KR101805704B1 - Lead recovery way the disintegration of the metal oil prices from anode slime electrolytic refining - Google Patents

Abstract

The present invention relates to a method of separating and collecting valuable metal included in anode slime of lead electrolytic refining. The method of separating and collecting valuable metal included in anode slime of lead electrolytic refining includes: a first step of separating anode slime of lead electrolytic refining including valuable metal into black metal, dust, and slag by oxidizing the anode slime in an induction furnace; a second step of separating the black metal obtained in the first step into Bi-litharge, silver anode, dust, and antimony slag by re-oxidizing the black metal; and a third step of separating the dust obtained in the first and second steps into Sb-Pb alloy and Sb-Pb slag by oxidizing the dust in an electric furnace, and collecting the Sb-Pb alloy and Sb-Pb slag. The method of separating and collecting valuable metal included in anode slime of lead electrolytic refining can recycle a resource by separating and collecting the remaining valuable metal which is not melted in a process of regenerating lead for a lead-acid battery in an electrochemical manner, and can minimize environmental pollution. Particularly, the method of separating and collecting valuable metal included in anode slime of lead electrolytic refining can obtain expensive metal at a high recovery rate by selectively separating the valuable metal, and can reduce processing time and costs by increasing a reaction speed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering and recovering valuable metals contained in a positive electrode slime of a lead-

The present invention relates to a method for separating and recovering valuable metals contained in a positive electrode slime of lead electrolytic refining, and more particularly, to a method for separating and recovering valuable metals such as Bi, Ag, Sb and Pb contained in a positive electrode slime Which is contained in a positive electrode slime of lead electrolytic refining so as to be separated and recovered.

In general, the residual residues that are deposited or suspended in lead-acid battery lead-acid electrolytic refining are called the anode slime.

In addition, the lead in the lead-acid battery recycling process is mostly lead-free.

These included components include Ag, Bi, Sb and the like, which cause many problems in battery materials.

In particular, in the electrolytic refining process, high-purity copper is manufactured by using lead-containing impurities.

However, the Pb content in the lead ore, which is the main material of lead smelting, is gradually decreasing, and the impurity content is relatively increased.

Among these impurities, Bi, Sb, Ag, Pb and the like are included in the valuable metal, and it is indispensable to recover them.

Therefore, in the lead-acid battery recycling process, the plastic component and the valuable metal component are separated and sorted, and then the selected valuable metal Pb component is selectively used for the refining process such as the dry-smelting process or the electrochemical process, Sb, Ag, and the like to be recycled.

Conventionally, there is a wet method as a method for recovering a noble metal from a cathode slime. However, this method is complicated and difficult in the separation and recovery process, and has a problem that the purity of silver and tin is low and the application range is limited.

Korean Patent Publication No. 10-1997-0074957 (December 10, 1997) Korean Patent No. 10-0207041 (July 1, 1999) Korean Patent No. 10-0415448 (2004.01.24) Korean Patent No. 10-1233779 (2013.02.15) Korean Patent No. 10-1481366 (2015.01.14)

The present invention has been made to solve the above-mentioned problems occurring in the prior art,

The present invention relates to a process for recovering valuable metals such as Bi, Ag, Sb and the like contained in a cathode slime generated in a lead electrolytic refining process through a series of steps, And to provide a recovery method.

In order to accomplish the above object, the present invention provides a method for separating and recovering valuable metals contained in a positive electrode slime of electrolytic refining of lead,

A first step of separating the anode slime of the lead electrolytic refining including a valuable metal by oxidization in an induction furnace to black metal, dust, and slag, respectively;

A second step of reoxidizing the black metal obtained in the first step and separating the black metal into bi-lysage, silver anode, dust, and antimony slag;

And a third step of separating the dusts obtained in the first and second steps into Sb-Pb alloy and Sb-Pb slag by oxidation in an electric furnace.

The induction furnace used in the first step is characterized by using a high frequency induction furnace.

The high frequency induction furnace includes a ceramic crucible for dissolving and burning the anode slime therein. The crucible is disposed outside the ceramic crucible, an AC power source is connected to the coil, and the inside of the high frequency induction furnace And an alternating current of 20 to 50 MHz is applied to the coil in a state of supplying oxygen to rapidly heat and dissolve the anode slime charged into the ceramic crucible.

In particular, the first step is characterized by using an immersion lance for supplying oxygen or air to the upper portion of the induction furnace during the oxidation process.

In the second step, the silver anode is electrolytically sampled.

Meanwhile, in the third step, the Sb-Pb alloy is recharged as an anode.

INDUSTRIAL APPLICABILITY The present invention has the effect of minimizing environmental pollution as well as recycling resources by separating and recovering the remaining valuable metals without being electrochemically dissolved in the lead-acid battery lead recycling process.

Particularly, the present invention has the effect of selectively separating a valuable metal and obtaining a high-priced metal at a high recovery rate.

Further, the present invention has the effect of improving the reaction rate and reducing the processing time and cost.

FIG. 1 is a graph comparing the recovered yield of valuable metals recovered in the present invention with the existing method.

Hereinafter, preferred embodiments of the present invention will be described.

The present invention relates to a method for manufacturing a lead-acid electrolytic cell, which comprises a first step of separating a cathode slime of a lead-containing electrolytic refining containing a valuable metal by oxidation in an induction furnace and separating the cathode slurry into black metal,

A second step of reoxidizing the black metal obtained in the first step and separating the black metal into bi-lysage, silver anode, dust, and antimony slag;

And a third step of separating the dusts obtained in the first and second steps into Sb-Pb alloy and Sb-Pb slag by oxidation in an electric furnace.

The method of recovering valuable metals contained in the positive electrode slime of lead electrolytic refining according to the present invention is characterized in that when a metal is electrolyzed as a positive electrode, it is not electrochemically dissolved and can recover high-purity metal from slime, and Bi, Ag, Sb, Pb and can be recovered at a high recovery rate.

In the first step, the anodic slime, which was not electrochemically dissolved, was dried and then oxidized in an induction furnace.

Here, a high frequency induction furnace was used as the induction furnace.

In the present invention, the high-frequency induction furnace includes a ceramic crucible for dissolving and burning the anode slime, an ice-circling coil is disposed outside the ceramic crucible, an AC power source is connected to the coil, An alternating current of 20 to 50 MHz is applied to the coil while oxygen is supplied to the inside of the ceramic crucible to quickly heat and dissolve the cathode slime charged into the ceramic crucible.

At this time, when the anode slime is oxidized, it is preferable to use a combustion stabilizer such as tin or tungsten.

Therefore, the anode slime of the lead electrolytic refining in the high frequency induction furnace can be oxidized in the induction furnace and separated into black metal, dust, and slag respectively.

In addition, it is preferable to use an immersion type lance for supplying oxygen or air to the upper part of the induction furnace in the oxidation process. This is because when the recovery rate is low due to a large loss of silver in the dust, This is to shorten the operating time.

Further, in the method of separating and recovering Bi-lysedge from the lead electrolytic refining anodic slime according to the present invention, the black metal obtained by the oxidation process is reoxidized to obtain silver anode and dust, and the antimony slag is supplied to the rotary furnace to separate.

Such Bi-lysing is reprocessed in a Bi-electric furnace, and the silver anode is electrolytically collected to separate and recover silver and tin.

And the dust is reduced in the Sb electric furnace to obtain Sb-Pb slag.

Here, the Sb-Pb alloy is anodically cast and the Sb-Pb slag is applied to an alloy electric furnace.

The average value of the precious metal content per ton of the lead-acid electrolytic slime cake was 15% of Ag, 0.1% of Au, 7% of Pb, 3% of Cu, 40% of Sb and 15% of Bi. After melting and refining the anode slime in the induction furnace, The average value of the valuable metals was 40% of Ag, 0.2% of Au, 7% of Pb, 6% of Cu, 10% of Sb and 25% of Bi.

The step of oxidizing and purifying Sb and Bi in black metal proceeds as follows

De-Sb operation: 2Sb + 3 / 2O ₂ Sb ₂ O ₃

De-Bi operation: 2Bi + 3 / 2O ₂ Bi ₂ O ₃

At that time, the average value of the precious metal per ton of dust was 0.5% of Ag, 0.7% of Au, Pb3%, Cu of 0.2%, Sb of 50% and Bi of 5%.

The process for melting and refining dust by introducing dust and coke into the high frequency induction furnace is as follows.

Sb ₂ O ₃ + 2C? 2Sb ⁰ + CO ₂ + CO

The process of producing 99.99% Ag cathode by electrolysis of Ag anode is precipitated by Ag ⁺ + e → Ag ⁰ reaction using AgNO ₃ as silver electrolytic solution.

The average value of the valence metal per ton of Ag slime is 40% of Ag and 10% of Au. The Ag slime is dissolved in HNO ₃ and the Ag powder is recovered as follows.

₃ Ag + 4HNO 3 → 3AgNO ₃ + 2H ₂ O + NO

As shown in FIG. 1, it can be seen that the recovery rate of the recovered migratory metal through the above-described process is increased by 2 to 3% compared to the conventional method.

Although the embodiments of the present invention have been described above in detail, it is to be understood that the scope of the present invention is not limited to the above embodiments and that various changes and modifications may be made without departing from the scope of the present invention. Of course.

Claims (6)

A first step of separating the anode slime of the lead electrolytic refining including a valuable metal by oxidization in an induction furnace to black metal, dust, and slag, respectively;
A second step of reoxidizing the black metal obtained in the first step and separating the black metal into bi-lysage, silver anode, dust, and antimony slag;
And a third step of oxidizing the dusts obtained in the first and second steps in an electric furnace to separate and recover the Sb-Pb alloy and the Sb-Pb slag. In the anode slurry of the lead electrolytic refining, A method for recovering valuable metals. The method of claim 1, wherein the induction furnace used in the first step is a high frequency induction furnace. The high frequency induction furnace according to claim 2, wherein the high frequency induction furnace includes a ceramic crucible for dissolving and burning a cathode slime therein, wherein an ice cooling coil is disposed outside the ceramic crucible, an AC power source is connected to the coil, Wherein the anode slurry charged into the ceramic crucible is rapidly heated and dissolved by applying an alternating current of 20 to 50 MHz to the coil while supplying oxygen to the inside of the induction furnace. A method for separating and recovering valuable metals contained in a cathode slime. The method according to claim 1, wherein an immersion lance for supplying oxygen or air to the upper portion of the induction furnace is used in the oxidation step in the first step. The method according to claim 1, wherein the silver anode is electrolytically collected in the second step. The method according to claim 1, wherein the Sb-Pb alloy is recycled to the anode in the third step.

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