JP6125458B2 - Resource recovery method and separation / recovery equipment from waste dry batteries - Google Patents

Description

  The present invention relates to a method and facility for separating and recovering manganese and zinc, which are main components of discarded manganese dry batteries and alkaline manganese dry batteries, and recycling them as resources, and a recovered material recovered by these methods.

  Recovering certain valuable metals from low-grade ores, concentrates, steelworks by-products, and industrial waste has often been difficult for cost reasons and has been implemented industrially. This has been limited to a very limited class of valuable metals. However, in recent years, it has become necessary to actively recover valuable metals from such materials due to the depletion of metal resources and the increase in transaction prices. For example, manganese, which is one of valuable metals, is regarded as an essential metal in various fields of industry, but there is concern that the demand will exceed the reserves in the future. In particular, since ironworks consume a large amount of manganese as a steelmaking raw material, the problem of securing a manganese source is extremely serious in the steelmaking field.

On the other hand, some dry batteries disposed of as industrial waste have a high manganese content. In Japan, an enormous amount of dry batteries are produced, consumed and discarded.
For example, typical manganese dry batteries and alkaline manganese dry batteries as primary batteries use manganese dioxide as the positive electrode material and zinc as the negative electrode material. In addition, a manganese battery sometimes uses zinc chloride as an electrolyte. And the annual production of these batteries is said to be about 50,000 tons / year in total in, for example, the results in FY2003.

  Therefore, if the technique of recovering manganese from these waste dry batteries and reusing it as a steelmaking raw material can be established, the above problem of securing a manganese source can be expected to be greatly solved. However, the current state of resource recycling of manganese batteries and alkaline manganese batteries discarded after the end of discharge is that zinc smelting manufacturers collect some of the zinc contained in the waste dry batteries, or some electric furnace manufacturers use iron or iron contained in the waste dry batteries. Only a portion of the carbon is being recovered. That is, a lot of resources are still recycled without being recycled and disposed of as waste materials.

Under such circumstances, various technologies for recycling not only zinc, iron, and carbon but also manganese have been proposed with respect to the technology for recycling the constituent materials of waste dry batteries.
For example, in Patent Document 1, manganese batteries and alkaline manganese batteries are selected from waste dry batteries, crushed and sieved to obtain powder particles, and zinc contained in the powder particles is dissolved with dilute hydrochloric acid or dilute sulfuric acid. Thus, a technique for leaving manganese and carbon in the dissolved residue has been proposed. According to the technique proposed in Patent Document 1, the zinc solution can be recycled as a zinc refining raw material, and the dissolved residue in which manganese dioxide and carbon mainly remain can be recycled as a manganese raw material.

  Patent Document 2 proposes a technique for separating and recovering manganese dioxide and zinc chloride from a waste dry battery. In this technology, a waste dry battery is physically treated to obtain a material containing a large amount of manganese and zinc. This material is washed with water, dissolved in hydrochloric acid, insoluble materials (carbon powder, etc.) are removed from the solution, and then chlorinated. A mixed aqueous solution of manganese and zinc chloride is used. Next, after this mixed aqueous solution is heated and concentrated, perchloric acid is further added and heated to oxidize manganese chloride in the mixed aqueous solution to manganese dioxide to insolubilize it, and then a solid mixture of manganese dioxide and zinc chloride is formed. obtain. Then, water is added to the obtained solid mixture to dissolve zinc chloride, followed by filtration to separate and recover manganese dioxide and zinc chloride. The zinc chloride in the solution is extracted and purified using an organic solvent. According to the technique proposed in Patent Document 2, the recovered product obtained by separating and recovering manganese dioxide and zinc chloride by the above operation is finished to a purity that can be recycled to dry battery production again.

  In Patent Literatures 3 to 8, waste batteries are sorted by performance, crushed, roasted, calcined, etc., so that manganese and zinc components contained in the waste batteries are mixed with manganese oxide and zinc oxide. And a technique for producing manganese-zinc ferrite using the mixture thus recovered as a raw material.

  On the other hand, the technology mainly targets minerals instead of waste dry batteries, but a technique for recovering valuable metals by leaching valuable metals from minerals into the processing liquid using microorganisms is also known. For example, in Patent Document 9, an iron-reducing bacterium is allowed to act to reduce trivalent iron to divalent iron. Using the divalent iron, a metal (cobalt) included in the group consisting of a metal oxide and a metal hydroxide is used. , Nickel, manganese, etc.) are leached to produce a leachate and a residue, the leachate and the residue are separated, and a desired metal is recovered. According to the technique proposed in Patent Document 9, valuable metals (cobalt, nickel, manganese, etc.) contained in the leachate can be recovered by a known method and used for a desired application.

JP 2007-012527 A Japanese Patent Laid-Open No. 11-191439 JP-A-9-82340 Japanese Patent Laid-Open No. 9-82339 Japanese Patent Laid-Open No. 7-85897 JP 7-81941 A JP-A-6-260175 JP-A-6-260174 JP 2007-113116 A

  However, in the technique proposed in Patent Document 1, zinc is dissolved from the granular material using dilute hydrochloric acid or dilute sulfuric acid, but for the purpose of improving the removal rate (dissolution rate) of zinc from the granular material. When the acid concentration is increased, a part of manganese contained in the powder is dissolved and the yield is deteriorated. In addition, when a part of manganese contained in the granular material is dissolved in this way, the dissolved manganese is recovered together with zinc at a later stage. Therefore, the final zinc recovery product contains a large amount of zinc, but it must be a waste because it contains manganese, making it impossible to recycle and reducing the overall cost. It becomes a factor. On the other hand, if the dissolution treatment conditions are slow, zinc cannot be completely removed from the powder and the separation between manganese and zinc becomes incomplete.

  The technology proposed in Patent Document 2 is very complicated, and it is easily imagined that the materials and labor to be collected for collection are more than the evaluation value of the collected items, so that resource recycling is economical. It cannot be established. Further, since perchloric acid and a large amount of organic solvent, which are highly dangerous, are used in the process of recovering the manganese and zinc components, there is a problem related to the safety of the work environment in addition to the high cost of the treatment.

  With the techniques proposed in Patent Documents 3 to 8, manganese and zinc cannot be recovered from the waste dry battery in a form separated from each other. That is, the techniques proposed in Patent Documents 3 to 8 are techniques for recovering a mixture of manganese oxide and zinc oxide from a waste dry battery, and thus the recovered manganese containing the zinc component is used as a steelmaking raw material. Impossible.

  The technique proposed in Patent Document 9 is a technique for leaching a metal from a mineral using a microorganism, and is known as a technique with a small burden on the environment without using a large amount of strong acid or organic solvent. However, when this technology is applied to waste dry batteries, the antibacterial properties of zinc that leach out together with manganese from the waste dry battery will increase when the solid-liquid ratio, that is, the ratio of the material to be treated (waste dry battery) to the leachate is increased to about 50 g / L. The leaching rate of the metal tends to decrease due to the inhibitory action that is considered to be caused by the action. In addition, a salt of chelated iron (iron complex) such as iron citrate used as a microorganism culture medium is generally expensive and somewhat disadvantageous in terms of cost. Therefore, even in the technique proposed in Patent Document 9, the material thrown for recovery may be more than the evaluation value of the recovered product, and it may be difficult to economically recycle resources.

  As described above, in the prior art, when recovering the manganese component and the zinc component from the waste dry battery, it was extremely difficult to recover the manganese component and the zinc component in a form separated from each other. Therefore, in the prior art, high purity manganese required as a steelmaking raw material has not been recovered, and a technique for recovering manganese from a waste dry battery and reusing it as a steelmaking raw material is desired.

  The present invention has been made in view of the above circumstances, and relates to a method and equipment for separating and recovering manganese and zinc from waste dry batteries, and in particular, almost completely separates manganese and zinc components contained in waste dry batteries. An object of the present invention is to provide a method and equipment for recovering manganese with very little zinc component at low cost and in a simple manner.

  The inventors of the present invention have made various studies on a technique for separating and recovering manganese and zinc components from waste dry batteries in order to search for a novel separation and recovery technique that overcomes the above-described problems of the prior art. Specifically, searching for means to separate and recover the manganese component and zinc component from the powder obtained by sorting manganese batteries and alkaline manganese batteries from waste batteries and further crushing and sieving them did.

When a manganese dry battery or an alkaline manganese dry battery is selected from the waste dry batteries, and these are crushed and sieved, the material constituting the dry battery is separated into the solid matter on the sieve and the granular material under the sieve. Of the materials constituting the dry battery, mainly iron-shell packaging materials, zinc cans, brass bars, paper materials, plastics, etc., are crushed into foil-like or piece-like solids and separated on a sieve. On the other hand, manganese dioxide, carbon, zinc chloride, ammonium chloride, caustic potash, or MnO (OH), Zn (OH) ₂ , Mn (OH) ₂ , ZnO, etc. generated by discharge become powder particles, To be separated. In addition, a trace amount iron may be inevitably mixed in a granular material.

  First, the present inventors perform acid leaching treatment on the above-mentioned powder particles, that is, powder particles mainly containing carbon together with manganese / zinc components to leach zinc in the powder particles. An attempt was made to collect the manganese component and the zinc component separately from each other by leaving the manganese component in the leaching residue. However, with such a method, it has become extremely difficult to keep the entire amount of the manganese component in the granular material in the leaching residue, and it has been clarified that a part of the manganese component is leached together with zinc.

  Accordingly, the present inventors have further studied and sought a means for completely separating and recovering the manganese component and the zinc component contained in the leachate. As a result, it was found that manganese can be precipitated and recovered as an oxide out of manganese and zinc dissolved in the leachate by simple means of allowing ozone to act on the leachate.

The leaching solution obtained by the above acid leaching treatment contains manganese ions and zinc ions. In addition, when the powder particles inevitably contain iron, iron in the powder particles is also leached during the acid leaching process, so that it is assumed that the leaching solution also contains iron ions.
If only the manganese component can be insolubilized and precipitated from such a leachate, the manganese component can be easily separated from zinc or iron and recovered. Therefore, the present inventors paid attention to the oxidation-reduction potential (ORP) and pH phase diagram (Eh-pH diagram) of each metal (manganese, zinc, iron).

  FIG. 1A is a state diagram (Eh-pH diagram) of the oxidation-reduction potential (ORP) and pH of manganese in an aqueous solution at 25 ° C. FIG. 1B is a state diagram (Eh-pH diagram) of the oxidation-reduction potential (ORP) and pH of zinc in an aqueous solution at 25 ° C. FIG. 1C is a phase diagram (Eh-pH diagram) of the oxidation-reduction potential (ORP) and pH of iron in an aqueous solution at 25 ° C. As shown in FIGS. 1A to 1C, in the Eh-pH diagram, the region where manganese is precipitated overlaps the region where iron and zinc are precipitated, and the manganese Eh-pH diagram shown in FIG. It can be seen that substances other than manganese also precipitate outside the area surrounded by circles. Therefore, when the state of redox potential (ORP) and pH is changed from the region where manganese, zinc, and iron are all dissolved (ionized), zinc or iron is oxidized first in most regions. Or it will solidify and precipitate as a hydroxide.

  However, the inventors of the present invention are the only one in which the manganese is solidified mainly as an oxide in the low pH / high ORP region (the region surrounded by a circle in the Eh-pH diagram of manganese shown in FIG. 1 (a)). It came to mind that there is an area to settle. The pH and redox potential (ORP) of the leachate containing manganese ions, zinc ions, and iron ions are shown in the Eh-pH diagram, where manganese is solidified and precipitated as an oxide (FIG. 1 (a)). By adjusting the pH and oxidation-reduction potential (ORP) of the manganese Eh-pH diagram (shown in the circle), it was conceived that only manganese can be insolubilized and precipitated as an oxide. .

  In addition, the present inventors further studied and sought a means for easily adjusting the pH and redox potential (ORP) of the leachate. As a result, by applying ozone to the leachate, the pH and redox potential (ORP) of the leachate were easily surrounded by circles in the manganese Eh-pH diagram shown in FIG. 1 (a). It was found that it was possible to adjust to (region).

  Furthermore, as a result of component analysis by the present inventors, it was confirmed that the precipitate (manganese oxide) obtained by allowing ozone to act as described above was a very high-purity manganese oxide. Then, by recovering the high-purity manganese oxide and the leaching residue obtained by the acid leaching treatment, it is possible to obtain a manganese recovery product in which zinc is almost completely separated from the granular material of the waste dry battery. I found out.

The present invention has been completed based on the above findings, and the gist thereof is as follows.
[1] A method for separating a manganese component and a zinc component contained in a waste dry battery from a waste dry battery, wherein a sorting step for sorting a manganese dry battery and / or an alkaline manganese dry battery from the waste dry battery, and sorting in the sorting step Crushing and sieving process for crushing and sieving waste dry batteries to obtain powder particles, and acid leaching treatment using acid solution to leach liquid containing manganese and zinc and leaching containing manganese An acid leaching step for obtaining a residue, a first solid-liquid separation step for solid-liquid separation of the leachate obtained in the acid leaching step and the leaching residue, and ozone for the leachate separated in the first solid-liquid separation step An ozone treatment step of oxidizing and precipitating manganese ions contained in the leachate to obtain a manganese-containing precipitate and a zinc ion-containing solution, and the manganese-containing product obtained in the ozone treatment step. A second solid-liquid separation step for solid-liquid separation of the precipitate and the zinc ion-containing solution, and the manganese component contained in the waste dry battery is the leaching residue and the manganese-containing precipitate, and is contained in the waste dry battery. A method for separating manganese and zinc from waste dry batteries, wherein the zinc component is separated as the zinc ion-containing solution.

[2] The waste according to [1], wherein the acid solution in the acid leaching step is dilute sulfuric acid having a mass% concentration of 1.4% to 45% or dilute hydrochloric acid having a mass% concentration of 1% to 14%. Method for separating manganese and zinc from dry cells.

[3] The method for separating manganese and zinc from a waste dry battery according to [1] or [2] above, wherein the solid-liquid ratio of the granular material and the acid solution in the acid leaching step is 50 g / L or more .

[4] A method for recovering a manganese component contained in a waste dry battery from a waste dry battery, comprising manganese separated from the waste dry battery according to any one of the above [1] to [3] A method for recovering manganese from a waste dry battery, wherein the precipitate is recovered as a manganese component.

[5] A method for recovering a manganese component contained in a waste dry battery from a waste dry battery, the leaching residue separated according to the method for separating manganese and zinc from the waste dry battery according to any one of the above [1] to [3] A method for recovering manganese from a waste dry battery, comprising a step of mixing a manganese-containing precipitate and a mixture of the leaching residue and the manganese-containing precipitate as a manganese component.

[6] A manganese component recovery product recovered by the manganese recovery method of [4] or [5].

[7] A method for recovering a zinc component contained in a waste dry battery from a waste dry battery, wherein the zinc ions are separated from the waste dry battery according to any one of the above [1] to [3]. An alkaline agent is added to the containing solution to convert the zinc ions in the zinc ion-containing solution into zinc-containing precipitates, and the zinc-containing precipitate obtained in the alkaline precipitation treatment step is subjected to solid-liquid separation. And a third solid-liquid separation step, wherein the zinc-containing precipitate separated in the third solid-liquid separation step is recovered as a zinc component.

[8] A zinc component recovery product recovered by the zinc recovery method of [7].

[9] A facility for separating the manganese component and the zinc component contained in the waste dry battery from the waste dry battery, wherein the sorting device sorts the manganese dry battery and / or the alkaline manganese dry battery from the waste dry battery; A crushing device for charging the waste dry battery to obtain a crushed product, a sieving device for obtaining a granule by sieving the crushed product obtained by the crushing device, and an acid An acid leaching bath that obtains a leaching solution containing manganese ions and zinc ions and a leaching residue containing manganese by performing an acid leaching treatment on the granular material using a solution, and a leaching solution and a leaching obtained in the acid leaching bath A first solid-liquid separation device for solid-liquid separation of the residue, and ozone is allowed to act on the leachate separated by the first solid-liquid separation device to oxidize and precipitate manganese ions contained in the leachate; An ozone treatment device for obtaining a precipitate and a zinc ion-containing solution, and a second solid-liquid separation device for solid-liquid separation of the manganese-containing precipitate obtained from the ozone treatment device and the zinc ion-containing solution. Features a facility for separating manganese and zinc from waste dry batteries.

[10] A facility for recovering manganese components contained in the waste dry battery from the waste dry battery, comprising the facility for separating manganese and zinc from the waste dry battery according to the above [9], .

[11] A facility for recovering the zinc component contained in the waste dry battery from the waste dry battery, the manganese and zinc separation facility from the waste dry battery of [9], and the second solid-liquid separation of the manganese and zinc separation facility An alkali precipitation treatment tank for storing a zinc ion-containing solution separated by an apparatus and subjecting the zinc ion-containing solution to an alkali precipitation treatment to obtain a zinc-containing precipitate, and a zinc-containing precipitation obtained in the alkali precipitation treatment tank A facility for recovering zinc from waste dry batteries, comprising a third solid-liquid separator for solid-liquid separation.

  According to the present invention, manganese and zinc in a waste dry battery can be separated almost completely by a simple method, and can be recovered with a high yield. Further, according to the present invention, since manganese with reduced zinc contamination can be recovered, the recovered manganese can be recycled as a steelmaking raw material, and the recovered zinc can be recycled as a zinc refining raw material. It becomes. As described above, since the present invention realizes the reuse of both manganese and zinc, which are the main components of a waste dry battery, the industrial significance is extremely large.

(A) A state diagram (Eh-pH diagram) of oxidation-reduction potential (ORP) and pH of manganese in an aqueous solution. (B) A state diagram (Eh-pH diagram) of redox potential (ORP) and pH of zinc in an aqueous solution. (C) A state diagram (Eh-pH diagram) of redox potential (ORP) and pH of iron in an aqueous solution. It is a flow figure explaining one form of the separation and recovery method of the present invention. It is a mimetic diagram showing one form of separation and recovery equipment of the present invention. It is a figure which shows the relationship between the sulfuric acid concentration of the acid solution in the acid leaching process of an Example, and a manganese leaching rate. It is a figure which shows the XRD analysis result of the manganese oxide collect | recovered in the Example. It is a figure which shows the manganese recovery rate at the time of ozone treatment of an Example, and a zinc recovery rate.

Hereinafter, the present invention will be specifically described.
First, a method for separating manganese and zinc from the waste dry battery of the present invention, a manganese recovery method, a manganese component recovery product, a zinc recovery method, and a zinc component recovery product will be described.

  The present invention is directed to one or two types of waste dry batteries of manganese dry batteries and alkaline manganese dry batteries. Then, the present invention provides an invention of a separation method for separating a manganese component and a zinc component contained in these waste dry batteries from each other, an invention of a recovery method for recovering each component separated according to the separation method, and the recovery It is the invention of the recovered material recovered according to the method.

FIG. 2 is a flowchart for explaining an embodiment of the present invention. As shown in FIG. 2, the method for separating manganese and zinc according to the present invention and the method for recovering manganese according to the present invention include a sorting step 1, a crushing / sieving step 2, an acid leaching step 3, a first solid-liquid separation step 4, ozone It has a processing step 5 and a second solid-liquid separation step 6.
In addition to the above steps 1 to 6, the manganese recovery method of the present invention may further include a mixing step 7 as a next step of the second solid-liquid separation step 6.
In addition to the above steps 1 to 6, the zinc recovery method of the present invention further includes an alkali precipitation treatment step 8 and a third solid-liquid separation step 9 as the next step of the second solid-liquid separation step 6. Have.

Sorting process Waste dry batteries are rarely collected separately for each type, and are generally collected in a mixed form. Therefore, in the present invention, first, one or both of a manganese dry battery and an alkaline manganese dry battery is selected from these discarded / recovered waste dry batteries. As a sorting method, any method such as manual sorting, machine sorting using a device that sorts using shape, radiation, or the like may be used. Exclude mercury batteries, nickel-cadmium batteries, etc. in waste dry batteries according to the selected sorting method.

Crushing / sieving step Next, the manganese dry cell and / or the alkaline manganese dry cell sorted in the sorting step are crushed. The purpose of crushing is to eliminate materials containing components other than manganese and zinc as much as possible from the constituent materials of manganese dry batteries and / or alkaline manganese dry batteries selected in the selection step.

Among the sorted waste batteries, manganese batteries are manganese dioxide (positive electrode material), carbon rod (current collector), zinc can (negative electrode material), zinc chloride or ammonium chloride (electrolyte), MnO ( In addition to OH) and Zn (OH) ₂ , packaging materials such as iron, plastic and paper are included. Among the selected waste batteries, alkaline manganese batteries are brass bars (current collectors) instead of the carbon bars (current collectors), zinc cans (negative electrode materials), zinc chloride or ammonium chloride (electrolyte). , Zinc powder, (negative electrode material), potassium hydroxide (electrolytic solution), etc., and Mn (OH) ₂ , ZnO, etc. produced by discharge.

When these materials are crushed, packaging materials (iron, plastic, paper, etc.), zinc cans, which are anode materials for manganese batteries, and brass rods, which are current collectors for alkaline manganese batteries, are foil-like or piece-like. It becomes a solid substance. On the other hand, manganese dioxide as positive electrode material, carbon rod as current collector of manganese dry battery, zinc powder as negative electrode material of alkaline manganese dry battery, MnO (OH), Zn (OH) ₂ , Mn (OH) generated by discharge ₂ , ZnO, etc., and various electrolytes become finer particles than the foil-like / flaky solids.

Therefore, after crushing the selected waste dry battery and sieving it with a sieve with a predetermined opening, large solids such as packaging materials are removed from the selected waste dry battery, mainly containing carbon with manganese and zinc components Can be obtained.
A crusher is usually used for crushing the sorted waste batteries. The type of the crusher is not particularly limited, and for example, a type in which the powder material and the packaging material constituting the dry battery are well separated after crushing is preferable. As such a thing, the biaxial rotation type crusher is mentioned, for example. The sieve opening used for sieving the above crushed material (sieving between a foil-like or piece-like solid and a granular material) is preferably about 1 mm or more and 20 mm or less. Further, it is more preferably about 1 mm or more and 10 mm or less, and further preferably about 1 mm or more and 3 mm or less.

As described above, through the crushing and sieving process, manganese dioxide, carbon, zinc chloride or ammonium chloride, caustic potash, and further generated by discharge are the main constituent materials of manganese dry batteries and / or alkaline manganese dry batteries. A granular material in which MnO (OH), Zn (OH) ₂ , Mn (OH) ₂ , ZnO or the like is mixed is obtained. Moreover, a trace amount of iron component is inevitably mixed in this granular material.

  In the crushing and sieving step, the zinc can, which is the negative electrode material of the manganese dry battery, is sieved as a foil-like or piece-like solid, but this zinc can is separately collected and recycled.

Acid leaching step In the acid leaching step, an acid leaching process is performed on the granular material obtained in the crushing and sieving step, that is, the granular material mainly containing a manganese / zinc component and carbon, using an acid solution. By this acid leaching treatment, zinc contained in the powder is leached and part of manganese contained in the powder is leached. Moreover, the carbon which is not leached out of the carbon contained in the granular material and the manganese contained in the granular material is left in the leaching residue.

The waste dry battery selected in the selection process includes MnO (OH) ₂ , Mn (OH) ₂ generated by discharge, and undischarged MnO ₂ . Of these, MnO (OH) and Mn (OH) ₂ are considered to dissolve in acid, but MnO ₂ is considered to hardly dissolve in acid. As is apparent from the half-reaction equation of MnO ₂ dissolution expressed by the following formula (1), it is necessary to reduce Mn from tetravalent to divalent for dissolution of MnO ₂ , and in addition to acids, This is because a reducing agent for supplying electrons is required.
MnO ₂ (solid) + 4H ⁺ + 2e- → Mn ²⁺ (dissolved) + 2H ₂ O… (1)

Therefore, when acid leaching treatment is performed on a granular material using an acid solution, manganese present as MnO (OH) or Mn (OH) ₂ out of manganese components contained in the granular material is leached into the acid solution. It is done. On the other hand, of the manganese component contained in the granular material, it is considered that MnO ₂ does not leach into the acid solution but remains as an leaching residue together with the carbon contained in the granular material. In addition, about the zinc component contained in a granular material, if the density | concentration of an acid is raised, the whole quantity will melt | dissolve (leaching).

  The acid used for the acid solution may be a general acid, and sulfuric acid, nitric acid, hydrochloric acid, and other acids can be used. However, in consideration of cost and ease of procurement, sulfuric acid or hydrochloric acid is used. preferable. When using sulfuric acid, it is preferable to use dilute sulfuric acid having a sulfuric acid concentration of 1.4% to 45% by mass. It is more preferable to use dilute sulfuric acid having a sulfuric acid concentration of 2% or more and 30% or less in terms of mass% concentration, and it is even more preferable to use dilute sulfuric acid having a sulfuric acid concentration of 5% or more and 25% or less of mass% concentration. When hydrochloric acid is used, it is preferable to use dilute hydrochloric acid having a hydrochloric acid concentration of 1% to 14% by mass. It is more preferable to use dilute hydrochloric acid having a hydrochloric acid concentration of 2% or more and 8% or less in terms of mass% concentration. Hydrochloric acid or sulfuric acid may be a commercially available one, but the cost of the acid can be reduced by diluting and using industrial or waste acid with a small amount of harmful metal components. Moreover, the mass% concentration here is a value obtained by multiplying 100 by dividing the acid mass in the acid solution by the mass of the entire solution.

  Regardless of which acid is used, the acid concentration required for the leaching of manganese and zinc is the solid-liquid ratio, the amount of powder, the content of manganese and zinc in the powder, the manganese in the powder. It varies depending on the form of zinc. Therefore, an optimal acid concentration can be determined by conducting a preliminary experiment assuming an actual machine in advance.

  From the viewpoint of improving the efficiency of acid leaching treatment, the solid-liquid ratio of the powder and acid solution (powder (g) / acid solution (L)) in the acid leaching process should be 50 g / L or more. preferable. The solid-liquid ratio is more preferably 100 g / L or more. However, if the solid-liquid ratio exceeds 800 g / L and becomes excessively high, there is a possibility that the viscosity will increase and handling problems may occur, or the yield during the first solid-liquid separation process described later may deteriorate. is there. Therefore, the solid-liquid ratio is preferably 800 g / L or less.

  A sufficient effect can be obtained even at room temperature (around 15 to 25 ° C.) for the acid leaching treatment temperature (atmosphere temperature or acid solution temperature), but heating may be performed. If heating is performed, the reaction efficiency can be expected to be improved. However, since heating costs are also required, it is only necessary to determine whether or not the heating can be performed in comparison with the obtained effect. The treatment time for the acid leaching treatment is preferably 5 minutes or more and 6 hours or less. Further, it is more preferably from 30 minutes to 4 hours, and even more preferably from 1 hour to 3 hours.

Through the above acid leaching process, almost all of the zinc component contained in the powder and the leachate from which manganese present as MnO (OH) and Mn (OH) ₂ out of the manganese contained in the powder was leached. Is obtained. Further, by the above acid leaching process, manganese present mainly as MnO ₂ among the manganese components contained in the granular material remains in the leaching residue. Therefore, in the above acid leaching step, a leaching residue containing manganese is also obtained. Note that almost the entire amount of carbon contained in the granular material also remains in the leaching residue. Moreover, since almost all of the zinc component contained in the granular material is leached, the leaching residue contains almost no zinc component.

First Solid-Liquid Separation Step In the first solid-liquid separation step, the leachate and leach residue obtained in the acid leaching step are subjected to solid-liquid separation. The solid-liquid separation means is not particularly limited, and may be any means selected from, for example, gravity sedimentation separation, filtration, centrifugation, filter press, membrane separation and the like.
As described above, the leaching residue contains a manganese component but hardly contains a zinc component. Therefore, the leaching residue separated by solid-liquid separation can be recovered as a manganese component. On the other hand, the leachate separated by solid-liquid separation is subjected to ozone treatment in the next ozone treatment step.

Ozone treatment process In the ozone treatment process, ozone is allowed to act on the leachate (leaching solution containing manganese ions and zinc ions) obtained in the acid leaching step, thereby oxidizing and precipitating manganese ions contained in the leachate, and containing manganese. A precipitate and a solution containing zinc ions are obtained. That is, in the ozone treatment process, only manganese ions out of manganese ions and zinc ions contained in the leachate are oxidized to manganese oxides (manganese-containing precipitates), thereby maintaining the zinc component in a dissolved state. While making the manganese component solid.

  Specifically, ozone is diffused into the leachate obtained in the acid leaching step to adjust the redox potential (ORP) of the leachate, and the pH and redox potential (ORP) of the leachate are shown in FIG. In the Eh-pH diagram shown in (c), it is assumed that only manganese is insolubilized (solidified) and precipitated as an oxide (region surrounded by circles in the Eh-pH diagram of manganese shown in FIG. 1 (a)). . Thereby, manganese dissolved in the leachate is preferentially insolubilized to become a solid.

  The leachate is acidic. Therefore, it is not usually necessary to adjust the pH of the leachate, and the pH of the leachate can be adjusted by simply diffusing ozone into the leachate separated in the first solid-liquid separation step and adjusting the oxidation-reduction potential (ORP). The oxidation-reduction potential (ORP) can be adjusted to a region where only manganese is insolubilized (solidified) and precipitated as an oxide in the Eh-pH diagram. However, the pH of the leachate may be measured prior to the ozone aeration just in case. If the measured pH is higher than the desired value, a slight acid (for example, a general acid such as sulfuric acid, nitric acid, hydrochloric acid, etc.) may be added.

As an Eh-pH diagram, for example,
Pourbaix, M. Atlas of electrochemical equilibria in aqueous solutions.National Association of Corrosion Engineers. (1974) 644p.
Can be used.

As is clear from FIGS. 1A to 1C, the region where manganese (Mn), zinc (Zn), and iron (Fe) are solidified varies depending on the concentration of each component in the solution. For example, when the Mn and Zn concentrations in the leachate are both 0.1M and the Fe concentration is 0.05M, in FIGS. 1 (a) to (c), Mn and Zn are 10 ⁰ M and 10 ⁻² M, respectively. The boundary between the lines (line * 1 in Fig. 1 (a) and line * 2 in Fig. 1 (b)) can be considered as a reference. Fe is between the 10 ⁰ M and 10 ^-2 M lines. Think about the boundary near 10 ^-2 M (line * 3 in Fig. 1 (c)). In this case, in FIGS. 1A to 1C, the pH and oxidation-reduction potential (ORP) of the region where manganese solidifies and precipitates as an oxide (the region surrounded by ○ in FIG. 1A) are as follows: As shown in FIG. 1 (a), it is understood that it is preferable that the pH is preferably about pH: 0.1 to less than 2.2 and “oxidation-reduction potential (ORP): about +0.9 V to +1.2 V”.

Further, FIGS. 1A to 1C are those when the water temperature is 25 ° C., but if the water temperature is different, temperature correction may be performed. As a correction method, a known method (for example, correction of an equilibrium multiplier by the Van't Hoff equation) may be performed.
Therefore, after confirming that the pH of the leachate is less than 2.2, ozone is diffused into the leachate to raise the oxidation-reduction potential (ORP) to +0.9 V or more, so that only manganese is solid as an oxide. It becomes possible to materialize and separate and precipitate from other elements.

Ozone is produced by an ultraviolet method, a discharge method, an electrolysis method or the like, but in industrial use, it is often produced by a method called silent discharge. In principle, when oxygen gas is passed through a silent discharge space generated by applying an alternating voltage between the electrodes, a part of the oxygen gas is activated and converted into ozone. At this time, ozone concentration, although it depends on the conditions that the concentration of the extent that the number ^{g / Nm 3 ~300g / Nm 3} . As the oxygen gas, a gas concentrated from air by a method such as PSA can be used, or a gas obtained by vaporizing liquid oxygen can be used.
As the amount of ozone diffused, ozone was diffused while observing the oxidation-reduction potential (ORP), and the oxidation-reduction potential (ORP) was a predetermined value (for example, the temperature of the leachate was 25 ° C., and Mn in the leachate , Zn and Fe concentrations are preferably adjusted to about +1 V or more when Mn: 0.1M, Zn: 0.1M, and Fe: 0.05M. In addition, since the required amount of ozone varies depending on the shape of the apparatus and the bubble diameter at the time of air diffusion, the most efficient method may be selected by comparing costs and the like.

By the above ozone treatment process, manganese in the leachate is preferentially insolubilized to become a solid, and most of zinc ions and iron ions are dissolved in the leachate. That is, a manganese-containing precipitate (mainly manganese dioxide MnO ₂ ) and a zinc ion-containing solution (including a small amount of iron ions) are obtained.

  In the ozone treatment step, the leachate during the ozone treatment becomes black due to the manganese oxide generated by the oxidation of manganese, making it difficult to visually determine the reaction progress state. Here, when the oxidation by ozone is insufficient, unreacted manganese ions are not precipitated as solids, leading to deterioration of the manganese component recovery rate.

  On the other hand, if ozone is allowed to act excessively, manganese oxide once generated becomes peroxide ions and redissolves, and the recovery rate deteriorates as in the case of insufficient ozone oxidation. As a result of the study by the present inventors on the reason, when the manganese oxidation reaction is excessive, the solid oxide of manganese is further oxidized to be dissolved in the solution as permanganate ions. It became clear that.

In FIG. 1 (a), the ORP in which manganese peroxide (the uppermost part in FIG. 1 (a), a substance called MnO ₄ ⁻ ) is mainly present is around + 1.6V even at pH 2, and this is actually The phenomenon that ORP rises to such a value is not usually observed. However, as a result of studies by the present inventors, it has been found that some manganese oxides become peroxides due to the action of ozone. At the same time, it was also confirmed that peroxide was generated after almost all manganese was solidified as an oxide.

  From these facts, it is necessary to determine the end point of the manganese oxidation reaction. Even if the end point of the manganese oxidation reaction is controlled by the reaction time, in the case of the leachate, the concentration and composition of the solution are slightly different for each leachate. It may be different, and the same recovery rate is not always obtained in the same reaction time. A similar problem arises when control by redox potential (ORP) is considered, and it is difficult to confirm a clear reaction end point.

On the other hand, the formation of manganese peroxide can be easily confirmed when the solution turns red. Therefore, it may be possible to determine the end point of the manganese oxidation reaction by observing the color of the leachate during the ozone treatment. However, as described above, in the presence of fine particles of manganese oxide (solid matter), the entire solution becomes manganese oxide. It becomes black which is the color of (MnO ₂ ), and discoloration of the leachate during ozone treatment cannot be determined. However, if manganese oxide (MnO ₂ ) is separated from the leachate during the ozone treatment, it is possible to observe the color change of the leachate, and to determine whether or not manganese peroxide is formed. it can.

Examples of means for separating manganese oxide (mainly MnO ₂ ) from the leachate during the ozone treatment include a means for separating the manganese oxide from the leachate by filtering or sedimenting the leachate. Therefore, in actual operation, in the ozone treatment process, a small part of the leachate during ozone treatment is extracted regularly or continuously, manganese oxide is separated from the extracted solution, and the color of the solution itself is observed. It is preferable to determine the end point of the oxidation reaction of manganese ions. Specifically, a small part of the leachate during ozone treatment is taken out, and the taken out leachate is filtered or left standing to separate the solid manganese oxide and the solution, and the color of the separated solution is changed. It is preferable to observe. Moreover, it is preferable to return the solution after observation to the ozone treatment step again and repeat this. Then, it is preferable to terminate the ozone treatment by determining that the manganese oxidation reaction is completed when the color of the solution after separating the manganese oxide turns red. Thus, if the end point of the manganese oxidation reaction is determined and the ozone treatment is completed, the recovery rate of the manganese component can be maximized.

Second solid-liquid separation step In the second solid-liquid separation step, the manganese-containing precipitate (mainly MnO ₂ ) obtained in the ozone treatment step and a zinc ion-containing solution (a solution in which manganese ions are precipitated from the leachate) are solidified. Separate the liquid. The solid-liquid separation means is not particularly limited, and may be any means selected from, for example, gravity sedimentation separation, filtration, centrifugation, filter press, membrane separation and the like. By the second solid-liquid separation step, each of the manganese component and the zinc component contained in the leachate can be separated into a manganese-containing precipitate and a zinc ion-containing solution.

As described above, a leaching residue containing a manganese component (mainly MnO ₂ ) but hardly containing a zinc component is obtained by the sorting step, crushing / sieving step, and acid leaching step. In addition, following the acid leaching step, the first solid-liquid separation step, the ozone treatment step, and the second solid-liquid separation step are performed, so that the manganese component (mainly MnO ₂ ) is contained but the zinc component is mostly contained. A manganese-containing precipitate and a zinc ion-containing solution containing almost no manganese ions.

  Therefore, by passing through the above steps, the manganese component and the zinc component can be extracted from the waste dry battery (powder) in a state where the manganese component and the zinc component are mixed. That is, the manganese component contained in the waste dry battery (powder particles) can be extracted as a leaching residue and a manganese-containing precipitate. Moreover, the zinc component contained in a waste dry battery (powder body) can be extracted as a zinc ion containing solution.

The above is the method for separating manganese and zinc from the waste dry battery of the present invention.
Moreover, the method for recovering manganese from the waste dry battery of the present invention is a method for recovering the manganese-containing precipitate separated in the second solid-liquid separation step as a manganese component. As described above, the manganese-containing precipitate separated in the second solid-liquid separation step contains almost no zinc component. In addition, since almost the entire amount of carbon contained in the waste dry battery (powder body) is separated as a leaching residue in the first solid-liquid separation step, the manganese-containing precipitate contains almost no carbon. Therefore, a high-purity manganese component (manganese oxide) can be recovered by recovering the manganese-containing precipitate as a manganese component.

  Further, the method for recovering manganese from the waste dry battery according to the present invention is added to the above-described selection process, crushing / sieving process, acid leaching process, first solid-liquid separation process, ozone treatment process, and second solid-liquid separation process. Furthermore, a mixing step can be provided as the next step of the second solid-liquid separation step.

In the mixing step, the leaching residue separated in the first solid-liquid separation step and the manganese-containing precipitate separated in the second solid-liquid separation step are mixed, and the leaching residue and the manganese-containing precipitate are mixed. Is collected as a manganese component. As described above, according to the method for separating manganese and zinc from the waste dry battery of the present invention, a leaching residue is obtained in the acid leaching step, and a manganese-containing precipitate is obtained in the ozone treatment step. Contains almost the entire amount of manganese components contained in the sorted waste battery (powder). In addition, these two kinds of solids hardly contain the zinc component contained in the sorted waste dry battery (powder particles). Therefore, by combining these two kinds of solids, the manganese of the sorted waste dry battery (powder particles) can be recovered with a yield of almost 100% while being almost completely separated from zinc.

The manganese component recovered material of the present invention is the manganese-containing precipitate or a mixture of the leaching residue and the manganese-containing precipitate.
The manganese-containing precipitate has a very low carbon content, and most of its components are MnO ₂ . Therefore, among the manganese component recovered materials recovered according to the method of the present invention, the manganese-containing precipitate is particularly suitable as a raw material for producing metal manganese among steelmaking raw materials of steelworks.

When only the manganese-containing precipitate is recovered as a manganese component, the manganese recovery rate from the waste dry battery (powder particles) is low, and the manganese remaining in the leaching residue is wasted. Therefore, from the viewpoint of improving the manganese recovery rate, it is preferable to recover the leaching residue as a manganese component. However, the leaching residue contains manganese oxide (MnO ₂ ) as a main component and also carbon contained in the waste dry battery (powder particles). This carbon can be a reducing agent for manganese when, for example, the recovered leaching residue is heated to reduce the main component manganese oxide. Therefore, when recovering only the above leaching residue as a manganese component, the recovered material can be a raw material that is somewhat convenient as a starting material for ferromanganese production among steelmaking raw materials in steelworks, but in that the carbon content is slightly too high There are challenges.

  Then, as a result of studies by the present inventors to solve the above problems, the inventors have come up with the idea of mixing and recovering the leaching residue and the manganese-containing precipitate. By mixing the leaching residue and the manganese-containing precipitate, a manganese component recovered material in which the carbon concentration is moderately reduced and the manganese recovery rate is remarkably improved is obtained. Among the recovered manganese components recovered according to the method of the present invention, the mixture of the leaching residue and the manganese-containing precipitate contains a small amount of carbon that can act as a reducing agent. Preferably used.

  On the other hand, the method for recovering zinc from the waste dry battery of the present invention is added to each of the above-described sorting step, crushing / sieving step, acid leaching step, first solid-liquid separation step, ozone treatment step, and second solid-liquid separation step. Furthermore, an alkali precipitation treatment step and a third solid-liquid separation step are provided as the next steps of the second solid-liquid separation step.

Alkaline precipitation treatment step In the alkali precipitation treatment step, an alkali agent is added to the zinc ion-containing solution separated in the second solid-liquid separation step, and the zinc ions in the zinc ion-containing solution are converted into zinc-containing precipitates. . The zinc ion-containing solution separated in the second solid-liquid separation step is an acidic solution containing zinc at a high concentration. By making the acidic solution alkaline, zinc can be insolubilized and precipitated as a hydroxide. it can.

  The type of the alkali agent is not particularly limited, but it is preferable to use caustic soda (NaOH), potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. However, when caustic soda (NaOH), which is a general alkali, is used as the alkali agent, precipitation of sodium salt may occur depending on the acid concentration, and the zinc content of the zinc-containing precipitate tends to decrease. For example, when a sulfuric acid-containing zinc ion-containing solution is made alkaline with caustic soda, sodium sulfate is precipitated together with zinc hydroxide. In such a case, if the precipitate is washed with water, sodium sulfate can be easily dissolved and removed. Therefore, a washing step may be added as necessary.

Third Solid-Liquid Separation Step In the third solid-liquid separation step, the zinc-containing precipitate obtained in the alkali precipitation treatment step is solid-liquid separated and recovered as a zinc component. The solid-liquid separation means is not particularly limited, and may be any means selected from, for example, means by dehydration and filtration, gravity sedimentation separation, centrifugation, filter press, membrane separation, and the like. Thereby, a high concentration zinc component can be collect | recovered and it can be used as a quality zinc refining raw material.

  Most of the components of the recovered zinc component of the present invention, that is, the zinc-containing precipitate separated in the third solid-liquid separation step, are zinc hydroxides. However, when the zinc-containing precipitate separated in the third solid-liquid separation step is dehydrated by heating to a temperature of, for example, more than 100 ° C., the entire amount is not a zinc hydroxide, but a part thereof is dehydrated and zinc In some cases, it is recovered as an oxide. The zinc component recovered product of the present invention, that is, the zinc-containing precipitate separated in the third solid-liquid separation step, may contain a trace amount of sodium salt such as sodium sulfate produced in the alkali precipitation treatment step. . This is due to the difference in the type of alkali used, the amount added, and the state of washing with water, and the presence or absence of contamination varies depending on the state of treatment.

  Since the zinc ion-containing solution separated in the second solid-liquid separation step may inevitably contain a small amount of iron ions, iron may be precipitated together with zinc in the alkali precipitation treatment step. Even in such a case, the iron content of the original powder obtained in the crushing / sieving step is not so high, so that a very small amount of iron is not a problem. However, if it is necessary to remove iron, when adding an alkali agent in the alkali precipitation treatment step, adjust the pH to about 4 to 5 and make air aeration before making the zinc ion-containing solution alkaline. If done, only iron can be insolubilized and recovered. Thereafter, if the residual solution is made alkaline to precipitate the zinc component, a zinc-containing precipitate containing no iron can be obtained.

  In addition, when the zinc ion-containing solution separated in the second solid-liquid separation process contains other trace metal elements (Cr, Cu, Ni, Pb, Cd, Hg, etc.), the zinc precipitation is also included in the alkali precipitation treatment process. By making the solution alkaline, most of the trace metals precipitate with zinc. However, since these contents are very small, it is considered that the concentration can be sufficiently removed in the subsequent zinc refining process.

  As described above, according to the present invention, it is possible to obtain a manganese component recovered material with a very small amount of zinc component mixed from the waste dry battery. The use of raw materials recovered from waste dry batteries reduces the amount of fresh manganese ore used and contributes to the effective use of resources. At the same time, since it is possible to reduce the amount of waste dry batteries that have been disposed of by landfill without being reused, costs for disposal can be reduced, and environmental pollution can be reduced.

  Next, the manganese and zinc separation equipment, the manganese recovery equipment, and the zinc recovery equipment from the waste dry battery of the present invention will be described. The facility of the present invention is a facility suitable for carrying out the above-described method of the present invention, that is, a method for separating manganese and zinc from waste dry batteries, a manganese recovery method, and a zinc recovery method.

  In FIG. 3, the schematic diagram of the installation of this invention is shown. As shown in FIG. 3, the manganese and zinc separation facility of the present invention is charged with a sorting device 10 for sorting manganese dry cells and / or alkaline manganese dry cells from waste dry cells, and a waste dry cell sorted by the sorting device 10. A crushing device 20a that performs crushing treatment and obtains a crushing product, a sieving device 20b that obtains a granular material by performing a sieving process on the crushing product obtained by the crushing device 20a, and a sieving An acid leaching treatment was performed on the granular material obtained by the separating apparatus 20b to obtain a leaching solution containing manganese ions and zinc ions and a leaching residue containing manganese. A first solid-liquid separation device 40 for solid-liquid separation of the leachate and leach residue, and ozone is applied to the leachate separated by the first solid-liquid separation device 40 to oxidize manganese ions contained in the leachate Precipitate and contain manganese Comprising an ozone processing device 50 for obtaining the sediment was a zinc ion-containing solution, a second solid-liquid separation device 60 for solid-liquid separating the resulting manganese-containing precipitate and zinc ion containing solution in the ozone processing device 50.

Further, the manganese recovery facility of the present invention includes the above-described manganese and zinc separation devices 10 to 60, for example, a leaching residue recovery tank 70a for recovering a leaching residue separated by the first solid-liquid separation device 40, a second A manganese-containing precipitate collection tank 70b for collecting the manganese-containing precipitate separated by the solid-liquid separator 60 may be provided.
Further, the manganese recovery facility of the present invention separates the leaching residue separated by the first solid-liquid separator 40 from the second solid-liquid separator 60 instead of the leaching residue recovery tank 70a and the manganese-containing precipitate recovery tank 70b. A mixture recovery tank 70c for mixing and recovering the manganese-containing precipitate formed may be provided. Furthermore, the manganese recovery facility of the present invention may include a mixture recovery tank 70c together with a leaching residue recovery tank 70a and a manganese-containing precipitate recovery tank 70b.

  In addition, the zinc recovery facility of the present invention stores the zinc ion-containing solution separated by each of the above-described manganese and zinc separation facilities 10 to 60 and the second solid-liquid separation device 60, and the zinc ion-containing solution is stored in the solution. An alkali precipitation treatment tank 80 that performs alkali precipitation treatment to obtain a zinc-containing precipitate, and a third solid-liquid separation device 90 that solid-liquid separates the zinc-containing precipitate obtained in the alkali precipitation treatment tank 80 are provided. Further, for example, a zinc component recovery tank 100 that recovers the zinc-containing precipitate separated by the third solid-liquid separator 90 as a zinc component may be provided.

As long as the various apparatuses, reaction tanks, and recovery tanks constituting these facilities have the respective functions described above, their structures and the like are not limited.
For example, the type of the sorting device is not particularly limited, and examples include a device that sorts using a shape, radiation, or the like. In addition, since sorting of a waste dry battery can also be performed by manual sorting, it is not always necessary to provide a sorting device.

  A normal crusher can be used as the crushing device. The type of the crusher is not particularly limited. For example, a type in which the packaging material constituting the dry battery and the granular material are well separated after crushing is preferable. As such a thing, the biaxial rotation type crusher is mentioned, for example.

  The sieving device is preferably provided with a sieve having an opening of 1 mm or more and 20 mm or less. The opening is more preferably 1 mm or more and 10 mm or less, and further preferably 1 mm or more and 3 mm or less.

In addition to providing a reaction tank for performing ozone treatment (ozone aeration) on the leachate, the ozone treatment apparatus periodically or continuously extracts a small portion of the leachate in the ozone aeration from the reaction tank, It is preferable to provide a separation / observation tank for separating the extracted leachate into manganese oxide (MnO ₂ ) and a solution. By providing a separation / observation tank, it is possible to observe the color of the solution obtained by separating the black manganese oxide (MnO ₂ ) from the leachate during the ozone treatment, and thus the end point of the manganese oxidation reaction can be determined. It becomes possible.

In the separation / observation tank, a filtration device or the like for separating the leachate extracted during the ozone treatment into manganese oxide (MnO ₂ ) and a solution may be provided. Alternatively, the extracted leachate may be allowed to stand to separate into manganese oxide (MnO ₂ ) and the solution without providing a special solid-liquid separator. Furthermore, a spectrophotometer for measuring the absorbance of the filtrate or the supernatant after standing may be provided in the separation / observation tank if allowed in terms of cost, installation space, and the like.

As each of the first to third solid-liquid separation devices, for example, any device selected from a filter press device, a membrane separation device, a gravity sedimentation separation device, a filtration device, a centrifugal separation device, and the like can be used.
As the acid leaching tank and the alkali precipitation treatment tank, for example, a general stirring tank having a tank equipped with a stirrer can be used.

  Moreover, it is preferable to equip the alkali precipitation tank with an apparatus for precipitating and separating iron ions inevitably mixed in the zinc ion-containing solution. Furthermore, assuming that, for example, sodium sulfate is precipitated together with the zinc-containing precipitate, an apparatus for washing the precipitate with water to dissolve and remove sodium sulfate is provided between the third solid-liquid separator and the alkaline precipitation tank. It may be attached to.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this Example.

  Manganese batteries and alkaline manganese batteries were selected from the waste batteries, and the sorted waste batteries were crushed and sieved with a sieve having an aperture of 2.8 mm to obtain powder particles of waste batteries. Table 1 shows the composition of the obtained granular material. In addition to the elements shown in Table 1, the obtained granular material contains oxygen derived from an oxide or hydroxide, some hydrogen, and moisture.

The following tests (1) to (3) were carried out using the powder obtained as described above.
(1) Acid leaching treatment The acid leaching treatment was carried out according to the present invention, and the manganese leaching rate and the zinc leaching rate from the granular material were determined.
Acid solutions diluted to various sulfuric acid concentrations were added to the powder and subjected to acid leaching treatment. As the acid solution, reagent sulfuric acid was used. The acid leaching treatment was performed while mixing and stirring the powder and the acid solution in the leaching tank. In addition, the scale of acid leaching treatment is small, and the increase in redox potential in the solution due to the dissolution of oxygen in the air during stirring may not be negligible. Processed.

  The amount of acid solution (mL), amount of granular material (g), acid solution sulfuric acid concentration (N), acid leaching time (h), and nitrogen aeration (mL / min) in acid leaching treatment are as follows: is there. In addition, the acid leaching process time shown below is the time measured from the time of mixing a granular material and an acid solution and starting stirring.

Acid solution: 100mL
Powder body: 10g (solid-liquid ratio 100g / L)
Sulfuric acid concentration: 1N (mass% concentration (mass fraction) about 4.6%), 2N (mass% concentration about 9.0%), 4N (mass% concentration about 17.4%), 6N (mass% concentration about 24.8%)
Acid leaching treatment time: 1h (stirring treatment)
Nitrogen aeration rate: 10mL / min

  After the acid leaching treatment, the obtained leachate and leaching residue were solid-liquid separated by filtering with a filter paper having a pore diameter of 1 μm, and the manganese concentration of the separated leachate was quantified by ICP emission spectrometry. Next, the mass of manganese in the leachate was determined based on the quantitative value, and the manganese leaching rate was determined by calculating the ratio of the mass of manganese in the leachate to the mass of manganese in the granular material (in terms of manganese element). The result of manganese leaching rate is shown in FIG.

As can be seen from FIG. 4, the manganese leaching rate increases as the sulfuric acid concentration of the acid solution increases, but the manganese leaching rate reaches about 30% even when the sulfuric acid concentration of the acid solution is increased to 6N. Stayed.
On the other hand, the zinc concentration of the leachate separated by the solid-liquid separation was quantified by ICP emission spectrometry. Subsequently, the zinc mass in the leachate was calculated | required based on the fixed value, and the zinc leaching rate was calculated | required by calculating the ratio (zinc element conversion) of the zinc mass in the leachate with respect to the zinc mass in a granular material. As a result, the zinc leaching rate was almost 100% regardless of the acid solution of any sulfuric acid concentration, and it was confirmed that almost all of the zinc contained in the powder was leached into the solution. It was done.

  In addition, for samples with a sulfuric acid concentration of 2N (mass% concentration of about 9.0%), after the acid leaching treatment, the obtained leachate and leach residue were separated by solid-liquid separation by filtering with a filter paper with a pore size of 1 μm, and the separated leach residue After drying at 105 ° C., the chemical components of the leaching residue after drying were analyzed by combustion-infrared absorption (C, S) and ICP emission analysis (other elements). Table 2 shows the chemical components of the leaching residue obtained by the analysis. In addition to the elements shown in Table 2, the leaching residue contains oxygen and some hydrogen derived from oxides and hydroxides.

  As shown in Table 2, the zinc content of the leaching residue was extremely low, less than 1% by mass, and it was confirmed that almost no zinc component was mixed. On the other hand, the manganese content of the leaching residue was about 42% by mass.

(2) Recovery of manganese component An acid solution diluted to a predetermined sulfuric acid concentration was added to the granular material, and an acid leaching treatment was performed. As the acid solution, reagent sulfuric acid was used. The acid leaching treatment was performed while mixing and stirring the powder and the acid solution in the leaching tank. In addition, the scale of acid leaching treatment is small, and the increase in redox potential in the solution due to the dissolution of oxygen in the air during stirring may not be negligible. Processed.

  The amount of acid solution (mL), amount of granular material (g), acid solution sulfuric acid concentration (N), acid leaching time (h), and nitrogen aeration (mL / min) in acid leaching treatment are as follows: is there. In addition, the acid leaching process time shown below is the time measured from the time of mixing a granular material and an acid solution and starting stirring.

Acid solution: 2000mL
Powder: 200g (solid / liquid ratio 100g / L)
Sulfuric acid concentration: 2N (mass% concentration about 9.0%)
Acid leaching treatment time: 1h (stirring treatment)
Nitrogen aeration: 200mL / min

  After the acid leaching treatment, the obtained leachate and the leaching residue were subjected to solid-liquid separation by suction filtration with a filter paper having a pore diameter of 1 μm. The separated leaching residue was dried, and its mass was measured to be about 108 g. On the other hand, ozone treatment was performed on the separated leachate. In the ozone treatment, an air stone was attached to the tip of the ozone supply tube, ozone gas was supplied from the bottom of the container, and the treatment was performed while stirring. The amount of leachate subjected to ozone treatment (mL), the amount of ozone diffused during ozone treatment (L / min), the stirring speed (rpm), and the time of ozone treatment (h) are as follows. The following ozone treatment time is the time from the start point of ozone aeration to the end point of ozone aeration.

Leachate volume: 2000mL
Ozone generator: EZ-OG-R4 (manufactured by Ecodesign)
Ozone generator current: 3.8A
Ozone diffused volume (as ozone and oxygen mixed gas): 1.8L / min (ozone concentration approx. 93g / Nm ³ , ozone action amount 10g / h)
Stirring speed (stirring speed of reaction tank): 260rpm
Ozone treatment time: 3h

  After the ozone treatment, suction filtration was performed with a filter paper having a pore size of 1 μm, and the resulting precipitate was dried at 105 ° C. The chemical composition of the precipitate after drying (mass approx. 35 g) is determined by combustion-infrared absorption method (C, S), ion chromatograph method (Cl), atomic absorption method (Hg), Karl Fischer method (crystal moisture), ICP The results obtained by the emission analysis method (remaining elements) are shown in Table 3. Moreover, the analysis result by XRD (X-ray diffraction) of the precipitate after drying is shown in FIG. Further, in the same manner as in (1) above, the manganese mass in the leachate before the ozone treatment is obtained, and the ratio of manganese mass in the precipitate to the manganese mass in the leachate (in terms of manganese element) is calculated. The manganese recovery rate was determined. Further, in the same manner as (1) above, the zinc mass in the leachate before the ozone treatment is obtained, and the ratio of the zinc mass in the precipitate to the zinc mass in the leachate (in terms of zinc element) is calculated. The zinc recovery rate was also determined. These results are shown in FIG.

As shown in FIG. 5, the precipitate obtained by the ozone treatment was manganese oxide “MnO ₂ ”, and it was confirmed that it was a manganese-containing precipitate. In addition, as shown in Table 3, the precipitate contains water, but the MnO ₂ content of the precipitate in a state where the water is completely removed becomes 97% by mass or more, and high purity is obtained through ozone treatment. It was found that the manganese oxide was obtained. Furthermore, as shown in Table 3, the zinc content of the precipitate was less than 1% by mass.

  Moreover, as shown in FIG. 6, 99.9% of manganese dissolved in the leachate can be recovered as a precipitate by performing ozone treatment. As described above, in the manganese recovery method of the present invention, a part of the manganese component contained in the waste dry battery (powder particles) is leached during the acid leaching treatment, but the manganese solution dissolved in the leachate by performing the ozone treatment. Almost the entire amount can be recovered as a manganese-containing precipitate (manganese oxide). Therefore, according to the manganese recovery method of the present invention, the manganese component can be recovered with an extremely high recovery rate by recovering the leaching residue obtained during the acid leaching treatment and the precipitate obtained during the ozone treatment.

From the above, it can be seen that the manganese recovery method of the present invention is an extremely excellent recovery method with no problem in terms of recovery rate (yield).
Furthermore, as shown in FIG. 6, in the precipitate obtained by the ozone treatment, only 0.1% of the zinc dissolved in the leachate was recovered, and almost all the zinc contained in the granular material was treated with the ozone treatment. It was confirmed that it was present in the later solution. Therefore, according to the manganese recovery method of the present invention, it is possible to recover a manganese-containing substance with a very small amount of zinc contamination by recovering the leaching residue obtained during the acid leaching treatment and the precipitate obtained during the ozone treatment. .

  Moreover, as shown in Table 3, among the metal elements contained in the precipitate obtained by the ozone treatment, all metal elements other than manganese, zinc, iron and potassium were below the lower limit of quantification. The reason why the content of metal elements other than manganese, zinc, iron, and potassium is not more than the lower limit of quantification is that the content in the waste dry battery (in the granular material) is originally very small. However, from the results of this example, it was found that metal elements other than manganese, zinc, and iron hardly precipitated by the ozone treatment and hardly mixed into the precipitate obtained by the ozone treatment.

  Moreover, as shown in Table 3, the precipitate (manganese oxide) obtained by the ozone treatment contains sulfur that seems to be derived from sulfuric acid. Thus, although the content rate of sulfur and potassium was slightly high, it was confirmed separately that the precipitate was easily reduced to about 0.1% by washing with water. However, for example, in the case where the precipitate (manganese oxide) is recovered after being recovered as a manganese component, sulfur and potassium in the precipitate are considered to be mostly volatilized or removed as slag. What is necessary is just to select suitably the presence or absence, the grade, etc. of water washing from the removal amount, sulfur required for the reduced manganese body, potassium content and the like. The water contained in the precipitate is water that does not volatilize at 105 ° C. and is crystal water that has entered the crystal of the manganese oxide. In manganese crystals, most of the water of crystallization is desorbed at temperatures up to about 300-400 ° C, so if a high degree of water removal is required, low moisture manganese oxides can be obtained by drying at about 300-400 ° C. Can be obtained.

  In this example, a relatively long ozone treatment time of about 3 hours was required to recover almost all the manganese dissolved in the leachate before the ozone treatment as an oxide. This is because the reaction system of this example is small at the laboratory level, and a large amount of unreacted ozone escapes to the upper part of the reaction vessel, and the diffused ozone is not efficiently used. Guessed. Therefore, when applying the present invention to an actual machine, by devising the reaction vessel shape of the ozone treatment device, or by applying a technology such as microbubbles or nanobubbles to the ozone treatment device, the bubble diameter is reduced, It is preferable to increase the dissolution efficiency of ozone in the leachate. If these measures are taken to increase the utilization efficiency of ozone, the ozone treatment time can be shortened and the amount of ozone used can be reduced.

(3) Recovery of zinc component In (2) above, sodium hydroxide is added to the filtrate (zinc ion-containing solution) obtained by suction filtration with a filter paper having a pore size of 1 μm after ozone treatment, and the pH of the filtrate Was raised to 10.8 to make it alkaline, and the filtrate was made into an alkaline solution to carry out an alkali precipitation treatment to obtain a yellowish white precipitate. Next, the obtained precipitate was washed with water, dried at 105 ° C., and then collected.

  As a result of analyzing the precipitate (recovered zinc component) after drying by XRD (X-ray diffraction), it was confirmed that the precipitate mainly contained an oxide of zinc. Table 4 shows the results of analysis of the chemical components of the dried precipitate (64 g) by combustion-infrared absorption (C, S) and ICP emission analysis (remaining elements). The precipitate shown in Table 4 contains oxygen and hydrogen derived from oxides and hydroxides in addition to the elements shown in Table 4.

  As shown in Table 4, the zinc content of the precipitate was 74.0%, indicating that it contained a high concentration of zinc. Usually, in the alkaline precipitation treatment, a hydroxide of zinc is detected, but the zinc of the precipitate obtained this time was an oxide. This is presumed that when dried at 105 ° C., a dehydration reaction occurred and the hydroxide changed to an oxide. In actual operation, it remains as a dehydrated cake or as a hydroxide if dried without application of temperature, but can be recovered as an oxide if dried at about 105 ° C. Therefore, the recovery method may be appropriately selected according to the subsequent usage, purpose and cost.

  The chemical components of the leaching residue obtained in (2) above were determined by combustion-infrared absorption method (C, S) and ICP emission analysis method (remaining elements). Next, the chemical components in the case where the leaching residue and the manganese-containing precipitate obtained in (2) above are mixed to form a mixture are the mass and chemical component of the leaching residue, and the mass and chemical component of the manganese-containing precipitate. Calculated from (see Table 3). The chemical components of the mixture are shown in Table 5. Note that the mixture shown in Table 5 contains oxygen and hydrogen derived from oxides and hydroxides, although the content is not measured.

  The mass of manganese contained in the mixture was calculated from the total mass of the leaching residue and manganese-containing precipitate obtained in (2) above and the chemical components of the mixture determined above. And the manganese component recovery rate from a granular material was calculated | required by calculating the ratio (manganese element conversion) of the manganese mass contained in the mixture with respect to the manganese mass contained in a granular material. Moreover, the mass of zinc contained in the zinc component recovered material was calculated from the precipitate obtained in (3) above, that is, the mass and chemical component of the zinc component recovered material. And the zinc component recovery rate from a granular material was calculated | required by calculating the ratio (zinc element conversion) of the zinc mass contained in the zinc component recovery material with respect to the zinc mass contained in a granular material. The recovery rates determined as described above are shown in Table 6 together with main chemical components of the mixture (manganese component recovered material) and the zinc component recovered material.

  Further, in the same manner as above, by calculating the ratio of manganese mass contained in the leaching residue with respect to the manganese mass contained in the granular material (in terms of manganese element), the recovery rate of manganese recovered as the leaching residue is calculated. Asked. Moreover, the recovery rate of the zinc collect | recovered as a leaching residue was calculated | required by calculating the ratio (zinc element conversion) of the zinc mass contained in the leaching residue with respect to the zinc mass contained in a granular material. Regarding the manganese-containing precipitate obtained in (2) above, in the same manner as described above, the ratio (recovery rate) at which manganese contained in the powder is recovered as the manganese-containing precipitate is determined, and the powder The ratio (recovery rate) at which zinc contained in the body was recovered as a manganese-containing precipitate was determined. The recovery rates determined above are shown in Table 6 together with the main chemical components of the leach residue and manganese-containing precipitate.

  As is clear from the results in Table 6, according to the present invention, manganese in the granular material obtained by crushing and sieving selected waste dry batteries (manganese dry batteries and / or alkaline manganese dry batteries) and While almost completely separating zinc, it is possible to recover almost the entire amount of both elements and to recycle them as manganese raw materials and zinc raw materials.

1… Sorting process
2… Crushing / sieving process
3… Acid leaching process
4 ... 1st solid-liquid separation process
5… Ozone treatment process
6 ... Second solid-liquid separation process
7… Mixing process
8… Alkaline precipitation treatment process
9… Third solid-liquid separation process
10… Sorting device
20a… Crusher
20b ... Sieving device
30… Acid leaching tank
40 ... 1st solid-liquid separator
50… Ozone treatment equipment
60 ... Second solid-liquid separator
70a… Leach residue collection tank
70b… Manganese-containing precipitate collection tank
70c… Mixture recovery tank
80… Alkaline precipitation tank
90… Third solid-liquid separator
100… Zinc component recovery tank

Claims (10)

  A method for recovering a manganese component contained in a waste battery from a waste battery, comprising a sorting step for sorting a manganese battery and / or an alkaline manganese battery from a waste battery, and crushing and sieving the waste battery selected in the sorting step Crushing and sieving step to obtain powder particles, and acid leaching step to obtain an leaching solution containing manganese and zinc and a leaching residue containing manganese by performing acid leaching treatment on the powder particles using an acid solution And a first solid-liquid separation step for solid-liquid separation of the leachate obtained in the acid leaching step and the leach residue, and ozone is allowed to act on the leachate separated in the first solid-liquid separation step. An ozone treatment step of oxidizing and precipitating manganese ions contained in the solution to obtain a manganese-containing precipitate and a zinc ion-containing solution, and the manganese-containing precipitate and zinc ion obtained in the ozone treatment step. A second solid-liquid separation step for solid-liquid separation of the contained solution, the manganese component contained in the waste dry battery as the leaching residue and the manganese-containing precipitate, and the zinc component contained in the waste dry battery as the zinc A method for recovering manganese from a waste dry battery, wherein the manganese-containing precipitate is recovered as a manganese component after being separated as an ion-containing solution.   The acid solution in the acid leaching step is dilute sulfuric acid having a mass% concentration of 1.4% to 45% or dilute hydrochloric acid having a mass% concentration of 1% to 14%. Manganese recovery method.   The method for recovering manganese from a waste dry battery according to claim 1 or 2, wherein the solid-liquid ratio of the powder and the acid solution in the acid leaching step is 50 g / L or more. Mixing the separated leaching residue and the manganese-containing precipitate to provide a mixture step of the leaching residue and the manganese-containing precipitate, and the mixture into the separated manganese-containing precipitate. 4. The method for recovering manganese from the waste dry battery according to any one of claims 1 to 3, wherein the manganese component is recovered as a manganese component .   A method for recovering zinc components contained in a waste battery from a waste battery, comprising a sorting step for sorting manganese batteries and / or alkaline manganese batteries from a waste battery, and crushing and sieving the waste batteries selected in the sorting step Crushing and sieving step to obtain powder particles, and acid leaching step to obtain an leaching solution containing manganese and zinc and a leaching residue containing manganese by performing acid leaching treatment on the powder particles using an acid solution And a first solid-liquid separation step for solid-liquid separation of the leachate obtained in the acid leaching step and the leach residue, and ozone is allowed to act on the leachate separated in the first solid-liquid separation step. An ozone treatment step of oxidizing and precipitating manganese ions contained in the solution to obtain a manganese-containing precipitate and a zinc ion-containing solution, and a manganese-containing precipitate and a zinc ion-containing solution obtained in the ozone treatment step. A second solid-liquid separation step for solid-liquid separation of the solution, the manganese component contained in the waste dry battery as the leaching residue and the manganese-containing precipitate, and the zinc component contained in the waste dry battery as the zinc ion After separating as a containing solution, an alkaline agent is added to the separated zinc ion-containing solution to make zinc ions in the zinc ion-containing solution into a zinc-containing precipitate, and the alkaline precipitation treatment step And a third solid-liquid separation step for solid-liquid separation of the zinc-containing precipitate obtained in step 3, and recovering the zinc-containing precipitate separated in the third solid-liquid separation step as a zinc component Zinc recovery method from waste dry batteries. Acid solution in the acid leaching step, from waste battery according to claim 5, characterized in that the weight percent concentration of 1.4% or more and 45% or less of dilute sulfuric acid or by mass% concentration of 1% to 14% or less of dilute hydrochloric acid Zinc recovery method. The method for recovering zinc from a waste dry battery according to claim 5 or 6 , wherein the solid-liquid ratio of the granular material and the acid solution in the acid leaching step is 50 g / L or more .   A facility for separating a manganese component and a zinc component contained in a waste battery from a waste battery, a sorting device for sorting a manganese battery and / or an alkaline manganese battery from a waste battery, and a waste battery sorted by the sorting device Using a crushing device to obtain a crushed product, a sieving device for obtaining a granule by sieving the crushed product obtained by the crushing device, and an acid solution An acid leaching tank obtained by subjecting the granular material to an acid leaching treatment to obtain a leaching solution containing manganese ions and zinc ions and a leaching residue containing manganese, and a leaching solution and a leaching residue obtained in the acid leaching bath. A first solid-liquid separation device for solid-liquid separation, and ozone is allowed to act on the leachate separated by the first solid-liquid separation device to oxidize and precipitate manganese ions contained in the leachate. And an ozone treatment device for obtaining a zinc ion-containing solution, and a second solid-liquid separation device for solid-liquid separation of the manganese-containing precipitate obtained from the ozone treatment device and the zinc ion-containing solution. Manganese and zinc separation equipment from waste dry batteries. A facility for recovering manganese components contained in the waste dry battery from the waste dry battery, comprising the facility for separating manganese and zinc from the waste dry battery according to claim 8 . An apparatus for recovering zinc components contained in the waste dry battery from the waste dry battery, wherein the manganese and zinc separation equipment from the waste dry battery according to claim 8 and the second solid-liquid separator of the manganese and zinc separation equipment The separated zinc ion-containing solution is stored, and the zinc ion-containing solution is subjected to an alkaline precipitation treatment to obtain a zinc-containing precipitate, and the zinc-containing precipitate obtained in the alkaline precipitation treatment vessel is obtained. A facility for recovering zinc from waste dry batteries, comprising a third solid-liquid separator for solid-liquid separation.

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