JP2009242845A - Electrolytic process of lead - Google Patents
Electrolytic process of lead Download PDFInfo
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- JP2009242845A JP2009242845A JP2008089484A JP2008089484A JP2009242845A JP 2009242845 A JP2009242845 A JP 2009242845A JP 2008089484 A JP2008089484 A JP 2008089484A JP 2008089484 A JP2008089484 A JP 2008089484A JP 2009242845 A JP2009242845 A JP 2009242845A
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
本発明は、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Pbを回収する方法に関する。 The present invention relates to a method for recovering Pb contained in non-ferrous smelting, melting furnaces for recycled materials such as bases and electronic components, and dry smoke ash generated from a dry furnace for melting industrial waste.
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Pb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、珪フッ素酸浴中にて電解精製することでPbを回収している。
また、特許文献１では、鉛を炭酸塩にする手法が開示されているが、後工程において、硝酸を用いている。
In order to recover Pb contained in non-ferrous smelting dry ash from non-ferrous smelting, furnaces for recycling raw materials such as bases 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 is treated with soda, and then the metal is anode cast, and then Pb is recovered by electrolytic purification in a silicofluoric acid bath.
Moreover, in patent document 1, although the method of converting lead into carbonate is disclosed, nitric acid is used in the post-process.
上記方法では、前処理工程が乾式法であり、排ガス処理設備を設置する必要性がある。
また、更に後工程の電解精製では、珪フッ素酸を用いていることから、排水にフッ素を処理する設備が必要となる。
In the above method, the pretreatment process is a dry method, and it is necessary to install an exhaust gas treatment facility.
Further, in the subsequent step of electrolytic purification, silicofluoric acid is used, so that an equipment for treating fluorine in the waste water is required.
特許文献１では、硝酸を使用していることから、溶液中から鉛を回収するために硫酸を添加し、硫酸鉛として回収している。しかし、本発明では、スルファミン酸で浸出された溶液を電解採取することで、板状の二酸化鉛と電着鉛として回収することができる。
従来の技術に対して、全てを湿式法により行う鉛の処理ができる方法が要望されている。 There is a demand for a method capable of processing lead, which is entirely performed by a wet method, over the prior art.
本発明者等は、上記の課題を解決するため以下の発明を成した。
（１）スルファミン酸100〜200g/Lの溶液中にPbを20〜120g/Lまで溶解させた溶液から電解採取により二酸化鉛と鉛メタルとして、鉛を回収する方法。
The present inventors made the following invention in order to solve the above-mentioned problems.
(1) A method for recovering lead as lead dioxide and lead metal by electrolytic extraction from a solution in which Pb is dissolved in a solution of sulfamic acid 100 to 200 g / L up to 20 to 120 g / L.
（２）電流密度を100A/m2以下で電解採取することで、鉛を平滑で良好な二酸化鉛と鉛のメタルとして回収する方法。 (2) A method of recovering lead as smooth and good lead dioxide and lead metal by electrowinning at a current density of 100 A / m 2 or less.
（３）添加剤として、膠200〜300mg/L、βナフトール100〜200mg/L添加することで、鉛を平滑で良好な二酸化鉛と鉛メタルとして回収する方法。 (3) A method of recovering lead as smooth and good lead dioxide and lead metal by adding 200 to 300 mg / L of glue and 100 to 200 mg / L of β-naphthol as additives.
（４）電解液の温度を30度以下にすることでスルファミン酸の劣化を防止し、電解採取としての回収率を99％以上にすることができる方法。 (4) A method in which deterioration of sulfamic acid can be prevented by setting the temperature of the electrolytic solution to 30 ° C. or less, and the recovery rate as electrowinning can be 99% or more.
（５）電解液の温度を20度以上にすることで、鉛を平滑で良好な二酸化鉛と鉛メタルとして回収する方法。 (5) A method of recovering lead as smooth and good lead dioxide and lead metal by setting the temperature of the electrolytic solution to 20 ° C. or higher.
本発明によれば、
（１）湿式法により、容易に鉛を効率良く回収できる方法を見出した。
（２）スルファミン酸で鉛を浸出した溶液を電解採取することで、鉛を平滑で良好な二酸化鉛と電着鉛として鉛を回収することができる方法を見出した。
According to the present invention,
(1) The present inventors have found a method capable of easily collecting lead efficiently by a wet method.
(2) The present inventors have found a method capable of recovering lead as smooth and good lead dioxide and electrodeposited lead by electrolytically collecting a solution in which lead is leached with sulfamic acid.
以下に本発明をさらに詳細に説明する。
原料は、本発明の鉛含有物は、鉛 45mass％、錫7mass％、ビスマス4mass％、銅1mass％、亜鉛8mass％含有する。
例えば、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を湿式処理する工程から産出する鉛滓（主成分：PbSO4）、銅転炉ダスト等がある。
上記鉛含有物を、水によりリパルプし、炭酸ソーダにより脱SO4した炭酸化残渣（主成分：PbCO3）とする。
炭酸ソーダは、鉛含有物中のSに対して、1.25〜１.5倍当量添加する。
鉛含有物を炭酸化した後、スルファミン酸浸出を行い、鉛を浸出後、電解採取することにより鉛を回収する。
該電解採取方法としては、その一例を図1に示す。
The present invention is described in further detail below.
The raw material contains 45 mass% of lead, 7 mass% of tin, 4 mass% of bismuth, 1 mass% of copper, and 8 mass% of zinc.
For example, lead iron (main component: PbSO4), copper produced from non-ferrous smelting, melting furnaces for recycling raw materials such as bases and electronic components, and dry smoke ash generated from dry furnaces for melting industrial waste There is converter dust.
The lead-containing compound, repulped with water, de SO 4 was carbonated residue by sodium carbonate (main component: PbCO 3) to.
Sodium carbonate is added in an amount equivalent to 1.25 to 1.5 times the amount of S in the lead-containing material.
After carbonation of the lead-containing material, sulfamic acid leaching is performed, and after leaching of lead, lead is collected by electrowinning.
An example of the electrolytic collection method is shown in FIG.
スルファミン酸100〜200g/Lの溶液に鉛を溶解し、鉛濃度を20〜120g/Lに調整した後、アノードとしてカーボン等の不溶解性アノード、カソードとして、Ti板又は、ステンレス板や鉛板を使用することで、アノード側に二酸化鉛、カソード側に電着鉛として鉛を回収することができることが判明した。
トータルスルファミン酸濃度を上げすぎると温度20度の場合、スルファミン酸濃度：213g/Lで飽和状態となり、アノードにスルファミン酸の結晶が析出し、カソードの電着状態が悪化することから、トータルスルファミン酸濃度として200g/L以下が最適である。
次にトータルスルファミン酸濃度が低いと溶液中に鉛が溶け込み難くなることから、スルファミン酸濃度としては、100〜200g/Lが最適である。
After dissolving lead in a sulfamic acid solution of 100 to 200 g / L and adjusting the lead concentration to 20 to 120 g / L, the anode is an insoluble anode such as carbon, the cathode is a Ti plate, a stainless steel plate, or a lead plate It was found that lead can be recovered as lead dioxide on the anode side and electrodeposited lead on the cathode side.
If the total sulfamic acid concentration is increased too much, at a temperature of 20 ° C, the sulfamic acid concentration will be saturated at 213 g / L, and sulfamic acid crystals will precipitate on the anode, resulting in a deterioration of the electrodeposition state of the cathode. The optimum concentration is 200 g / L or less.
Next, when the total sulfamic acid concentration is low, it is difficult for lead to dissolve in the solution. Therefore, the optimal sulfamic acid concentration is 100 to 200 g / L.
次に電流密度と電着状態および電流効率の関係を確認した結果、図2に示す通り、電流密度100A/m2以上では、カソードの電着が荒れると共に電流効率が低下することから、電流密度として100A/m2以下が最適である。 Next, as a result of confirming the relationship between the current density, the electrodeposition state, and the current efficiency, as shown in FIG. 2, when the current density is 100 A / m2 or more, the cathode electrodeposition becomes rough and the current efficiency decreases. 100A / m2 or less is optimal.
電着状態を良好にするために電解液に添加剤として膠およびβナフトールを添加した結果、図3に示す通り、膠：２００〜３００mg/L、βナフトール：１００〜２００mg/Lが最も電着が平滑で良好な二酸化鉛と電着鉛として鉛を回収することができた。 As a result of adding glue and β-naphthol as additives to the electrolytic solution to improve the electrodeposition state, glue: 200-300 mg / L, β-naphthol: 100-200 mg / L is the most electrodeposited as shown in FIG. There was smooth and good lead dioxide and lead could be recovered as electrodeposited lead.
電解液の温度に関して、液温を30度以上まで上げた結果、電着状態は、良好であったが、電解液であるスルファミン酸溶液が加水分解し、スルファミン酸中の硫酸イオンと溶液中の鉛イオンが化合し、硫酸鉛として電槽内に析出するといった問題点が発生する。 図4で示す通り、温度30℃以上からスルファミン酸劣化率が上昇することから、温度30度以下が最適である。逆に温度を20度以下にした場合、スルファミン酸溶液の劣化は、防止することができるが、図5に示す通り、20℃以下では、カソードの電着が悪化することから、電解液の温度管理として、20〜30℃が最適である。 Regarding the temperature of the electrolytic solution, as a result of raising the liquid temperature to 30 ° C. or more, the electrodeposition state was good, but the sulfamic acid solution as the electrolytic solution was hydrolyzed, and sulfate ions in the sulfamic acid and the solution in the solution There is a problem that lead ions are combined and lead sulfate is deposited in the battery case. As shown in FIG. 4, since the sulfamic acid deterioration rate increases from a temperature of 30 ° C. or higher, a temperature of 30 ° C. or lower is optimal. Conversely, when the temperature is set to 20 ° C. or lower, deterioration of the sulfamic acid solution can be prevented, but as shown in FIG. 5, when the temperature is 20 ° C. or lower, cathode electrodeposition deteriorates. As a management, 20-30 ° C is optimal.
（実施例１） 電着鉛を良好にする方法
スルファミン酸100g/L溶液に炭酸鉛を溶かし込み、鉛濃度80g/L、遊離スルファミン酸濃度20g/Lに調整する。循環液として、鉛濃度40g/L、遊離スルファミン酸濃度60g/Lを作製し、電槽内の滞留時間を1時間になるように給液する。
鉛補充液としては、鉛濃度80g/L、遊離スルファミン酸濃度20g/Lを作製し、電解採取により二酸化鉛と鉛メタルとして抜き出される鉛量分を補充液で補充していく。添加剤としては、膠300mg/L、βナフトール100mg/Lになるように電解液に添加する。
(Example 1) Method for improving electrodeposited lead Lead carbonate is dissolved in a sulfamic acid 100 g / L solution to adjust the lead concentration to 80 g / L and the free sulfamic acid concentration to 20 g / L. As the circulating fluid, a lead concentration of 40 g / L and a free sulfamic acid concentration of 60 g / L are prepared and supplied so that the residence time in the battery case is 1 hour.
As a lead replenisher, a lead concentration of 80 g / L and a free sulfamic acid concentration of 20 g / L are prepared, and the replenisher replenishes the amount of lead extracted as lead dioxide and lead metal by electrowinning. As additives, 300 mg / L of glue and 100 mg / L of β-naphthol are added to the electrolyte.
電解液の温度管理としては、20〜30℃になるように冷凍機およびヒーターにより調整する。
アノードとしては、不溶性アノードとしてカーボンを使用する。カソードとしては、鉛板でよいが、懸垂性を考慮した場合、ステンレス板のほうが最適である。
As temperature control of electrolyte solution, it adjusts with a refrigerator and a heater so that it may become 20-30 degreeC.
As the anode, carbon is used as an insoluble anode. As the cathode, a lead plate may be used, but a stainless plate is more suitable in consideration of suspension.
上記の条件において、電流密度を100A/m2、通電時間96時間で実施することで、平滑で良好な二酸化鉛と電着鉛を回収することができると共に電流効率として、アノード側で40％以上、カソード側で90％以上の鉛を回収することが出来る。 Under the above conditions, the current density is 100 A / m 2 and the energization time is 96 hours, so that smooth and good lead dioxide and electrodeposited lead can be recovered and the current efficiency is 40% or more on the anode side. 90% or more of lead can be recovered on the cathode side.
Claims (4)
A lead electrolysis method characterized in that, by setting the temperature of the electrolytic solution to 20 ° C to 30 ° C, deterioration of sulfamic acid can be prevented and smooth and good lead dioxide and lead metal can be recovered.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012072481A (en) * | 2010-09-27 | 2012-04-12 | Jx Nippon Mining & Metals Corp | Electrolysis method of lead |
| CN105671590A (en) * | 2014-12-03 | 2016-06-15 | Jx日矿日石金属株式会社 | Method for electrolytically refining lead in sulfamate bath |
| CN106048654A (en) * | 2016-07-19 | 2016-10-26 | 云南祥云飞龙再生科技股份有限公司 | Technology for preparing lead through ammonia electroreduction in ammonium chloride |
| CN106065485A (en) * | 2016-07-19 | 2016-11-02 | 云南祥云飞龙再生科技股份有限公司 | A kind of ammonium sulfate ammonia electroreduction produces splicer's skill |
-
2008
- 2008-03-31 JP JP2008089484A patent/JP2009242845A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012072481A (en) * | 2010-09-27 | 2012-04-12 | Jx Nippon Mining & Metals Corp | Electrolysis method of lead |
| CN105671590A (en) * | 2014-12-03 | 2016-06-15 | Jx日矿日石金属株式会社 | Method for electrolytically refining lead in sulfamate bath |
| CN106048654A (en) * | 2016-07-19 | 2016-10-26 | 云南祥云飞龙再生科技股份有限公司 | Technology for preparing lead through ammonia electroreduction in ammonium chloride |
| CN106065485A (en) * | 2016-07-19 | 2016-11-02 | 云南祥云飞龙再生科技股份有限公司 | A kind of ammonium sulfate ammonia electroreduction produces splicer's skill |
| CN106065485B (en) * | 2016-07-19 | 2018-12-14 | 云南祥云飞龙再生科技股份有限公司 | A kind of ammonium sulfate ammonia electroreduction produces splicer's skill |
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