JP2008045202A - Method for producing metal nanopowder using gas-phase reaction method - Google Patents

Method for producing metal nanopowder using gas-phase reaction method Download PDF

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JP2008045202A
JP2008045202A JP2007014915A JP2007014915A JP2008045202A JP 2008045202 A JP2008045202 A JP 2008045202A JP 2007014915 A JP2007014915 A JP 2007014915A JP 2007014915 A JP2007014915 A JP 2007014915A JP 2008045202 A JP2008045202 A JP 2008045202A
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gas
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chloride
nanopowder
nickel
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JP4546975B2 (en
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Hwa Young Lee
イ・ファ−ヨン
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Korea Institute of Science and Technology KIST
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing metal nanopowder where, in the method for producing metal powder where a metal chloride is evaporated, and is thereafter brought into reduction reaction with gaseous hydrogen at high temperature, so as to produce metal powder, a small amount of gaseous ammonia is simultaneously fed together with the gaseous hydrogen, thus metal nanopowder with a grain size smaller than that by an ordinary method and an extremely narrow grain size distribution can be produced inexpensively. <P>SOLUTION: Quartz tubes 1, 2 with different diameters are introduced into first and second tubular furnaces 3, 4. The first tubular furnace is used for evaporating a metal chloride 5 as the raw material while feeding gaseous nitrogen, and the second tubular furnace is used for simultaneously feeding gaseous hydrogen and gaseous ammonia while keeping the feed of the gaseous nitrogen, and causing reduction reaction with the evaporated metal chloride vapor. In the case of nickel chloride, it is evaporated at 780 to 850°C in the first tubular furnace, and, in the second tubular furnace, nickel nanopowder is produced at 500 to 900°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は金属ナノ粉末の製造方法に関し、より詳しくは、金属塩化物を蒸発させた後、アンモニアガス雰囲気下で、高温で水素ガスと還元反応させることにより、非常に均一な粒度を有する金属ナノ粉末を製造する方法に関する。   The present invention relates to a method for producing metal nanopowder, and more specifically, after metal chloride is evaporated, a metal nanoparticle having a very uniform particle size is obtained by a reduction reaction with hydrogen gas at high temperature in an ammonia gas atmosphere. The present invention relates to a method for producing a powder.

最近、全世界的にナノ技術に関心が集中しており、これに関する研究開発が活発に行われ、各種ナノ材料の製造及び応用に関する新しい技術が国内外で続々と報告されている。このようなナノ技術の特徴は、既存の素材や材料が有する物性を画期的に改善することにより、実現不可能であると考えられていた様々な製品を現実的に実現可能にすることである。例えば、半導体回路の線幅を１００ナノメートル以下にすることにより、従来の水準に比べて集積度を大きく向上させることができ、新しい概念のメモリチップであるＭＲＡＭの実現、各種高性能センサ、及び化学触媒などに広範囲に応用できる。   Recently, attention has been focused on nanotechnology all over the world, and research and development related to this has been actively conducted, and new technologies relating to the production and application of various nanomaterials have been reported one after another in Japan and overseas. The feature of such nanotechnology is to make it possible to realistically realize various products that were thought to be impossible by improving the physical properties of existing materials and materials. is there. For example, by reducing the line width of a semiconductor circuit to 100 nanometers or less, the degree of integration can be greatly improved as compared to the conventional level. Realization of a new concept memory chip MRAM, various high-performance sensors, It can be applied to a wide range of chemical catalysts.

金属ナノ粉末を製造するための方法としては、液相で化学反応を起こさせてナノサイズの金属を沈殿させる方法、および気相で高温熱分解して金属ナノ粉末を得る方法が知られているが、これら２つの方法においては、原料として金属アルコキシドなどの有機金属化合物を使用するのが一般的である。しかし、有機金属化合物は、その多くが非常に高価であるため、金属ナノ粉末の大量生産には経済性の問題が伴う。   Known methods for producing metal nanopowder include a method in which a chemical reaction is caused in a liquid phase to precipitate a nanosized metal, and a method in which a metal nanopowder is obtained by high-temperature pyrolysis in a gas phase. However, in these two methods, it is common to use an organometallic compound such as a metal alkoxide as a raw material. However, since many of the organometallic compounds are very expensive, mass production of metal nanopowder involves economic problems.

このような有機金属化合物を使用して金属ナノ粉末を製造する方法以外の超微粒子製造方法としては、ガス蒸発法、高温で金属シュウ酸塩を水素ガスで還元する方法、金属塩化物蒸気を水素ガスで還元する方法、金属カルボニル化合物を熱分解する方法、金属水溶液に水素ガスを注入して還元する方法などを挙げることができる。   The ultrafine particle production method other than the method of producing metal nanopowder using such an organometallic compound includes a gas evaporation method, a method of reducing metal oxalate with hydrogen gas at a high temperature, and metal chloride vapor by hydrogen. Examples thereof include a method of reducing with a gas, a method of thermally decomposing a metal carbonyl compound, and a method of reducing by injecting hydrogen gas into an aqueous metal solution.

このうち、特に工業的に関心を集めている方法は、金属塩化物蒸気を水素ガスで還元する方法であり、原料として非常に安価な金属塩化物を使用する。この方法は、金属塩化物を適当な温度で加熱して蒸発させ、これにより得られた金属塩化物蒸気と還元ガスである水素との高温反応により所望の粒度を有する金属ナノ粉末を得る。   Among them, the method that is attracting industrial interest is a method of reducing metal chloride vapor with hydrogen gas, and uses a very inexpensive metal chloride as a raw material. In this method, the metal chloride is heated and evaporated at an appropriate temperature, and a metal nanopowder having a desired particle size is obtained by a high-temperature reaction between the metal chloride vapor thus obtained and hydrogen as a reducing gas.

前述した各種原料でナノ金属を製造する方法に関する資料としては、特許文献１〜６などがある。   There are Patent Documents 1 to 6 as materials relating to the method for producing nanometals using the various raw materials described above.

前述した金属ナノ粉末の製造方法のうち、ガス蒸発法などの物理的方法の場合、化学的方法に比べて結晶性が良好で粒度分布が非常に狭いという利点はあるが、装置コスト及び工程コストが高いため、化学的方法に比べて全般的な製造コストが高いという欠点があった。例えば、ニッケルナノ粉末をガス蒸発法で製造する場合、水素還元法で製造する場合に比べて約２倍の製造コストが必要である。   Among the metal nanopowder production methods described above, the physical method such as the gas evaporation method has the advantages that the crystallinity is good and the particle size distribution is very narrow compared to the chemical method. Therefore, there is a drawback that the overall production cost is high compared to the chemical method. For example, when manufacturing nickel nanopowder by the gas evaporation method, the manufacturing cost is about twice as high as when manufacturing by the hydrogen reduction method.

これに対し、金属塩化物を水素還元する方法により金属ナノ粉末を製造する場合は、製造コストが比較的安価で工業的な大量生産が可能であるという利点はあるが、高温での化学反応の精密な制御が難しいため、生産されたナノ粉末の粒度分布が広いという欠点があった。これは、金属塩化物蒸気と水素ガスとが反応する過程で生成された金属粒子核同士が衝突して粒度が大きくなる現象のためであり、通常の方法で高温反応を行う場合、このような現象の制御が極めて難しいという問題があった。
米国特許第６，５２１，０１６号明細書 米国特許第６，３１６，３７７号明細書 米国特許第５，６９８，４８３号明細書 特開２００２−２６６００７号公報 特開２００２−２５５５１５号公報 特開２００２−０６７０００号公報 On the other hand, when producing metal nanopowder by the method of reducing metal chloride with hydrogen, there are advantages that the production cost is relatively low and industrial mass production is possible, but chemical reaction at high temperature is not possible. Since precise control is difficult, there is a drawback that the produced nano-powder has a wide particle size distribution. This is due to the phenomenon that metal particle nuclei generated in the process of reaction of metal chloride vapor and hydrogen gas collide with each other to increase the particle size. There was a problem that it was extremely difficult to control the phenomenon.
US Pat. No. 6,521,016 US Pat. No. 6,316,377 US Pat. No. 5,698,483 JP 2002-266007 A JP 2002-255515 A JP 2002-067000 A

本発明は、このような問題を解決するためになされたもので、金属塩化物を原料として使用してこれを蒸発させた後、高温で水素ガスとの還元反応によりニッケルナノ粉末を製造する方法において、通常の方法に比べて生成されたナノ粉末の粒度が小さく、かつ粒度分布が非常に狭いナノ粉末を非常に安価に製造できる手段を提供することを目的とする。   The present invention has been made to solve such problems, and uses a metal chloride as a raw material to evaporate it, and then produces a nickel nanopowder by a reduction reaction with hydrogen gas at a high temperature. Therefore, an object of the present invention is to provide means capable of producing a nanopowder having a smaller particle size and a very narrow particle size distribution than those obtained by a conventional method at a very low cost.

上記の目的を達成するために、本発明による金属ナノ粉末の製造方法は、窒素ガスを供給しながら原料である金属塩化物を蒸発させる工程と、窒素ガスの供給を維持しながら水素ガスとアンモニアガスを同時に供給して、前記蒸発させた金属塩化物蒸気との還元反応により金属ナノ粉末を得る工程とを含む。   In order to achieve the above object, a method for producing metal nanopowder according to the present invention includes a step of evaporating metal chloride as a raw material while supplying nitrogen gas, and hydrogen gas and ammonia while maintaining the supply of nitrogen gas. And simultaneously supplying gas to obtain metal nanopowder by a reduction reaction with the evaporated metal chloride vapor.

この場合、窒素ガスの供給と水素ガスの供給とは独立して行われることが好ましい。   In this case, the supply of nitrogen gas and the supply of hydrogen gas are preferably performed independently.

また、供給ガスである窒素ガス：水素ガスの割合は１：１〜５：１の範囲であり、水素ガス：アンモニアガスの割合は５：１〜１０：１の範囲であることが好ましい。   Further, the ratio of nitrogen gas: hydrogen gas as the supply gas is preferably in the range of 1: 1 to 5: 1, and the ratio of hydrogen gas: ammonia gas is preferably in the range of 5: 1 to 10: 1.

また、前記金属塩化物は、ニッケル塩化物、タングステン塩化物、鉄塩化物、クロム塩化物、及び銅塩化物から選択されるいずれか１つであることが好ましい。   The metal chloride is preferably any one selected from nickel chloride, tungsten chloride, iron chloride, chromium chloride, and copper chloride.

また、前記金属塩化物がニッケル塩化物の場合、ニッケル塩化物の蒸発温度は７８０〜８５０℃の範囲であり、蒸発したニッケル塩化物蒸気と水素ガス及びアンモニアガスとの反応温度は５００〜９００℃の範囲であることが好ましい。   When the metal chloride is nickel chloride, the evaporation temperature of nickel chloride is in the range of 780 to 850 ° C., and the reaction temperature of the evaporated nickel chloride vapor with hydrogen gas and ammonia gas is 500 to 900 ° C. It is preferable that it is the range of these.

本発明による気相反応法を用いた金属ナノ粉末の製造方法は、ニッケル塩化物を原料として使用してこれを蒸発させた後、高温で水素ガスとの還元反応によりニッケルナノ粉末を製造する方法において、水素ガスと共にアンモニアガスを注入することにより、通常の方法に比べて生成されたニッケルナノ粉末の粒度が小さく、かつ粒度分布が非常に狭い均一なニッケルナノ粉末を製造できるという利点がある。   The method for producing metal nanopowder using the vapor phase reaction method according to the present invention is a method for producing nickel nanopowder by using nickel chloride as a raw material and evaporating it, followed by a reduction reaction with hydrogen gas at a high temperature. In this case, by injecting ammonia gas together with hydrogen gas, there is an advantage that uniform nickel nanopowder having a small particle size distribution and a very narrow particle size distribution can be produced as compared with a normal method.

また、本発明は、ニッケル塩化物を水素還元する方法でニッケルナノ粉末を製造することにより、従来のガス蒸発法や高温熱分解法に比べて製造コストが比較的安価であると共に工業的な大量生産が可能であるという特徴がある。   In addition, the present invention produces nickel nanopowder by a method in which nickel chloride is reduced by hydrogen, thereby making the production cost relatively low compared with the conventional gas evaporation method and high-temperature pyrolysis method and industrial mass production. It has the feature that production is possible.

以下、本発明による金属ナノ粉末の製造方法を詳細に説明する。   Hereinafter, a method for producing metal nanopowder according to the present invention will be described in detail.

本発明の目的は、ニッケル塩化物（ＮｉＣｌ２）を蒸発させ、これにより得た金属塩化物蒸気と水素ガスとの高温還元反応によりニッケルナノ粉末を生成する過程で、水素ガスと共に少量のアンモニアガス（ＮＨ３）を注入することにより達成できる。 An object of the present invention is to evaporate nickel chloride (NiCl 2 ) and produce nickel nanopowder by a high-temperature reduction reaction between the metal chloride vapor obtained thereby and hydrogen gas, and a small amount of ammonia gas together with hydrogen gas. This can be achieved by injecting (NH 3 ).

ここで、水素ガスと混合して注入するアンモニアガスは、水素ガスより比較的還元性が低く、かつ粒子表面での吸着性が非常に強いため、還元反応により生成されたニッケルナノ粒子核に付着して、粒子核同士が凝集する現象を抑制したり、ナノ粒子が急速に成長するのを防止することにより、粒度分布が狭くて均一なサイズを有するニッケルナノ粉末の製造を可能にする。アンモニアガスを加えずに水素ガスだけで還元工程を行った場合、製造されたニッケル粉末の粒度が不均一であり、特に全体的に平均粒度が非常に大きくなるため、上記の効果を達成することができない。   Here, ammonia gas mixed and injected with hydrogen gas is relatively less reducible than hydrogen gas and has a very strong adsorptivity on the particle surface, so it adheres to the nickel nanoparticle nuclei produced by the reduction reaction. Thus, it is possible to manufacture nickel nanopowder having a narrow particle size distribution and a uniform size by suppressing the phenomenon of aggregation of particle nuclei and preventing the nanoparticles from growing rapidly. When the reduction process is performed only with hydrogen gas without adding ammonia gas, the particle size of the produced nickel powder is non-uniform, especially the average particle size becomes very large as a whole. I can't.

以下、例を挙げて本発明の方法をより詳細に説明する。   Hereafter, an example is given and the method of this invention is demonstrated in detail.

図１に示すように、まず、直径が異なる２つの石英管１、２を準備し、大きい石英管１の内部に小さい石英管２を挿入する。ここで、小さい石英管２の長さは大きい石英管１の半分程度にする。準備した石英管１、２をそれぞれ温度制御が可能な２つの管状炉３、４に導入する。これら２つの管状炉３、４のうち、第１管状炉３（蒸発炉）は、塩化ニッケル（ＮｉＣｌ２）を加熱して蒸気にするためのものであり、第２管状炉４（反応炉）は、蒸気化した塩化ニッケルと水素ガスとの還元反応のためのものである。このように準備した装置に、塩化ニッケル５を耐火容器６に入れて小さい石英管２の中間部位に装入する。また、２つのガス注入管７、８を準備し、図１に示すように、第１ガス注入管７は小さい石英管２の内部に、第２ガス注入管８は大きい石英管１の内部に挿入し、排出管９を連結した後にゴム栓１０で石英管１を密封する。 As shown in FIG. 1, first, two quartz tubes 1 and 2 having different diameters are prepared, and a small quartz tube 2 is inserted into a large quartz tube 1. Here, the length of the small quartz tube 2 is about half that of the large quartz tube 1. The prepared quartz tubes 1 and 2 are introduced into two tubular furnaces 3 and 4 each capable of temperature control. Of these two tubular furnaces 3 and 4, the first tubular furnace 3 (evaporation furnace) is for heating nickel chloride (NiCl 2 ) into steam, and the second tubular furnace 4 (reaction furnace). Is for the reduction reaction between vaporized nickel chloride and hydrogen gas. In the apparatus prepared in this way, nickel chloride 5 is placed in a refractory container 6 and charged into an intermediate portion of the small quartz tube 2. Further, two gas injection pipes 7 and 8 are prepared. As shown in FIG. 1, the first gas injection pipe 7 is placed inside the small quartz pipe 2 and the second gas injection pipe 8 is placed inside the large quartz pipe 1. After inserting and connecting the discharge tube 9, the quartz tube 1 is sealed with a rubber plug 10.

前述のように装置の組立が終わった後、第１ガス注入管７に窒素ガスを約３０分間、十分に流して石英管２内部の空気を排出させる。空気の排出が終わった後、塩化ニッケルが位置する第１管状炉３の温度を７８０〜８５０℃まで昇温して塩化ニッケルを蒸発させる。蒸発温度が前記範囲より低いと塩化ニッケルの蒸発速度が遅すぎ、前記範囲より高いと不要なエネルギー消費が発生する。   After assembling the apparatus as described above, nitrogen gas is sufficiently allowed to flow through the first gas injection pipe 7 for about 30 minutes to discharge the air inside the quartz pipe 2. After the discharge of air is finished, the temperature of the first tubular furnace 3 where the nickel chloride is located is raised to 780 to 850 ° C. to evaporate the nickel chloride. When the evaporation temperature is lower than the above range, the evaporation rate of nickel chloride is too slow, and when it is higher than the above range, unnecessary energy consumption occurs.

一方、反応炉である第２管状炉４の温度も、反応温度である５００〜９００℃まで予め昇温し、昇温が終わると、第１ガス注入管７からの窒素ガスの供給はそのまま維持しながら、第２ガス注入管８から反応ガスである水素ガスと共にアンモニア（ＮＨ３）ガスを同時に供給することにより、ニッケルナノ粉末を製造する。反応温度が前記範囲より低いと還元率が低下し、前記範囲より高いとエネルギーコストが上昇する。 On the other hand, the temperature of the second tubular furnace 4 as the reaction furnace is also raised in advance to the reaction temperature of 500 to 900 ° C., and when the temperature rise is finished, the supply of nitrogen gas from the first gas injection pipe 7 is maintained as it is. Meanwhile, nickel nanopowder is manufactured by simultaneously supplying ammonia (NH 3 ) gas together with hydrogen gas as a reaction gas from the second gas injection pipe 8. When the reaction temperature is lower than the above range, the reduction rate decreases, and when it is higher than the above range, the energy cost increases.

本発明において、供給ガスである窒素、水素、及びアンモニアガスの割合は、窒素：水素の割合が１：１〜５：１の範囲であり、かつ水素：アンモニアガスの割合が５：１〜１０：１の範囲であることが適当である。このようなガスの混合割合は、均一な粒度のニッケルナノ粉末の製造に適した範囲であり、ガスの混合割合が前記範囲を外れると、ニッケル粒子が不均一になったり還元率が低下する。   In the present invention, the ratios of nitrogen, hydrogen, and ammonia gas that are supply gases are such that the ratio of nitrogen: hydrogen is 1: 1 to 5: 1, and the ratio of hydrogen: ammonia gas is 5: 1-10. A range of 1 is appropriate. Such a gas mixing ratio is in a range suitable for producing nickel nanopowder with a uniform particle size. If the gas mixing ratio is out of the above range, the nickel particles become non-uniform or the reduction rate decreases.

本発明において石英管を２つ使用してガス注入管を独立して設置した理由は、水素を塩化ニッケル試料側に直接供給した場合、蒸発していない塩化ニッケルと水素とが反応して塩化ニッケル試料の表面で直ちにニッケル金属が生成されるためである。   In the present invention, the reason why the gas injection pipe is independently installed using two quartz tubes is that when hydrogen is directly supplied to the nickel chloride sample side, nickel chloride that has not evaporated reacts with hydrogen to react with nickel chloride. This is because nickel metal is immediately generated on the surface of the sample.

また、前述した本発明の方法により製造されたニッケルナノ粉末は、供給ガスと共に外部に排出され、液相捕集器などを利用してニッケルナノ粉末を回収する。しかし、本発明において、生成されたニッケルナノ粉末の捕集方法はこれに限定されるものではない。   Moreover, the nickel nanopowder produced by the above-described method of the present invention is discharged to the outside together with the supply gas, and the nickel nanopowder is recovered using a liquid phase collector or the like. However, in the present invention, the method for collecting the produced nickel nanopowder is not limited to this.

また、本発明において、水素ガスとアンモニアガスを使用した金属ナノ粉末の製造における対象金属はニッケルに限定されず、金属塩化物を蒸発させて水素との還元反応により金属粉末を製造できるタングステン、鉄、クロム、銅などの金属に適用することもできる。   In the present invention, the target metal in the production of metal nanopowder using hydrogen gas and ammonia gas is not limited to nickel, but tungsten, iron that can produce metal powder by evaporating metal chloride and reducing reaction with hydrogen It can also be applied to metals such as chromium and copper.

本発明による気相反応法を用いた金属ナノ粉末の製造方法は、ニッケル塩化物を原料として使用してこれを蒸発させた後、高温で水素ガスとの還元反応によりニッケルナノ粉末を製造する方法において、水素ガスと共にアンモニアガスを注入することにより、通常の方法に比べて生成されたニッケルナノ粉末の粒度が小さく、かつ粒度分布が非常に狭い均一なニッケルナノ粉末を製造することができる。   The method for producing metal nanopowder using the vapor phase reaction method according to the present invention is a method for producing nickel nanopowder by using nickel chloride as a raw material and evaporating it, followed by a reduction reaction with hydrogen gas at a high temperature. In this case, by injecting ammonia gas together with hydrogen gas, it is possible to produce uniform nickel nanopowder having a small particle size and a very narrow particle size distribution compared to the usual method.

以下、本発明の具体的な工程条件及び特徴を次の実施例により詳細に説明する。   Hereinafter, specific process conditions and features of the present invention will be described in detail with reference to the following examples.

実施例１
塩化ニッケル（ＮｉＣｌ２）５ｇを耐火容器に入れ、図１に示すように本発明の装置を組み立てた後、第１ガス注入管から窒素ガスを３０分間流した。石英管内部の空気の排出が終わった後、反応炉の温度を９００℃、蒸発炉の温度を７８０℃に昇温し、昇温が終わると、窒素の供給はそのまま維持し、第２ガス注入管から水素ガスとアンモニアガスを同時に供給して、ニッケルナノ粉末を製造した。ここで、窒素：水素の供給割合は１：１にし、水素：アンモニアガスの供給割合は１０：１にした。塩化ニッケルと水素との反応により生成されたニッケルナノ粉末は、供給ガスと共に外部に排出させ、排出ガスを灯油が充填された液相捕集器を通過させることにより、ニッケルナノ粉末を回収した。 Example 1
After putting 5 g of nickel chloride (NiCl 2 ) in a refractory container and assembling the apparatus of the present invention as shown in FIG. 1, nitrogen gas was allowed to flow from the first gas injection pipe for 30 minutes. After exhausting the air inside the quartz tube, the temperature of the reactor is raised to 900 ° C. and the temperature of the evaporation furnace is raised to 780 ° C. When the temperature rises, the supply of nitrogen is maintained and the second gas is injected. Nickel nanopowder was manufactured by simultaneously supplying hydrogen gas and ammonia gas from the tube. Here, the supply ratio of nitrogen: hydrogen was 1: 1, and the supply ratio of hydrogen: ammonia gas was 10: 1. Nickel nanopowder produced by the reaction between nickel chloride and hydrogen was discharged to the outside together with the supply gas, and the nickel nanopowder was recovered by passing the exhaust gas through a liquid phase collector filled with kerosene.

このような本発明の方法により製造されたニッケルナノ粉末の粒度を分析した結果、図２に示すように、平均粒度は４５ｎｍで、粒度範囲は２０〜８０ｎｍであり、アンモニアガスを供給しない方法に比べて粒度が小さくて均一度が大きく向上した。   As a result of analyzing the particle size of the nickel nanopowder produced by the method of the present invention, as shown in FIG. 2, the average particle size is 45 nm, the particle size range is 20 to 80 nm, and no ammonia gas is supplied. Compared with the smaller particle size, the uniformity was greatly improved.

実施例２
塩化ニッケル５ｇを耐火容器に入れ、実施例１と同様に本発明の装置を組み立てた後、第１ガス注入管から窒素ガスを３０分間流した。石英管内部の空気の排出が終わった後、反応炉の温度を５００℃、蒸発炉の温度を８５０℃に昇温し、昇温が終わると、実施例１と同様の方法で、第２ガス注入管から水素ガスとアンモニアガスを同時に供給した。ここで、窒素：水素の供給割合は５：１にし、水素：アンモニアガスの供給割合は５：１にした。塩化ニッケルと水素との反応により生成されたニッケルナノ粉末は、実施例１と同様の方法で、液相捕集器を使用して回収した。 Example 2
After putting 5 g of nickel chloride into a refractory container and assembling the apparatus of the present invention in the same manner as in Example 1, nitrogen gas was allowed to flow from the first gas injection pipe for 30 minutes. After the discharge of air inside the quartz tube is finished, the temperature of the reactor is raised to 500 ° C. and the temperature of the evaporation furnace is raised to 850 ° C. When the temperature rise is finished, the second gas is produced in the same manner as in Example 1. Hydrogen gas and ammonia gas were simultaneously supplied from the injection tube. Here, the supply ratio of nitrogen: hydrogen was 5: 1, and the supply ratio of hydrogen: ammonia gas was 5: 1. Nickel nanopowder produced by the reaction between nickel chloride and hydrogen was recovered using a liquid phase collector in the same manner as in Example 1.

このような本発明の方法により製造されたニッケルナノ粉末の粒度を分析した結果、図３に示すように、平均粒度は３７ｎｍで、粒度範囲は１５〜７５ｎｍであり、従来の方法に比べて粒度が小さくて均一度が大きく向上した。   As a result of analyzing the particle size of the nickel nanopowder produced by the method of the present invention, the average particle size is 37 nm and the particle size range is 15 to 75 nm as shown in FIG. Is small and the uniformity is greatly improved.

以上、本発明を、図示の実施例を中心に説明したが、これは例示にすぎず、本発明が多様な変形及び様々な実施例を含むことは本発明が属する技術の分野における通常の知識を有する者であれば理解できるであろう。   The present invention has been described above mainly with reference to the illustrated embodiments. However, this is merely an example, and it is understood that the present invention includes various modifications and various embodiments in the technical field to which the present invention belongs. Anyone who has

本発明が適用されるニッケルナノ粉末の製造装置の模式図である。It is a schematic diagram of the manufacturing apparatus of nickel nanopowder to which the present invention is applied. 本発明により製造されたニッケルナノ粉末の写真である。2 is a photograph of nickel nanopowder produced according to the present invention. 本発明により製造されたニッケルナノ粉末の写真である。2 is a photograph of nickel nanopowder produced according to the present invention.

符号の説明Explanation of symbols

１、２ 石英管
３、４ 管状炉
５ 塩化ニッケル
６ 耐火容器
７、８ ガス注入管
９ 排出管
１０ ゴム栓 1, 2 Quartz tube 3, 4 Tubular furnace 5 Nickel chloride 6 Refractory vessel 7, 8 Gas injection tube 9 Discharge tube 10 Rubber stopper

Claims (5)

窒素ガスを供給しながら原料である金属塩化物を蒸発させる工程と、
窒素ガスの供給を維持しながら水素ガスとアンモニアガスを同時に供給して、前記蒸発させた金属塩化物蒸気との還元反応により金属ナノ粉末を得る工程と、
を含むことを特徴とする金属ナノ粉末の製造方法。 Evaporating the metal chloride as a raw material while supplying nitrogen gas;
A step of simultaneously supplying hydrogen gas and ammonia gas while maintaining supply of nitrogen gas to obtain metal nanopowder by a reduction reaction with the evaporated metal chloride vapor;
The manufacturing method of the metal nanopowder characterized by including. 窒素ガスの供給と水素ガスの供給とを独立して行う、請求項１記載の金属ナノ粉末の製造方法。   The method for producing metal nanopowder according to claim 1, wherein the supply of nitrogen gas and the supply of hydrogen gas are performed independently. 供給ガスである窒素ガス：水素ガスの割合が１：１〜５：１の範囲であり、水素ガス：アンモニアガスの割合が５：１〜１０：１の範囲である、請求項１記載の金属ナノ粉末の製造方法。   The metal according to claim 1, wherein the ratio of nitrogen gas: hydrogen gas as the supply gas is in the range of 1: 1 to 5: 1 and the ratio of hydrogen gas: ammonia gas is in the range of 5: 1 to 10: 1. Manufacturing method of nanopowder. 前記金属塩化物が、ニッケル塩化物、タングステン塩化物、鉄塩化物、クロム塩化物、及び銅塩化物から選択されるいずれか１つである、請求項１記載の金属ナノ粉末の製造方法。   The method for producing metal nanopowder according to claim 1, wherein the metal chloride is any one selected from nickel chloride, tungsten chloride, iron chloride, chromium chloride, and copper chloride. 前記金属塩化物がニッケル塩化物であり、ニッケル塩化物の蒸発温度が７８０〜８５０℃の範囲であり、蒸発したニッケル塩化物蒸気と水素ガス及びアンモニアガスとの反応温度が５００〜９００℃の範囲である、請求項４に記載の金属ナノ粉末の製造方法。   The metal chloride is nickel chloride, the evaporation temperature of nickel chloride is in the range of 780 to 850 ° C., and the reaction temperature of the evaporated nickel chloride vapor with hydrogen gas and ammonia gas is in the range of 500 to 900 ° C. The manufacturing method of the metal nanopowder of Claim 4 which is these.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102764895A (en) * 2012-07-30 2012-11-07 北京科技大学 Device and method for preparing high-purity ultrafine nickel powder
JP2018165391A (en) * 2017-03-28 2018-10-25 日本新金属株式会社 Method for producing tungsten fine powder
JP7236063B1 (en) 2021-11-10 2023-03-09 コリア インスティチュート オブ インダストリアル テクノロジー Inorganic powder production apparatus and production method

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KR102572729B1 (en) * 2021-11-10 2023-08-31 한국생산기술연구원 Inorganic powder manufacturing apparatus and manufacturing method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59170211A (en) * 1983-03-14 1984-09-26 Toho Aen Kk Production of ultrafine powder
JPS6148506A (en) * 1984-08-10 1986-03-10 Mitsui Toatsu Chem Inc Refining method of fine particle by gaseous phase process
WO2002102533A1 (en) * 2001-06-14 2002-12-27 Toho Titanium Co., Ltd. Method for producing metal powder and metal powder, and electroconductive paste and monolithic ceramic capacitor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0412008A (en) * 1990-04-27 1992-01-16 Mitsubishi Petrochem Co Ltd Production of magnetic powder
JPH1180816A (en) 1997-09-10 1999-03-26 Sumitomo Metal Mining Co Ltd Nickel powder for conductive paste and its production
KR100526728B1 (en) * 2003-05-13 2005-11-09 한국과학기술연구원 Preparation of Tungsten Nano-Powder from Tungsten Chlorides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59170211A (en) * 1983-03-14 1984-09-26 Toho Aen Kk Production of ultrafine powder
JPS6148506A (en) * 1984-08-10 1986-03-10 Mitsui Toatsu Chem Inc Refining method of fine particle by gaseous phase process
WO2002102533A1 (en) * 2001-06-14 2002-12-27 Toho Titanium Co., Ltd. Method for producing metal powder and metal powder, and electroconductive paste and monolithic ceramic capacitor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102764895A (en) * 2012-07-30 2012-11-07 北京科技大学 Device and method for preparing high-purity ultrafine nickel powder
JP2018165391A (en) * 2017-03-28 2018-10-25 日本新金属株式会社 Method for producing tungsten fine powder
JP7236063B1 (en) 2021-11-10 2023-03-09 コリア インスティチュート オブ インダストリアル テクノロジー Inorganic powder production apparatus and production method
JP2023071129A (en) * 2021-11-10 2023-05-22 コリア インスティチュート オブ インダストリアル テクノロジー Apparatus and method for producing inorganic powder

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