JPH06346268A - Electrolytic production of magnesium-potassium mother alloy - Google Patents
Electrolytic production of magnesium-potassium mother alloyInfo
- Publication number
- JPH06346268A JPH06346268A JP13462093A JP13462093A JPH06346268A JP H06346268 A JPH06346268 A JP H06346268A JP 13462093 A JP13462093 A JP 13462093A JP 13462093 A JP13462093 A JP 13462093A JP H06346268 A JPH06346268 A JP H06346268A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- magnesium
- cathode
- electrolysis
- potassium
- 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.)
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- Electrolytic Production Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、合金製造においてカル
シウム（Ｃａ）とマグネシウム（Ｍｇ）を添加するため
の母合金の製造に関するものである。FIELD OF THE INVENTION The present invention relates to the production of a master alloy for the addition of calcium (Ca) and magnesium (Mg) in alloy production.
【０００２】[0002]
【従来の技術】Ｍｇ合金においてＣａは有用な合金元素
であり、Ｃａ添加のためには金属Ｃａ又は１５〜２０％
Ｃａを含むＭｇ母合金が用いられている。鋳鉄の組織改
良のためには、ＭｇおよびＣａはそれぞれ有効であるこ
とが知られているが、Ｍｇ合金もそのまま、あるいはＮ
ｉ等と合金化して組織改良用の母合金として使用され
る。2. Description of the Related Art Ca is a useful alloying element in Mg alloys. To add Ca, metallic Ca or 15 to 20% is added.
An Mg mother alloy containing Ca is used. It is known that Mg and Ca are respectively effective for improving the structure of cast iron, but the Mg alloy itself or N
Used as a master alloy for improving the structure by alloying with i, etc.
【０００３】従来、１５〜２０％Ｃａ−Ｍｇ合金は、当
然のことながらＣａとＭｇを鉄製るつぼ等で共融解して
製造される。Ｃａは塩化カルシウムの溶融塩電解によっ
て得られるが、Ｃａの電解は電流効率も悪く、理論電解
電圧に対してかなり高い電圧をかけるので電力原単位も
高くなり、高価なものであった。例えば、丸善発行の
「電気化学便覧」によれば、電解槽電圧２５Ｖ、電流効
率５０％、電力原単位３０〜５０Ｋｗｈ／ｋｇであり、
塩化カルシウム（ＣａＣｌ２）からＣａを得る理論電解
電圧約３．２Ｖに比し、著しく大きい。また、Ｃａは空
気中で表面に直ちに酸化膜や、窒化膜を生じ、やがて生
石灰、炭酸石灰に変って白粉を生じて、損耗する。Conventionally, a 15-20% Ca-Mg alloy is naturally produced by co-melting Ca and Mg in an iron crucible or the like. Although Ca is obtained by molten salt electrolysis of calcium chloride, the electrolysis of Ca is poor in current efficiency and a considerably high voltage is applied with respect to the theoretical electrolysis voltage. For example, according to "Electrochemical Handbook" published by Maruzen, the electrolytic cell voltage is 25 V, the current efficiency is 50%, and the electric power consumption rate is 30 to 50 Kwh / kg.
This is significantly higher than the theoretical electrolysis voltage of about 3.2 V for obtaining Ca from calcium chloride (CaCl 2 ). Further, Ca immediately forms an oxide film or a nitride film on the surface in the air, and eventually turns into quick lime or lime carbonate to produce white powder, which is worn.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、Ｃａ当りで
みて高電流効率であり、低電力原単位のＭｇ−Ｃａ合金
を直接製造でき、かつ長期間の保存においてもＣａが劣
化しない合金を提供することを目的としている。DISCLOSURE OF THE INVENTION The present invention provides an alloy which has a high current efficiency in terms of Ca, can directly produce a low power consumption unit of Mg-Ca alloy, and does not deteriorate Ca even during long-term storage. It is intended to be provided.
【０００５】[0005]
【課題を解決するための手段】本発明の要旨は、炭素材
を陽極として、また塩化カルシウムを主成分とする溶融
塩上の溶融金属マグネシウムを陰極として電解を行な
い、陰極に析出した金属カルシムウを溶融金属マグネシ
ウム中に溶解させることを特徴とするマグネシウム‐カ
ルシウム母合金の電解製造方法である。本発明は、Ｍｇ
−Ｃａ合金を低い電力原単位で製造でき、得られる合金
も常温の空気中で酸化をほとんど受けない。The gist of the present invention is to carry out electrolysis using a carbon material as an anode and molten metal magnesium on a molten salt containing calcium chloride as a main component as a cathode to obtain metal calcium hydroxide deposited on the cathode. It is an electrolytic manufacturing method of a magnesium-calcium master alloy, which is characterized in that it is dissolved in molten metal magnesium. The present invention is based on Mg
-Ca alloys can be produced with low power consumption, and the resulting alloys are hardly oxidized in normal temperature air.
【０００６】以下、本発明を詳細に説明する。本発明の
構成をもっとも簡単に示したのが、図１である。図１に
おいて、１は鋳鋼製の容器である。マグネシウムおよび
カルシウムと反応しない金属は数多いが、もっとも容易
に入手できるものは鉄であり、鋳鉄、鋳鋼、鋼板溶接製
の筒体等を容器とするのがよい。クロムモリブデンも侵
され難いのでクロムメッキをするか、１２クロム耐熱鋼
やクロム系ステンレスにより耐熱性、耐酸化性を有する
ものを用いると更によい。The present invention will be described in detail below. The structure of the present invention is shown most simply in FIG. In FIG. 1, 1 is a container made of cast steel. Although there are many metals that do not react with magnesium and calcium, the most easily available metal is iron, and it is preferable to use cast iron, cast steel, a steel plate welded cylinder, or the like as the container. Chromium-molybdenum is also less likely to be attacked, so it is more preferable to perform chrome plating, or to use 12 chrome heat-resistant steel or chrome-based stainless steel having heat resistance and oxidation resistance.
【０００７】この容器を加熱炉炉体２の中に入れ、ガ
ス、電気等で加熱し、内部の塩浴を溶融する。４は、必
要に応じて設置する隔壁でマグネシアのような耐火物を
用いる。５は、炭素質の電極であって、ピッチ、無煙
炭、オイルコークスを混練成型し焼成したものか、ある
いは電極黒鉛を用いる。図１は、陽極を１本で代表して
いるが、浴の抵抗を減ずるため容器の大きさに応じて多
数本にすることもできる。６は、陽極への導電線であ
り、７は陰極への導電線である。This container is placed in the furnace body 2 of the heating furnace and heated by gas, electricity or the like to melt the salt bath therein. Reference numeral 4 is a partition wall that is installed as needed, and a refractory material such as magnesia is used. Reference numeral 5 denotes a carbonaceous electrode, which is obtained by kneading and firing pitch, anthracite, and oil coke, or uses electrode graphite. Although FIG. 1 shows one anode as a representative, a large number of anodes can be used depending on the size of the container in order to reduce the resistance of the bath. 6 is a conductive wire to the anode, and 7 is a conductive wire to the cathode.
【０００８】８は、電解浴であり、ＣａＣｌ２を主成分
とする溶融塩であるが、融点を下げるため例えば、弗化
カルシウム（ＣａＦ２）１５％を添加した浴を用いる。
他に少量の塩化カリウム（ＫＣｌ）等を加えてもよい。
９は、浮遊する溶融Ｍｇであり、投入口１０から投入す
る。陰極の導電線７から容器１を介して浮遊する溶融マ
グネシウムに導電され、陰極を形成する。電解により陰
極に生成するＣａは、溶融Ｍｇ中に直ちに溶解してＭｇ
−Ｃａ合金となる。ＣａＣｌ２の分解電圧は、８００℃
で約３．２Ｖであるが、本実験では２．７〜２．９Ｖで
あり、合金化により生成自由エネルギーが減少するもの
と思われる。Reference numeral 8 is an electrolytic bath, which is a molten salt containing CaCl 2 as a main component, but for lowering the melting point, for example, a bath to which 15% of calcium fluoride (CaF 2 ) is added is used.
Besides, a small amount of potassium chloride (KCl) or the like may be added.
9 is a molten Mg that floats, and is charged through the charging port 10. The conductive wire 7 of the cathode is conducted to the molten magnesium floating through the container 1 to form the cathode. The Ca generated in the cathode by electrolysis is immediately dissolved in molten Mg
-It becomes a Ca alloy. The decomposition voltage of CaCl 2 is 800 ℃
Is about 3.2 V, but in the present experiment it is 2.7 to 2.9 V, and it is considered that the free energy of formation is reduced by alloying.
【０００９】一方、炭素極５に生成する塩素（Ｃｌ２）
は、導出管１１より吸引して、捕収して利用するか、あ
るいはアルカリ等で吸収して処理する。得られたＭｇ−
Ｃａ合金は、排出口（図示されていない）から柄杓で汲
み出し、鋳型に注入して母合金とする。On the other hand, chlorine (Cl 2 ) formed at the carbon electrode 5
Is either sucked from the lead-out pipe 11 and collected for use, or is absorbed by an alkali or the like for processing. Obtained Mg-
Ca alloy is pumped out from a discharge port (not shown) with a ladle and poured into a mold to form a mother alloy.
【００１０】電解浴の温度は、Ｍｇの融点以上であっ
て、出来るだけ低い温度がよい。前記ＣａＣｌ２−１５
％ＣａＦ２浴の融点は、６６４℃なので、７００℃程度
で電解ができる。但し、４０〜５０％の合金を得るには
７５０℃まで昇温する必要がある。また、得られるＭｇ
−Ｃａ合金を間欠的または連続的に若干量を残しつつ交
換し、Ｃａが適当量浮遊Ｍｇ中に残るようにし、更に溶
融点にもＫＣｌを１０％程度加えて融点を下げれば、６
００℃近い温度で電解を行なうことができる。The temperature of the electrolytic bath is preferably the melting point of Mg or higher and as low as possible. The CaCl 2 -15
Since the melting point of the% CaF 2 bath is 664 ° C., electrolysis can be performed at about 700 ° C. However, in order to obtain a 40 to 50% alloy, it is necessary to raise the temperature to 750 ° C. Also, the obtained Mg
-Ca alloy is intermittently or continuously exchanged while leaving a small amount so that Ca remains in an appropriate amount in suspended Mg, and KCl is also added to the melting point at about 10% to lower the melting point.
Electrolysis can be performed at a temperature close to 00 ° C.
【００１１】Ｃａの電解を行なってＭｇ中のＣａ濃度が
高くなると、Ｃａが電解浴中に溶解して、一部は陽極で
酸化される。また、溶解したものは、捕収が困難であ
る。電解浴の温度が高いほど溶解量がふえ、こうして電
流効率が低下する。実験の結果では、Ｃａ４５％程度ま
では電流効率は余り低下しないが、４５％から徐々に低
下し、５０％以上から稍々急激に電流効率が低下する。
このため、本発明によるＭｇ−Ｃａ合金の製造は、Ｃａ
５０％までとするのが有利である。また、６５％以上で
はほとんど電流効率が０となり、製造することができな
い。When Ca is electrolyzed to increase the Ca concentration in Mg, Ca is dissolved in the electrolytic bath and a part is oxidized at the anode. Further, the dissolved one is difficult to collect. The higher the temperature of the electrolytic bath, the greater the amount of dissolution, thus lowering the current efficiency. According to the result of the experiment, the current efficiency does not decrease so much up to about 45% Ca, but gradually decreases from 45%, and the current efficiency decreases sharply from 50% or more.
Therefore, the production of the Mg-Ca alloy according to the present invention is
Up to 50% is advantageous. Further, if it is 65% or more, the current efficiency becomes almost 0, and it cannot be manufactured.
【００１２】電流密度は、陽極に対して０．５〜３Ａ／
ｃｍ2 と高目にとれるが、陰極に対しては図１からみる
ように十分小さくてもよい。図２は、図１と余り変らな
いが、小型の実験装置である。２１は１２クロム耐熱鋼
の容器であり、この中に２２の同じ１２クロム耐熱鋼の
筒体をおきこれを介して溶融Ｍｇに導電して陰極とす
る。２３はマントルヒーターであり、これによって容器
全体を加熱して溶融塩２８を融解する。The current density is 0.5 to 3 A / a with respect to the anode.
Although it can be as high as cm 2 , it may be sufficiently small for the cathode as seen from FIG. 2 is not so different from FIG. 1, but is a small experimental device. Reference numeral 21 denotes a 12-chromium heat-resistant steel container, in which the same 12-chromium heat-resistant steel cylinder 22 is placed, through which the molten Mg is electrically conductive to serve as a cathode. Reference numeral 23 is a mantle heater, which heats the entire container to melt the molten salt 28.
【００１３】[0013]
【実施例】以下、本発明を実施例により具体的に説明す
る。実施例１ 図２の実験装置を使用して、ＣａＦ２１２％、ＫＣｌ８
％、残余ＣａＣｌ２からなる電解浴を用い、Ｍｇ２００
ｇを投入し、６８０℃に保って電解を行なった。陽極電
流密度１．５Ａ／ｃｍ2 で８０Ａの電流を通して２時間
の電解を行なった。電解槽電圧は、５．２９Ｖであっ
た。２時間後にＭｇ融液を汲み上げて鋳型に注ぎ、約２
９０ｇの合金を得た。この合金の分析を行なった結果、
Ｃａ濃度は３２．０％であった。Ｍｇの損失がないと仮
定して計算した電流効率は７８．８％、電源等の抵抗損
失を除いてのＣａ当りの電力源単位は８９７０Ｋｗｈ／
ｔとなる。EXAMPLES The present invention will be specifically described below with reference to examples. Using an experimental apparatus of Example 1 FIG. 2, CaF 2 12%, KCl8
%, Using an electrolytic bath comprising the balance CaCl 2, MG200
g was added and electrolysis was performed while maintaining the temperature at 680 ° C. Electrolysis was carried out for 2 hours by passing a current of 80 A at an anode current density of 1.5 A / cm 2 . The electrolytic cell voltage was 5.29V. After 2 hours, pump up the Mg melt and pour it into the mold.
90 g of alloy was obtained. As a result of analyzing this alloy,
The Ca concentration was 32.0%. The current efficiency calculated assuming that there is no loss of Mg is 78.8%, and the power source unit per Ca excluding the resistance loss of the power source is 8970 Kwh /
t.
【００１４】実施例２ 図２に示す実験装置を使用して、ＣａＦ２１５％、残り
ＣａＣｌ２からなる電解浴を用い、Ｍｇ２００ｇを投入
し、７５０℃に保って電解を行なった。実施例１と同じ
電流条件で３時間４５分の電解を行なった。平均の電解
槽電圧は、５．５０Ｖであった。終了後Ｍｇ融液を汲み
上げて鋳型に注ぎ、３６０ｇの合金を得た。この合金の
分析の結果、Ｃａ濃度は４５．０％であった。Ｍｇの損
失がなかったものとして計算すると、電流効率は７３．
１％、電源等の抵抗損失を除いてのＣａ当りの電力源単
位は１０，０７０Ｋｗｈ／ｔとなる。実施例１、２のい
ずれの合金も新らしい破面を空気中に曝しておいても僅
かに白く曇る程度であり、５ｃｍ角程度の塊の重量増加
は０．１％にみたなかった。 Example 2 Using the experimental apparatus shown in FIG. 2, 200 g of Mg was added using an electrolytic bath consisting of 15% CaF 2 and the rest CaCl 2 , and electrolysis was carried out at 750 ° C. Electrolysis was performed under the same current conditions as in Example 1 for 3 hours and 45 minutes. The average electrolytic cell voltage was 5.50V. After the completion, the Mg melt was pumped up and poured into a mold to obtain 360 g of an alloy. As a result of analysis of this alloy, the Ca concentration was 45.0%. When calculated assuming that there was no Mg loss, the current efficiency was 73.
1%, the power source unit per Ca is 10,070 Kwh / t excluding the resistance loss of the power source and the like. In each of the alloys of Examples 1 and 2, even if the new fracture surface was exposed to the air, it was slightly clouded in white, and the weight increase of a lump of about 5 cm square was not found to be 0.1%.
【００１５】[0015]
【発明の効果】本発明の電解製造方法によると、Ｃａ当
りでみて電力原単位は、従来技術で示したＣａのそれと
比して数分の１に低くなり、また、得られる合金もＣａ
についてみると酸化等による変質は少ない。従って、従
来のＭｇ−Ｃａ母合金に代る製造方法であるとともに、
得られるＭｇ−Ｃａ母合金もＣａの用途を代替しうる。According to the electrolytic production method of the present invention, the electric power consumption per Ca is reduced to a fraction of that of Ca shown in the prior art, and the obtained alloy is also Ca.
The deterioration caused by oxidation is small. Therefore, as well as a manufacturing method that replaces the conventional Mg-Ca master alloy,
The resulting Mg-Ca master alloy can also replace the use of Ca.
【図１】典型的な電解炉の構造である。FIG. 1 is a typical electrolysis furnace structure.
【図２】本発明の実施例に使用した実験装置である。FIG. 2 is an experimental apparatus used in an example of the present invention.
１ 鋳鋼製容器 ２ 加熱炉炉体 ３ ガスバーナー ４ 隔壁 ５ 炭素質電極 ６ 陽極導電線 ７ 陰極導電線 ８ 溶融塩の電解浴 ９ 陰極に接し浮遊するＭｇ １０ Ｍｇの投入口 １１ 塩素ガスの導出管 ２１ 耐熱鋼容器 ２２ 耐熱鋼筒体 ２３ マントルヒーター ２４ 隔壁 ２５ 炭素質電極 ２６ 陽極導電線 ２７ 陰極導電線 ２８ 溶融塩の電解浴 ２９ 陰極に接し浮遊するＭｇ ３０ Ｍｇの投入口兼Ｍｇ−Ｃａ合金の汲出口 ３１ 塩素ガスの導出管 1 Cast Steel Container 2 Heating Furnace Body 3 Gas Burner 4 Partition Wall 5 Carbonaceous Electrode 6 Anode Conductive Wire 7 Cathode Conductive Wire 8 Electrolyte Bath of Molten Salt 9 Mg 10 Floating in Contact with Cathode Charge Port 11 Chlorine Gas Outlet Pipe 21 Heat-Resistant Steel Container 22 Heat-Resistant Steel Tube 23 Mantle Heater 24 Partition Wall 25 Carbonaceous Electrode 26 Anode Conductive Wire 27 Cathode Conductive Wire 28 Molten Salt Electrolyte Bath 29 Mg 30 Floating in Contact with Cathode and Mg-Ca Alloy Pumping port 31 Chlorine gas outlet pipe
Claims (1)
する溶融塩を電解浴とし、溶解塩上の溶融金属マグネシ
ウムを陰極として電解を行ない、陰極に析出した金属カ
ルシウムを溶融金属マグネシウム中に溶解させることを
特徴とするマグネシウム‐カルシウム母合金の電解製造
方法。1. A carbon material is used as an anode, a molten salt containing calcium chloride as a main component is used as an electrolytic bath, and molten metal magnesium on the molten salt is used as a cathode for electrolysis. Metal calcium deposited on the cathode is placed in molten metal magnesium. A method for electrolytically manufacturing a magnesium-calcium master alloy, which comprises melting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13462093A JPH06346268A (en) | 1993-06-04 | 1993-06-04 | Electrolytic production of magnesium-potassium mother alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13462093A JPH06346268A (en) | 1993-06-04 | 1993-06-04 | Electrolytic production of magnesium-potassium mother alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06346268A true JPH06346268A (en) | 1994-12-20 |
Family
ID=15132647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13462093A Withdrawn JPH06346268A (en) | 1993-06-04 | 1993-06-04 | Electrolytic production of magnesium-potassium mother alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06346268A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998049373A1 (en) * | 1997-04-30 | 1998-11-05 | Sumitomo Sitix Of Amagasaki, Inc. | Metal magnesium electrolyzer |
| CN103173785A (en) * | 2013-04-16 | 2013-06-26 | 中国科学院青海盐湖研究所 | Method for preparing magnesium metal through electrolysis by using novel magnesium deep eutectic solvent |
| WO2018059706A1 (en) * | 2016-09-30 | 2018-04-05 | Siemens Aktiengesellschaft | Method for storing energy and/or generating energy on the basis of calcium and/or magnesium and power station with a steam turbine |
-
1993
- 1993-06-04 JP JP13462093A patent/JPH06346268A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998049373A1 (en) * | 1997-04-30 | 1998-11-05 | Sumitomo Sitix Of Amagasaki, Inc. | Metal magnesium electrolyzer |
| US6129821A (en) * | 1997-04-30 | 2000-10-10 | Alcan International Limited | Metal magnesium electrolyzer |
| CN103173785A (en) * | 2013-04-16 | 2013-06-26 | 中国科学院青海盐湖研究所 | Method for preparing magnesium metal through electrolysis by using novel magnesium deep eutectic solvent |
| WO2018059706A1 (en) * | 2016-09-30 | 2018-04-05 | Siemens Aktiengesellschaft | Method for storing energy and/or generating energy on the basis of calcium and/or magnesium and power station with a steam turbine |
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