JP6453743B2 - Method for electrolytic purification of lead using sulfamic acid bath - Google Patents
Method for electrolytic purification of lead using sulfamic acid bath Download PDFInfo
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Description
本発明は、スルファミン酸浴による鉛の電解精製方法に関し、特に、非鉄製錬、基盤や電子部品などリサイクル原料の溶融炉、及び産業廃棄物を溶融処理する乾式炉より発生する乾式煙灰中に含まれている鉛を回収するスルファミン酸浴による鉛の電解精製方法に関する。 The present invention relates to a method for electrolytic purification of lead using a sulfamic acid bath, and is particularly included in non-ferrous smelting, melting furnaces for recycling raw materials such as foundations and electronic components, and dry smoke ash generated from dry furnaces for melting industrial waste. The present invention relates to a method for electrolytic purification of lead using a sulfamic acid bath for recovering lead.
非鉄製錬、基盤や電子部品などリサイクル原料の溶融炉、及び産業廃棄物を溶融処理する乾式炉より非鉄製錬の乾式煙灰中に含まれている鉛を回収するため、煙灰を硫酸浸出し、硫酸鉛にした後、電気炉で溶融還元を行う。溶融還元により分離されたメタルをソーダ処理し、その後、メタルをアノード鋳造した後、スルファミン酸浴中にて電解精製することで鉛を回収している。 In order to recover lead contained in non-ferrous smelting dry ash from non-ferrous smelting, melting furnaces for recycling raw materials such as foundations and electronic parts, and dry furnaces for melting industrial waste, fumes are leached with sulfuric acid, After changing to lead sulfate, smelting reduction is performed in an electric furnace. The metal separated by smelting reduction is treated with soda, and then the metal is anode cast, and then lead is recovered by electrolytic purification in a sulfamic acid bath.
このような鉛の電解精製技術として、例えば、特許文献１には、スルファミン酸浴での電解精製において、１段階目の電流密度を５０Ａ／ｍ2以下で電気分解を２時間以上行った後、２段階目として１００Ａ／ｍ2以下で電気分解を行うことで高純度の鉛を回収する鉛の電解方法が開示されている。そして、このような構成によれば、高Ｂｉ品位のアノードに対しても高純度の鉛を回収することができると記載されている。 As such a lead electrolytic purification technique, for example, in Patent Document 1, in electrolytic purification in a sulfamic acid bath, electrolysis is performed for 2 hours or more at a current density of the first step of 50 A / m 2 or less, As a second stage, a lead electrolysis method is disclosed in which high-purity lead is recovered by performing electrolysis at 100 A / m 2 or less. And it is described that according to such a structure, highly purified lead can be collect | recovered also with respect to a high Bi quality anode.
従来のスルファミン酸浴による鉛の電解精製を実施すると、浴液中に白色の残渣が見られ、さらに電解液中の鉛濃度が低下する問題が生じていた。即ち、白色の残渣は電槽の底に堆積するが、ある程度堆積すると電槽から取り出す必要があり、そのために電解を中止することとなり、白色の残渣が多いとその頻度が多くなっていた。また、電解液中の鉛濃度の低下がみられると鉛の電着状況が悪くなる場合もあった。その原因は、以下の反応によってスルファミン酸浴による鉛の電解精製中のスルファミン酸が分解することであり、白色残渣は硫酸鉛として堆積し、電解液中の鉛濃度が低下していた。
ＳＯ3ＮＨ2 - ＋ Ｈ2Ｏ → ＳＯ4 2- ＋ ＮＨ4 +
Ｐｂ2+ ＋ ＳＯ4 2- → ＰｂＳＯ4↓
When electrolytic refining of lead with a conventional sulfamic acid bath is performed, a white residue is observed in the bath solution, and there is a problem that the lead concentration in the electrolyte solution is further reduced. That is, the white residue is deposited on the bottom of the battery case, but if it accumulates to some extent, it is necessary to remove it from the battery case. Therefore, the electrolysis is stopped, and the frequency of the white residue increases. Further, when the lead concentration in the electrolytic solution is decreased, the electrodeposition of lead may be deteriorated. The cause is that sulfamic acid during the electrolytic purification of lead in the sulfamic acid bath is decomposed by the following reaction, and the white residue is deposited as lead sulfate, and the lead concentration in the electrolytic solution is reduced.
SO 3 NH 2 − + H 2 O → SO 4 2− + NH 4 +
Pb 2+ + SO 4 2- → PbSO 4 ↓
本発明者らは上記課題を解決するために研究を重ねたところ、スルファミン酸の分解率を所定値以下に制御することにより、スルファミン酸浴による鉛の電解精製において、白色残渣の生成を抑制し、電解液中の鉛濃度の低下を抑制することができることを見出した。 The inventors of the present invention have made researches to solve the above-mentioned problems, and by controlling the decomposition rate of sulfamic acid to a predetermined value or less, the generation of white residue is suppressed in the electrolytic purification of lead using a sulfamic acid bath. The inventors have found that the decrease in the lead concentration in the electrolytic solution can be suppressed.
以上の知見を背景にして完成した本発明は一側面において、鉛アノードを用いた、スルファミン酸浴による鉛の電解精製方法において、スルファミン酸の分解率を０．０６％／日以下に制御して電解精製を行うスルファミン酸浴による鉛の電解精製方法である。 The present invention completed on the background of the above knowledge, in one aspect, in a method for electrolytic purification of lead using a sulfamic acid bath using a lead anode, the decomposition rate of sulfamic acid is controlled to 0.06% / day or less. This is a method for electrolytic purification of lead using a sulfamic acid bath for electrolytic purification.
本発明のスルファミン酸浴による鉛の電解精製方法は一実施形態において、スルファミン酸浴におけるスルファミン酸濃度を、スルファミン酸浴における鉛濃度よりも、さらに２０〜６０ｇ／Ｌ高い濃度に調整しながら電解精製を行う。 In one embodiment of the method for electrolytic purification of lead using a sulfamic acid bath according to the present invention, electrolytic purification while adjusting the sulfamic acid concentration in the sulfamic acid bath to a concentration that is 20 to 60 g / L higher than the lead concentration in the sulfamic acid bath. I do.
本発明のスルファミン酸浴による鉛の電解精製方法は別の一実施形態において、スルファミン酸浴における電解液温度を１５〜３０℃に調整しながら電解精製を行う。 In another embodiment of the method for electrolytic purification of lead using a sulfamic acid bath of the present invention, electrolytic purification is performed while adjusting the electrolyte temperature in the sulfamic acid bath to 15 to 30 ° C.
本発明によれば、スルファミン酸浴による鉛の電解精製において、白色残渣の生成を抑制し、電解液中の鉛濃度の低下を抑制することができる。そして、白色残渣を電槽から取り出す頻度を抑えることができる。また、電解液中の鉛濃度の低下を抑えることで鉛濃度の管理が容易となり、良好な鉛の電着状況が得られるようになる。さらに、電解精製中のスルファミン酸の補充の頻度が少なくなる効果もある。 ADVANTAGE OF THE INVENTION According to this invention, in the electrolytic purification of lead by a sulfamic acid bath, the production | generation of a white residue can be suppressed and the fall of the lead concentration in electrolyte solution can be suppressed. And the frequency which takes out a white residue from a battery case can be suppressed. Further, by suppressing the decrease in the lead concentration in the electrolytic solution, the lead concentration can be easily managed, and a good lead electrodeposition state can be obtained. Furthermore, there is an effect that the frequency of replenishment of sulfamic acid during electrolytic purification is reduced.
以下に本発明をさらに詳細に説明する。
本発明のスルファミン酸浴による鉛の電解精製方法は、スルファミン酸の分解率を０．０６％／日以下に制御して電解精製を行う。さらに、スルファミン酸浴におけるスルファミン酸濃度を、スルファミン酸浴における鉛濃度よりも、さらに２０〜６０ｇ／Ｌ高い濃度に調整しながら電解精製を行うことが好ましく、スルファミン酸浴における電解液温度を１５℃〜３０℃に調整しながら電解精製を行うことが好ましい。
The present invention is described in further detail below.
In the method for electrolytic purification of lead using the sulfamic acid bath of the present invention, electrolytic purification is performed by controlling the decomposition rate of sulfamic acid to 0.06% / day or less. Furthermore, it is preferable to perform electrolytic purification while adjusting the sulfamic acid concentration in the sulfamic acid bath to a concentration that is 20 to 60 g / L higher than the lead concentration in the sulfamic acid bath, and the electrolytic solution temperature in the sulfamic acid bath is 15 ° C. It is preferable to perform electrolytic purification while adjusting to -30 ° C.
スルファミン酸浴による鉛の電解精製におけるアノード反応及びカソード反応を以下に示す：
・アノード反応：Ｐｂ ＋ ２ＳＯ3ＮＨ2 - → Ｐｂ（ＳＯ3ＮＨ2）2 ＋ ２ｅ-
・カソード反応：Ｐｂ（ＳＯ3ＮＨ2）2 ＋ ２ｅ- → Ｐｂ ＋ ２ＳＯ3ＮＨ2 -
The anodic and cathodic reactions in the electrolytic purification of lead in a sulfamic acid bath are shown below:
Anode reaction: Pb + 2SO 3 NH 2 − → Pb (SO 3 NH 2 ) 2 + 2e −
Cathode reaction: Pb (SO 3 NH 2 ) 2 + 2e − → Pb + 2SO 3 NH 2 −
電解精製の対象となる原料（鉛含有物）としては、特に限定されないが、例えば、銅鉱石を自溶炉処理及び転炉処理した後、転炉ダストを硫酸処理した後の硫酸鉛を炭酸ナトリウムにより炭酸鉛にした後、電気炉で溶融還元を行い、分離したメタルをソーダ処理することで得られる鉛含有物等も挙げられる。電解精製の対象となる原料（鉛含有物）の成分としては、鉛が主成分で６０mass％以上あればよく、例えば、鉛７０〜９０mass％、錫０．０４mass％、ビスマス５〜３０mass％を含有する鉛含有物でも良い。 Although it does not specifically limit as a raw material (lead-containing material) used as the object of electrolytic refining, For example, after processing copper ore into a flash smelting furnace process and a converter process, lead carbonate after converting a converter dust into sulfuric acid is sodium carbonate. The lead-containing material etc. which are obtained by carrying out melt | dissolution reduction | restoration with an electric furnace after carrying out to lead carbonate by an electric furnace and carrying out the soda process of the isolate | separated metal are also mentioned. As a component of the raw material (lead-containing material) to be subjected to electrolytic purification, lead should be 60 mass% or more as a main component, for example, lead 70 to 90 mass%, tin 0.04 mass%, and bismuth 5 to 30 mass% are contained. Lead-containing material may be used.
上記鉛含有物を用いてアノードの形状に鋳造し、アノードに用いて電解精製を行う。アノードのサイズとしては、カソードのサイズに比べ小さくすることで、エッジ効果を防ぐことができ、平滑で良好な電着鉛を回収することができる。 The lead-containing material is used to cast into the shape of an anode, and the anode is used for electrolytic purification. By making the anode size smaller than the cathode size, the edge effect can be prevented, and smooth and good electrodeposited lead can be recovered.
電解液中のスルファミン酸の分解率を０．０６％／日以下に制御することで、硫酸鉛の堆積を低減することができる。また、電解液中の鉛濃度の低下を抑制することができる。さらにスルファミン酸浴による鉛の電解精製中のスルファミン酸の劣化を良好に抑制し、スルファミン酸の補充の頻度を抑えることができる。一方、０．０６％／日を超えると硫酸鉛の発生が多くなり、アノードからの鉛の溶出が間に合わず、電解液中の鉛濃度の低下を招く。さらに、多量の硫酸鉛の発生は、電解精製を中止して電槽の底に堆積した硫酸鉛の取出しの頻度を多くする。また、スルファミン酸の分解が進むとスルファミン酸の所定の濃度を保持するためにスルファミン酸の補充が頻繁となる。スルファミン酸の分解率は、好ましくは、０．０４％／日以下、より好ましくは０．０２％／日以下である。
なお、スルファミン酸分解率（ｄ）は、以下の式で表される：
ｄ = Ａd／ Ａ0
・Ａd：分解したスルファミン酸量
Ａd＝残渣重量×Ｐｂ品位×（９７／２０７）
上記「９７」はスルファミン酸分子量、上記「２０７」はＰｂ原子量
・Ａ0：初期スルファミン酸量
本発明では１日あたりのスルファミン酸分解率としているが、分解したスルファミン酸量は、５日後の残渣重量から１日あたりを平均で算出することが望ましい。
By controlling the decomposition rate of sulfamic acid in the electrolytic solution to 0.06% / day or less, the deposition of lead sulfate can be reduced. Moreover, the fall of the lead concentration in electrolyte solution can be suppressed. Furthermore, the deterioration of sulfamic acid during electrolytic purification of lead by a sulfamic acid bath can be satisfactorily suppressed, and the frequency of replenishment of sulfamic acid can be suppressed. On the other hand, if it exceeds 0.06% / day, the generation of lead sulfate increases, the elution of lead from the anode is not in time, and the lead concentration in the electrolytic solution is lowered. Furthermore, the generation of a large amount of lead sulfate stops electrolytic refining and increases the frequency of extraction of lead sulfate deposited on the bottom of the battery case. Further, as the decomposition of sulfamic acid proceeds, sulfamic acid is frequently replenished to maintain a predetermined concentration of sulfamic acid. The decomposition rate of sulfamic acid is preferably 0.04% / day or less, more preferably 0.02% / day or less.
The sulfamic acid decomposition rate (d) is expressed by the following formula:
d = A d / A 0
A d : amount of decomposed sulfamic acid A d = residue weight × Pb quality × (97/207)
“97” is the molecular weight of sulfamic acid, “207” is the amount of Pb atom / A 0 : initial sulfamic acid amount In the present invention, the decomposition rate of sulfamic acid per day is used, but the amount of decomposed sulfamic acid is the residue after 5 days It is desirable to calculate the average per day from the weight.
電解液中のスルファミン酸濃度を、電解液中の鉛濃度（ｇ／Ｌ）よりも、さらに２０〜６０ｇ／Ｌ高い濃度（以下、超過分とも言う）に調整することが好ましい。例えば、本発明における電解液中のスルファミン酸濃度は、電解液中の鉛濃度が８０ｇ／Ｌの場合には、電解液中のスルファミン酸濃度を１００〜１４０ｇ／Ｌに調整することが好ましい。なお、正確には、スルファミン酸の濃度は、鉛のモル数に対するモル数の濃度と示すべきであるが、スルファミン酸の分子量と鉛の原子量が近いことから、実際は、スルファミン酸濃度をそのまま鉛の濃度と対比しても問題ない。
なお、電解液中のスルファミン酸濃度を、電解液中の鉛濃度（ｇ／Ｌ）の濃度よりも、さらに６０ｇ／Ｌより高い濃度とするとスルファミン酸の分解率が高くなり、０．０６％／日以下に制御することが困難となる。一方、２０ｇ／Ｌ未満では、スルファミン酸の添加の効果がなくなるおそれがある。電解中はスルファミン酸の分解が進み、濃度は低下していくので、必要に応じてスルファミン酸を添加することで２０ｇ／Ｌ以上を保持することができるが、スルファミン酸の分解率が０．０６％／日を超える場合には、添加の頻度が多くなり、硫酸鉛の堆積が多くなる。
It is preferable to adjust the sulfamic acid concentration in the electrolytic solution to a concentration (hereinafter also referred to as excess) that is 20 to 60 g / L higher than the lead concentration (g / L) in the electrolytic solution. For example, the sulfamic acid concentration in the electrolytic solution in the present invention is preferably adjusted to 100 to 140 g / L when the lead concentration in the electrolytic solution is 80 g / L. To be precise, the concentration of sulfamic acid should be expressed as the concentration of moles relative to the number of moles of lead. However, since the molecular weight of sulfamic acid is close to the atomic weight of lead, the concentration of sulfamic acid is actually the same as that of lead. There is no problem even if compared with the concentration.
If the concentration of sulfamic acid in the electrolytic solution is set to a concentration higher than 60 g / L than the concentration of lead (g / L) in the electrolytic solution, the decomposition rate of sulfamic acid is increased to 0.06% / It becomes difficult to control to less than a day. On the other hand, if it is less than 20 g / L, the effect of adding sulfamic acid may be lost. During electrolysis, the decomposition of sulfamic acid proceeds and the concentration decreases. Therefore, if necessary, sulfamic acid can be maintained at 20 g / L or more by adding sulfamic acid, but the decomposition ratio of sulfamic acid is 0.06. When it exceeds% / day, the frequency of addition increases, and the deposition of lead sulfate increases.
スルファミン酸浴における電解液温度は１５℃〜３０℃とするのが好ましい。３０℃を超えると、スルファミン酸浴による鉛の電解精製中のスルファミン酸の分解が大きくなるおそれがあり、さらにスルファミン酸の分解が大きくなることにより硫酸鉛の堆積が増加し、電解液中の鉛濃度が低下するおそれがある。ただし、電解液温度が低すぎると、鉛の電着状況が悪くなるおそれがあるため、１５℃以上が好ましく、２０℃以上がより好ましい。 The electrolyte temperature in the sulfamic acid bath is preferably 15 ° C to 30 ° C. If the temperature exceeds 30 ° C., the decomposition of sulfamic acid during the electrolytic purification of lead by the sulfamic acid bath may increase, and further the decomposition of sulfamic acid increases the deposition of lead sulfate, leading to lead in the electrolyte. Concentration may decrease. However, if the electrolyte temperature is too low, the electrodeposition of lead may be deteriorated, so 15 ° C. or higher is preferable, and 20 ° C. or higher is more preferable.
電解液中の鉛濃度を６０〜８０ｇ／Ｌとするのが好ましい。このような構成により、電解精製によってカソードに電着した鉛の良好な電着状況が得られる。スルファミン酸の分解率が０．０６％／日を超える場合には、電解液中の鉛濃度の低下が見られるため、適正な範囲に制御することが困難になる。従って、０．０６％／日以下であれば、電解液中の鉛濃度を６０〜８０ｇ／Ｌとの狭い範囲に調整することが容易となる。電解液中の鉛濃度は、７０〜８０ｇ／Ｌとするのがより好ましい。 The lead concentration in the electrolytic solution is preferably 60 to 80 g / L. With such a configuration, a good electrodeposition state of lead electrodeposited on the cathode by electrolytic purification can be obtained. When the decomposition rate of sulfamic acid exceeds 0.06% / day, a decrease in the lead concentration in the electrolytic solution is observed, so that it is difficult to control within an appropriate range. Therefore, if it is 0.06% / day or less, it becomes easy to adjust the lead concentration in the electrolytic solution to a narrow range of 60 to 80 g / L. The lead concentration in the electrolytic solution is more preferably 70 to 80 g / L.
電解液中のその他の成分である平滑剤としては、ノイゲンＢＮ−１３９０（以下、「ノイゲン」は登録商標）又はノイゲンＢＮ−２５６０を１〜７００ｍｇ／Ｌ添加することが好ましい。これにより、より平滑で良好な電着鉛を回収することができる。なお、ノイゲンＢＮ−１３９０、ノイゲンＢＮ−２５６０は、ポリオキシエチレンモノナフチルエーテルを主成分とする非イオン界面活性剤であり、第一工業製薬の商品である。ノイゲンＢＮ−１３９０はポリオキシエチレンモノナフチルエーテルを９０％、残りは水の非イオン界面活性剤である。 It is preferable to add 1 to 700 mg / L of Neugen BN-1390 (hereinafter, “Neugen” is a registered trademark) or Neugen BN-2560 as a smoothing agent which is another component in the electrolytic solution. Thereby, smoother and better electrodeposited lead can be recovered. Neugen BN-1390 and Neugen BN-2560 are nonionic surfactants mainly composed of polyoxyethylene mononaphthyl ether and are products of Daiichi Kogyo Seiyaku. Neugen BN-1390 is 90% polyoxyethylene mononaphthyl ether and the rest is a nonionic surfactant in water.
電解の電流密度は、５０〜１００Ａ／ｍ2に制御することが好ましい。これにより、より平滑で良好な電着鉛を回収することができる。 The current density of the electrolysis, it is preferable to control the 50~100A / m 2. Thereby, smoother and better electrodeposited lead can be recovered.
以下に本発明の実施例を示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。 Examples of the present invention are shown below, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
（実験例１：スルファミン酸濃度の影響）
電解液の組成として、鉛濃度及びスルファミン酸濃度を表１に記載の濃度に調整した溶液に、平滑剤としてノイゲンＢＮ−１３９０を１０ｍｇ／Ｌになるように添加した。鉛含有物を鋳造して得られた鉛板をアノードとし、ステンレス板をカソードとして、交互に電槽に装入した。電極装入後、電槽内に上記電解液を補充し、電解液の電槽内滞留時間が１時間程度になるように給液することで、電槽内の濃度分布を均等にした。電解液の液温を表１に記載の温度に調整しながら、表１に記載の電流密度で通電して電解精製を５日間行い、電着鉛を回収した。また、例１−２、例１−３、例１−４、例１−５、では、５日間のスルファミン酸の分解率[％]を０．３％以下に制御した。
この結果、例１−１では、電着表面に荒れが顕著に現れ、例１−６、例１−７では、電解液中の鉛濃度の低下が抑制できなかった。また、例１−６ではスルファミン酸の分解率が０．４％、例１−７ではスルファミン酸の分解率が０．９％であった。一方、例１−２、例１−３、例１−４、例１−５、では、白色残渣の生成を抑制し、電解液中の鉛濃度の低下を抑制することができた。図１に、例１−３（スルファミン酸濃度の超過分３０ｇ／Ｌ）、例１−６（スルファミン酸濃度の超過分８０ｇ／Ｌ）、例１−７（スルファミン酸濃度の超過分１３０ｇ／Ｌ）の、スルファミン酸分解率を表すグラフを示す。なお、表１及び２において、「スルファミン酸濃度（超過分）」は、「電解液のスルファミン酸濃度（電解液中の鉛の濃度を超えた分）」を示す。
(Experimental example 1: Effect of sulfamic acid concentration)
As a composition of the electrolytic solution, Neugen BN-1390 was added as a smoothing agent to a solution in which the lead concentration and the sulfamic acid concentration were adjusted to the concentrations shown in Table 1 so as to be 10 mg / L. A lead plate obtained by casting the lead-containing material was used as an anode, and a stainless plate was used as a cathode, and the batteries were alternately charged. After the electrode was charged, the electrolyte solution was replenished in the battery case, and the concentration distribution in the battery case was made uniform by supplying the electrolyte solution so that the residence time of the electrolyte solution in the battery case was about 1 hour. While adjusting the temperature of the electrolytic solution to the temperature shown in Table 1, the current density shown in Table 1 was applied to conduct electrorefining for 5 days, and electrodeposited lead was collected. In Examples 1-2, 1-3, 1-4, and 1-5, the decomposition rate [%] of sulfamic acid for 5 days was controlled to 0.3% or less.
As a result, in Example 1-1, roughness appeared remarkably on the electrodeposition surface, and in Examples 1-6 and 1-7, a decrease in the lead concentration in the electrolytic solution could not be suppressed. In Example 1-6, the decomposition rate of sulfamic acid was 0.4%, and in Example 1-7, the decomposition rate of sulfamic acid was 0.9%. On the other hand, in Example 1-2, Example 1-3, Example 1-4, and Example 1-5, the production | generation of the white residue was suppressed and the fall of the lead concentration in electrolyte solution could be suppressed. FIG. 1 shows Example 1-3 (excess of sulfamic acid concentration 30 g / L), Example 1-6 (excess of sulfamic acid concentration 80 g / L), Example 1-7 (excess of sulfamic acid concentration 130 g / L) ) Shows a sulfamic acid decomposition rate. In Tables 1 and 2, “sulfamic acid concentration (excess)” indicates “sulfamic acid concentration of electrolytic solution (exceeding lead concentration in electrolytic solution)”.
（実験例２：電解温度の影響）
電解液の組成として、鉛濃度及びスルファミン酸濃度を表２に記載の濃度に調整した溶液に、平滑剤としてノイゲンＢＮ−１３９０を１０ｍｇ／Ｌになるように添加した。鉛含有物を鋳造して得られた鉛板をアノードとし、ステンレス板をカソードとして、交互に電槽に装入した。電極装入後、電槽内に上記電解液を補充し、電解液の電槽内滞留時間が１時間程度になるように給液することで、電槽内の濃度分布を均等にした。電解液の液温を表２に記載の温度に調整しながら、表２に記載の電流密度で通電して電解精製を５日間行い、電着鉛を回収した。また、例２−２、例２−３では、５日間のスルファミン酸の分解率[％]を０．３％以下に制御した。
この結果、例２−１は鉛の電着が悪くなった。一方、例２−５、例２−６では、電解液中の鉛濃度の低下が抑制できなかった。また、例２−５ではスルファミン酸の分解率が３．５％を超え、例２−６ではスルファミン酸の分解率が７％を超えた。一方、例２−２、例２−３、例２−４では、白色残渣の生成を抑制し、電解液中の鉛濃度の低下を抑制することができた。図２に、例２−２（電解液温１５℃）、例２−４（電解液温３０℃）、例２−６（電解液温５０℃）の、スルファミン酸分解率を表すグラフを示す。
(Experimental example 2: Influence of electrolysis temperature)
As a composition of the electrolytic solution, Neugen BN-1390 was added as a smoothing agent to a solution in which the lead concentration and the sulfamic acid concentration were adjusted to the concentrations shown in Table 2 so as to be 10 mg / L. A lead plate obtained by casting the lead-containing material was used as an anode, and a stainless plate was used as a cathode, and the batteries were alternately charged. After the electrode was charged, the electrolyte solution was replenished in the battery case, and the concentration distribution in the battery case was made uniform by supplying the electrolyte solution so that the residence time of the electrolyte solution in the battery case was about 1 hour. While adjusting the temperature of the electrolytic solution to the temperature shown in Table 2, the electrode was subjected to electrolytic refining for 5 days with the current density shown in Table 2 to recover the electrodeposited lead. Moreover, in Example 2-2 and Example 2-3, the decomposition rate [%] of sulfamic acid for 5 days was controlled to 0.3% or less.
As a result, in Example 2-1, lead electrodeposition was poor. On the other hand, in Example 2-5 and Example 2-6, a decrease in the lead concentration in the electrolytic solution could not be suppressed. In Example 2-5, the decomposition rate of sulfamic acid exceeded 3.5%, and in Example 2-6, the decomposition rate of sulfamic acid exceeded 7%. On the other hand, in Example 2-2, Example 2-3, and Example 2-4, the production | generation of the white residue was suppressed and the fall of the lead concentration in electrolyte solution could be suppressed. FIG. 2 is a graph showing the sulfamic acid decomposition rate of Example 2-2 (electrolyte temperature 15 ° C.), Example 2-4 (electrolyte temperature 30 ° C.), and Example 2-6 (electrolyte temperature 50 ° C.). .
Claims (1)
スルファミン酸浴におけるスルファミン酸濃度を、スルファミン酸浴における鉛濃度よりも、さらに２０〜６０ｇ／Ｌ高い濃度に調整し、且つスルファミン酸浴における電解液温度を１５〜３０℃に調整し、５日間以上、スルファミン酸の分解率を０．０６％／日以下に制御して、鉛濃度を６０〜８０ｇ／Ｌに維持しながら電解精製を行い、スルファミン酸浴による鉛の電解精製において発生する白色残渣の生成を抑制することを特徴とするスルファミン酸浴による鉛の電解精製方法。 In a method for electrolytic purification of lead using a sulfamic acid bath using a lead anode,
Adjust the sulfamic acid concentration in the sulfamic acid bath to a concentration that is 20 to 60 g / L higher than the lead concentration in the sulfamic acid bath, and adjust the electrolyte temperature in the sulfamic acid bath to 15 to 30 ° C. for 5 days or more. , white residue decomposition rate of sulfamic acid 0.06% / day with the control below, have rows electrolytic refining while maintaining the lead concentration in 60～80G / L, occurring in the electrolytic refining of lead by sulfamic acid bath A method for electrolytically refining lead using a sulfamic acid bath , characterized in that the production of lead is suppressed .
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| US14/957,370 US10106904B2 (en) | 2014-12-03 | 2015-12-02 | Method for electrolytically refining lead in sulfamate bath |
| CN201811463689.6A CN110079827B (en) | 2014-12-03 | 2015-12-03 | Electrolytic purification method of lead based on sulfamic acid bath |
| CN201510875275.4A CN105671590A (en) | 2014-12-03 | 2015-12-03 | Electrolytic purification method of lead based on sulfamic acid bath |
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| US4098658A (en) * | 1974-07-25 | 1978-07-04 | Ginatta Marco | Method of extracting metals from spent electric storage batteries |
| JPS5964791A (en) * | 1982-09-30 | 1984-04-12 | Mitsubishi Metal Corp | Lead with low count number of radioactive alpha particle and electrolytic purification thereof |
| IT1245449B (en) * | 1991-03-13 | 1994-09-20 | Ginatta Spa | HYDRO-METALLURGICAL PROCEDURE FOR THE PRODUCTION OF LEAD IN THE FORM OF METAL FROM MATERIALS CONTAINING OXIDES, PARTICULARLY FROM THE ACTIVE SUBSTANCE OF THE ACCUMULATORS |
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