡｒガスを流量１５０ＮＬ／ｍｉｎで用いた。 As a raw material to be subjected to the thermal plasma treatment, a powder having a purity of 99.9% Ru and an average particle diameter of 10 μm obtained by a metal oxyhydrochlorination method was used. And this raw material powder was thrown into the plasma at a rate of 20 g per minute in a state mixed with Ar gas having a flow rate of 1 NL / min. A small high-frequency plasma generator with an output of 10 kW was used for plasma generation. Ar gas was used as the working gas at a flow rate of 20 NL / min. Ar gas was used as the carrier gas at a flow rate of 150 NL / min.
以上の操業条件にて装置を１０分間稼動した後、６０分間冷却して、フィルタに付着した粉末を回収し、回収した粉末の粒径を電子顕微鏡で測定した。粒径は最も大きなものでも０．１μｍ程度であり、目標とする１μｍ以下の平均粒径を十分に満足するものであった。なお、得られたルテニウム超微粉末の純度は９９．９％、比表面積は９．４ｍ２／ｇであり、この値から計算した粉末の平均粒径は０．０５μｍであった。また、Ｘ線の半価幅から超微粉末の有する結晶粒のサイズを測定したところ、平均で約５０ｎｍであり、ほぼ単結晶の粒子からなる超微粉末が得られた。 The apparatus was operated for 10 minutes under the above operating conditions, then cooled for 60 minutes, the powder adhering to the filter was recovered, and the particle size of the recovered powder was measured with an electron microscope. The largest particle size was about 0.1 μm, and sufficiently satisfied the target average particle size of 1 μm or less. The obtained ruthenium ultrafine powder had a purity of 99.9% and a specific surface area of 9.4 m 2 / g, and the average particle diameter of the powder calculated from this value was 0.05 μm. Further, when the size of the crystal grains of the ultrafine powder was measured from the half-value width of the X-ray, the average was about 50 nm, and an ultrafine powder consisting of almost single crystal particles was obtained.
本発明であれば、例えば触媒や粉末冶金原料といった用途に最適なルテニウム超微粉末とすることができる。 If it is this invention, it can be set as the ruthenium ultrafine powder optimal for uses, such as a catalyst and a powder metallurgy raw material, for example.
１ チャンバー、２ （高周波）プラズマトーチ、３ 原料供給管、４ ガスに乗せた原料粉末、５ （高周波）熱プラズマ、６ 搬送ガス、７ 回収容器（フィルタ入り）、８ ポンプ 1 chamber, 2 (high frequency) plasma torch, 3 raw material supply pipe, 4 raw material powder on gas, 5 (high frequency) thermal plasma, 6 carrier gas, 7 collection container (with filter), 8 pump
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009287054A (en) * | 2008-05-27 | 2009-12-10 | Toda Kogyo Corp | Method for producing inorganic material and metallic material by high frequency plasma process |
| CN101289229B (en) * | 2007-01-29 | 2010-12-22 | 日矿金属株式会社 | Method for producing ammonium hexachlororuthenate and ruthenium powder, as well as ammonium hexachlororuthenate |
| KR101143860B1 (en) | 2009-12-24 | 2012-05-22 | 희성금속 주식회사 | Manufacturing method of a Ru powder and Ru target material using a waste-Ru target |
| WO2012150757A1 (en) * | 2011-05-04 | 2012-11-08 | 희성금속 주식회사 | Preparation method of ruthenium (ru) powder for preparation of ruthenium target |
| JP2013510243A (en) * | 2009-11-10 | 2013-03-21 | テクノロジアン テュトキムスケスクス ヴェーテーテー | Nanoparticle production method and nanoparticle production apparatus |
| KR101285284B1 (en) | 2011-04-26 | 2013-07-11 | 희성금속 주식회사 | Manufacturing method of a high purity Ru powder and target using a waste Ru target |
-
2003
- 2003-11-26 JP JP2003395152A patent/JP2005154834A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289229B (en) * | 2007-01-29 | 2010-12-22 | 日矿金属株式会社 | Method for producing ammonium hexachlororuthenate and ruthenium powder, as well as ammonium hexachlororuthenate |
| JP2009287054A (en) * | 2008-05-27 | 2009-12-10 | Toda Kogyo Corp | Method for producing inorganic material and metallic material by high frequency plasma process |
| JP2013510243A (en) * | 2009-11-10 | 2013-03-21 | テクノロジアン テュトキムスケスクス ヴェーテーテー | Nanoparticle production method and nanoparticle production apparatus |
| KR101143860B1 (en) | 2009-12-24 | 2012-05-22 | 희성금속 주식회사 | Manufacturing method of a Ru powder and Ru target material using a waste-Ru target |
| KR101285284B1 (en) | 2011-04-26 | 2013-07-11 | 희성금속 주식회사 | Manufacturing method of a high purity Ru powder and target using a waste Ru target |
| WO2012150757A1 (en) * | 2011-05-04 | 2012-11-08 | 희성금속 주식회사 | Preparation method of ruthenium (ru) powder for preparation of ruthenium target |
| KR101206416B1 (en) | 2011-05-04 | 2012-11-29 | 희성금속 주식회사 | Method of manufacturing ruthenium powder for fabricating Ru Sputtering Target |
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