JP6017179B2 - Method for recovering metal from metal oxide waste and apparatus for carrying out the method - Google Patents

Description

  The present invention relates to a method for recovering a metal from a metal oxide waste, in particular, a method for recovering a manganese alloy from a manganese oxide waste, and a smelting reduction apparatus suitable for carrying out the method.

Lithium ion secondary batteries are lightweight and have high electric capacity, and thus are used as secondary batteries for various portable devices. However, lithium cobalt oxide is the mainstream as the positive electrode active material.
Recently, lithium ion secondary batteries using lithium manganate having characteristics comparable to lithium cobaltate as a positive electrode material have been developed. In particular, the manganese-based positive electrode material has a spinel structure in which the basic structure remains even when lithium is removed from the positive electrode during charging, and thus has high stability and is excellent in durability and safety. In addition, since manganese is cheaper than cobalt, manganese-based positive electrode materials are expected to become the mainstay when lithium-ion batteries for automobiles are expected to expand dramatically in the future.

By the way, manganese itself has traditionally been used as a positive electrode material for manganese batteries and alkaline manganese dry batteries. However, as mentioned above, the price of bullion is low and it cannot be recovered and reused on an industrial scale. It wasn't clear and was almost disposed of by landfill.
However, as described above, if it is used for automobiles in the future, it will be generated at the time of cleaning used products, product scraps (scraps), manufacturing process scraps generated in the battery manufacturing process, and battery manufacturing equipment. Since a large amount of manganese oxide waste is produced in the form of sludge and the landfill site is approaching its limit, it is no longer allowed to dispose of it in the same way as before.

  Thus, a number of methods for recovering metals from lithium ion secondary batteries have been proposed, but most of them are cobalt and nickel, which are expensive in metal price. Further, in Patent Document 1, not only cobalt and manganese but also manganese is one of the objects to be recovered. As a conventional recovery method including Patent Document 1, all of these are hydrometallurgical processes in which solvent extraction is performed by acid dissolution. However, it can be said that the hydrometallurgical process is not suitable for recovering manganese with a low metal price because of the large equipment scale and the cost added to the cost.

JP 2009-193778 A

Even if the price of manganese is low, disposal should be avoided as much as possible from the viewpoint of effective utilization of resources. Although it is recovered as pure metal in hydrometallurgy, it is not necessarily pure metal. The base nickel-containing alloy can be used as an additive alloy for producing stainless steel.
Nevertheless, an object of the present invention is to provide a new and cost-effective useful recovery method and an apparatus suitable for carrying out the method.

  The present invention has been made to solve the above-mentioned problems, and the invention of claim 1 is based on a metal oxide waste that recovers a metal as an alloy or a metal by melting reduction from the metal oxide waste. In this metal recovery method, the furnace body is tilted, the waste is melted by the flame from the oxygen burner while rotating the furnace body in a horizontal position, and then the reducing material is charged when the furnace body is put in an upright position. And a metal recovery method characterized in that the reduction of waste is promoted by ejecting an inert gas from the bottom side.

The invention according to claim 2 is the method for recovering metal from the metal oxide waste according to claim 1, wherein the positive electrode foil scrap of the lithium ion secondary battery is crushed and sieved according to the particle size, and the smaller particle size and the larger particle size The one having a smaller particle size is subjected to a smelting reduction treatment as a metal oxide waste, and the one having a larger particle size is used as a reducing material in which aluminum as an electrode base material is dominant. The metal recovery method is characterized in that it is charged during processing and recovered as a manganese-based nickel-containing alloy.

The invention of claim 3 is a smelting reduction apparatus for carrying out the metal recovery method from the metal oxide waste according to claim 1 or 2, wherein the furnace body is tilted and the attitude of the furnace body is tilted. The furnace body posture changing means to be changed, the rotating means for rotating around the axis when the furnace body is in a horizontal posture, the oxygen burner facing the axial one end side opening portion so as to be able to advance and retreat in the horizontal posture , Bubbling means for blowing an inert gas to the other axial end that forms the bottom when the furnace body is in an upright posture, and in the horizontal posture, the oxygen burner operates and the furnace body rotates to promote melting, so that the upright posture A smelting reduction apparatus characterized in that reduction is sometimes promoted by charging a reducing material and operation of the bubbling means.

According to a fourth aspect of the present invention, in the smelting reduction apparatus according to the third aspect, the furnace body posture changing means is constituted by a pair of rotation support means for rotatably supporting the furnace body from both sides. The dynamic support means includes a lifting fulcrum portion that lifts and supports the furnace body, a base, and a lower end that is pivotally supported by the base, and an upper end that is pivotally fixed to the outer surface of the furnace body. And a fluid pressure cylinder disposed on both sides of the lifting fulcrum at an interval in the axial direction, and the furnace body is rotated by a link operation of the pair of fluid pressure cylinders. Device.

  According to a fifth aspect of the present invention, in the smelting reduction apparatus according to the third or fourth aspect, the bubbling means is configured to selectively supply the gas by switching between the inert gas and the air, The smelting reduction apparatus is characterized in that the supply gas is switched when a predetermined tilt angle is obtained between the posture and the upright posture.

  According to the recovery method of the present invention, manganese-based alloys can be recovered from metal oxide wastes, particularly wastes derived from lithium ion secondary batteries, in a cost-effective manner.

It is a mimetic diagram of metal recovery equipment concerning an embodiment of the invention. It is a longitudinal cross-sectional view of the furnace main body and burner part at the time of the horizontal attitude | position of the smelting reduction apparatus with which the metal recovery equipment of FIG. 1 was equipped. It is a longitudinal cross-sectional view at the time of the upright attitude | position of the furnace main body of FIG. It is the front view seen from the one end side opening part of the said furnace main body explaining the rotation support means of the furnace main body of FIG. FIG. 5 is a cross-sectional view taken along line AA in FIG. 4. It is a BB cross-sectional view of FIG. It is the side view which looked at FIG. 4 from the one side. It is explanatory drawing explaining operation | movement of the rotation mechanism of FIG. It is an electrical block diagram of the bag ring means with which the smelting reduction apparatus of FIG. 2 was equipped. It is explanatory drawing of the limit switch mechanism with which the smelting reduction apparatus of FIG. 2 was equipped. It is explanatory drawing of the limit switch mechanism with which the smelting reduction apparatus of FIG. 2 was equipped. It is explanatory drawing of the interlocking relationship of the furnace main body and ladle of the smelting reduction apparatus of FIG.

A typical example of the manganese oxide-based waste to be collected is positive electrode foil waste of a lithium ion secondary battery.
The positive electrode foil is prepared by adding a conductive material carbon and a binder (for example, polyvinylidene fluoride (PVDF)) to a powdered positive electrode active material and preparing a slurry using N-methyl-2-pyrrolidone as a solvent. It was applied to. In the case of manganese oxide, the positive electrode active material is LiMn ₂ O ₄ having a spinel structure or LiMnO ₂ having a zigzag layer structure, and LiCoO ₂ or LiCo _1-X Ni _X O having a layered rock salt structure. ₂ , LiNiO ₂ etc. are added.

  Since the positive foil often contains a significant amount of nickel, if this is used as an alloy source, it will be alloyed when melted to lower the liquidus point and be recovered at a relatively low temperature. It is advanced. Moreover, since it is recovered as a manganese-based nickel-containing alloy, it can be effectively used as an additive to stainless steel. Furthermore, since the positive electrode foil may contain aluminum as an electrode, it can be used as an aluminum source for the reducing material.

The positive electrode foil scraps can be efficiently recovered as a manganese-based nickel-containing alloy using the metal recovery facility 1 shown in FIG.
The metal recovery facility 1 is further provided with a crushing unit 97, a storage unit 99, and a conveyor 101, centering on the smelting reduction apparatus 3 and the recovery unit 89, and the positive foil scrap is divided into two stages by the crushing unit 97. After crushing and sieving, the larger particle size is separated into a reducing material that is predominantly aluminum, which is an electrode base material, and a metal oxide to be reduced, and is stored in the storage unit 99, and then loaded on the conveyor 101 Then, it is supplied to the smelting reduction apparatus 3 for processing, and after phase separation into a manganese-based nickel-containing alloy and slag, the recovery unit 89 recovers the manganese-based nickel-containing alloy.

Hereinafter, the configuration and operation of each part of the smelting reduction apparatus 3 will be described.
In FIG. 2, reference numeral 5 indicates a furnace body of the smelting reduction apparatus 3. The furnace body 5 has a cylindrical shape, and the inner surfaces at both axial ends are tapered. In this figure, the furnace body 5 is in a horizontal position, and when the furnace body 5 is in an upright position, as shown in FIG. 3, one end side in the axial direction comes to the upper side and the other end side comes to the lower side. One end side that comes to the upper side is an opening 7, and the other end side that comes to the lower side is provided with a furnace bottom portion 9 and has a bottomed shape. Six plugs 11 are embedded in the axial center of the furnace bottom 9. A gas hose insertion portion 13 is attached to the outside of the furnace bottom portion 9, and an insertion hole 15 of the gas hose insertion portion 13 communicates with the plug 11 described above. The gas hose insertion portion 13 has a swivel joint structure and is not affected by rotation around the axis on the furnace body 5 side.
A pair of annular guide rails 17 are attached to the outer peripheral surface of the furnace body 5 at a distance.

Next, the rotation mechanism of the furnace body 5 will be described.
As shown in FIGS. 4 to 7, the furnace body 5 is housed in a frame body 19.
4 and 5, reference numeral 21 denotes a base side frame, and a helical bevel gear motor 23 is installed on the base side frame 21. Rotating shafts 29 and 29 are fastened to both ends of the output shaft 25 of the helical bevel gear motor 23 via couplings 27 and 27, respectively. A driving roller 31 is connected to each rotating shaft 29. Each rotating shaft 29 is rotatably supported by a pair of self-aligning roller bearings 33 and 33 installed on the base side frame 21, and the driving roller 31 is located between the self-aligning roller bearings 33 and 33. ing. The rotation shaft 29 on the drive roller 31 side extends toward one end side of the base side frame 21.

Two pairs of self-aligning roller bearings 33, 33 are also installed near the other end of the base side frame 21. A rotating shaft 35 is rotatably inserted and supported by each pair of self-aligning roller bearings 33, 33, and a driven roller 37 is rotatably supported by the rotating shaft 35. These two rotating shafts 35 and 35 are arranged in a straight line. The rotation shafts 29 and 29 on the drive roller 31 side and the rotation shafts 35 and 35 on the driven roller 37 side are arranged in parallel with a predetermined interval.
With the above arrangement, the driving roller 31 and the driven roller 37 can be rotated clockwise or counterclockwise as viewed from the direction shown in FIG.

  Reference numeral 39 denotes a guide roller. Two guide rollers 39 are provided on the base-side frame 21 with a space therebetween, and are both disposed between the driving roller 31 and the driven roller 37. The shaft of each guide roller 39 is supported by a tapered roller bearing 41 and rises vertically from the base side frame 21 so that each guide roller 39 can rotate clockwise or counterclockwise as viewed from the direction shown in FIG. It has become.

4 and 6, reference numeral 43 denotes a top frame, and a pair of guide rollers 39, 39 are also installed on the top frame 43 so as to face the pair of guide rollers 39, 39 on the base frame 21 side. Has been.
Reference numeral 45 denotes an adjustment roller. The adjustment roller 45 is rotatably supported at each of the four corners of the top frame 43. Each adjustment roller 45 can be rotated clockwise or counterclockwise as viewed from the direction shown in FIG.

  In FIG. 7, reference numeral 47 denotes a side frame, and a pair of guide rollers 39, 39 are similarly installed on the side frame 47, and a pair of guides are similarly opposed to the opposite side frame 47. Rollers 39 and 39 are installed.

  The furnace body 5 is positioned horizontally on the pair of driving rollers 31 and 31 and the pair of driven rollers 37 and 37 on the base frame 21 side so that the opening 7 on one axial end side faces the front as viewed from FIG. In addition, a pair of guide rollers 39, 39 installed on the base side frame 21, the top side frame 43, and the both side frames 47, respectively, are annular guides on the outer surface of the furnace body 5. The positional deviation of the furnace body 5 is regulated by hitting the rails 17 and 17 from the inner side. Further, when the furnace body 5 is thermally expanded, the positional deviation is regulated by hitting the adjusting roller 45 of the top frame 43. Thus, the furnace body 5 is stably supported in the frame body 19 from the three-dimensional direction. In this state, the rotational force is received from the helical bevel gear motor 23 via the output shaft 25, the coupling 27, and the rotation shaft 29, and the drive rollers 31 and 31 as the rotation means rotate, and follow the roller. By rotating 37, 37, the furnace body 5 rotates around its axis.

Next, the rotation mechanism of the furnace body 5 will be described.
As shown in FIG. 4, a pair of leg portions 49 are arranged on both sides of the body portion of the furnace body 5, and a self-aligning roller bearing 51 is installed on the upper end side of each leg portion 49. Has been.
A pair of support shafts 53, 53 are connected to the intermediate portion of the outer surface of the furnace body 5 so as to form a straight line orthogonal to the axial direction, and each support shaft 53 rotates to the self-aligning roller bearing 51 described above. It is supported freely. Therefore, the support shaft 53 and the self-aligning roller bearing 51 constitute a lifting fulcrum portion of the furnace body 5.

  In FIG. 4, reference numeral 55 denotes a hydraulic cylinder, which is arranged with the movable portion 57 facing upward. As shown in FIG. 7, a mounting portion 61 is installed on the base 59 extending to the foot side of the leg portion 49, and the lower end portion of the hydraulic cylinder 55 is pivotally supported by the mounting portion 61. Yes. The upper end portion is pivotally supported with respect to the outer surface of the furnace body 5 so as to be rotatable. With the above-described configuration, a pair of hydraulic cylinders 55 and 55 are disposed on both sides of the body portion of the furnace body 5 so as to face each other with one support shaft 53 interposed therebetween.

Therefore, as shown in FIG. 8, a link mechanism including a pair of hydraulic cylinders 55 and 55 and the furnace body 5 as elements is formed on both sides of the body portion of the furnace body 5.
Of the pair of hydraulic cylinders 55, one is an upward tilting cylinder 55L, which is a driving cylinder for upward tilting, and the other is a downward tilting cylinder 55R, which is a driving cylinder for downward tilting. The ascending tilt cylinder 55L and the descending tilt cylinder 55R are opposed to each other with the body portion of the furnace body 5 interposed therebetween.
The ascending tilt cylinder 55L and the descending tilt cylinder 55R are alternatively driven, and the non-moving cylinder follows. Therefore, the upward tilt cylinder 55L and the downward tilt cylinder 55R are both expanded and contracted by the driving force of either one of the hydraulic cylinders 55, that is, the furnace body 5 is rotated with the support shaft 53 as a fulcrum.

As shown in FIG. 8, the furnace body 5 is rotated together with the frame body 19 by the link operation of the link mechanisms on both sides of the body portion of the furnace body 5 to change the posture.
FIG. 8 (1) shows the furnace body 5 in a horizontal posture during melting and standby. At this time, hydraulic pressure is supplied to the downward tilting cylinder 55R, and it extends as shown by an arrow.
FIG. 8 (2) shows the change of the posture to accept the material, and the furnace body 5 is tilted backward so that the opening 7 is on the upper side. At this time, hydraulic pressure is supplied to the upward tilting cylinder 55L, and it is extended as shown by the arrow.
FIG. 8 (3) shows the furnace body 5 in an upright posture during material reception / reduction. At this time, hydraulic pressure is supplied to the upward tilting cylinder 55L, and it is extended as shown by the arrow.
FIG. 8 (4) shows that the furnace body 5 is tilted forward so that the opening 7 is on the lower side when the posture is changed to the hot water. At this time, hydraulic pressure is supplied to the downward tilting cylinder 55R, and it extends as shown by an arrow.
FIG. 8 (5) shows the time when the hot water is discharged, and the furnace body 5 is largely inclined forward with the opening 7 on the lower side. At this time, hydraulic pressure is supplied to the downward tilting cylinder 55R, and it extends as shown by an arrow.

FIG. 9 shows a gas supply means, and a gas hose 63 of this gas supply means is inserted into a gas hose insertion portion 13 attached to the outside of the furnace bottom portion 9 of the furnace body 5 described above. In the gas hose 63, an argon gas supply path 65 and an air supply path 67 as an inert gas are joined together in the middle to form one gas hose 63. Electromagnetic valves 69 and 69 are inserted in the argon gas supply path 65 and the air supply path 67, respectively, and argon gas or air enters the furnace main body 5 from the furnace bottom 9 side by these alternative opening and closing operations. Can be supplied alternatively. Argon gas is supplied at a high pressure to promote reduction, and the flow rate is adjusted by the flow rate adjusting valve 71.
Bubbling means is constituted by the gas supply means and the plug 11 penetrating the furnace bottom 9 connected thereto.

Next, a control mechanism for switching the attitude of the furnace body 5 and the supply gas will be described.
In this smelting reduction apparatus 3, as shown in FIG. 10, dog plates 73 </ b> A to 73 </ b> F are connected to a support shaft 53 protruding from one side of the furnace body 5, and another dog plate 75 is also connected to the support shaft 53. Thus, it rotates with the support shaft 53. Limit switches 77A to 77F are attached to the dog plates 73A to 73F, and two limit switches 79L and 79R are attached to the upper end side of the leg 49 corresponding to the dog plate 75, respectively.

  As shown in FIG. 10, the dog plates 73 </ b> A to 73 </ b> F are divided into those in which the convex portions 74 do not have the detection width range (73 </ b> A, 73 </ b> C, 73 </ b> D, 73 </ b> E) and those having the detection width range (73 </ b> B, 73 </ b> F). In the case of the rear tilt end (= upright posture), back tilt horizontal (= horizontal posture), forward tilt horizontal (= horizontal posture) and forward tilt end (= forward tilted posture) of the furnace body 5 It is a dog plate, switching the supply gas (= + switching between argon high pressure gas and air) and cylinder operation switching (= operation switching between the rising tilt cylinder 55L and the falling tilt cylinder 55R) are the latter type. It is a dog plate.

When the limit switches 77A, 77C, 77D, 77E are pressed and turned on, the supply of hydraulic pressure to the hydraulic cylinders 55, 55 is stopped and maintained at that hydraulic pressure, so that the furnace body 5 is supported in the posture at that time. .
By turning on the limit switch 77A at the rearward tilt end, the furnace body 5 is maintained in the upright posture shown in FIG. 8 (3), and the limit switch 77C for the rearward tilt return and the limit switch 77D for the rearward tilt horizontal are turned on. Thus, the furnace body 5 is maintained in the horizontal posture shown in FIG. 8A, and is maintained in the forward inclined posture by turning on the limit switch 77E at the forward inclined end.
The reason why the return horizontal is divided into the backward tilt horizontal (= horizontal posture) and the forward tilt return horizontal (= horizontal posture) is because the actual width of the limit switch 77 is taken into consideration.
Further, as shown in FIG. 11, when the limit switch 79R is turned on by being pressed by the convex portion 76 of the dog plate 75, further backward tilt is restricted, and when the limit switch 79L is turned on, further forward Tilt is regulated. This mechanism is an emergency mechanism for preventing an excessive tilt due to an abnormality of the furnace body 5.
With the above configuration, the position of the furnace body 5 is controlled so as to surely stop at the main position.

Further, when the limit switch 77F is turned ON / OFF, the cylinder to be operated is switched between the ascending tilt cylinder 55L and the descending tilt cylinder 55R. When the limit switch 77F is turned ON, the ascending tilt cylinder 55L becomes operable. Ready to operate.
Thereby, the alternative operation | movement of the hydraulic cylinder 55 is ensured.

Next, the supply gas is switched by turning ON / OFF the limit switch 77B, and the electromagnetic valve 69 on the argon gas supply path 65 is opened by turning ON the limit switch 77B, and the high pressure argon gas is adjusted by the flow rate adjusting valve 71. Then, the gas is blown into the furnace main body 5 through the gas hose 63, and the electromagnetic valve 69 on the air supply path 67 is opened by turning OFF, so that air is blown into the furnace main body 5.
Thus, the supply gas is switched when the furnace body 5 reaches a predetermined tilt angle. It should be noted that the rotation of the furnace body 5 is temporarily stopped when switching from OFF to ON.

As shown in FIG. 2, the smelting reduction apparatus 3 is provided with a burner unit 81. The hood 83 of the burner portion 81 is connected to and communicates with the opening 7 when the furnace body 5 is in a horizontal posture. The upper end side of the hood 83 is opened and serves as a gas discharge port. The nozzle portion 85 enters the hood 83, and the jet outlet at the tip thereof faces the furnace bottom portion 9 side of the furnace body 5.
The burner portion 81 is mounted on a movable carriage 87, and can move forward and backward with respect to the furnace body 5 by the movement of the carriage 87.

When the metal recovery facility 1 having the above-described configuration is used, the furnace body 5 is warmed to some extent by preheating or leaving a small amount of molten metal in the previous operation. Then, the furnace body 5 is placed in an upright posture as shown in FIG. 8 (3), and first, metal oxide waste and quicklime (CaO) are charged, and then the furnace body 5 is placed in FIG. 8 (1). As shown in FIG. 2, the combustion flame is blown into the furnace body 5 in the horizontal attitude rotating as shown in FIG. 2 from the opening 7 side by the combustion heat and the heat transfer of the furnace body 5. Encourage melting. Quicklime is a flux for adjusting the basicity (CaO + MgO / SiO ₂ + Al ₂ O ₃ ), but charging at this stage lowers the melting point of the waste and promotes dissolution.
During the melting operation, air is jetted into the furnace body 5 to prevent the plug 11 at the furnace bottom 9 from being blocked.

  After the molten state (M) is reached, the furnace body 5 is returned to the posture shown in FIG. 8 (3), and the bubbling means is operated while charging the reducing material predominantly of aluminum as shown in FIG. Then, argon gas is spouted from the furnace bottom 9 side to form bubbles (B), whereby hot water is stirred and reduction is promoted.

  As shown in FIG. 12, after the reduction is completed, molten slag comes to the upper layer of the furnace body 5 due to the density difference, and the molten alloy comes to the lower side, so the moving carriage 95 is moved to separate the hot water into two stages. First, the molten slag is recovered by the ladle 91 of the recovery unit 89, and then the molten alloy is recovered by the ladle 93.

If this smelting reduction apparatus 3 is used, both the melting and the reduction can be carried out in the same furnace as described above, so that the working efficiency is good.
By removing the aluminum content from the waste material charged in the melting stage in advance, it can be heated efficiently using an oxygen burner, and alumina (Al ₂ O ₃ ) or silica (SiO ₂ ) produced by reduction of manganese oxide. ₂ ) Molten slag formed by combining with calcium oxide has a low melting point and good fluidity, so that it is easy to separate and recover. Therefore, the metal part and the slag part can be separated efficiently.
And since the aluminum part can be used as a reducing material, all the waste can be utilized. Moreover, the waste can also be effectively utilized by using together the Si scrap derived from a solar cell as a reducing material as needed.

  Manganese is an element that is relatively difficult to reduce. However, since bubbling increases the chance of contact with aluminum and silicon that combine with oxygen, manganese oxide is reduced smoothly once it is in a molten state. . (In addition, when nickel and cobalt are contained in the waste, nickel and cobalt are elements that are more easily reduced than manganese, and are reduced in preference to manganese.)

When recovering manganese or a manganese-based alloy from waste, preliminary steps such as roasting and pulverization are not particularly required as long as the waste can be charged into the furnace.
When the waste is a positive electrode material of a lithium ion secondary battery, a binder such as polyvinylidene fluoride (PVDF) is included, and the cleaning waste liquid sludge contains an organic solvent such as N-methyl-2-pyrrolidone. However, when they are heated in the furnace, they are removed by decomposition and combustion prior to melting of the waste, so that they are not mixed into the recovered metal phase.
In addition, when the waste is derived from a lithium ion secondary battery, manganese and the like form a composite oxide together with lithium, but are decomposed into manganese oxide and lithium oxide as the furnace is heated. Manganese oxide is reduced by aluminum or silicon and distributed to molten metal, while lithium oxide is incorporated into molten slag due to its physical properties.

The positive electrode active material is generated not only as used lithium ion secondary batteries, product scraps (deteriorated products), cathode material manufacturing process scraps, but also as dust collection ash for battery manufacturing facilities. In the process of cleaning the coating equipment for applying the substance to the foil, it also comes out as a cleaning waste liquid, but both become objects to be treated in the present invention.
Manganese oxide is also used as a positive electrode material for manganese batteries and alkaline manganese dry batteries. Furthermore, since manganese is also frequently used in the plating film, it is also contained in the plating sludge. Therefore, these wastes are also objects to be treated in the present invention.
Thus, regardless of the origin of the waste, according to the method of the present invention, manganese can be recovered as a manganese-based alloy from various manganese oxide-based wastes.
However, unlike the positive electrode foil scraps, the above-mentioned materials usually do not include a material that can be a reducing material such as aluminum. Therefore, it is necessary to prepare the reducing material separately.

The positive electrode foil scraps of the lithium ion secondary battery were processed.
First, in the crushing part 97, primary crushing was performed to 40 mm or less by a uniaxial high-speed shredder, this was secondarily crushed by using a hammer impact crushing apparatus, and sieved to 0.5 mm up and 0.5 mm under. As shown in Table 1, by optimizing the number of rotations of the hammer, the aluminum component and the oxide as the electrode base material were successfully separated at 0.5 mm up and 5 mm under.

  The secondary crushed product having an evaluation of “O” was granulated and briquetted under the following conditions to facilitate handling.

  Charge 500 kg of briquette-shaped battery waste (0.5 mm under) and 300 kg of quicklime into the furnace body 5 that has been heated in advance, start melting the battery waste, and monitor the furnace when the exhaust gas reaches 900 ° C. Then, when the temperature reached 1450 ° C., the mode shifted to the reduction mode, and granulated briquette-like aluminum was added while being divided into 40 kg portions, and hot water was discharged when 8 minutes had passed.

Analysis of the recovered metal and slag components revealed the following.
Metalization rate = recovered metal amount / (recovered metal amount + loss metal amount in slag) × 100 = 90.8%
Mn distribution ratio = Mn content in recovered metal / (Mn content in recovered metal + Mn content in slag) × 100 = 87.5%
Moreover, it was as follows when the component of the collection | recovery metal was analyzed (n = 8).
Mn = 65.85 mass%, Ni = 20.50 mass%, Co = 5.24 mass%
This was as expected.

  As described above, according to the present invention, a manganese-based nickel-containing alloy that can be used as an additive alloy for producing stainless steel was successfully produced from lithium ion secondary battery waste.

  If the smelting reduction apparatus of this invention is utilized, the manganese oxide waste, especially the waste derived from the positive electrode material of a lithium ion secondary battery can be recycled by a system with high cost performance.

DESCRIPTION OF SYMBOLS 1 ... Metal recovery equipment 3 ... Melting reduction apparatus 5 ... Furnace main body 7 ... Opening part (furnace main body) 9 ... Furnace bottom part 11 ... Plug 13 ... Gas hose insertion part 15 ... Insertion hole 17 ... Guide rail 19 Frame body 21 Base frame 23 Helical bevel gear motor 25 Output shaft 27 Coupling 29 Rotating shaft 31 Drive roller 33 Self-aligning roller bearing 35 Rotating shaft 37 Followed roller 39 Guide roller 41 Conical roller bearing 43 Top frame 45 Adjusting roller 47 Side frame 49 Leg 51 Self-aligning roller bearing 53 · · · Support shaft 55 · · · Hydraulic cylinder 57 · · · Moving part 59 · · · Base 61 · · · Mounting portion 63 · · · Gas hose 65 · · · Argon gas supply route 67 · · · Air supply route 69 · · · Electromagnetic Valve 71 ... Flow control valve 73 (A to F) ... Dog plate 75 ... Dog plate 77 (A to F) ... Limit switch 79 ... Limit switch 81 ... Burner section 83 ... Hood 85 ... Nozzle Section 87 ... Moving carriage 89 ... Recovery section 91, 93 ... Ladle 95 ... Moving carriage 97 ... Crushing section 99 ... Storage section 101 ... Conveyor

Claims (5)

In a method for recovering a metal from a metal oxide waste, the metal is recovered from the metal oxide waste by melting reduction as an alloy or metal.
The furnace body is tilted and the waste is dissolved by the flame from the oxygen burner while rotating when the furnace body is in a horizontal position. After that, when the furnace body is placed in an upright position, a reducing material is charged and not discharged from the bottom side. A metal recovery method characterized by expelling active gas to promote reduction of waste. In the metal recovery method from the metal oxide waste according to claim 1,
Lithium ion secondary battery positive electrode foil scraps are crushed and sieved by particle size and separated in advance into smaller and larger particles,
The one with the smaller particle size is subjected to smelting reduction treatment as metal oxide waste,
A metal recovery method , wherein the larger particle size is charged as a reducing material predominantly of aluminum as an electrode base material during the smelting reduction treatment and recovered as a manganese-based nickel-containing alloy. A smelting reduction apparatus for performing the metal recovery method from the metal oxide waste according to claim 1 or 2,
A cylindrical furnace body, the furnace body attitude changing means for changing the position of the furnace body by tilting, rotating means for rotating on the axis around at horizontal position of the furnace body, the one axial end at the horizontal position An oxygen burner opposed to the side opening so as to be able to advance and retreat, and bubbling means for blowing an inert gas to the other axial end that forms the bottom when the furnace body is in an upright posture,
An oxygen burner operates in the horizontal posture and the furnace body rotates to promote melting, and in the upright posture, reduction is promoted by charging a reducing material and operating the bubbling means. In the smelting reduction apparatus according to claim 3,
The furnace body posture changing means is composed of a pair of rotation support means for rotatably supporting the furnace body from both sides,
Each rotation support means includes a lifting fulcrum portion that lifts and supports the furnace body, a base, and a lower end that is pivotally supported by the base, and an upper end that is pivotally fixed to the outer surface of the furnace body. And a fluid pressure cylinder disposed on both sides of the lifting fulcrum at an interval in the axial direction, and the furnace body is rotated by a link operation of the pair of fluid pressure cylinders. Reduction device. In the smelting reduction apparatus according to claim 3 or 4,
The bubbling means is configured to selectively supply gas by switching between inert gas and air, and when the tilt angle reaches a predetermined angle between the horizontal posture and the upright posture of the furnace body, the supply gas is supplied. A smelting reduction apparatus characterized by switching between.

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