WO2012157957A2 - Method for manufacturing multi-mineral from waste battery - Google Patents

Abstract

The present invention relates to manufacturing a multi-mineral by inserting a ground product from a disassembled waste battery into sulfuric acid water and leaching same to manufacture the multi-mineral, in which ferrous sulfate, zinc sulfate, manganese sulfate, potassium sulfate, and cobalt sulfate are present in the form of a mixture, from a waste alkali manganese battery containing manganese and zinc, wherein by leaching by means of inserting a specific amount of metal during the leaching step for manufacturing the multi-mineral, the multi-mineral in which ferrous sulfate, zinc sulfate, manganese sulfate, potassium sulfate, and cobalt sulfate are present in the form of the mixture, can be effectively manufactured, and the multi-mineral manufactured thereby can be used in manufacturing medicine, drinks, food, fertilizers, and animal fodder.

Description

Method for preparing complex mineral from waste battery

The present invention is a method for producing a composite mineral from a waste battery.

The waste battery used in the present invention is an alkaline manganese waste battery containing manganese and zinc, with manganese dioxide (Mn0 ₂ 30-35 wt%, zinc oxide (Zno) 20-25 wt%, iron oxide (Fe ₂ O ₃ ) 5-9 Weight percent, cobalt (CoO) 0 to 1% by weight, potassium (K) 1 to 4%, iron (Fe) 12 to 18% by weight and lithium cobalt oxide battery is selected from the predominant cobalt oxide They are in the reality that most are classified as waste.

In the present invention, the waste battery is pulverized by a pulverizer, and the iron (Fe) component is 5 to 10 mm in size, and the remainder is pulverized into a powder having an average particle size of 100 to 120 mesh, which is then poured into sulfuric acid water and leached by heating and stirring. The leaching of manganese sulphate is completed by leaching the composition to maintain a certain amount of water, and zinc powder is added to the solution obtained in the leaching to remove heavy metals, and then the filtered leaching solution is dried by heating and dried to obtain ferrous sulfate (FeSO4), It is to obtain a composite mineral in which manganese sulfate (MnSO 4), zinc sulfate (ZnSO 4), cobalt sulfate (CoSO 4) and potassium sulfate (K ₂ S04) exist in a complex form.

In addition, the present invention is a component necessary for the grinding by mixing a certain amount of dust in the electric furnace of the steel mill and the electric furnace of the ferro-manganese manufacturing plant to compensate for the lack of zinc, iron and manganese in the pulverized product obtained by crushing the waste battery The invention includes producing a composite mineral by matching the composition ratio of.

Conventionally, a method of manufacturing manganese sulfate or zinc sulfate using a waste battery has been proposed, but it is not known to manufacture a composite mineral from a waste battery.

It is invented to secure the above drawbacks of the present invention.

The present invention collects a lithium cobalt oxide battery, including a manganese and zinc-containing alkaline manganese waste battery, and then pulverize and put it into sulfuric acid water to be leached by heating and stirring a certain amount of metals (eg Fe, FeMn, Fezn) By leaching, ferrous sulfate, manganese sulfate, zinc sulfate, cobalt sulfate, and potassium sulfate can be leached smoothly to produce composite minerals in mixed form at lower cost. In addition, it can be used for animal feed, and if the waste battery crushing lacks iron, manganese, zinc and cobalt components, zinc sulfate is added by supplementing the shortage by adding ferro-manganese dust in steel mills and ferro-manganese mills. It is easy to adjust the content of ferrous sulfate and manganese sulfate, which makes it possible to produce more complex minerals. To ensure that

In the present invention as described above, the manganese dioxide contained in the waste battery is present in the form of manganese dioxide, so it is not leached when leaching into sulfuric acid water. Leaching becomes easy.

In addition, the metal material can be made of iron (Fe), zinc (Zn) or metal iron (Fe, Zn) or ferro manganese (FeMn) made by reducing the electric furnace of a steel mill, so that the metal material can be inexpensively contained in the raw materials of waste battery grinding products. Components such as iron oxide, zinc oxide, and potassium cobalt oxide can be completely leached into potassium sulfate with ferrous sulfate, zinc sulfate, and cobalt sulfate. After the first filtration, foreign substances are removed and zinc powder is added to the filtered solution to remove heavy metals. After solidifying, the leaching solution is filtered and then dried by heating the leaching solution obtained in the final step, thereby obtaining a composite mineral in which potassium sulfate, ferrous sulfate, zinc sulfate, manganese sulfate, and cobalt sulfate are present as a mixture.

Therefore, the composite mineral prepared in this way can be used for food, medicine, fertilizer, beverage, and animal feed manufacturing, which makes it possible to recycle waste batteries, and to obtain the benefits of a single profit that can prevent environmental pollution caused by waste batteries.

In particular, if the cobalt oxide, manganese, zinc, iron components necessary for the composite mineral composition is insufficient in the leaching step, by adding a specific component that can supplement the above components to leach in sulfuric acid water to make up the components insufficient in the composite mineral You will be able to make suitable composite minerals.

Therefore, the present invention can produce a composite mineral in which various minerals coexist at a simple and low cost, thereby obtaining high economical effects.

The present invention collects and pulverizes waste batteries such as alkaline manganese waste batteries or lithium cobalt oxide batteries containing manganese and zinc, but the iron (Fe) component is pulverized to an average particle diameter of 100 to 120 mesh size with a size of 5 to 10 mm. Raw material preparation step;

The prepared waste battery pulverized product was poured into sulfuric acid water in which sulfuric acid and water were mixed at a weight ratio of 6: 5 to 5: 5, and leached by heating and stirring at 95 ° C. for 1 to 3 hours, in which the total amount of metal was 1 to 15% by weight. A leaching step of leaching the composition to be maintained in the range to be;

This material removal step of removing the material such as paper plastic by first filtering the leached solution,

A heavy metal removal step of adding heavy metal powder (Znpowder) to 1 to 2% by weight of the leachate from which foreign substances are removed to solidify the heavy metal, and filtering the leach solution to remove the heavy metal;

Ferrous sulfate (FeSO4), manganese sulfate (MnSO4), zinc sulfate (ZnSO4), potassium sulfate (K ₂ SO4), and cobalt sulfate (CoSO4) were mixed by heating and drying the leaching solution from which heavy metals were removed. It is a method for producing a composite mineral present.

The resulting composite mineral has a mixing ratio of ferrous sulfate 32%, manganese sulfate 31%, zinc sulfate 33%, potassium sulfate 2%, cobalt sulfate 2%.

On the other hand, the present invention includes the addition of agitation and leaching by selectively adding the electric furnace dust of the steel mill electric furnace ferro manganese manufacturing plant in order to adjust the amount of metal components in the leaching step and crushing the waste battery in the grinding raw material preparation step This involves mixing the furnace dust of the ferro-manganese manufacturing plant or the electric furnace of the steel mill in a certain proportion without separating the scrap iron (Fe) component to form a pulverized raw material, and also adding manganese dioxide to the waste battery grinding. It includes the addition of a certain amount of manganese ore crushed powder containing manganese carbonate and leaching by adding magnesium and cobalt oxide to the sulfuric acid water in the leaching step, and also chromium, iodine, vanadium, sulphate in the dried composite mineral This involves the production of composite minerals by adding certain materials, such as nium, in certain proportions It is a law.

Example 1

120g of waste battery powder containing metal iron component was added to 360g of sulfuric acid solution and stirred for 3 ~ 5 hours while maintaining the temperature at 95 ℃. 5 ~ 7g of zinc powder was added to the filtrate to solidify the heavy metal so that it could not pass through the filtering network. Next, after stirring for 1 hour, the filtrate obtained by filtering the reaction solution was heated to 210 ° C and dried.

At this time, a complex mineral having a heavy metal (pb, cd, etc.) of 0.011 ppm or less and ferric sulfate 27 g, zinc sulfate 37 g, manganese sulfate 33 g, cobalt sulfate 1 g, and potassium sulfate 2 g was obtained as a mixture.

Example 2

120 g of waste battery powder was added to 360 g of sulfuric acid water, and the reaction was carried out for 1 hour while maintaining the temperature at 95 ° C. Then, 20 g of metal was added and reacted for 2 to 3 hours. 5 to 7 g of zinc powder was added to the filtered solution to solidify heavy metals. After stirring for 1 hour, the reaction solution was filtered and the filtrate was filtered and the filtrate was heated to 220 ° C and dried. At this time, the heavy metal (pb, cd, etc.) was 0.01PPM or less, ferrous sulfate 30g, zinc sulfate 31g, 34 g of manganese sulfate, 3 g of cobalt sulfate, and 2 g of potassium sulfate were obtained as a complex mineral.

Example 3

Put 120g of electric roaster into 360g of sulfuric acid water, and react for 1 hour while maintaining the temperature at 95 ℃, add 20g of metal, react for 2 ~ 3 hours, and add 5 ~ 7g of zinc powder to the filtered solution to solidify heavy metals. After passing through the mixture, the mixture was stirred for 1 hour, and the filtrate obtained by filtering the reaction solution was heated to 225 ° C to obtain a product.

At this time, a composite mineral having a heavy metal (pb, cd, etc.) of 0 PPM or less and ferrous sulfate 34g, zinc sulfate 32g, manganese sulfate 29g, cobalt sulfate 3g, and potassium sulfate 2g was present as a mixture.

Example 4

60 g of electric furnace was added to 360 g of sulfuric acid water, and the temperature was maintained at 95 ° C., followed by stirring for 1 to 2 hours, and further 60 g of alkaline manganese waste battery grinder containing metal iron was stirred for 2 to 3 hours, and the filtrate was filtered. 7 g of zinc powder was added to the mixture, followed by stirring for 1 hour, and then the reaction solution was filtered to obtain a filtrate obtained by heating at 223 ° C.

At this time, a composite mineral having a heavy metal (pb.cd, etc.) of 0PPM or less, ferrous sulfate 33g, zinc sulfate 35g, manganese sulfate 32g, and a mixture thereof was obtained.

Example 5

120 g of a waste battery grinding product containing metal iron and 3 g of lithium and cobalt oxide battery grinding materials were added to 360 g of aqueous sulfate, and the mixture was stirred at a temperature of 95 ° C. for 2 to 3 hours, and the reaction product was filtered. 7 g of powder was added thereto, stirred for 1 hour, and the filtrate obtained by filtration was heated to 210 ° C. to obtain a dry product.

In this case, a composite mineral having a heavy metal (pb.cd, etc.) of 0.001 PPM or less and present in a mixture of 3 g of cobalt sulfate, ferrous sulfate 30 g, zinc sulfate 30 g, and manganese sulfate 37 g was obtained.

Example 6

Into the 360g of sulfuric acid, 80g of electric furnace dust and 40g of ferro-manganese mill are heated and stirred at a temperature of 95 ° C. for 1 hour, 3g of ferromangan powder, 2g of scrap iron powder, and 5g of metal made of electric furnace. 5 to 7 g of zinc powder was added to the filtrate obtained by further heating and stirring the reaction solution, and the reaction solution was stirred for 1 hour. The filtrate obtained by filtering the reaction was heated and dried at 220 ° C. to be less than 0PPM of heavy metal (pb.cd, etc.), and sulfuric acid. 30 g of ferrous iron, 34 g of zinc sulfate, 33 g of manganese sulfate, and 3 g of cobalt sulfate were obtained as a complex mineral.

Example 7

Into the 360g of sulfuric acid, 70g of electric furnace of steel mill and 35g of manganese dioxide ore crushed powder were added and stirred by heating at 95 ° C for 1 hour. 3 g of zinc powder was added to the filtrate, and the reaction mixture was stirred for 1 hour. The filtrate was dried by heating at 205 ° C. The heavy metal was 0 PPM, 33 g of ferrous sulfate, 34 g of zinc sulfate, and sulfuric acid. 33 g of manganese was obtained as a complex mineral present in the mixture.

Example 8

360 g of water of sulfuric acid and 120 g of lithium cobalt oxide battery powder were added thereto, and the mixture was heated and stirred at 95 ° C. for 2 hours to adjust the reaction solution to PH 5, followed by heating and drying the filtrate to obtain 250 g of cobalt sulfate.

Claims (4)

1. Collecting and crushing spent batteries such as alkaline manganese waste batteries containing manganese and zinc, and lithium cobalt oxide batteries, and preparing the raw materials for crushing iron (Fe) with 5-10mm size and the rest with an average particle size of 100-120 mesh. Wow

   The waste battery pulverized product was poured into sulfuric acid water in which sulfuric acid and water were mixed at a weight ratio of 6: 5 to 5: 5, and leached by heating and stirring at 95 ° C. for 1 to 3 hours, in which the total amount of metal was 1 to 15% by weight. A leaching step of leaching by formulating to keep in a range

   Foreign material removal step of removing foreign matter by filtering the leached solution and

   A heavy metal removal step of removing heavy metals from the filtrate by solidifying heavy metals by adding 1 ~ 2 wt% of zinc powder to the leaching solution from which foreign substances are removed;

   Drying the leaching solution from which heavy metals are removed is heated to 220 to 280 ° C. to produce a composite mineral in which ferrous sulfate, manganese sulfate, zinc sulfate, potassium sulfate, and cobalt sulfate are present in a mixed mineral mixture. How to manufacture
2. The method of claim 1, wherein the waste battery pulverized product is formed by mixing a waste battery pulverized product with a dust of a ferro-manganese manufacturing plant or an electric furnace of a steel mill with a predetermined amount or singly.
3. The method of manufacturing a complex mineral from a spent battery according to claim 1, comprising adding a certain amount of manganese ore powder when mixing the steel mill electric furnace with the waste battery powder.
4. The metal material of claim 1 is a complex mineral from a waste battery comprising iron or iron and zinc mixed metal (FeZn) or waste manganese (FeMn) grinding or scrap metal (Fe) grinding processed steel mill electric furnace. How to