JPWO2018168472A1 - Method of producing metallic manganese - Google Patents

Abstract

A method for producing high-grade metallic manganese, which comprises subjecting a granular material (Mn-containing substance) to a water-washing treatment, dissolving chlorine contained therein in water, and then subjecting it to solid-liquid separation treatment to separate and remove chlorine. Get a minute. The obtained solid content is subjected to a drying process, and then the solid content subjected to the drying process is mixed with a flux, charged into an arc melting furnace, electrically energized and heated, and the solid content is mixed. Slag manganese. Next, the molten slag obtained by slagging is transferred to a ladle, and a reducing agent and flux are charged into the ladle to reduce the molten slag and perform reduction treatment to convert it into molten metal (manganese metal). Thereby, high quality metallic manganese can be manufactured. In addition, it is preferable to classify | select the manganese dry battery and / or the alkaline manganese dry battery from a waste dry battery, and to set it as the granular material obtained by grind | pulverizing and sieving the Mn containing material used as a raw material.

Description

  The present invention relates to a method for producing metallic manganese (hereinafter also referred to as metallic Mn), and more particularly to a method for producing high-grade metallic manganese using a manganese-containing substance recovered from a waste dry battery or the like as a raw material.

  In the steel field, manganese is an element which has conventionally been widely used as a useful element, and has recently become an important element particularly in the production of high-tensile steel sheets for automobiles.

  As manganese used in the steel field, high purity manganese is required when used in the component adjustment stage which is the final stage of steel product manufacture. For this reason, usually the manganese used at this stage is electrolytic metallic manganese produced by the electrolysis method. The electrolysis method is a method of dissolving manganese raw material (manganese source) such as manganese ore with acid such as sulfuric acid, removing impurities by solvent extraction, etc. and then electrolyzing it to metal manganese, which is a high purity metal Manganese can be obtained. However, this method is expensive in electrolysis cost, and the electrode plate can not be enlarged due to problems such as peeling, and it is difficult to automate and requires manual work, and the wastewater treatment of selenium added to enhance electrolytic efficiency There are various problems, such as the difficulty of manufacturing, and the establishment of alternative manufacturing methods is required.

  As a general production method of metallic manganese other than the electrolysis method, there are blast furnace method, thermit method and the like. The blast furnace method is a method in which manganese ore, which is a manganese raw material (manganese source), is charged together with coke into a blast furnace and refined, and can be manufactured relatively inexpensively, but it contains impurities such as silicon and carbon, and powder There are problems that it is difficult to use the raw materials of the above, and that the raw materials containing highly volatile substances such as zinc, sodium and potassium can not be used. Further, the thermit method is a method of obtaining metal manganese by mixing a metal such as magnesium or aluminum with a manganese raw material (manganese source) such as manganese ore to obtain metallic manganese, but such as magnesium or aluminum Since expensive metals are used for reduction and heating, there is a problem that the manufacturing cost is increased and it is economically disadvantageous. Under such circumstances, industrial production of metallic manganese is currently performed only by the electrolysis method.

  In addition, manganese ores such as manganese oxide ore and manganese carbonate ore are generally used as manganese raw materials (manganese source) in the production of manganese metal, but these natural resources are limited, There is a risk of exhaustion. In particular, since steelmaking plants consume a large amount of manganese as a steelmaking raw material, securing of a manganese source is an extremely important problem also in the steelmaking field. In recent years, the price of manganese ore, which is a raw material, tends to rise due to its depletion.

  In recent years, attempts have been made to actively recover manganese from low-grade ore, concentrate, by-products from steel mills, industrial waste, etc., due to such exhaustion of metal resources and rise in transaction prices. It is done. For example, some dry batteries disposed as industrial waste have a high manganese content. Manganese dry batteries and alkaline manganese dry batteries that are representative of primary batteries use manganese dioxide as a positive electrode material. Therefore, if it is possible to establish a technology for recovering manganese from these waste dry batteries and reusing it as a steelmaking raw material, it is expected to effectively contribute to securing a manganese source. In addition, a huge amount of dry cells are produced, consumed and discarded all over the world. In the dry battery, zinc is used as a negative electrode material.

  However, under the present circumstances, recovery of part of zinc by a zinc smelting maker or recovery of part of iron or carbon by an arc melting furnace maker is performed from a manganese dry cell or an alkaline manganese dry cell discarded after the end of discharge. It can not be said that resource recycling has been carried out sufficiently. Under the present circumstances, many resources are used for landfill processing as waste materials without being recycled without being used.

  Therefore, various techniques have recently been proposed to recover not only zinc, iron and carbon but also manganese from waste batteries.

  In Patent Document 1, a step of sorting manganese batteries and alkaline manganese batteries from waste dry batteries, a step of crushing and sieving to obtain powder particles, and dissolving the obtained powder particles with dilute hydrochloric acid or dilute sulfuric acid are carried out. A process for the recovery of manganese dioxide and carbon-containing mixtures having a step is described. According to the technique described in Patent Document 1, it is possible to simultaneously recover manganese dioxide and a carbon component simultaneously without causing a large loss, and the recovered mixture can be used as a starting material for producing ferromanganese. There is.

  Patent Document 2 describes a method of separating and collecting manganese dioxide and zinc chloride from a waste dry battery. According to the technology described in Patent Document 2, a material containing a large amount of manganese and zinc is obtained from waste dry batteries, which is washed with water if necessary and then dissolved in hydrochloric acid, and the solution is purified by removing impure components and heated. Concentrate, add perchloric acid to the concentrate and heat to obtain a solid mixture of manganese dioxide and zinc chloride, dissolve the solid mixture in water and filter, separate and collect manganese dioxide and zinc chloride from the waste dry battery How to According to the technology described in Patent Document 2, the obtained zinc chloride is dissolved in an organic solvent to remove the mixed insoluble alkali metal salts, thereby purifying zinc chloride. Also, it is said that the recovered manganese dioxide and zinc chloride have a purity which can be used again for dry battery manufacture.

  Patent Document 3 describes a metal recovery method. The technology described in Patent Document 3 causes iron reducing bacteria to act on the group consisting of metal oxides and metal hydroxides, reduces trivalent iron to divalent iron, and uses the obtained divalent iron. , Leaching metals such as cobalt, nickel, manganese, etc., which are included in the group consisting of metal oxides and metal hydroxides, to form a leaching solution and a residue, separate the obtained leaching solution and the residue, and obtain a desired metal It is a metal recovery method to recover. As a group consisting of metal oxides and metal hydroxides, wastes such as deep-sea bottom mineral resources, metal-containing oxide minerals (land minerals), metal-containing incineration residues and the like are mentioned. According to the technique described in Patent Document 3, low-grade metals contained in metal oxides and metal hydroxides can be recovered at high speed and high efficiency. In addition, metals such as cobalt, nickel and manganese contained in the leachate can be recovered using a conventional method.

  Patent Document 4 describes a method of producing metallic manganese. In the technique described in Patent Document 4, a manganese oxide-containing substance is charged together with a reducing agent in a heating furnace, and heating is performed until the furnace temperature in the heating furnace reaches 1200 ° C. or more to reduce manganese oxide, and then 700 ° C. It is a manufacturing method of metallic manganese which cools to the following and discharges it out of the furnace. In the technology described in Patent Document 4, a waste dry battery, manganese ore or the like can be used as the manganese oxide-containing substance, and a carbon-based reducing agent such as coal, coke, graphite or the like is used as the reducing agent.

  Patent Document 5 describes a method of separating manganese and zinc from a waste dry battery. The technology described in Patent Document 5 selects manganese dry batteries and / or alkaline manganese dry batteries from waste dry batteries, crushes the selected dry batteries, and sifts them into powder and granules, using an acid solution for the powder and granules. An acid leaching treatment is performed to obtain a leaching solution from which manganese and zinc are leached, and a leaching residue containing manganese, solid-liquid separation, and then ozone is applied to the separated leachate to obtain manganese-containing precipitates and zinc ions A solution containing solid solution is obtained, solid-liquid separation is carried out, the manganese component contained in the waste dry battery is used as a leaching residue and a manganese containing precipitate, and the zinc component contained in the waste dry battery is separated as a zinc ion containing solution It is a manganese and zinc separation method.

Japanese Patent Application Publication No. 2007-12527 Unexamined-Japanese-Patent No. 11-191439 JP 2007-113116 A JP, 2011-94207, A JP, 2015-206077, A

  However, in the Mn-containing material recovered by each technique described in Patent Documents 1 to 3, the contained Mn is considered to be an oxide or a hydroxide, and can be used, for example, as an iron-making material. There is a problem that further reduction of Mn is required to achieve the state, the manufacturing process becomes complicated, and as a result, the cost becomes high. Manganese is by no means an expensive metal as a rare metal, and an increase in manufacturing cost hinders the practical application of the technology. In the technique described in Patent Document 3, there is a problem that the culture medium of the microorganism and the drug added as a complexing agent serving as a nutrient source of the microorganism are expensive. In addition, metal Mn manufactured by the technique described in Patent Document 4 often has a high carbon content (concentration) due to residual carbon used as a reducing agent, and the quality as metal Mn is lowered. There's a problem. Further, in the technology described in Patent Document 5, at present, equipment for generating ozone (ozone generation equipment) is expensive, and a large amount of power is required. On, I'm leaving a problem.

  The present invention solves the problems of the prior art and provides a method for producing metallic manganese which can be easily and inexpensively and easily produce metallic manganese comparable to electrolytic metallic manganese which can be used as a raw material for iron making. The purpose is

  The present inventors diligently studied the method of improving the grade of metallic manganese in order to achieve the above-mentioned purpose. As a result, if a manganese-containing substance is charged into an electric furnace (as a typical example, an arc melting furnace) together with a reducing agent and a flux, and reduction processing is performed in the electric furnace, it can be used as a substitute for electrolytic metal manganese. It was conceived that high purity manganese could be produced inexpensively. Furthermore, according to this method, it was also found that "a substance obtained by sorting, crushing and sieving waste dry batteries" (powder and powder) can be used as it is as a manganese source (manganese-containing substance). However, powder and granules obtained by sorting, crushing and sieving waste dry batteries may contain zinc and carbon in addition to manganese as main components, and may further contain chlorine. Found out.

  Therefore, if the powder and granular material (manganese-containing material) is subjected to heat treatment as a pretreatment, the carbon contained in the "manganese-containing material" (powder and granular material) can be burned off and removed, and the electric furnace thereafter It was conceived that the grade of the metallic manganese obtained by the reduction treatment in can be easily improved. In addition, at the time of a reduction process, the zinc contained in granular material is reduce | restored and it becomes a metal body (metallic zinc). It was also found that zinc contained in the granular material can be volatilized and removed at the time of reduction because the boiling point of metallic zinc is low.

  Furthermore, in the case where chlorine is contained in the manganese-containing substance (particulate matter), the present inventors are concerned about the generation of harmful substances during reduction treatment or heat treatment, and therefore manganese is pretreated as a pretreatment. It has been found that it is necessary to apply a treatment to remove chlorine to the contained substance (particulate matter). The inventors of the present invention have further found that it is effective to subject a manganese-containing substance (particulate matter) to a water-washing treatment as the "treatment for removing chlorine".

  Thus, the present inventors give each component other than manganese contained in the manganese-containing material (waste dry battery powder) by subjecting the manganese-containing material (waste dry battery powder) to the above-mentioned pretreatment in advance. Have been easily separated and removed, and it has been found that high quality (high purity) metallic manganese can be manufactured (recovered) at low cost.

  The present inventors have found that it is necessary to reduce the contamination of metallic manganese in the reduction treatment as much as possible in order to produce a further high grade of metallic manganese. Therefore, the present inventors charge a manganese-containing material together with a flux into an arc melting furnace prior to the reduction step, and apply a slag production step of slagging the manganese component, and thereafter, the manganese which has been slagged (manganese (manganese) It was conceived to carry out a reduction step to reduce slag). According to this, it has been found that the contamination of the molten metal manganese (molten metal) is less and the grade of the obtained metal manganese can be further improved.

The present invention has been completed based on such findings, with further studies. That is, the gist of the present invention is as follows.
[1] A method for producing metallic manganese, which obtains metallic manganese by reducing a manganese-containing substance,
The manganese-containing substance is subjected to a water washing process in which water is added and washed as a slurry,
Then, the slurry washed with water is subjected to solid-liquid separation treatment to separate solid content,
The obtained solid content is heated to be subjected to a drying treatment for removing water contained in the solid content,
The dried solid content is charged into an electric furnace together with a flux, and heating is performed by energization in the electric furnace to perform a slag production process using manganese in the solid content as a manganese slag.
A method for producing metallic manganese, which transfers the manganese slag obtained by the slag production process to a ladle, puts a reducing agent into the ladle, and reduces the manganese slag to obtain metallic manganese.
[2] The method for producing metallic manganese according to [1], wherein the manganese-containing substance is a substance obtained by sorting, crushing and sieving a waste dry battery.
[3] The method for producing metallic manganese according to [1] or [2], wherein the ratio of solid content to liquid in the slurry in the water washing treatment is 1:10 to 5:10 in mass ratio.
[4] The method for producing metallic manganese according to any one of [1] to [3], wherein the water washing time in the water washing treatment is 15 minutes or more.
[5] The method for producing metallic manganese according to any one of [1] to [4], wherein the reducing agent used in the reduction treatment is metallic aluminum and / or metallic silicon.
[6] The method for producing metallic manganese according to any one of [1] to [5], wherein the flux used in the slag production process or the reduction process is a substance containing CaO as a main component.

  According to the present invention, metal manganese that can replace electrolytic metal manganese can be manufactured inexpensively, and has an industrially significant effect.

FIG. 1 is an explanatory view showing the flow of the method for producing metallic manganese of the present invention.

Means for carrying out the invention

  The present invention is a method for producing metallic manganese, wherein a manganese-containing substance is used as a raw material, and the raw material is subjected to reduction treatment to give metallic manganese. In the present invention, the manganese-containing material used as the raw material is not particularly limited, but it is preferable to use a material containing 10% by mass or more of manganese, 0.03% by mass or more of zinc, and 0.1% by mass or more of carbon. Furthermore, it is preferable to use the powdery granular material (waste dry battery granular material) obtained by sorting the waste dry battery, crushing and sieving.

  The term "sorting" as used herein refers to a process of sorting alkaline dry batteries and / or alkaline manganese dry batteries from waste dry batteries. In this "sorting" step, an alkaline dry battery and / or an alkaline manganese dry battery are sorted out of the discarded and recovered dry batteries. The sorting method is not particularly limited as long as it is a method that can exclude mercury dry batteries, Ni-Cd batteries, etc., and any commonly used methods such as hand sorting, machine sorting using shape, radiation, etc. may be used. .

  In addition, “crushing” as used herein refers to a process of crushing the selected alkaline dry battery and / or alkaline manganese dry battery. A crusher is usually used to crush the sorted waste dry batteries. Although there is no need to particularly limit the type of crusher, a crusher of a type in which the packaging material or the like constituting the dry battery and the powder particles are well separated after crushing, for example, a twin-screw rotary crusher Is preferred.

When these dry batteries are crushed, packaging materials (iron, plastic, paper, etc.), zinc cans that are negative electrode materials of manganese dry batteries, and brass rods that are current collectors of alkaline manganese dry batteries are in the form of foil or flakes. It becomes a thing. On the other hand, manganese dioxide which is a positive electrode material of a manganese dry battery, a carbon rod which is a current collector of the manganese dry battery, zinc powder which is a negative electrode material of an alkaline manganese dry battery, MnO (OH), Zn (OH) ₂ and Mn produced by discharge (OH) ₂ , ZnO, etc., and various electrolytic solutions become finer powder particles than the above-described foil-like and flake-like solid substances.

Therefore, if the sorted waste dry batteries are crushed and then sieved using a sieve with a predetermined opening, large solid substances such as packaging materials are removed from the sorted waste dry batteries, and the main components of manganese dry batteries and / or alkaline manganese dry batteries Powder composed of manganese dioxide, carbon, zinc chloride or ammonium chloride, iron, potassium hydroxide, MnO (OH), Zn (OH) ₂ , Mn (OH) ₂ , ZnO etc. produced by discharge which are constituent materials Granules (waste dry battery granules) can be obtained. In addition, it is preferable to set it as about 1 mm or more and 20 mm or less, and more preferably about 1 mm or more and 10 mm or less of the mesh size of the sieve used for sieving of a crushed material.

  The obtained waste dry battery powder contains manganese, zinc, and carbon as main components (elements), and further contains a certain amount of chlorine. Therefore, in the case of producing metallic manganese using waste dry battery powder as a raw material, the degree of separation and removal of zinc, carbon and chlorine becomes important. The flow of the method for producing metallic manganese of the present invention is shown in FIG.

  In the present invention, as a pretreatment, the manganese-containing material (waste dry battery powder) is subjected to water washing treatment, solid-liquid separation treatment, and drying treatment in this order before pretreatment.

  First, as a pretreatment, the manganese-containing material (waste dry battery powder) as a raw material is subjected to water washing treatment. In the water washing process, water is added to the manganese-containing substance (waste dry battery powder) to form a slurry, and the slurry is washed with water. Specifically, it is preferable that the water washing process be a process in which a manganese-containing substance (waste dry battery particles) is charged into a container, water is added to form a slurry, and stirring is performed for a predetermined time. As a result, chlorine contained in the manganese-containing material (waste dry battery powder) can be dissolved in the added water, and chlorine can be removed from the manganese-containing material (waste dry battery powder).

  In the water washing treatment in the present invention, the ratio of the amount of water added to the amount of the manganese-containing substance (waste dry battery powder), that is, the solid-liquid ratio is preferably 5:10 or less in mass ratio. If the amount of solid manganese-containing material (waste dry battery powder) is increased beyond the solid-liquid ratio described above, handling as a slurry becomes difficult. On the other hand, when the amount of solids is reduced and the solid-liquid ratio is reduced, the container for washing needs to be enlarged, which is economically disadvantageous. Therefore, the solid-liquid ratio is preferably in the range of 1:10 to 5:10, and more preferably 1:10 or more and 3:10 or less.

  In addition, it is preferable that the time of the water washing process be 15 minutes (hereinafter referred to as "min") or more in order to ensure dissolution of chlorine in water. In addition, since washing with water for a long time is economically disadvantageous such as an increase in the size of the container, it is preferable to set the washing time to about 1 hour (hereinafter referred to as "hr") or less.

  Next, solid-liquid separation treatment is performed on the manganese-containing material (waste dry battery powder) subjected to the water washing treatment. The manganese-containing substance (waste dry battery granular material) after the water washing treatment is separated into solid content and separated liquid (water) by solid-liquid separation treatment. The separated liquid (water) contains dissolved chlorine, whereby the contained chlorine can be separated and removed from the manganese-containing substance (waste dry battery powder). The solid-liquid separation treatment in the present invention can be carried out using a commonly used method such as gravity sedimentation, centrifugal filtration, filter press, membrane separation and the like.

  Next, the solid content obtained through the water washing treatment-solid-liquid separation treatment is subjected to a drying treatment. The drying process is a process of removing water in the solid content obtained through the water washing process-solid-liquid separation process. The drying treatment is not particularly limited as long as the treatment can remove water in the solid content and can be 0.1 mass% or less, which is the concentration of water that can be introduced into the electric furnace. Specifically, it is preferable to charge the solid content obtained through the water-washing treatment-solid-liquid separation treatment into a drying furnace or the like heated to a temperature of about 300 to 600 ° C., and hold for 30 minutes or more .

  The solid content (manganese-containing material) obtained through the water washing treatment-solid-liquid separation treatment-drying treatment is then subjected to a slag production treatment. The slag production process is a process using an electric furnace. Here, an arc melting furnace is a typical example of the electric furnace to be used, but in addition, a resistance furnace, an induction melting furnace, or the like can be used. Hereinafter, the electric furnace is described as an arc melting furnace. Moreover, it is preferable to set it as a tiltable furnace for the discharge of the produced | generated molten slag.

The solid content (manganese-containing substance) obtained through the drying treatment is mixed with a trace amount of metal manganese as a current-carrying material and a flux (a steel making agent), and is charged into an arc melting furnace. Then, the charged raw material is heated and melted by energization through a graphite electrode of an arc melting furnace. At this time, the temperature of the molten metal (the molten metal is referred to as “molten metal” or “molten metal”) is 1600 ° C. or higher. Manganese contained in the manganese-containing substance becomes MnO.Mn ₂ O ₃ (generally Mn ₃ O ₄ ) at 800 ° C. or higher, and thus manganese contained in the manganese-containing substance heated to the above temperature is a slag component It becomes. Also, most of the carbon contained in the manganese-containing material is burned off. At this time, carbon partially reduces contained manganese and zinc. In addition, most of the reduced zinc is metal zinc, but since the boiling point of metal zinc is 907 ° C., metal zinc becomes gas and evaporates (volatilizes). The evaporated zinc rapidly reacts with oxygen in the air to form zinc oxide, which is captured as dust and collected by a bag filter.

  In addition, most of the contained carbon is burned and removed, but since it has affinity with the metal component rather than the slag component, part of the carbon is further reduced by the molten metal manganese charged for current conduction. It is contained in some molten manganese. Here, high-grade metallic manganese can be used as a final component modifier of manganese steel, and specifically, the Mn + Al concentration is 90% by mass or more, the carbon (C) concentration is 0.2% by mass or less, It means that the phosphorus (P) concentration is 0.05% by mass or less and the sulfur (S) concentration is 0.05% by mass.

  As described above, in the slag production process, most of the manganese in the solid content (manganese-containing material), which is the raw material, is a slag component and a part is a metal component. In addition, most of the carbon contained in the solid content (manganese-containing substance) is burned off, only a part is present in the metal component, and hardly present in the slag component. In addition, most of the zinc contained in the solid content (manganese-containing substance) is removed by evaporation.

Next, a reduction treatment is performed. In the reduction step, first, the arc melting furnace which has completed the slag production process is tilted, and only the slag component obtained in the slag production process is moved to another pan (ladle), and the metal component is left in the arc melting furnace. This makes it possible to separate manganese and carbon. The metal component left in the arc melting furnace can be repeatedly used as a current-carrying metal material in the next slag production process. If it is necessary to adjust the reducing agent and the CaO / Al ₂ O ₃ ratio to the slag component transferred to the ladle, mix the flux (foil making agent) and reduce the slag component in the ladle, Obtain molten metal manganese. In the reduction of manganese, it is preferable from the viewpoint of reaction promotion that stirring is performed by a common method such as bubbling argon gas or the like. The reduction reaction proceeds due to the heat capacity held by the slag component and the reaction heat of the reducing agent, but may be heated by means such as arc discharge if the heat quantity is insufficient. Thereby, the molten slag becomes a molten metal manganese, and high-grade manganese can be recovered.

  As the reducing agent used in the reduction step of the present invention, metal aluminum, metal silicon and carbon can be exemplified, but in the case of producing high grade metal manganese, carbon easily mixed in metal manganese (product) is high grade It is not suitable as a reducing agent for producing metallic manganese, and metallic aluminum and / or metallic silicon is preferable. Note that inexpensive ferrosilicon can also be used instead of metal silicon. In that case, the iron concentration in the product (metallic manganese) is high, but when it is used as a steelmaking raw material, iron can be used as metallic manganese because it does not become an impurity.

  In addition, in the reduction step of the present invention, when metal aluminum and / or metal silicon is used as the reducing agent, so-called divided charging is performed in which the metal aluminum and / or metal silicon which is the reducing agent is divided in plural times. It is preferable to set it. As a result, heat generation due to the aluminum thermite reaction can be made uniform, excessive heating can be prevented, evaporation (blowing loss) of the molten metal (metal Mn) can be suppressed, and the Mn yield can be improved. In addition, in the case of partial charging of the reducing agent, it is preferable to separately charge the flux in order to make the reaction uniform.

  The blending amount of the reducing agent should be at least the amount (theoretical reduction equivalent) of the reducing agent necessary to completely carry out the reduction reaction using manganese as the metal manganese, as an oxide contained in the manganese slag or as a hydroxide. Needless to say, it is preferable to examine the appropriate amount in advance by experiment.

The flux used in the slag production process and the reduction process of the present invention preferably contains CaO as a main component. As a substance which has CaO as a main component, quick lime, limestone, slaked lime can be illustrated. The amount of the flux, CaO / _Al 2 _{O 3} ratio, adjusted with. Although the CaO / Al ₂ O ₃ ratio is 0.55, good progress of the reaction can be obtained if it is within the range of about 0.4 to 1.0. If it is less than 0.4, manganese oxide in the slag can not be reduced, and if it exceeds 1.0, the amount of free quick lime will be large, the melting point of the slag will be too high, and the amount of slag will be too large. For this reason, the amount of flux, and flux amount in terms of CaO, the ratio of the amount of reducing agent in terms of oxide (mass ratio), with CaO / _Al 2 _{O 3} ratio 0.4 to 1. It is preferable to adjust so as to be in the range of 0.

  Hereinafter, the present invention will be further described based on examples.

  Manganese dry batteries and / or alkaline manganese dry batteries are sorted from waste batteries, and the sorted waste batteries are crushed using a twin-screw rotary crusher, and sieved with an opening of 3 mm, Waste dry battery particles were obtained. The composition of the obtained granular material is shown in Table 1. In addition to the elements shown in Table 1, the obtained granular material contains oxygen and moisture derived from oxides and hydroxides.

  First, 50 g of the obtained granular material was charged (charged) into a container (beaker), 500 mL of distilled water was added thereto, and a water-washing treatment was performed to wash with a solid-liquid ratio of 1:10 by mass ratio. . In addition, it was set as the process which the water washing time set to water washing time shown in Table 2: 5, 15, and 30 minutes, and stirred in a container.

  Then, the powder particles subjected to the water washing treatment were subjected to filtration using 5 C filter paper as solid-liquid separation treatment, and separated into solid content and separated liquid. Chlorine analysis was performed on the obtained solid content. The results are shown in Table 2.

  From Table 2, the chlorine content in the granular material (waste dry battery granular material) can be sufficiently less than 0.1% by mass in the water-washing treatment for about 15 minutes. The chlorine content of less than 0.1% by mass is the target chlorine content of the raw material that can be introduced into the arc melting furnace in the slag production process.

  Next, the amount of powder particles obtained and the amount of distilled water added are changed so that the solid-liquid ratio changes between 1:10 and 5:10, and the amount is charged into a container (beaker) Water-washing treatment to wash. In addition, it was set as the process which stirs in a container by fixing to processing time: 15 minutes for water washing. Next, the powder particles subjected to the water washing treatment were subjected to filtration using 5 C filter paper as solid-liquid separation treatment, and separated into solid content and separated liquid. Chlorine analysis was performed on the obtained solid content. The results are shown in Table 3.

  From Table 3, even in the slurry in which the solid content ratio was increased to 5: 10, the amount of chlorine in the powder particles (waste dry battery powder particles) was sufficiently less than 0.1 mass% by washing with water. It can be confirmed that the influence of the solid-liquid ratio on the chlorine content after the water washing treatment is small. In this experiment, since the container was made small, sufficient stirring could be performed by strengthening the stirring, but when the container was made large, uniform stirring was possible until the solid-liquid ratio was around 3:10. Although relatively easy, it is expected that uniform stirring becomes difficult when the solid-liquid ratio is increased to about 5:10. Therefore, when the size of the apparatus is increased as described below (more than 20 kg of powder particles and several tons scale), the solid-liquid ratio is preferably about 3:10 from the viewpoint of ease of stirring. In addition, after performing water washing processing which adds 67 kg of water to 20 kg of granular materials and carries out stirring washing so that it may become solid-liquid ratio 3:10, when it filters using a centrifugal filter, recovery rate 92 mass% The water-washed granular material having a water content of 20% by mass was obtained. It has been confirmed that the solid-liquid ratio of this level can be implemented without problems in the water washing process and the solid-liquid separation process.

  From such a thing, it was judged that the water-washing process of manganese containing substance (waste dry battery granular material) makes a solid-liquid ratio about 5:10 or less, and the process which makes water-washing time about 15 minutes or more is enough.

  Next, 70 kg of powder particles (waste dry battery particles) are subjected to water washing treatment with a solid-liquid ratio of 3:10 and a washing time of 15 minutes, and then subjected to solid-liquid separation treatment with a centrifugal filter to obtain solid content I got Next, the obtained solid content is subjected to a drying treatment (300 ° C. × 120 min) in a drying furnace, then charged with 4 kg of metal manganese for current application and 10 kg of flux (lime) and charged in an arc melting furnace and energized. A molten slag (manganese slag) was obtained by applying a slag production process to melt it. The composition of the obtained molten slag is shown in Table 4.

Table 4 shows that the obtained molten slag is a slag which has manganese oxide as a main component, and both zinc and carbon become very low concentration. Incidentally, alumina Al ₂ O ₃ is obtained by mixing the refractory of the furnace body.

  Thus, the slag production process is finished, 60 kg of the obtained molten metal slag is transferred to a ladle by tilting the arc melting furnace, and then 15 kg of reducing agent: metallic aluminum and 14 kg of lime are put into the ladle. And a reduction process to obtain molten metal (metallic manganese), thereby providing an example of the present invention. After completion of the reduction step, the molten slag is discharged, and then the obtained molten metal (metallic manganese) is poured into a mold and solidified to obtain a product. The obtained product (metallic manganese) was 35.1 kg.

  The composition of the obtained metal manganese (invention example) is shown in Table 5.

  As a comparison, 50 kg of granular materials as a raw material was subjected to water washing treatment with a solid-liquid ratio of 3:10 and a water washing time of 15 minutes, and then subjected to solid-liquid separation treatment with a centrifugal filter to obtain solid content. Next, the obtained solid content is heated in a drying furnace and subjected to drying treatment (300 ° C. × 120 min), and then 4 kg of metal manganese for current application and 15 kg of flux (lime) and 10 kg of metal aluminum as a reducing agent Then, it was charged into an arc melting furnace, was energized, was melted, and was subjected to a reduction treatment to cause a reduction reaction to obtain a molten metal (metallic manganese slag). The same process as the inventive example was performed except that the slag manufacturing process was omitted. The composition of the obtained metallic manganese (comparative example) is shown in Table 5. In addition, the composition of existing electrolytic manganese and extremely low phosphorus extremely low carbon ferromanganese is also shown as a comparison.

  From Table 5, in the example of the present invention, most of zinc and carbon are removed and there is no residue. In addition, in order to maintain the strong reduction state, manufacturing is performed in which the metal aluminum is adjusted to remain to some extent in the molten metal, so in the example of the present invention, the aluminum concentration is high. However, in the field of iron making, since aluminum is added as a deoxidizing agent at the final adjustment stage of the manganese concentration, there is no problem if the aluminum concentration is known, since aluminum remains in the metal manganese. Therefore, it is understood that the inventive example (metallic manganese) can be used as a substitute for electrolytic metallic manganese. On the other hand, in the comparative example where the slag production process is omitted, the amount of carbon (C) which is an impurity is high although the Mn + Al concentration is 90 mass% or more (94.0 mass%) and almost the same level as the invention example. .

Claims (6)

A method of producing metallic manganese which reduces metallic containing material to obtain metallic manganese,
The manganese-containing substance is subjected to a water washing process in which water is added and washed as a slurry,
Then, the slurry washed with water is subjected to solid-liquid separation treatment to separate solid content,
The obtained solid content is heated to be subjected to a drying treatment for removing water contained in the solid content,
The dried solid content is charged into an electric furnace together with a flux, and heating is performed by energization in the electric furnace to perform a slag production process using manganese in the solid content as a manganese slag.
A method for producing metallic manganese, which transfers the manganese slag obtained by the slag production process to a ladle, puts a reducing agent into the ladle, and reduces the manganese slag to obtain metallic manganese.   The method for producing metallic manganese according to claim 1, wherein the manganese-containing material is a material obtained by sorting, crushing and sieving a waste dry battery.   The method for producing metallic manganese according to claim 1 or 2, wherein a ratio of solid content to liquid in the slurry in the water washing treatment is 1:10 to 5:10 in mass ratio.   The method for producing metallic manganese according to any one of claims 1 to 3, wherein the water washing time in the water washing treatment is 15 minutes or more.   The method for producing manganese metal according to any one of claims 1 to 4, wherein the reducing agent used in the reduction treatment is metal aluminum and / or metal silicon.   The method for producing metallic manganese according to any one of claims 1 to 5, wherein the flux used in the slag production process or the reduction process is a substance containing CaO as a main component.

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