JPS6096734A - Perfect recovery of valuable from waste manganese dry battery - Google Patents

Abstract

PURPOSE:To perfectly recover valuables from a dry battery, by applying heat treatment to the dry battery crushed under pressure in a first process to recover Hg and Cd as metal vapor while recovering Zn as a molten phase, and recovering Fe and Mn by reducing treatment in a second process. CONSTITUTION:After dry battery is crushed under pressure, the crushed one is heated to 400-600 deg.C in a heating furnace with a metal vapor condenser in a first process and Zn is recovered as a molten phase, Hg and Cd as metal vapors, and Fe, Mn and graphite are receovered as solids. The solids recovered in the first process are heated to 700-1,100 deg.C in a reductive atmosphere of a second process and, after cooling, Fe is separated and recovered by magnetic flotation. Further, aqueous sulfuric acid solution is added to the solid residue, to dissolve and extract Mn while graphite is separated and recovered by filtering.

Description

[Detailed Description of the Invention] The present invention is a method for completely recovering valuable materials from waste manganese dry batteries, and its purpose is to separate and recover the valuable materials in manganese dry batteries, thereby eliminating the pollution problem associated with disposal. Along with resolving
The objective is to provide a method that can contribute to resource saving measures by completely recovering valuable materials.

In recent years, with the development of electric appliances such as portable radios and portable tape recorders, and various electric toys, the number of dry batteries used has reached an enormous amount, and the number of waste manganese dry batteries being disposed of is increasing year by year.

However, the discarded manganese dry batteries contain various valuable substances such as iron, zinc, manganese, mercury, cadmium, and graphite, which is not desirable for resource conservation measures.

For this reason, 2.3 methods for recovering valuable materials from waste manganese dry batteries have been proposed (Japanese Unexamined Patent Publications Nos. 50-1094 and 51-69261).

However, all of the above-mentioned methods have the main purpose of recovering manganese, zinc, manganese, zinc, iron, etc., and recovery of other Hf, Cd, etc. is not necessarily sufficient.

As a result of further research on the above-mentioned conventional method, the present inventors found that
By adopting the structure described in the claims, it is possible to obtain a method for completely recovering various valuable substances in waste manganese dry batteries.

That is, the present invention involves crushing a waste manganese dry battery to the extent that it destroys its airtightness, and then heating it in a metal vapor condenser additional heat furnace for 400 min.
At the same time, iron and manganese are recovered by heating to ~600℃ to dissolve and recover zinc.

A first step in which graphite is recovered as a solid and metal vapor or metal compound vapor generated by heating is recovered, and the solid recovered in the first step is heated to 700 to 1
Waste manganese comprising the steps of heating to 100°C, cooling, separating and recovering iron by magnetic separation, adding an aqueous sulfuric acid solution to dissolve and extracting manganese, and a second step of overperforming graphite. This is a method for completely recovering valuable materials from dry batteries.

To explain the present invention in more detail, in the first step, a waste manganese dry battery (hereinafter referred to as a dry battery) is crushed to the extent that its airtightness is destroyed. That is, the crushing is to prevent explosion of the dry battery during heat treatment, as well as to promote dissolution of the Zn can inside the battery and evaporation of Hf, Cd, and other metal vapors. It is sufficient to deform it and crush it to the extent that the airtightness with the outer iron protective can is broken. Therefore, subsequent separation of solid matter is easy.

After the crushing treatment, the dry battery is separately heated at 400 to 600° C. for 1 to 6 hours in a metal vapor condenser heating furnace.

The heating furnace is advantageously an electric furnace such as a low frequency furnace or a high frequency furnace, but the heating method is not necessarily limited to the electric furnace.

By the heat treatment in the heating furnace, the Zn can is melted to form a molten phase, and metals with low vapor pressure such as H5' and Cd or metal compounds such as Hf/C1 and ZNCZ2 are evaporated to form a gas phase. do.

On the other hand, solid phases such as Fe and Mn contained in the dry cell are not melted in the heat treatment and are taken out in a solid phase, so they can be easily separated. In addition, the molten phase of zinc and the Fe
To separate solid phases such as Mn, graphite, etc., tap only the molten phase after heating in a heating furnace to separate it, or tap the molten phase and solid phase simultaneously from the heating furnace and provide a partition plate. If the molten phase is collected in a ladle, it can be easily separated.

Further, various organic polymers contained in the dry battery are decomposed and carbonized by the heat treatment, and the decomposed gases can be cooled and collected by the condenser, so that contamination by these decomposed gases can be avoided.

Metals and compounds such as HF and Cd (including some ZnCt2) obtained by the above heat treatment are cooled and solidified, and then dissolved in hydrochloric acid, and the pH is adjusted with NH4OH as appropriate, and Hf is a chelate resin for mercury adsorption. So, Cd again
(containing some Zn and Pb) is a chelate resin or an ion exchange resin, and after recovering each separately, the P solution is concentrated and NH
Collect as a 4Cl solution. Note that, if necessary, the Hg vapor may be recovered by reacting with metal aluminum to form an HP-AL amalgam.

On the other hand, the molten phase of boiling still contains trace amounts of Fe, Mn, and P.
b.

This is crude zinc containing metals such as Cd. After dissolving it in hydrochloric acid, it is oxidized to oxidize Fe, Mn, etc., separated by Δgol, purified, and recovered as a zinc chloride solution with a concentration of 50%. . If Cd, Pb, etc. are included in this molten phase, Fe, Mn, etc. can be removed by oxidation, further separated, and recovered by dissolving in hydrochloric acid together with the metal vapor in the gas phase.

Next, Fe separated and recovered in the first step.

The solid material containing Mn, graphite, zinc and zinc compounds that could not be separated in the first step was separated at 700 ml as the second step.
Heat treatment at ~1100°C for 1 to 6 hours. In this heat treatment, graphite is contained in the solid material, and a reducing atmosphere is formed by heating, so that the M
There is an advantage that n+ 03 is reduced to MnO which is easily soluble in sulfuric acid, and that the contained zinc and zinc compounds can be recovered as impurity-free.

Next, this is once separated into iron and other compounds using a vibrating sieve, etc., and after the iron is separated by magnetic separation, dilute sulfuric acid is added to this to extract MnO as MnSO4, and the graphite contained is After being overperformed, it is suitably neutralized with Ca(OH)z, etc., and if necessary, impurities are overperformed and recovered as a manganese sulfate solution. The zinc recovered by the drum may be recovered as is or sent to the molten phase recovery step in the first step.

That is, in the present invention, after crushing the dry battery, Hg, Cd, etc. with low vapor pressure are recovered as metal vapor by the heat treatment in the first step, and also as a molten phase of Zn. *Zn is dissolved in hydrochloric acid and recovered as zinc chloride, and solids such as Fe and Mn contained in the molten phase are oxidized and separated. In the second step, solids such as Fe and Mn are further oxidized and separated. By removing and separating Fe, dissolving and extracting Mn in sulfuric acid, and recovering it as an aqueous solution of manganese sulfate, the lee, Zn + Mn contained in the dry battery can be removed.
Of course, valuable metals such as Hf and Cd can also be recovered, which not only contributes to resource conservation but also reduces Hr.
By recovering , Cd, etc., a so-called closed system can be formed, and pollution problems can be completely eliminated.

The drawing shows one embodiment of the present invention, and as is clear from this flow note, HP is produced by crushing and heating a dry battery.

Metals such as Cd and H? Compounds with low vapor pressure such as C1 and ZnCtz can be recovered as a gas phase, while Zn
can be recovered as a molten phase, and Fe and Mn mixed in the molten phase can be recovered as ZnC4 after being removed as oxides.

In addition, solid phases such as iron, manganese oxide, graphite, and unmolten zinc or zinc compounds are removed by heating to evaporate zinc, etc., then separated by magnetic separation to remove iron, and then extracted with sulfuric acid to extract the manganese component. By recovering it as a manganese solution, many valuable substances in dry batteries can be completely separated and recovered. In addition, some of the materials recovered by the present invention can be reused as chemicals, and the manganese sulfate solution can be reused as an electrolyte during the production of electrolytic manganese dioxide, which is an effective resource saving measure. be.

Further, as is clear from the drawings, the present invention uses Fe.

In addition to recovering Mn, Zn, graphite, etc., H! Since it is a so-called closed stem that can effectively recover i', Cd, etc., there is also the effect that there is no risk of causing pollution problems.

The present invention will be explained below with reference to Examples.

Example 20 used UM-I type manganese dioxide batteries,
After being crushed and deformed in a crusher, it was placed in a quartz crucible and heated to 500°C in a 2°KVA high frequency furnace with a metal vapor condenser.
, heated for 3 hours.

The metal vaporized by the heating is cooled and collected in a metal vapor condenser with a water-sealed boulder, and dissolved in hydrochloric acid.
After adjusting the pH to 1 to 2 with ammonia water, mercury is adsorbed on a mercury adsorption resin, and then pH is adjusted with ammonia water.
After adjusting to H7, Cd, Zn, P
b is adsorbed and recovered. After concentrating P'o,
It was recovered as an aqueous ammonia chloride solution.

Further, after separating the melt obtained from the high frequency furnace and the solid, the melt is dissolved in dilute hydrochloric acid, hydrogen peroxide is added and oxidized, and the precipitate is mixed with the solid.

The R solution is further purified by adding zinc powder and concentrated to 50%.
Recover as zinc chloride aqueous solution.

On the other hand, the solid material is again introduced into the high frequency furnace,
After sealing, heat at 1000°C for 3 hours. At this time, the evaporating zinc vapor is cooled and collected in a condenser.

After the heat treatment, iron is recovered using a magnetic separator, dilute sulfuric acid is added to the residue to dissolve and extract manganese as manganese sulfate, the graphite is recovered by filtration, and after neutralization with calcium carbonate, The manganese sulfate solution is recovered by removing impurities.

Table 1 shows the weight composition of the valuable materials in the waste manganese dry battery, and Table 2 shows the total recovery rate of each valuable material.

Table 1 Table 2 Note that Hg and Cd can be completely recovered using adsorbents, and can be treated in a closed system without being emitted outside the reaction system.

[Brief explanation of the drawing]

The drawings are 70-/- sheets of one embodiment of the present invention.

Claims (1)

[Claims] The waste manganese dry battery is crushed to the extent that its airtightness is destroyed, and the zinc is melted and recovered by heating it to 400-600°C in a metal vapor condenser additional heat furnace, while iron, manganese,
A first step in which graphite etc. is recovered as a solid substance and metal vapor or metal compound vapor generated by heating is recovered, and the solid substance recovered in the first step is heated in a reducing atmosphere for 700~
Waste manganese comprising the steps of heating to 1100°C, cooling, separating and recovering iron by magnetic separation, adding an aqueous sulfuric acid solution to dissolve and extracting manganese, and then filtering and separating graphite. Complete recovery method for valuables from dry batteries