JPS59113104A - Manufacture of molybdenum powder - Google Patents
Manufacture of molybdenum powderInfo
- Publication number
- JPS59113104A JPS59113104A JP22195282A JP22195282A JPS59113104A JP S59113104 A JPS59113104 A JP S59113104A JP 22195282 A JP22195282 A JP 22195282A JP 22195282 A JP22195282 A JP 22195282A JP S59113104 A JPS59113104 A JP S59113104A
- Authority
- JP
- Japan
- Prior art keywords
- reduction
- molybdenum
- powder
- molybdenum powder
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は高融点金属であるモリブデン粉末の製造方法に
係り、特に還元用材料から金属粉末を生成する還元工程
の改善に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing molybdenum powder, which is a high melting point metal, and particularly relates to an improvement in a reduction process for producing metal powder from a reducing material.
普通モリブデン粉末を製造するＫは、モリブデン含有鉱
石を精製する等の工程を経てモリブデン還元用の材料と
し、これをボートに入れて還元雰囲気とした高温還元炉
に挿入し、所定の加熱処理を行い、モリブデン粉末が生
成されている。このとき用いられる材料は通常モリブデ
ン酸のアンモニタ人塩が使用されている。K, which normally produces molybdenum powder, undergoes processes such as refining molybdenum-containing ore to become a material for molybdenum reduction, which is then placed in a boat and inserted into a high-temperature reduction furnace with a reducing atmosphere, where it is subjected to prescribed heat treatment. , molybdenum powder has been produced. The material used at this time is usually ammonium salt of molybdic acid.
このようにモリブデン酸アンモニウム（（ＮＨ，）。Thus ammonium molybdate ((NH,).
Ｍｏｂ、）をボー）Ｋ所定食入れて水素雰囲気の高温炉
に挿入し温度を上げると、アンモニアと水などを放出し
ながら、ボート表面の材料粉末は酸化モリブデン（Ｍｏ
ｓｓ）となシ、内部は酸化そリプデン（ＭｏＯｌ 、
Ｍｏ４０１＋等）が生成し、さらに還元が進むとこれら
はＭｏｏｔに変っていくものである。このＭａｉｌをさ
らに別の高温還元炉に入れ、高温水素雰囲気中で所定の
条件にて還元してモリブデン粉末が生成される。このよ
うにしてモリブデン粉末を生成すると、工程中にアンモ
ニア等有害物が放出され、又精製にあたヤ強酸を使用す
るなど作業環境がよくなく、公害の点からも問題が多く
、さらに原料購入の観点から経済的に有利でない点もあ
って、モリブデン粉末を得る還元工程の改善が要望され
ていた。Mob, ) is placed in a high-temperature furnace with a hydrogen atmosphere and the temperature is raised.While ammonia and water are released, the material powder on the surface of the boat becomes molybdenum oxide (Mo).
ss) and the inside is oxidized triglyceride (MoOl,
(Mo401+, etc.) are generated, and as the reduction further progresses, these transform into Moot. This Mail is further placed in another high-temperature reduction furnace and reduced under predetermined conditions in a high-temperature hydrogen atmosphere to produce molybdenum powder. When molybdenum powder is produced in this way, harmful substances such as ammonia are released during the process, and the working environment is not good as strong acids are used for refining, causing many problems in terms of pollution. Since it is not economically advantageous from the viewpoint of
そのため還元用の材料として三酸化モリブデン（ＭｏＯ
ａ）の使用によって前記の不具合を除去しようとした。Therefore, molybdenum trioxide (MoO
An attempt was made to eliminate the above drawback by using a).
しかしながらこのようにＭｏｂ＠を使用するときには次
のような問題が生じてきた。すなわちボートに材料を入
れて還元炉にて予備還元を行うときＭｏ０１からＭｏｂ
、への還元反応は強い発熱反応を伴うため融点の低いＭ
ｎＯ３は未反応部分が溶融して、これがボートに入れら
れた材料の還元して生成されたＭｏｂ、の表面を佳うよ
うになり、還元ガスが内部へ浸透して行くのを妨げるよ
うになって以後のスムースな還元を困難にしてしまう。However, when using Mob@ in this way, the following problems have arisen. In other words, when putting materials into the boat and performing preliminary reduction in the reduction furnace, from Mo01 to Mob
Since the reduction reaction to , is accompanied by a strong exothermic reaction, M with a low melting point
The unreacted portion of nO3 melts, and this protects the surface of the mob, which was created by reducing the material put in the boat, and prevents the reducing gas from penetrating inside. This makes it difficult to make a smooth return.
さらに溶融したＭｏＯ３によってＭｏｏｔが結合し、還
元後のモリブデン粉末が強固な塊状を形成することが多
い。したがって還元ガスの供給量を少なくしたり、水蒸
気等を加えたシなどして発熱反応を制御しながら徐々に
還元作業を行わねばならず、作業能率が悪く、塊状のモ
リブデンが形成されると細かく粉砕したりなどする必要
も生じ、作業能率とともに歩留の低下を来たすなど、種
々不具合があった。Furthermore, Moot is bonded by the molten MoO3, and the molybdenum powder after reduction often forms a solid lump. Therefore, reduction work must be carried out gradually while controlling the exothermic reaction by reducing the amount of reducing gas supplied or adding water vapor, etc., resulting in poor work efficiency and the formation of lumpy molybdenum. There were various problems, such as the need for pulverization, which caused a decrease in work efficiency and yield.
本発明はこれらの不具合をなくすためになされたもので
あって、モリブデン還元用の材料からきわめて効率的に
公害発生という不具合もなくモリブデン粉末を経済的に
得ることを目的とする１、〔発明の概要〕
本発明のモリブデン粉末製造方法は、モリブデン還元用
材料として三酸化モリブデンに２０〜５０重ｔ％のモリ
ブデン酸アンモニウムを混合し友ものを用い、湿潤還元
雰囲気中にて予備還元を行ってのらさらに高温還元を行
い、良品質のモリブデン粉末を効率よく生成する工業的
に有用な製造方法である。The present invention has been made to eliminate these problems, and aims to economically obtain molybdenum powder from materials for molybdenum reduction very efficiently and without the problem of generating pollution. Overview] The method for producing molybdenum powder of the present invention involves pre-reduction in a moist reducing atmosphere using molybdenum trioxide mixed with 20 to 50% by weight of ammonium molybdate as a molybdenum reducing material. This is an industrially useful production method that further performs high-temperature reduction to efficiently produce high-quality molybdenum powder.
本発明の実施例について以下説明する。 Examples of the present invention will be described below.
実施例１゜
純三酸化モリブデン（Ｍｏｓｓ）にモリブデン酸アンモ
ニウム（アンモニウムパラモリプデート（ＮＴ（ｔ）ａ
ＭＯ７０２４・４ Ｈ２Ｏ、アンモニラムダイモリプデ
ート（Ｎｌ（＊）＊Ｍｏ２０フ） ｆｒ：３０重ｆｋチ
混合して、これを所定量ボートに入れ、６００゛〜７０
０℃に加熱した連続式還元炉に入れ、毎時３ｋｇの量を
搬送させる。Example 1 Ammonium molybdate (ammonium paramolypdate (NT(t)a) was added to pure molybdenum trioxide (Moss).
MO7024.4 H2O, ammonium dimoripdate (Nl (*) * Mo20f) fr: Mix 30 heavy fk, put the specified amount into a boat, and boil at 600゛~70
It is placed in a continuous reduction furnace heated to 0°C and transported at a rate of 3 kg per hour.
このとき炉内は水蒸気を加えた水素ガスを向流させ、３
時間の予備還元を行った。この生成物をよく混合して１
０００℃で３時間水素雰囲気中で高温還元を行った。At this time, inside the furnace, hydrogen gas with water vapor added is made to flow counter-currently.
I made a preliminary reduction in time. Mix this product well and
High temperature reduction was performed at 000° C. for 3 hours in a hydrogen atmosphere.
最初の予備還元を行ったときほとんどＭｏ Ｏ２となり
、ボートに入れられた材料の底部の約１／２０以下の厚
さの部分にＭｏ４０Ｈ１が残存するだけであった。When the first pre-reduction was carried out, it was mostly Mo 2 O 2 and only Mo 4 0 H 1 remained at the bottom of the material placed in the boat, less than about 1/20th the thickness.
上部のＭｏｂ、の硬さを測定すると２．５ ＃ （ブシ
ュプルゲージ測定による値）であった。このブシュプル
ゲージによる測定は、ダイヤルゲージの端部に棒が取着
されていて、押し棒の先端に１０朋直径の円錐チップが
とりつけられ、棒の円筒状部分を１０ＩｉＩ押しこんだ
ときの力をゲージではかり、こ、の力を被測定物の硬さ
の比較としたものである。The hardness of the upper Mob was measured to be 2.5 # (value measured by bush pull gauge). Measurement using this bush-pull gauge involves a rod attached to the end of the dial gauge, a conical tip with a diameter of 10 mm attached to the tip of the push rod, and the force when the cylindrical part of the rod is pushed in by 10 IiI. is measured with a gauge, and the force of this is compared with the hardness of the object being measured.
このように高温還元したものは、酸素量は０．２〜０．
３％、粒径は３〜４μｍの軟かいモリブデン金属粉末で
あって、モリブデン粉末として使用するに何らの支障の
ない良品質のものが得られた。The amount of oxygen in the product reduced at high temperature is 0.2 to 0.
3%, a soft molybdenum metal powder with a particle size of 3 to 4 μm, and was of good quality and had no problems when used as molybdenum powder.
実施例２゜
純三酸化モリブデン（ＭＯＯ３）にモリブデン酸アンモ
ニウムを５０重ｔ％混合し、これを所定量ボートに入れ
て、６００６〜７００℃に加熱した連続式還元炉に毎時
３ ｋｇの量を搬送するように挿入する。Example 2 Pure molybdenum trioxide (MOO3) was mixed with 50% by weight of ammonium molybdate, a predetermined amount of this was put into a boat, and 3 kg/hour was put into a continuous reduction furnace heated to 6006 to 700°C. Insert for transport.
このとき炉内は水蒸気を加えた水素ガスを向流させ、３
時間の予備還元を行った。予備還元を行ったボート内の
材料はボート底部までＭＯＯ！となり、この上層の酸化
物の硬さはブシュゾルゲージ測定で２〜２．５ ｋｇで
あった。この生成物を混合してのら１０００℃で３時間
水素雰囲気中で高温還元を行った。At this time, inside the furnace, hydrogen gas with water vapor added is made to flow counter-currently.
I made a preliminary reduction in time. The materials in the boat that have been pre-restored are MOO to the bottom of the boat! The hardness of this upper layer oxide was 2 to 2.5 kg as measured by Busch sol gauge. The products were mixed and then subjected to high temperature reduction at 1000° C. for 3 hours in a hydrogen atmosphere.
このようにして生成された粉末は、酸素量は０．２チ以
下で、粒径は３〜４μｍの軟かいモリブデン金属粉末で
あった。モリブデン粉末として使用するに何ら支障のな
い良好な品質のものがイ＃られた。The powder thus produced was a soft molybdenum metal powder with an oxygen content of 0.2 inches or less and a particle size of 3 to 4 μm. A molybdenum powder of good quality without any problems was found to be suitable for use as molybdenum powder.
参考例１゜
還元用材料として純三酸化モリブデン（Ｍｏｓｓ）を用
い、６００１〜７００℃に加熱した連続式還元炉にボー
トに材料を入れて挿入し、毎時３ ｋｇの割合で湿潤水
素気流中を搬送した。ボート内の材料上層は相当に硬化
したＭｏＯ２が生じ、内部も底部から３１５の厚さ１で
は還元不良のＭＯ４Ｑ＋が残存した。上部のＭｏＯ２の
ブシュゾルゲージ値は６ ｋｇ以上であった。Reference Example 1゜ Using pure molybdenum trioxide (Moss) as the reducing material, the material was placed in a boat and inserted into a continuous reduction furnace heated to 6001 to 700°C, and the material was heated in a humid hydrogen stream at a rate of 3 kg/hour. Transported. A considerably hardened MoO2 was formed in the upper layer of the material inside the boat, and poorly reduced MO4Q+ remained inside the boat at a thickness of 315 mm from the bottom. The Busch sol gauge value of the upper MoO2 was more than 6 kg.
前記予備還元された生成物を粉砕後１０００℃で３時間
水素雰囲気中で高温還元を行った。The pre-reduced product was pulverized and then subjected to high-temperature reduction at 1000° C. for 3 hours in a hydrogen atmosphere.
このようにして生成したモリブデン粉末は硬く結合して
おり、これを粉砕して酸素量を測定したところ２％であ
った。The molybdenum powder thus produced was tightly bound, and when it was pulverized and the oxygen content was measured, it was 2%.
参考例２
三酸化モリブデンにモリブデン酸アンモニウムを１０重
量％混合したものを還元用材料として参考例１．と同じ
ように還元作業を行った。予備還元後ボードの材料の底
部から１／３の部分は未還元部分（ＭＯ４０１＋ ）と
して残シ、上部のＭｏ０ｔのブシュゾルゲージ値は４．
５ ｋｇであり、高温還元してのらのモリブデン粉末は
硬目であって、粉砕後の酸素量は約１チであった。Reference Example 2 Reference Example 1. Using a mixture of molybdenum trioxide and ammonium molybdate at 10% by weight as the reducing material. Reduction work was done in the same way. After preliminary reduction, the bottom 1/3 of the board material remains as an unreduced portion (MO401+), and the bush sol gauge value of Mo0t at the top is 4.
The molybdenum powder was hard after being reduced at a high temperature, and the amount of oxygen after pulverization was about 1 inch.
前記忙説明した実施例、参考例から分るように、本発明
の方法によると三酸化モリブデンにモリブデン酸アンモ
ニウムを混合したものを材料として還元すると、水素ガ
スが効率よくボート内の還元用材料中に浸透して何らの
支障を起こすことなく還元作業が行われて良品質のモリ
ブデン粉末が得られるものである。モリブデン酸アンモ
ニウムの混合量は２０％よシ少ないとその効果を発揮で
きず、又５０チをこえるとアンモニアの発生などにより
公害の点から不都合を生ずるので多くても５０弼までの
混合が好適である。As can be seen from the Examples and Reference Examples described above, according to the method of the present invention, when a mixture of molybdenum trioxide and ammonium molybdate is reduced as a material, hydrogen gas is efficiently absorbed into the reducing material in the boat. Molybdenum powder of high quality can be obtained by reducing the molybdenum powder without causing any problems. If the amount of ammonium molybdate mixed is less than 20%, the effect cannot be exhibited, and if it exceeds 50%, it will cause problems in terms of pollution due to the generation of ammonia, so it is preferable to mix the amount up to 50% at most. be.
本発明の方法によってモリブデン粉末が生成されるとき
、還元炉にて加熱されて行く途中に急激な発熱現象を起
こすことがなく、還元ガスの適確な浸透がはかられ、モ
リブデン粉末として凝固することがなく、又、酸化物と
して残存することもなく、品質のよいモリブデン粉末が
能率よく生成されるものであって、さらに公害の点から
も十分な改善がはかられ、本発明方法は工業的に有用な
方法である。When molybdenum powder is produced by the method of the present invention, there is no sudden heat generation phenomenon during heating in the reduction furnace, appropriate penetration of reducing gas is ensured, and the molybdenum powder is solidified. Molybdenum powder of good quality can be efficiently produced without any residue or residue as oxides, and sufficient improvements have been made in terms of pollution, making the method of the present invention industrially viable. This is a useful method.
代理人 弁理士 井 上 −男 ２１Agent Patent Attorney Inoue - Male 21
Claims (1)
造するにあたシ、三酸化モリブデンにモリブデン酸アン
モニウムを２０〜５０重量優混合したものを材料として
還元炉に挿入し湿潤水素ガス雰囲気中にて予備還元して
のち高温還元を行うことを特徴とするモリブデン粉末の
製造方法。To produce molybdenum powder by reducing the material for molybdenum reduction, a mixture of molybdenum trioxide and ammonium molybdate in an amount of 20 to 50% by weight is inserted into a reduction furnace and heated in a wet hydrogen gas atmosphere. A method for producing molybdenum powder, which comprises preliminary reduction and then high-temperature reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22195282A JPS59113104A (en) | 1982-12-20 | 1982-12-20 | Manufacture of molybdenum powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22195282A JPS59113104A (en) | 1982-12-20 | 1982-12-20 | Manufacture of molybdenum powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59113104A true JPS59113104A (en) | 1984-06-29 |
Family
ID=16774725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22195282A Pending JPS59113104A (en) | 1982-12-20 | 1982-12-20 | Manufacture of molybdenum powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59113104A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5976217A (en) * | 1995-10-31 | 1999-11-02 | Schwarzkopf Technologies, Corporation | Method for the reduction of metallic compounds |
| US6113668A (en) * | 1996-11-04 | 2000-09-05 | Schwarzkopf Technologies Corp. | Process for manufacture of powder compact feed materials for fine grained hardmetal |
| CN102728845A (en) * | 2012-07-10 | 2012-10-17 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powders with low ferrum |
| CN103273073A (en) * | 2013-06-30 | 2013-09-04 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powder by molybdenum trioxide |
-
1982
- 1982-12-20 JP JP22195282A patent/JPS59113104A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5976217A (en) * | 1995-10-31 | 1999-11-02 | Schwarzkopf Technologies, Corporation | Method for the reduction of metallic compounds |
| US6113668A (en) * | 1996-11-04 | 2000-09-05 | Schwarzkopf Technologies Corp. | Process for manufacture of powder compact feed materials for fine grained hardmetal |
| CN102728845A (en) * | 2012-07-10 | 2012-10-17 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powders with low ferrum |
| CN103273073A (en) * | 2013-06-30 | 2013-09-04 | 金堆城钼业股份有限公司 | Method for preparing molybdenum powder by molybdenum trioxide |
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