JP4147297B2 - Metal recovery apparatus and metal recovery method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal recovery apparatus that recovers a desired metal from a solution containing metal ions, and a metal recovery method using the metal recovery apparatus.
[0002]
[Prior art]
As a metal recovery method and a metal recovery device for recovering a desired metal from a solution containing metal ions, for example, Patent Document 1 introduces iron scrap containing copper into a non-oxidizing acid solution in which copper is dissolved However, it describes a precipitated copper method for recovering copper contained in dissolved copper and iron scrap as dead copper, and Patent Document 2 contacts a copper-containing etching waste liquid with a metal having a higher ionization tendency. The copper recovery method and the recovery device are described in which a copper powder is deposited to introduce a gas into the obtained copper slurry.
[0003]
[Patent Document 1]
Japanese Patent Laid-Open No. 50-2621
[Patent Document 2]
Japanese Patent Laid-Open No. 6-146021
[0004]
[Problems to be solved by the invention]
Since the method described in Patent Document 1 is a so-called batch-type processing method, it is necessary to recover waste copper generated by stopping the apparatus for each processing batch and to input raw materials such as iron scrap containing copper. There was a limit to increasing productivity. The method is a technique for recovering copper in a hydrochloric acid solution in the form of copper chloride, and the recovered copper is in the form of copper chloride that can be easily handled with a pump or the like. However, when the copper in the sulfuric acid solution is to be recovered by this method, the recovered copper is in a form having a large sedimentation property such as metallic copper or cuprous oxide, and it is difficult to apply the method.
On the other hand, although the method described in Patent Document 2 can recover the copper powder by continuous operation from the copper-containing etching waste liquid, since the iron material is filled in the drum, The surface of the iron material is easily coated. If the surface of the iron material is coated with copper, it is considered that the elution of iron ions into the etching waste liquid is hindered and copper recovery becomes difficult. Therefore, it is necessary to replace the iron material coated with copper with an iron material having a fresh surface. However, when exchanging the iron material, it is necessary to open the drum and replace the internal iron material. There was a limit to raising
[0005]
The present invention has been made to solve the above-mentioned problems, and a lump of a metal (hereinafter referred to as a base metal) having a lower ionization tendency than a desired metal is included in a solution containing metal ions. In addition to continuously collecting the desired metal, it suppresses the surface of the base metal mass from being coated with the desired metal, and when the surface of the base metal mass is coated with the deposited metal, it is easy And a metal recovery method using the metal recovery device
[0006]
[Means for Solving the Problems]
A first means for solving the above-described problem is a metal recovery device for recovering a desired metal from a solution containing metal ions,
A drum-like container installed rotatably around an inclined rotation axis, and a rotating means for rotating the container in a forward and reverse direction,
In the inner periphery from the container opening end to the bottom end of the container, a baffle portion having a spiral shape is provided,
The metal recovery device is characterized in that a detachable sieving portion is provided at the opening end of the container.
[0007]
The second means is a metal recovery method using the metal recovery apparatus described in the first means.
[0008]
The third means is the metal recovery method according to the second means,
The solution containing the metal ions is a metal recovery method characterized in that it is a sulfuric acid acidic solution prepared from smoke ash and residue generated in the smelting process.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described with reference to the drawings.
1 is a schematic side view of a metal recovery device and an accessory device according to the present invention, FIG. 2 is a schematic plan view of FIG. 1, and FIGS. 3 (a) to 3 (c) are FIG. 4 is a cross-sectional view taken along line BB of FIG. 2, FIG. 5 is a cross-sectional view taken along line CC of FIG. 2, and FIG. 7 is a container shown in FIGS. FIG.
1 and 2, the drum-like (for example, substantially barrel-shaped) container 10 of the metal recovery apparatus according to the present invention is capable of inclining its rotation axis 11 with respect to a horizontal plane at a desired inclination angle θ. It is installed on the gantry 21 through (not shown), and can be rotated forward and reverse by the rotating means 20. The lower end of the container 10 is closed as a bottom end 19, but the upper end is opened to form a container opening end 12. A hopper 13 is provided above the container opening end 12, and a desired material such as the metal ion-containing solution 1 or the base metal scrap 2 is introduced into the container 10 from the hopper 13 through the container opening end 12. Can do. Reference numeral 22 denotes an appropriate valve. On the other hand, a discharge chute 14 is provided below the container opening end 12 to guide the processed solution 3 and the generated metal particles overflowing from the container opening end 12 to a predetermined place such as the conveyor 30.
[0010]
Reference numeral 51 denotes a scrap yard, and the base metal scrap 2 stored here is put into the hopper 13 by the crane 52.
Reference numeral 30 denotes a conveyor, which separates the processed solution 3 and the generated metal particles from the container overflow end 12 through the discharge opening chute 14 and dropped into solid-liquid separation. The object 4 is transferred to the accumulation yard 53 and stored. The treated solution 3 which is a liquid component is transferred to the pump tank 41 through the overflow tank 36, and is transported to a thickener (not shown) or the like by the pump 42 and appropriately processed.
[0011]
3A to 3C show schematic longitudinal cross sections of the container 10.
First, FIG. 3A shows a state in which the container 10 is filled with the metal ion-containing solution 1 and the base metal scrap 2 and is rotated forward by the rotation axis 11. A baffle portion 16 having a spiral shape with the rotation axis core wire 11 as the center is provided on the inner wall of the container 10.
Here, the baffle portion 16 will be described with reference to FIG. 7 which is a perspective view inside the container 10.
As shown in FIG. 7, a baffle portion 16 having a spiral shape is provided on the inner wall of the container 10, and when the container 10 rotates forward, the contents such as the base metal scrap 2 are placed on the bottom on the left side of the drawing. It has the structure which conveys to the edge 19 and conveys to the container opening end 12 of the left side toward the drawing in the case of reverse rotation. FIG. 7 shows an example in which two baffle portions are provided, but one or three or more may be used as desired.
[0012]
Here, it returns to Fig.3 (a).
A disc-shaped filter is detachably provided as a sieve part 15 around the container opening end 12, but a sieve opening 18 is provided at the center of the sieve part 15. Accordingly, the hopper 13 described with reference to FIGS. 1 and 2 feeds the base metal scrap 2 and the like into the container 10 through the sieve opening 18 even when the sieve part 15 is installed at the container opening end 12. It is something that can be done.
Further, in order to inject the metal ion-containing solution 1 into the container 10, a conduit 17 having an appropriate valve 22 is provided from the outside of the container 10 to the bottom end 19 of the container through the opening of the sieve portion 15. This is a preferred configuration.
[0013]
A discharge chute 14 is provided below the container opening end 12, and the treated solution 3 and metal particles overflowing from the container opening end 12 of the container 10 are passed through after being sieved by the sieving portion 15. It is guided and dropped onto the conveyor 30 provided below the discharge chute 14. A preferred configuration of the conveyor 30 will be described later with reference to FIGS.
[0014]
3 (b) and 3 (c) show a state where the container 10 described in FIG. 3 (a) is rotating in the reverse direction. In FIG. 3 (b), reference numeral 4 denotes metal deposited in the conveyor 30. A granular material is shown, and the screen portion 15 is removed in (c).
[0015]
4 and 5 show a longitudinal section of the conveyor 30. FIG.
In FIG. 4, the conveyor 30 has a conveyor housing 32 and a chain conveyor 31 rotating in the housing (rotating counterclockwise in FIG. 4). The conveyor housing 32 is a substantially rectangular parallelepiped, and the upper portion is opened. One end (the precipitated copper yard side described in FIG. 2) of the bottom surface in the longitudinal direction becomes a rising slope toward the end, and the conveyor housing inclined portion 34 is formed. Is forming.
Sprockets 39 are rotatably supported at four points of the ridge portion of the conveyor housing and the starting portion of the conveyor housing inclined portion 34, and the chain conveyor 31 is hooked on the sprocket 39.
[0016]
A plurality of scrapers 37 are attached to the chain conveyor 31 at predetermined intervals, and the scraper 37 moves along the inner wall of the conveyor housing 32 along the inner wall of the conveyor housing 32. And move while keeping the gap 38.
Moreover, the overflow wall 36 is provided in the side wall of the conveyor housing | casing 32, and when the solution 3 after a process is inject | poured in the conveyor housing | casing 32, the lower half of the conveyor housing | casing 32 is immersed substantially. Is done.
[0017]
This scraper 37 and the conveyor housing | casing 32 are further demonstrated using FIG.
In the conveyor 30 shown in FIG. 5, the chain conveyor 31 rotates around the inner wall in the conveyor housing 32, and the scraper 37 attached to the chain conveyor 31 is spaced from the inner wall of the conveyor housing 32. Move while keeping. As described above, the lower half of the conveyor housing 32 is substantially immersed in the treated solution 3.
[0018]
Here, returning to FIG. 4, the bottom surface of the conveyor housing 32 on the accumulation yard 53 side is inclined upward to form the conveyor housing inclined portion 34, and the chain conveyor 31 also moves upward along this. A discharge port 35 is provided at the uppermost portion of the conveyor casing inclined portion 34. Below the discharge port 35 is a deposition yard 53 on which metal particles 4 are deposited.
[0019]
Next, the metal recovery process using the above-described metal recovery apparatus and accessory apparatus according to the present invention will be described for each process.
[0020]
[Preparation process of metal ion-containing solution]
First, the metal ion-containing solution 1 is a solution containing the metal to be recovered as ions. In the present invention, various metals such as copper, tin, lead, silver, and gold are targeted as metals to be recovered. Moreover, the liquid property of the metal ion containing solution 1 is acidic, and it is preferable that it is sulfuric acid acidity and nitric acid acidity.
Examples of such a metal ion-containing solution 1 include a sulfuric acid acidic solution prepared from smoke ash and residues generated in a smelting process, waste liquid generated in various plating processes, etching processes, and the like.
[0021]
[Base metal lump preparation process]
Base metal mass refers to metals having a property that ionization tendency is lower than the metal to be recovered, and when the metal ion is tin, lead, copper, silver, gold, etc., as the base metal mass, magnesium, Aluminum, zinc, iron, nickel, or the like can be used. And the layer of the metal which should be collect | recovered is produced | generated on the surface of a base metal lump using the difference of the ionization tendency of the metal and base metal lump which should be collect | recovered.
Furthermore, in this Embodiment, it is preferable to use the base metal scrap 2 as a base metal lump. This is because the base metal mass is a support for generating a metal layer to be recovered on the surface. That is, the form of the base metal mass is a solid mass at normal temperature, and the preferable mass shape is a scrap shape having a variety of shapes such as waste materials. For example, there are a linear shape, a plate shape, a scrap can in which the can is crushed by a press or the like. There are many different scrap shapes, especially asymmetric shapes, corners, individual weights, and uneven surface conditions. Therefore, in the metal recovery process described later, the generation location of the metal layer to be recovered on the base metal scrap 2 is unevenly distributed and is thickly attached depending on the location. Then, when the base metal scraps 2 collide with each other, the collision direction and the stress are various, so that the metal layer to be collected generated on the base metal scrap 2 is easily peeled off.
The base metal scrap 2 can be a plated material or a clad material as long as the productivity is not lowered or the subsequent process is not adversely affected.
For example, when copper is recovered from a solution containing copper ions as the metal ion-containing solution 1, a scrap material of clad iron material whose half surface is coated in a bimetal shape with copper can be used as the base metal scrap 2.
[0022]
[Metal ion-containing solution and base metal scrap charging process]
As shown in FIG. 1, the base metal scrap 2 accumulated in the scrap yard 51 is put into the container 10 from the hopper 13 using the crane 52. Moreover, although the metal ion containing solution 1 is also thrown in in the container 10 from the hopper 13, it is also a preferable structure to throw in using the conduit | pipe 17 demonstrated in Fig.3 (a). When the metal ion-containing solution 1 is charged, the lower the pH of the solution, the faster the reaction and the better, but for example, impurities such as a copper ion-containing solution obtained from smoke ash and the like contain various impurities other than the desired metal. In the case of a solution, in order to avoid the influence of these impurities, it may be preferable to adjust the pH to increase.
[0023]
Either of the metal ion-containing solution 1 and the base metal scrap 2 may be input first, but from the viewpoint of liquid level control in the container 10, it is preferable to input the base metal scrap 2 first.
[0024]
As the charging ratio between the metal ion-containing solution 1 and the base metal scrap 2, an optimum value is determined in advance according to the combination of the metal to be recovered and the base metal lump, and then it is input.
[0025]
[Stirring step]
In order to peel off the metal layer to be recovered generated on the surface of the base metal scrap 2 from the surface by the reaction between the metal ion-containing solution 1 and the base metal scrap 2 charged in the container, stress is applied to the surface. From this point, the metal layer is peeled off, and an impact force and a friction force are suitable for this stress.
Therefore, as an apparatus used in this process, for example, when the container into which the metal ion-containing solution 1 and the base metal scrap 2 are charged rotates, the base metal scrap 2 lumps and the metal ion-containing solution 1 is stirred. However, it is preferable that the base metal scrap 2 in the reaction repeatedly collides and frictions.
[0026]
Here, when performing the stirring step, the position of the container opening end 12 can be adjusted by controlling the inclination angle θ of the rotation axis 11 relative to the horizontal plane. For example, if the inclination angle θ is small, the position of the container opening end 12 becomes low, and the volume of the metal ion-containing solution 1 that can be stored in the container 10 decreases, but increases as the inclination angle θ approaches 90 °. To do. That is, by adjusting the inclination angle θ of the rotation axis 11, the volume of the metal ion-containing solution 1 that can be stored in the container 10 can be varied, thereby storing the solution in the container 10. Can be controlled. And the collection | recovery amount, recovery rate, etc. of the metal from a solution can be controlled by controlling the storage time in the container 10 inside the metal ion containing solution 1. FIG. Therefore, preferable reaction conditions between the metal ion-containing solution 1 and the base metal scrap 2 can be obtained by adjusting the position of the container opening end 12 in accordance with the concentration of the metal ion-containing solution 1, the temperature, and the reaction state with the base metal scrap 2. Can be maintained.
[0027]
Here, a stirring device having the above-described configuration and a stirring process using the same will be described with reference to FIG.
A baffle portion 16 is installed on the inner wall of the container 10. By rotating the container 10 with the rotation axis 11, the baffle portion 16 stirs and mixes the metal ion-containing solution 1 and the base metal scrap 2 inside the container. Furthermore, it is preferable that the baffle portion 16 has a spiral structure so as to convey the base metal scrap 2 to the bottom end 19 of the container when the rotation is normal. The base metal scrap 2 transported to the bottom end 19 by the baffle portion 16 having a spiral structure is deposited there, but the base metal scrap is coaxial with the rotation direction due to the lift-up effect by the baffle portion 16 and the side wall of the rotating container, and in the same direction. Two deposits are raised. At this time, heavy pressure due to friction force and accumulated weight is applied to the base metal scraps 2, but soon, the base metal scrap 2 falls from the vicinity of the raised top to a valley and is released from this friction and heavy pressure. At the time of the fall, a collision occurs with another base metal scrap 2 and an impact force is applied.
Further, the base metal scrap 2 continues to receive stress from the spiral baffle portion 16 toward the bottom end.
Thus, since friction, impact force, and stress are applied to the surface of the base metal scrap 2 inside the rotating container 10, the metal layer to be collected generated on the surface of the base metal scrap 2 is peeled and becomes metal particles. The peeled metal particles settle below the container 10 or are dispersed in the metal ion-containing solution 1.
[0028]
The impact force at the time of falling of the base metal scrap 2 can be adjusted by controlling the liquid surface position of the metal ion-containing solution 1, the input flow rate, the rotational speed of the container 10, and the inclination. Although it is preferable that the rotation speed of the container 10 is fast, it is preferable to set it appropriately according to the size of the container 10 and the amount of the base metal scrap 2 in order to sufficiently maintain the impact force.
[0029]
In the stirring step, a configuration in which the metal ion-containing solution 1 is continuously charged while the rotation of the container 10 is continued is also preferable. When the metal ion-containing solution 1 is continuously added, the reaction can be repeated and continuously performed, and at the same time, if the metal concentration of the treated solution 3 overflowing from the container opening end 12 is appropriately analyzed, The reaction state can be confirmed, and the amount of the metal ion-containing solution 1 input, the amount of base metal scrap 2 and the liquid level in the container 10 may be adjusted according to the analysis value.
[0030]
The metal particles peeled off from the metal layer of the base metal scrap 2 thus obtained are metal particles having a diameter of several mm or less, and thus have a shape suitable for transportation and conveyance. The quality is generally high, and it can be used as a raw material for metal smelting or as an additive.
[0031]
On the other hand, in the agitation step, the sieve portion 15 provided around the container opening end 12 is preferably of a filter type that performs selection based on the dimensional difference of the shape of what passes therethrough. The sieve portion 15 having the configuration allows the treated solution 3 and the metal particles dispersed therein to pass through and overflow the container 10, and the base metal scrap 2 falls from the container 10. To prevent.
[0032]
Accordingly, the sieving part 15 has a sieving opening 18 concentric with the container opening end 12 so that even if the container 10 rotates, the area of the sieving part 15 in contact with the treated solution 3 is constant. It is preferable to keep it.
[0033]
Further, a conduit 17 for introducing the metal ion-containing solution 1 from the outside of the container 10 through the sieve opening 18 and in the vicinity of the bottom end 19 of the container 10 is disposed. Therefore, it is also preferable to supply to the vicinity of the bottom end 19. As described above, the vicinity of the bottom end 19 is a place where the base metal scrap 2 is continuously subjected to friction, impact force and stress due to the action of the baffle portion 16, so the metal ion-containing solution 1 is first introduced here. Then, after sufficiently reacting with the base metal scrap 2 to form a metal layer to be recovered, or after making the metal layer thicker, it is directed to the container opening end 12 as the solution 3 after treatment, thereby recovering the metal. Can increase productivity. Further, at this time, as described above, the volume of the metal ion-containing solution 1 inside the container 10 is controlled by controlling the inclination of the rotation axis 11 relative to the horizontal plane of the container 10 and adjusting the position of the container opening end 12. Residual time etc. can be adjusted and the recovery amount, recovery rate, etc. of the metal from the metal ion containing solution 1 can be adjusted. Therefore, the position of the container opening end 12 may be adjusted according to the concentration of the metal ion-containing solution 1, the liquid temperature, and the reaction status with the base metal scrap 2.
[0034]
Similarly, from the viewpoint of metal recovery productivity, when the metal ion-containing solution 1 or the base metal scrap 2 is replenished during the stirring step, the sieve portion 15 is installed even if the sieve portion 15 is installed at the container opening end 12. It can be additionally charged into the container 10 by the hopper 13 and the conduit 17 through the opening 18.
[0035]
Furthermore, in the agitation step, unnecessary materials such as resins mixed in the base metal scrap 2 etc. float on the liquid surface of the solution 3 after the treatment, but these unnecessary materials such as resins from the sieve opening 18, The container 10 can be taken out.
[0036]
Further, as will be described later, by allowing the sieve portion 15 to be detachable from the container 10, the solution 3, base metal scrap 2, metal particles, and the like after processing inside the container 10 can be discharged simultaneously, and maintenance of the container 10 can be performed. Can be easily.
In addition, as the sieve part 15, a commercially available punching metal etc. can be used suitably.
[0037]
[Recovery process]
When the stirring step proceeds and the metal ion-containing solution 1 becomes the solution 3 after the treatment and the metal particles are sufficiently formed, a step of recovering the solution 3 and the metal particles after the treatment is performed.
This recovery process will be described with reference to FIG.
First, as shown in FIG. 3B, in the recovery process, the container 10 is rotated in the reverse direction along the rotation axis 11. Then, the treated solution 3, the base metal scrap 2, and the metal particles in the container 10 are transported toward the container opening end 12 by the baffle portion 16. Here, the base metal scrap 2 is left inside the container 10 by the sieving part 15, but the treated solution 3 and the metal particles pass through the sieving part 15 and overflow from the container opening end 12.
[0038]
[Transportation / separation process]
Next, the transportation / separation process will be described.
The treated solution 3 and metal particles that have passed through the sieving part 15 and overflowed from the container opening end 12 are guided to the discharge chute 14 where the direction is controlled and the container is arranged below the chute. Held in. If the conveyor mentioned above is used as this container, a metal particle can be conveyed, separating the solution 3 and metal particle after a process, and is suitable. Here, with reference to FIG. 4 and FIG. 5, separation of the solution 3 after processing and metal particles and conveyance of the metal particles using the conveyor will be described.
First, as shown in FIG. 4, the processed solution 3 introduced into the conveyor casing 32 previously set below the discharge chute 14 is stored in the lower half of the conveyor casing 32 in general. The metal particles settle down below the solution.
When the treated solution 3 is stored in the conveyor casing 32, the liquid level is controlled by the overflow bar 36. At this time, the lower half of the chain conveyor 31 is below the liquid level. The upper half is preferably located above the liquid level.
[0039]
The settled metal particles are conveyed to the right side in FIG. 4 by a scraper 37 provided on the chain conveyor 31 shown in FIGS. 4 and 5, and above the liquid surface of the solution 3 after the treatment in the conveyor housing inclined portion 34. Moving. When the scraper 37 ascends along the slope in the conveyor casing inclined portion 34, the treated solution 3 flows downward from the slope through the gap 38 between the conveyor casing 32 and the scraper 37, and the metal particles are By being transported upward, the treated solution 3 and the metal particles are separated from each other, and the separated metal particles 4 reach the discharge port 35 and spontaneously fall from there, and a predetermined position in the deposition yard 53 To deposit.
As a different embodiment, it is possible to arrange a hopper or the like below the discharge port 35 so that the dropped metal particles are transferred to the next process by a transfer machine and continuously supplied. .
[0040]
The treated solution 3 that has flowed out of the conveyor housing 32 into the overflow basket 36 is guided to, for example, a thickener and processed appropriately.
[0041]
[Maintenance process]
If the recovery efficiency of the metal particles by the base metal scrap 2 decreases with the progress of the above-described stirring process and recovery process, a maintenance process for exchanging the base metal scrap is performed.
This maintenance process will be described with reference to FIG.
First, as shown in FIG.3 (c), a sieve part is removed from the container opening end 12, and the container 10 is reversely rotated. Then, the baffle portion 16 causes the base metal scrap 2 whose recovery efficiency has been lowered to be discharged from the container opening end 12.
Thus, the maintenance process in the container 10 can be carried out only by the detachment operation of the sieve portion 15 and the reverse rotation operation of the container 10.
[0042]
Here, in FIG. 4, the treated solution 3, metal particles and the like are discharged simultaneously with the base metal scrap 2 during the above-described maintenance process, but the conveyor 30 has a solid content regardless of the form of the solid content. Therefore, it is also preferable to separate and recover the base metal scrap 2 whose recovery efficiency has fallen by an appropriate means at the discharge port 35, for example.
[0043]
【Example】
(Example 1)
As an example of the present invention, a process of recovering copper particles as metal particles from smoke ash generated in a flash smelting furnace in copper smelting will be described, and the present invention will be described in more detail.
In this example, copper is a metal to be recovered, and the liquidity is sulfuric acid acid. When recovering copper contained in ash generated in copper smelting, the ash is once dissolved in sulfuric acid, This is because it is most effective in recovering copper from a solution obtained by dissolving copper in an acid solution and neutralizing the solution, and has a greater cost advantage than recovering by other methods.
[0044]
[Preparation process of metal ion-containing solution]
The smoke ash contains valuable metals such as copper, and its content is about 7%. Sulfuric acid is added to the smoke ash, and copper and the like contained in the smoke ash are dissolved with sulfuric acid. And when the thing which is not melt | dissolved in a sulfuric acid is removed, the pH of the said sulfuric acid solution is 1 or less strong acid. This is neutralized once and the pH is raised to 1 to 3. If there is a precipitate after neutralization, it is removed to obtain a copper sulfate solution containing copper ions, which is defined as a metal ion-containing solution.
At this time, the lower the pH, the faster the reaction, which is preferable. However, when impurities other than copper, such as smoke ash, are miscellaneous, the pH should be adjusted to avoid the influence of these impurities. Sometimes it is good.
[0045]
[Base metal lump preparation process]
When the metal ions to be recovered are copper ions and the solvent is a sulfuric acid solution, the base metal mass is preferably iron. This is because iron is easy to obtain, and it is easy to operate because it does not require any special place or atmosphere for handling.
Further, in the present example, iron scrap was used as the base metal mass because the base metal mass was a carrier for generating a copper layer on the surface. That is, the shape of the base metal mass is a solid mass at normal temperature, and the preferable mass shape is a scrap shape having a variety of shapes such as a waste iron material. For example, there are linear and plate-shaped iron scraps, and scrap cans that have been crushed by a press or the like. There are a wide variety of scrap shapes, especially asymmetric shapes and corners, individual weights vary greatly, and surface conditions are not constant. Therefore, in the copper recovery process described later, the generation location of the copper layer on the iron scrap is unevenly distributed and is thickly attached depending on the location. And when iron scraps collide, since the collision direction and stress become various, the copper layer produced | generated on the iron scrap becomes easy to peel.
[0046]
[Metal ion-containing solution and base metal scrap charging process]
Internal volume 8m ^Three A substantially barrel-shaped container was prepared, and a spiral baffle plate was installed inside the container. A sieve opening made of punching metal is installed at the container opening end, and the sieve opening is provided with a sieve opening concentric with the container opening end. Furthermore, a conduit for supplying the copper ion-containing liquid into the container was provided from the outside of the container through the sieve opening.
An iron scrap consisting of a scrap can was put into this container, and a sulfuric acid-containing copper-containing solution obtained from smoke ash was injected through a conduit while the container was rotated forward.
[0047]
The input ratio of the copper ion-containing liquid and iron scrap is preferably such that iron is 1.2 or more when the molar ratio of copper to iron is 1 in the container. This is because when the molar ratio of iron is 1.2 or more, the copper layer is generated quickly and the copper recovery efficiency is improved.
Therefore, the copper concentration of the copper-containing solution in the container and the weight of the iron scrap are measured, and the input ratio of the copper ion-containing liquid and the iron scrap is adjusted so that the molar ratio of copper / iron is 1.5. did.
[0048]
[Stirring step]
The angle of inclination of the rotation axis of the container is 15 °, the rotation speed is 5 RPM, and the injection amount of the copper-containing solution is 6 m in total. ^Three / Hr.
By controlling the inclination angle of the rotation axis, the amount of the copper-containing solution in the container and the residence time can be controlled, and the impact force when the iron scrap falls at the bottom end of the container can be controlled.
A larger number of rotations is more preferable for the reaction, but the number of rotations capable of keeping the iron scrap in a preferable state is appropriately set according to the size of the container, the amount of iron scrap, and the like.
[0049]
In order to repeat this stirring step and continuously carry out, a copper-containing solution was continuously supplied from the conduit, and iron scrap was appropriately added to prevent the copper / iron molar ratio from being 1.2 or less. In addition, the copper and iron concentrations in the treated copper-containing solution overflowing from the container opening are appropriately analyzed to confirm the reaction status of the stirring process, and the injection amount of the copper-containing solution and the amount of iron scrap input according to the analysis value The inclination of the container was adjusted.
As a result, friction and impact force are applied to the surface of the iron scrap inside the rotating container, and the copper layer generated in the meantime is peeled off, and the peeled copper particles settle down under the container or are treated. It overflowed from the container opening together with the later copper-containing solution. This stirring step was carried out continuously for 45 days.
[0050]
FIG. 6 shows the analysis results of the copper concentration of the injected copper-containing solution and the treated solution in this stirring process.
FIG. 6 shows the analysis result (g / l) of the copper concentration on the vertical axis, the elapsed days (days) on the horizontal axis, the copper concentration of the copper-containing solution, and the copper concentration of the solution after the treatment by ○. It is a graph.
From the results of FIG. 6, it was found that the copper recovery from the copper-containing solution was stably operated for 45 days.
[0051]
[Recovery process] / [Transport / separation process]
The copper particles obtained after the stirring step and the solution after treatment were put into a conveyor case, and the precipitated copper particles were separated by solid-liquid separation at the conveyor case inclined part while being transported by a scraper. Then, the copper particles were deposited in the precipitated copper yard, and the solution after the treatment was treated with a thickener as a post-process, or charged again into the container.
In the above 45-day test, the total copper ion-containing solution was 19500 m. ^Three The total amount of iron scrap (iron grade 80%) input was 240 tons. The recovered copper was 197 tons, and 53% of the amount of copper in the copper ion-containing solution could be recovered. The quality was 85%.
[0052]
(Example 2)
The same equipment, reaction conditions, and copper ion-containing solution as in Example 1 were used, except that clad material scrap in which copper was coated on approximately 50% of the iron surface was used instead of iron scrap as the base metal lump. The process which collect | recovers copper from the said copper ion containing solution was implemented continuously for 32 hours. The total copper ion containing solution is 640m ^Three Clad scrap (iron grade 65%) totaled 3 tons.
As a result, the recovered copper was 3.3 tons and the quality was 85%.
[0053]
【The invention's effect】
As described above in detail, the present invention is a metal recovery device for recovering a desired metal from a solution containing metal ions,
A drum-like container installed rotatably around an inclined rotation axis, and a rotating means for rotating the container in a forward and reverse direction,
A baffle portion having a spiral shape is provided on the inner periphery of the container from the upper open end to the lower bottom end,
It is a metal recovery device provided with a detachable sieve part at the opening end.
According to the collecting and collecting apparatus, a solution containing metal ions and a base metal lump are introduced into the container from the open end of the container, and the container is rotated forward by a rotating means so that the base metal lump collides with each other in the solution. Thus, the desired metal layer generated on the surface can be peeled off and granulated, and at the same time, the desired metal layer can be generated again on the surface. Next, the container is reversely rotated by the rotating means, the contents of the container are conveyed to the open end, and the processed solution and the desired metal particles are passed through the sieve portion continuously. Desired metal particles could be collected, and the base metal lump could be easily replaced by removing the sieve part as necessary.
[Brief description of the drawings]
FIG. 1 is a schematic side view of a metal recovery device and an accessory device according to the present invention.
FIG. 2 is a schematic plan view of a metal recovery device and an accessory device according to the present invention.
3 is a cross-sectional view taken along the line AA in FIG.
4 is a cross-sectional view taken along the line BB in FIG.
FIG. 5 is a cross-sectional view taken along the line CC of FIG.
FIG. 6 is an analysis result of the copper ion concentration in the injected copper-containing solution and the treated copper-containing solution according to the example.
FIG. 7 is a perspective view of the inside of the container 10 shown in FIGS.
[Explanation of symbols]
1. Metal ion-containing solution
2. Base metal scrap
3. Solution after treatment
4). Metal particles
10. container
11. Rotation axis core wire
12 Container open end
13. hopper
14 Discharge chute
15. Sieve
16. Baffle
17. conduit
18. Sieve opening
19. Bottom edge
20. Rotating means

Claims (3)

A metal recovery device for recovering a desired metal from a solution containing metal ions,
A drum-like container installed rotatably around an inclined rotation axis, and a rotating means for rotating the container in a forward and reverse direction,
In the inner periphery from the container opening end to the bottom end of the container, a baffle portion having a spiral shape is provided,
A metal recovery apparatus characterized in that a detachable sieving portion is provided at the open end of the container. The solution containing metal ions and the base metal mass are put into a drum-like container provided with a baffle portion having a spiral shape on the inner periphery from the opening end to the bottom end,
By rotating the container in a direction in which the solution containing the metal ions and the base metal mass are conveyed to the bottom end, the base metal mass rolls, and the base metal mass during the reaction while stirring the metal ion-containing solution After colliding each other and repeating friction, peeling off the metal layer to be collected generated on the base metal lump surface to make metal particles,
A metal recovery method comprising: reversely rotating the container, transporting the base metal mass and the metal particles toward the container opening end, taking out the metal particles from the container, and collecting the metal particles. The metal recovery method according to claim 2,
The metal ion-containing solution is a sulfuric acid acidic solution prepared from smoke ash and residue generated in a smelting process.

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