JPH0867922A - Method for removing nickel in lead by dry process refining - Google Patents
Method for removing nickel in lead by dry process refiningInfo
- Publication number
- JPH0867922A JPH0867922A JP6205265A JP20526594A JPH0867922A JP H0867922 A JPH0867922 A JP H0867922A JP 6205265 A JP6205265 A JP 6205265A JP 20526594 A JP20526594 A JP 20526594A JP H0867922 A JPH0867922 A JP H0867922A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- lead
- sulfur
- separated
- 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.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は鉛成分中のニッケルの
除去方法に関し、特に、乾式精錬による鉛中のニッケル
除去方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing nickel in lead, and more particularly to a method for removing nickel in lead by dry refining.
【０００２】[0002]
【従来の技術】一般に、ホウエン鉱石などの原料鉱石か
ら鉛を工業的に製造するには、シャフト炉または反射炉
による還元精錬で粗鉛とし、さらに精製を要するものは
乾式または電解精錬を行なって純度の高い鉛地金を得る
ようにしている。2. Description of the Related Art Generally, in order to industrially produce lead from raw ore such as houwen ore, crude lead is produced by reduction refining in a shaft furnace or reverberatory furnace, and those requiring further refining are subjected to dry or electrolytic refining. We are trying to obtain high-purity lead metal.
【０００３】このような鉛地金に関するＪＩＳ規格（Ｊ
ＩＳ Ｈ ２１０５，１９５５）に関して規定されてい
る化学成分には、不純物としてのＮｉの規定はない。The JIS standard (J
The chemical composition specified for ISH 2105, 1955) does not specify Ni as an impurity.
【０００４】一方、鉛地金の主たる用途である鉛蓄電池
を精錬原料として再利用する場合、すなわち廃鉛電池の
電極部分等を原料とするリサイクル鉛の精錬では、得ら
れる粗鉛中には、Ｎｉが０．００６〜０．０２５％（重
量％、以下同じ）存在することが知られている。そし
て、図１のＮｉ−Ｐｂの状態図からも明らかなように、
金属鉛中では常温でＮｉは０．０２３％程度固溶可能で
ある。On the other hand, when reusing a lead storage battery, which is the main use of lead metal, as a refining raw material, that is, when refining recycled lead from the electrode parts of a waste lead battery, etc. It is known that Ni is present in an amount of 0.006 to 0.025% (% by weight, the same applies hereinafter). And, as is clear from the state diagram of Ni-Pb in FIG.
At room temperature, Ni can be dissolved in about 0.023% in metallic lead.
【０００５】[0005]
【発明が解決しようとする課題】このようなＮｉを含有
する鉛を鉛電池の電極に形成すると、Ｎｉは再充電時に
ガス発生の原因となり、電解液中に溶出して汚染する元
素となる。したがって、鉛地金中のＮｉ成分は、可及的
に低くするべきであり、具体的には、鉛電池用電極とな
る鉛地金については、特に、Ｎｉの含有量を０．００１
０％以下とすることが好ましい。When lead containing Ni as described above is formed on the electrode of a lead battery, Ni becomes an element which causes gas generation during recharging and elutes in the electrolyte to contaminate it. Therefore, the Ni component in the lead metal should be as low as possible. Specifically, the lead metal used as the electrode for the lead battery has a Ni content of 0.001 or less.
It is preferably 0% or less.
【０００６】これまでに知られたＮｉその他の不純物の
含有量が低い精錬方法としては、電解精錬法があるが、
これより製造効率のよい精錬方法である乾式精錬におけ
るＮｉを除去する技術については、これまでに開示され
ていない。An electrolytic refining method is known as a refining method having a low content of Ni and other impurities.
A technique for removing Ni in dry refining, which is a refining method with higher production efficiency than this, has not been disclosed so far.
【０００７】そこで、この発明の課題は、上記した従来
技術の問題点を解決して、乾式精錬によって鉛中のニッ
ケル含有量を可及的に低レベル化できるようにし、ま
た、Ｎｉの含有量を０．００１０％以下とすることが可
能である乾式精錬による鉛中のニッケル除去方法とする
ことである。Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art so that the nickel content in lead can be made as low as possible by dry refining, and the Ni content can be reduced. Is 0.0010% or less, and is a method for removing nickel in lead by dry refining.
【０００８】[0008]
【課題を解決するための手段】上記の課題を解決するた
め、この発明においては、ニッケル含有の鉛原料を還元
精錬して粗鉛を製造し、この溶融状態の粗鉛に硫黄また
は硫黄と硫化鉄の混合物を添加混合し、上層に分離生成
した硫化ニッケルを除去することからなる乾式精錬によ
る鉛中のニッケル除去方法としたのである。In order to solve the above problems, according to the present invention, crude lead is produced by reducing and refining a nickel-containing lead raw material, and sulfur or sulfur and sulfur are mixed with the molten crude lead. This is a method for removing nickel in lead by dry refining, which comprises adding and mixing a mixture of iron and removing the nickel sulfide separated and formed in the upper layer.
【０００９】または、ニッケル含有の鉛原料を還元精錬
して粗鉛を製造し、溶融状態の粗鉛に硫黄または硫黄と
硫化鉄の混合物を混合し、次いで酸化剤を混合し加熱昇
温して上層に分離したニッケルの酸化物を除去すること
からなる乾式精錬による鉛中のニッケル除去方法とした
のである。Alternatively, a nickel-containing lead raw material is subjected to reduction refining to produce crude lead, and sulfur or a mixture of sulfur and iron sulfide is mixed with molten crude lead, and then an oxidizing agent is mixed and heated and heated. The method for removing nickel in lead by dry refining consists of removing the nickel oxide separated in the upper layer.
【００１０】または、上記のニッケル除去処理を行なっ
た後、さらに硝酸ナトリウムおよび水酸化ナトリウムを
混合して上層に分離したニッケルの複合酸化物を除去す
ることからなる乾式精錬による鉛中のニッケル除去方法
としたのである。Alternatively, a method for removing nickel in lead by dry refining, which comprises performing the above nickel removal treatment and then further mixing sodium nitrate and sodium hydroxide to remove the nickel composite oxide separated in the upper layer. It was.
【００１１】または、上記したいずれかのニッケル除去
処理を行なった後、さらにリンまたは金属−リン化合物
を混合して上層に分離したニッケルのリン化物を除去す
ることからなる乾式精錬による鉛中のニッケル除去方法
としたのである。Alternatively, nickel in lead by dry refining, which comprises performing one of the above nickel removal treatments and then further mixing phosphorus or a metal-phosphorus compound to remove the nickel phosphide separated in the upper layer. The removal method was adopted.
【００１２】以下に、その詳細を述べる。この発明にお
けるニッケル含有の鉛原料は、主として鉛蓄電池の電極
部分等のリサイクル原料の他、これとホウエン鉱などの
鉱石との混合物その他であってもよく、特に限定して用
いるものではない。The details will be described below. The nickel-containing lead raw material in the present invention may be mainly a recycled raw material such as an electrode portion of a lead storage battery, or a mixture of this with ore such as houenite and the like, and is not particularly limited and used.
【００１３】この発明に用いる粗鉛を製造するための還
元精錬方法としては、焙焼反応法、または焙焼還元法と
いったいずれも周知の粗鉛の精製方法を採用すればよ
い。収率のよい後者の場合では、シャフト炉、反射炉に
より脱硫と還元を行ない、さらに石灰石、ケイ酸塩鉱、
鉄鉱、クズ鉄、コークスなどと共に溶融すると、カラ
ミ、カワ、ヒカワ、粗鉛の順に４層に分離するので、最
下槽の粗鉛をサイフォン式に流出させて得ることができ
る。As a reduction refining method for producing crude lead used in the present invention, any known refining method for crude lead such as roasting reaction method or roasting reduction method may be adopted. In the latter case where the yield is high, desulfurization and reduction are performed by a shaft furnace and a reverberatory furnace, and further limestone, silicate ore,
When it is melted with iron ore, scrap iron, coke, etc., it is separated into four layers in order of Karami, Kawa, Hikawa, and crude lead, so that the crude lead in the bottom tank can be obtained by siphoning out.
【００１４】このようにして得られる粗鉛に添加する硫
黄、または硫黄と硫化鉄の混合物のうち、硫化鉄は、Ｆ
ｅＳ、Ｆｅ2 Ｓ3 、ＦｅＳ2 のいずれの化合物であって
もよい。硫黄（Ｓ）と前記硫化鉄の混合比率は、粗鉛中
のＮｉ含有量（予想量）に対応して適宜に変更するの
で、限定されるものではないが、主として鉛蓄電池の電
極部分を原料とした場合に、硫黄：硫化鉄＝１：３（重
量比）として好ましい結果を得ている。Of the sulfur added to the crude lead thus obtained or the mixture of sulfur and iron sulfide, iron sulfide is F
It may be any compound of eS, Fe 2 S 3 and FeS 2 . The mixing ratio of sulfur (S) and iron sulfide is appropriately changed according to the Ni content (expected amount) in the crude lead, and is not limited, but mainly the electrode portion of the lead storage battery is used as a raw material. In this case, the preferable result was obtained with sulfur: iron sulfide = 1: 3 (weight ratio).
【００１５】また、上記同様の理由によって、粗鉛に対
する硫黄、または硫黄と硫化鉄の混合物の配合量は、限
定されるものではないが、主として鉛蓄電池の電極部分
を原料とした粗鉛１０００重量部に対して、０．５〜
２．０重量部の硫黄または硫黄と硫化鉄の１：３混合物
を添加して好ましい結果を得ている。For the same reason as above, the compounding amount of sulfur or the mixture of sulfur and iron sulfide with respect to crude lead is not limited, but 1000 wt. 0.5 to
2.0 parts by weight of sulfur or a 1: 3 mixture of sulfur and iron sulfide have been added with good results.
【００１６】この発明において、粗鉛に硫黄または硫黄
と硫化鉄の混合物を添加混合し、続いて添加する酸化剤
は、前記硫黄などの添加混合により生じた硫化ニッケル
を酸化するために添加するものであり、たとえば、硝酸
ナトリウム、硝酸カリウム、二酸化鉛（ＰｂＯ2 ）を具
体例として挙げることができる。このような酸化剤の粗
鉛に対する配合量は、前述のとおり、粗鉛中のＮｉ含有
量（予想量）に対応して適宜に変更するので、限定され
るものではないが、前記同じ材料からなる粗鉛１０００
重量部に対して、１〜２重量部を添加して好ましい結果
を得ている。In the present invention, sulfur or a mixture of sulfur and iron sulfide is added to and mixed with crude lead, and an oxidizing agent added subsequently is used to oxidize nickel sulfide produced by the addition and mixing of sulfur and the like. As specific examples, sodium nitrate, potassium nitrate, and lead dioxide (PbO 2 ) can be given. As described above, the compounding amount of such an oxidizing agent with respect to the crude lead is appropriately changed in accordance with the Ni content (expected amount) in the crude lead, and thus is not limited, but from the same material as above. 1000 crude lead
A preferable result was obtained by adding 1 to 2 parts by weight to the parts by weight.
【００１７】なお、このように酸化剤を添加した後、３
３０〜４２０℃の溶融粗鉛を４８０〜５２０℃に昇温す
る。なぜなら、４８０℃未満の低温では、酸化反応が遅
くて実用性が低く、５２０℃を越える高温では、鉛の酸
化が過度に進むので好ましくないからである。After adding the oxidizing agent in this way, 3
The molten crude lead of 30 to 420 ° C. is heated to 480 to 520 ° C. This is because if the temperature is lower than 480 ° C., the oxidation reaction is slow and the practicality is low, and if the temperature is higher than 520 ° C., the oxidation of lead proceeds excessively, which is not preferable.
【００１８】上記したニッケル酸化物の除去処理後、さ
らに硝酸ナトリウムおよび水酸化ナトリウムを混合して
上層に分離したニッケルの酸化物を除去する方法は、通
常、脱アンチモン、脱錫、脱砒素に適用するハリス法と
呼ばれる複合酸化物の生成反応による精製方法を応用し
たものである。この方法により、Ｎａ−Ｎｉ−Ｏの複合
酸化物が生成され、Ｎｉを含む化合物として分離除去で
きるようになる。After the above nickel oxide removal treatment, the method of further mixing sodium nitrate and sodium hydroxide to remove the nickel oxide separated in the upper layer is usually applied to antimony removal, tin removal and arsenic removal. This is an application of a purification method called a Harris method called a complex oxide formation reaction. By this method, a complex oxide of Na-Ni-O is generated, and it becomes possible to separate and remove it as a compound containing Ni.
【００１９】上記したニッケル除去処理を行なった後、
さらに添加するリンとしては、リンの同素体である赤リ
ン（白リンと黒リンの固溶体）、紅リン（赤リンの微細
なもの）、紫リン、黒リンなどを挙げることができる。
また、このようなリンを溶融粗鉛中に添加すると、酸化
して消耗しやすく、また刺激臭が発生して作業に不都合
であるため、前記したリンに代えて金属−リン化合物を
用いることが好ましい。このような金属−リン化合物と
しては、たとえば、リン化カルシウム（Ｃａ3Ｐ2 ）、
リン化鉛（ＰｂＰ5 ）が挙げられる。After performing the above nickel removal treatment,
Examples of phosphorus added include red phosphorus (solid solution of white phosphorus and black phosphorus) which is an allotrope of phosphorus, red phosphorus (fine red phosphorus), purple phosphorus, black phosphorus and the like.
Further, when such phosphorus is added to the molten crude lead, it is easily oxidized and consumed, and irritating odor is generated, which is inconvenient for work. Therefore, it is preferable to use a metal-phosphorus compound instead of the above-mentioned phosphorus. preferable. Such metal - As the phosphorus compound, for example, phosphide calcium (Ca 3 P 2),
Lead phosphide (PbP 5 ) may be mentioned.
【００２０】このようなリンまたは金属−リン化合物の
粗鉛中への配合割合は、粗鉛１０００重量部に対して
０．１〜０．２重量部である。なぜなら、０．１重量部
未満の少量では、通常の攪拌では接触反応が遅くなり、
０．２重量部を越えて多量に添加すると、リンの損失が
多くなって好ましくないからである。The proportion of such a phosphorus or metal-phosphorus compound in crude lead is 0.1 to 0.2 parts by weight with respect to 1000 parts by weight of crude lead. The reason is that if the amount is less than 0.1 part by weight, the catalytic reaction will be delayed with normal stirring,
This is because if a large amount is added in an amount exceeding 0.2 parts by weight, the phosphorus loss increases, which is not preferable.
【００２１】[0021]
【作用】この発明の乾式精錬による鉛中のニッケル除去
方法において、粗鉛に硫黄または硫黄を添加混合する
と、Ｎｉ3 Ｓ2 などのニッケルの硫化物が生成し、溶融
粗鉛中の上層に分離したものを除去できる。In the method of removing nickel in lead by dry refining according to the present invention, when sulfur or sulfur is added to and mixed with crude lead, nickel sulfide such as Ni 3 S 2 is produced and separated into an upper layer in molten crude lead. You can remove what you did.
【００２２】上記処理に代えて硫黄と硫化鉄の混合物を
添加混合すると、さらに効率よくニッケルの硫化物が生
成し、溶融粗鉛中の上層に分離したものを除去（除滓）
できる。When a mixture of sulfur and iron sulfide is added and mixed instead of the above treatment, nickel sulfide is produced more efficiently, and the separated upper layer in the molten crude lead is removed (slag).
it can.
【００２３】以上の硫化処理による除滓の後、直ちに加
熱昇温し、酸化剤を添加混合すると、粗鉛中に残留する
硫化物以外のニッケル成分が、２ＮｉＳ＋Ｏ2 →２Ｎｉ
Ｏ＋Ｓ2 の反応にしたがい、酸化ニッケルとなって溶融
粗鉛中の上層に分離し、これを除去できる。Immediately after the slag is removed by the sulfurization treatment, the temperature is raised by heating, and an oxidizer is added and mixed. As a result, nickel components other than the sulfide remaining in the crude lead become 2NiS + O 2 → 2Ni.
According to the reaction of O + S 2 , nickel oxide is formed and separated into the upper layer in the molten crude lead, which can be removed.
【００２４】このことは、図２に示した２ＭＳ＋Ｏ2 ＝
２ＭＯ＋Ｓ2 （式中、ＭはＮｉまたはＰｂを表わす。）
反応の標準自由エネルギー変化と温度の関係図におい
て、２ＰｂＳ−２ＰｂＯと２ＮｉＳ−２ＮｉＯのΔＦ°
〔ｋｃａｌ〕の差を利用した処理法であるといえる。This means that 2MS + O 2 = shown in FIG.
2MO + S 2 (In the formula, M represents Ni or Pb.)
In the relationship diagram of the change in standard free energy of reaction and temperature, ΔF ° of 2PbS-2PbO and 2NiS-2NiO
It can be said that this is a processing method utilizing the difference in [kcal].
【００２５】このようにしてニッケル除去処理を行なっ
た後、粗鉛中にさらに硝酸ナトリウムおよび水酸化ナト
リウムを混合すると、分離していない酸化ニッケルおよ
び未酸化のニッケル成分が、Ｎａ−Ｎｉ−Ｏの複合酸化
物となって、溶融粗鉛中の上層に分離し、これを除去で
きる。After the nickel removal treatment is carried out in this way, when sodium nitrate and sodium hydroxide are further mixed in the crude lead, nickel oxide and unoxidized nickel components which have not been separated are converted into Na--Ni--O. It becomes a complex oxide, which is separated into the upper layer in the molten crude lead and can be removed.
【００２６】前記溶融粗鉛中にリンまたは金属−リン化
合物を混合すると、Ｎａ−Ｎｉ−Ｏの複合酸化物以外の
ニッケル成分が、Ｎｉ−Ｐ化合物となって、溶融粗鉛中
の上層に分離し、これを除去できる。（参考のため、図
３にＮｉ−Ｐ化合物生成の自由エネルギー変化ΔＧ°／
ｋｃａｌと温度の関係を示した。）When phosphorus or a metal-phosphorus compound is mixed in the molten crude lead, nickel components other than the complex oxide of Na-Ni-O become Ni-P compounds and are separated into an upper layer in the molten crude lead. And you can remove it. (For reference, the free energy change ΔG ° /
The relationship between kcal and temperature is shown. )
【００２７】[0027]
〔実施例１〕鉛蓄電池の電極部分等のリサイクル原料を
シャフト炉により脱硫と還元を行ない、さらに石灰石、
ケイ酸塩鉱、鉄鉱、クズ鉄、コークスと共に溶融し、最
下槽の粗鉛をサイフォン式に流出させて分離した。Example 1 A shaft furnace is used for desulfurization and reduction of a recycled material such as an electrode portion of a lead storage battery, and further limestone,
It was melted together with silicate ore, iron ore, scrap iron and coke, and the crude lead in the bottom tank was siphoned out and separated.
【００２８】この粗鉛を３３０〜３８０℃に保持し、粗
鉛１０００重量部に対して０．５〜２．０重量部の硫黄
を添加し、２０〜３０分間攪拌して溶融粗鉛中の上層に
分離したニッケルの硫化物を除去した。なお、前記硫黄
の添加量は、Ｎｉ3 Ｓ2 としてニッケル化合物を除去す
ると仮定した理論量の１０〜５０倍量であるが、粗鉛中
に銅を共存させてもよい場合は、前記硫黄の混合量より
低い量であってもよい。This crude lead was maintained at 330 to 380 ° C., 0.5 to 2.0 parts by weight of sulfur was added to 1000 parts by weight of crude lead, and the mixture was stirred for 20 to 30 minutes to obtain a mixture of molten crude lead. The nickel sulfide separated in the upper layer was removed. The amount of the sulfur added is 10 to 50 times the theoretical amount assumed to remove the nickel compound as Ni 3 S 2. However, when copper may coexist in the crude lead, the sulfur The amount may be lower than the mixed amount.
【００２９】この処理は異なる原料サンプル５種類につ
いて行ない、処理前の粗鉛中のＮｉ％と処理後のＮｉ％
を調べて表１に示した。This treatment was carried out on five different raw material samples, and the Ni% in the crude lead before the treatment and the Ni% after the treatment were treated.
Was examined and shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】〔実施例２〕実施例１のＮｉ除去処理にお
いて、粗鉛を３３０〜３８０℃に保持し、粗鉛１０００
重量部に対して０．５〜２．０重量部の硫黄と硫化鉄の
１：３（重量比）混合物を添加すること以外は全く同様
にして粗鉛中の上層に分離したニッケルの硫化物を除去
した。Example 2 In the Ni removal treatment of Example 1, crude lead was maintained at 330 to 380 ° C.
Nickel sulfide separated in the upper layer in crude lead in exactly the same manner except that 0.5 to 2.0 parts by weight relative to parts by weight of a 1: 3 (weight ratio) mixture of sulfur and iron sulfide was added. Was removed.
【００３２】この処理は異なる原料サンプル５種類につ
いて行ない、処理前の粗鉛中のＮｉ％と処理後のＮｉ％
を調べて表２に示した。This treatment was carried out for five kinds of different raw material samples. Ni% in the crude lead before the treatment and Ni% after the treatment
Was examined and shown in Table 2.
【００３３】[0033]
【表２】 [Table 2]
【００３４】表２の結果からも明らかなように、実施例
２のＮｉ除去処理は、実施例１に比べてニッケル含有量
を可及的に低レベル化できることがわかる。As is clear from the results shown in Table 2, the Ni removal treatment of Example 2 can lower the nickel content as much as possible as compared with Example 1.
【００３５】〔実施例３〕実施例２のＮｉ除去処理後、
溶融粗鉛を４８０〜５２０℃に加熱昇温し、硝酸ナトリ
ウムからなる酸化剤１０を溶融粗鉛１０００重量部に対
して１．０〜２．０重量部を添加し、粗鉛中の上層に分
離したニッケルの酸化物を除去した。[Embodiment 3] After the Ni removal treatment of Embodiment 2,
The molten crude lead is heated to 480 to 520 ° C. and heated, and the oxidizer 10 made of sodium nitrate is added in an amount of 1.0 to 2.0 parts by weight with respect to 1000 parts by weight of the molten crude lead. The separated nickel oxide was removed.
【００３６】この処理は異なる原料サンプル５種類につ
いて行ない、処理前（硫化処理後）の粗鉛中のＮｉ％と
処理後のＮｉ％を調べて表３に示した。This treatment was carried out on five kinds of raw material samples, and the Ni% in the crude lead before the treatment (after the sulfurating treatment) and the Ni% after the treatment were examined and shown in Table 3.
【００３７】[0037]
【表３】 [Table 3]
【００３８】表３の結果からも明らかなように、実施例
３のＮｉ除去処理は、硫化処理による実施例２に比べて
ニッケル含有量を低レベル化できることがわかる。ま
た、処理効率からみると、硫化処理のほうが有効であっ
た。As is clear from the results shown in Table 3, the Ni removal treatment of Example 3 can lower the nickel content as compared with Example 2 by the sulfurating treatment. From the viewpoint of treatment efficiency, the sulfurating treatment was more effective.
【００３９】〔実施例４〕実施例３のＮｉ除去処理後、
溶融粗鉛を４８０〜５２０℃に保持し、硝酸ナトリウム
および水酸化ナトリウムの５：３（重量比）混合物を溶
融粗鉛１０００重量部に対して８〜１０重量部を数回に
分けて添加し、攪拌して粗鉛中の上層に分離したＮａ−
Ｎｉ−Ｏの複合酸化物を除去した。Example 4 After the Ni removal treatment of Example 3,
The molten crude lead was kept at 480 to 520 ° C., and a 5: 3 (weight ratio) mixture of sodium nitrate and sodium hydroxide was added in 8 to 10 parts by weight to 1000 parts by weight of the molten crude lead in several portions. , Na-
The Ni-O composite oxide was removed.
【００４０】この処理は異なる原料サンプル５種類につ
いて行ない、処理前（硫化処理後）の粗鉛中のＮｉ％と
処理後のＮｉ％を調べて表３に示した。This treatment was carried out for 5 kinds of raw material samples, and the Ni% in the crude lead before the treatment (after the sulfurating treatment) and the Ni% after the treatment were examined and shown in Table 3.
【００４１】[0041]
【表４】 [Table 4]
【００４２】表４の結果からも明らかなように、実施例
４のＮｉ除去処理は、実施例１、実施例２および硝酸ナ
トリウムを用いた酸化処理によりＮｉ除去を行なった実
施例３に比べて、ニッケル含有量を可及的に低レベル化
できることがわかる。As is clear from the results shown in Table 4, the Ni removal treatment of Example 4 is different from that of Examples 1 and 2 and that of Example 3 in which Ni was removed by the oxidation treatment using sodium nitrate. It can be seen that the nickel content can be made as low as possible.
【００４３】〔実施例５〕実施例４のＮｉ除去処理後、
溶融粗鉛を４８０〜５２０℃に保持し、赤リン粉末を溶
融粗鉛１０００重量部に対して０．１〜０．２重量部を
添加し、５〜１５分攪拌して粗鉛中の上層に分離したＮ
ｉ−Ｐ化合物を除去した。なお、前記赤リンの添加量
は、Ｎｉ3 Ｐとして化合する理論量の２０〜６０倍量と
した。[Embodiment 5] After the Ni removal treatment of Embodiment 4,
The molten crude lead was kept at 480 to 520 ° C., 0.1 to 0.2 parts by weight of red phosphorus powder was added to 1000 parts by weight of molten crude lead, and the mixture was stirred for 5 to 15 minutes to form an upper layer in the crude lead. Separated into N
The iP compound was removed. The amount of red phosphorus added was 20 to 60 times the theoretical amount of Ni 3 P combined.
【００４４】この処理は異なる原料サンプル５種類につ
いて行ない、リン化処理前（酸化処理後）の粗鉛中のＮ
ｉ％と処理後のＮｉ％を調べて表５に示した。This treatment was carried out for five different raw material samples, and N in the crude lead before the phosphating treatment (after the oxidization treatment) was
The i% and the Ni% after the treatment were investigated and shown in Table 5.
【００４５】[0045]
【表５】 [Table 5]
【００４６】表５の結果からも明らかなように、実施例
５のＮｉ除去処理は、アルカリ混合物を用いた酸化処理
による実施例４に比べてニッケル含有量を可及的に低レ
ベル化でき、Ｎｉの含有量を全て０．００１０％以下と
することが可能になることがわかる。As is clear from the results in Table 5, the Ni removal treatment of Example 5 can lower the nickel content as much as possible as compared with Example 4 by the oxidation treatment using the alkali mixture, It can be seen that the Ni content can all be made 0.0010% or less.
【００４７】[0047]
【効果】この発明は、以上説明したように、粗鉛に硫黄
または硫黄と硫化鉄の混合物を添加混合する処理、次い
で酸化剤を混合し加熱昇温する処理、硝酸ナトリウムお
よび水酸化ナトリウムを混合する処理、さらには上記各
処理を行なった後、さらにリンまたは金属−リン化合物
を混合する処理を行ない、各処理毎または所定の一連の
処理後に溶融粗鉛中に分離したニッケル化合物を除去す
るようにしたので、乾式精錬によって鉛中のニッケル含
有量を可及的に低レベル化できる利点がある。[Effect] As described above, the present invention is a process of adding and mixing sulfur or a mixture of sulfur and iron sulfide to crude lead, then a process of mixing an oxidizing agent and heating and heating, mixing sodium nitrate and sodium hydroxide. Treatment, and further, after performing each of the above treatments, a treatment of further mixing phosphorus or a metal-phosphorus compound is performed to remove the nickel compound separated in the molten crude lead after each treatment or a predetermined series of treatments. Therefore, there is an advantage that the nickel content in lead can be made as low as possible by dry refining.
【００４８】また、上記全ての処理を組み合わせて行な
うことにより、Ｎｉの含有量を０．００１０％以下とす
ることが可能になる利点もある。There is also an advantage that the Ni content can be made 0.0010% or less by performing all of the above processes in combination.
【図１】Ｎｉの固溶域を示すＰｂ−Ｎｉの状態図FIG. 1 is a phase diagram of Pb-Ni showing a solid solution region of Ni.
【図２】２ＭＳ＋Ｏ2 ＝２ＭＯ＋Ｓ2 なる反応の標準自
由エネルギー変化と温度の関係を示す図表FIG. 2 is a chart showing the relationship between the change in standard free energy of the reaction 2MS + O 2 = 2MO + S 2 and the temperature.
【図３】Ｎｉ−Ｐ化合物生成の標準自由エネルギー変化
と温度の関係を示す図表FIG. 3 is a chart showing the relationship between the change in standard free energy of Ni-P compound formation and temperature.
Claims (4)
鉛を製造し、この溶融状態の粗鉛に硫黄または硫黄と硫
化鉄の混合物を添加混合し、上層に分離生成した硫化ニ
ッケルを除去することからなる乾式精錬による鉛中のニ
ッケル除去方法。1. A crude lead is produced by reducing and refining a nickel-containing lead raw material, and sulfur or a mixture of sulfur and iron sulfide is added and mixed to the crude lead in a molten state to remove nickel sulfide separated and produced in an upper layer. A method for removing nickel in lead by dry refining, which comprises:
鉛を製造し、溶融状態の粗鉛に硫黄または硫黄と硫化鉄
の混合物を混合し、次いで酸化剤を混合し加熱昇温して
上層に分離したニッケルの酸化物を除去することからな
る乾式精錬による鉛中のニッケル除去方法。2. A nickel-containing lead raw material is reduced and refined to produce crude lead. Sulfur or a mixture of sulfur and iron sulfide is mixed with molten crude lead, and then an oxidizing agent is mixed and heated to heat. A method for removing nickel in lead by dry refining, which comprises removing the nickel oxide separated in the upper layer.
なった後、さらに硝酸ナトリウムおよび水酸化ナトリウ
ムを混合して上層に分離したニッケルの複合酸化物を除
去することからなる乾式精錬による鉛中のニッケル除去
方法。3. In lead by dry refining, which comprises performing the nickel removal treatment according to claim 2 and further mixing sodium nitrate and sodium hydroxide to remove the nickel composite oxide separated in the upper layer. Nickel removal method.
除去処理を行なった後、さらにリンまたは金属−リン化
合物を混合して上層に分離したニッケルのリン化物を除
去することからなる乾式精錬による鉛中のニッケル除去
方法。4. A dry refining process, which comprises performing the nickel removal treatment according to claim 1, 2 or 3, and further mixing phosphorus or a metal-phosphorus compound to remove the nickel phosphide separated in the upper layer. Method for removing nickel from lead by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6205265A JP2706220B2 (en) | 1994-08-30 | 1994-08-30 | Nickel removal method from lead by dry refining. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6205265A JP2706220B2 (en) | 1994-08-30 | 1994-08-30 | Nickel removal method from lead by dry refining. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0867922A true JPH0867922A (en) | 1996-03-12 |
| JP2706220B2 JP2706220B2 (en) | 1998-01-28 |
Family
ID=16504124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6205265A Expired - Lifetime JP2706220B2 (en) | 1994-08-30 | 1994-08-30 | Nickel removal method from lead by dry refining. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2706220B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4947213A (en) * | 1972-01-07 | 1974-05-07 | ||
| JPS5976835A (en) * | 1982-10-25 | 1984-05-02 | Sumitomo Metal Mining Co Ltd | Dry refining method of lead |
| JPH0649558A (en) * | 1992-08-05 | 1994-02-22 | Sumitomo Metal Mining Co Ltd | Production of low-lead high-purity metallic nickel |
-
1994
- 1994-08-30 JP JP6205265A patent/JP2706220B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4947213A (en) * | 1972-01-07 | 1974-05-07 | ||
| JPS5976835A (en) * | 1982-10-25 | 1984-05-02 | Sumitomo Metal Mining Co Ltd | Dry refining method of lead |
| JPH0649558A (en) * | 1992-08-05 | 1994-02-22 | Sumitomo Metal Mining Co Ltd | Production of low-lead high-purity metallic nickel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2706220B2 (en) | 1998-01-28 |
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