JP6902324B2 - Hydrometallurgy - Google Patents

Description

The present invention relates to a technique of a hydrometallurgical device used in a smelting process for extracting a metal from an ore, and more particularly to a technique of a hydrometallurgical device having an ultrafine bubble generator for generating fine bubbles in a liquid.

Conventionally, in metal smelting, dry smelting and hydrometallurgy are generally known as methods for separating impurities from ore. Of these, in hydrometallurgy, the metal-containing ore is crushed into a slurry, and acid is sprayed to leach the oxidized metal, and the leachate obtained by this is treated by solvent extraction or the like to be sparingly soluble. A method of separating the impurities of the above and recovering the metal from the liquid containing the metal oxide from which the impurities have been removed by electrowinning using an insoluble electrode is known (see, for example, Patent Document 1).

Further, in recent years, a technique for using ultrafine bubbles having a bubble size (diameter) of less than 100 μm at normal temperature and pressure in a liquid such as tap water, lakes / rivers, and seawater has attracted attention. The ultrafine bubbles have physicochemical properties such as a very large surface area and a self-pressurizing effect, and by utilizing these properties, a technique used for wastewater purification, cleaning, gas dissolution, stirring, etc. Has been developed.

Conventionally, as a method of generating ultrafine bubbles having the above characteristics, a liquid jet nozzle is arranged around a nozzle that discharges a gas pumped by a compressor, and bubbles discharged from the nozzle by the jet force of the liquid jet nozzle are generated. A method of tearing and making finer is known. Further, a method of subdividing the bubbles while applying the bubbles formed by stirring to the mesh member and passing them through is also known (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2011-21219 Japanese Patent No. 3958346

In hydrometallurgy, in the leaching step of crushing an ore containing a metal oxide into a slurry and spraying an acid to leach the metal, the reaction can be promoted by using an oxidizing agent containing oxygen in combination. However, when an oxidant containing oxygen is used in combination in such a leaching step, the reaction tank is filled with a strongly acidic acid, and the temperature is as high as about 100 ° due to the heat of reaction. The nozzle that emits oxygen is liable to deteriorate. Therefore, it is necessary to frequently perform maintenance of the nozzle and the like. Further, since the slurry has a high viscosity, it is not possible to generate a jet flow having a sufficient speed by the liquid jet nozzle, and it is not possible to miniaturize the bubbles. In order to further promote the reaction, it was necessary to efficiently dissolve the oxidizing agent in the acid in the reaction vessel.

Therefore, in view of the above problems, the present invention provides a hydrometallurgical apparatus having strong acid resistance and high temperature resistance and capable of efficiently dissolving an oxidizing agent in a slurry containing an acid in a reaction vessel.

The problem to be solved by the present invention is as described above, and next, the means for solving this problem will be described.

That is, in claim 1, an acid is sprayed on a slurry obtained by crushing a metal-containing ore to leach metal ions from the ore, and electrocollection is performed from a liquid containing metal ions using an insoluble electrode. In a wet smelting device that recovers metal, a reaction tank in which crushed ore is put into acid and leached by oxidizing the metal contained in the ore, and a gas is supplied as ultrafine bubbles inside the reaction tank. The ultrafine bubble generator includes an ultrafine bubble generator , the bubble generating medium which is a conductor formed of a carbon-based porous material, a pumping means for pumping a gas, and the pumping means to a central portion. A rotating shaft provided with a passage in the rotating shaft that communicates with the means, and a plurality of rotating bodies provided so as not to rotate relative to the rotating shaft and having a passage in the rotating body that communicates with the passage in the rotating shaft. generating medium, said through rotary body passageway and communicating, is fixed to the rotary member, the ultra-fine bubble generation device includes a pressure regulating valve for adjusting the pressure of the gas to be pumped from the pumping means, the pressure adjusting A control device for controlling the opening degree of the valve is provided, and the control device controls the pressure of the gas in the rotating body at the lower part to be larger than the pressure of the gas in the rotating body at the upper part.

In claim 2, the bubble generating medium is formed in a substantially streamlined cross-sectional view so that the wall thickness at the beginning portion in the rotation direction is thick and the wall thickness at the end portion in the rotation direction is thin .

As the effect of the present invention, the following effects are exhibited.

In claim 1, maintenance can be simplified by forming the bubble generating medium with a carbon-based material having high acid resistance and high temperature resistance. Further, since the bubble generating medium is formed of a porous member made of a carbon-based material, the oxidizing agent can be generated as ultrafine bubbles without generating a jet with a liquid jet nozzle or the like. By supplying the oxidizing agent as ultrafine bubbles into the slurry containing the acid, the dissolution efficiency of the gas becomes 80% or more, and the chance of contact with the metal contained in the ore increases, so that the metal contained in the slurry is oxidized. Be promoted. Further, since it is not necessary to arrange a member such as a liquid jet nozzle in the reaction tank, maintenance can be simplified. Further, by rotating the rotating body, it is possible to separate it from the bubble generating medium at the moment when the ultrafine bubbles generated on the surface of the bubble generating medium are generated. Therefore, ultrafine bubbles having a small particle size can be generated by a simple method. Further, it is possible to eliminate the difference in the amount of ultrafine bubbles generated depending on the depth at which the rotating body is arranged.

In claim 2, the bubble generating medium fixed to the rotating body can be rotated even in the liquid of the reaction vessel having a high viscosity.

The front view which showed the overall structure of the hydrometallurgical apparatus which concerns on one Embodiment of this invention. A front sectional view of the leaching device according to the first embodiment of the present invention. The front sectional view of the ultrafine bubble generator which concerns on 1st Embodiment of this invention. A partial perspective view of the ultrafine bubble generator according to the first embodiment of the present invention. The plan sectional view of the ultrafine bubble generator which concerns on 1st Embodiment of this invention. (A) A cross-sectional view taken along the line AA of the bubble generating medium according to the first embodiment of the present invention. (B) Partially enlarged cross-sectional view of the bubble generating medium according to the first embodiment of the present invention. A front sectional view of the leaching device according to the second embodiment of the present invention. A partial perspective view of the ultrafine bubble generator according to the second embodiment of the present invention. The front sectional view of the ultrafine bubble generator which concerns on 2nd Embodiment of this invention. A front sectional view of the leaching device according to the third embodiment of the present invention. A partially enlarged cross-sectional view of the bubble generating medium according to the third embodiment of the present invention. The front sectional view of the leaching device which concerns on 4th Embodiment of this invention. FIG. 3 is an enlarged cross-sectional view of a bubble generating medium according to a fourth embodiment of the present invention.

Next, embodiments of the invention will be described.
First, the overall configuration of the hydrometallurgical apparatus 1 according to the embodiment of the present invention will be described with reference to FIG.
The hydrometallurgical apparatus 1 crushes a metal-containing ore into a slurry, sprays an acid on the slurry to leach the oxidized metal, and treats the leachate obtained thereby by solvent extraction or the like to separate impurities. This is a device for recovering a metal from a liquid containing a metal oxide from which impurities have been removed by electrowinning using an insoluble electrode. The metals to be recovered include rare earth metals (rare earths), copper, zinc, titanium, gold and the like. The acid to be sprayed is sulfuric acid, nitric acid, hydrochloric acid or the like.
The hydrometallurgical apparatus 1 includes an leaching device 2 that sprays an acid on a metal-containing ore to leach the oxidized metal, and a separating device 3 that treats the leachate obtained thereby by solvent extraction or the like to separate impurities. A recovery device 4 for recovering a metal from a liquid containing a metal oxide from which impurities have been removed by electrowinning using an insoluble electrode is provided. In the present embodiment, the leaching device 2, the separating device 3, and the collecting device 4 are separately formed in order to explain, but they are configured as one device unit and all the devices are arranged in the device unit. It may be configured.

<First Embodiment>
Next, the leaching device 2 constituting the hydrometallurgy device 1 will be described in detail with reference to FIGS. 2 to 5.
The leaching device 2 is a reaction tank 11 in which crushed ore is put into an acid and leached by oxidizing a metal contained in the ore, and an ultrafine bubble generation that supplies gas as ultrafine bubbles inside the reaction tank 11. The device 12 is provided.

The reaction tank 11 is a cylindrical or polygonal tubular container, and a charging port 11A for charging crushed ore is formed above the reaction tank 11. Further, below the reaction vessel 11, a pull-out port 11B for pulling out the metal (metal oxide) oxidized by the acid as slag is formed. The reaction tank 11 is made of an acid resistant material. Further, the reaction tank 11 is formed so as to have a height of several meters to several tens of meters.

The ultrafine bubble generator 12 is a device for generating ultrafine bubbles in a liquid. Here, the hyperfine bubbles mean bubbles having a size (diameter) of less than 100 μm at normal temperature and pressure. As shown in FIGS. 2 and 3, the ultrafine bubble generator 12 is a device that supplies gas as ultrafine bubbles inside the reaction tank 11, and is a pumping means provided outside the reaction tank 11. At least one of a rotating shaft 23 having a rotating shaft passage 22 communicating with the compressor 21 in the central portion and a rotating internal passage 24 provided in the central portion so as to be non-rotatable relative to the rotating shaft 23 and communicating with the rotating shaft passage 22. The rotating body 25 and the bubble generating medium 26 communicating with the rotating body passage 24 and fixed to the rotating body 25 are provided. When the ultrafine bubble generator 12 is used, a portion below the middle portion of the rotating shaft 23 is arranged in the liquid of the reaction tank 11.

The pumping means is a device for pumping gas to the bubble generating medium 26 via the passage 22 in the rotating shaft and the passage 24 in the rotating body, and is composed of the compressor 21 in the present embodiment. The gas to be pumped is a gas used as an oxidant, such as air, oxygen, ozone or hydrogen peroxide.
The rotating shaft 23 is a member that is rotated by the driving means, and is composed of an outer cylinder 31 that is rotatably formed by the driving means and an inner cylinder 32 that is formed inside the outer cylinder 31. A driving means is connected to the upper end of the rotating shaft 23.
The driving means is a means for driving the rotating shaft 23, and more specifically, the driving means is composed of a rotary joint 33 for rotating the outer cylinder 31 of the rotating shaft 23. The rotary joint 33 is a driving means having a space for passing gas inside, and is connected to the outer cylinder 31. Further, in the internal space 33A of the rotary joint 33, the upstream side is connected to the compressor 21, and the downstream side is connected to the passage 22 in the rotating shaft.

The rotating shaft 23 is hollow, and a passage 22 in the rotating shaft for passing gas is provided in the hollow central portion thereof. The rotation shaft inner passage 22 is provided inside the outer cylinder 31 of the rotation shaft 23, and is composed of an inner cylinder 32 formed in a tubular shape. The inner cylinder 32 is configured to be non-rotatable even when the outer cylinder 31 is rotating, and a passage 22 in the rotating shaft is provided inside the inner cylinder 32. A rotating body 25 is provided below the rotating shaft 23 so as not to rotate relative to the outer cylinder 31. In the present embodiment, the rotating body 25 is provided at the lower end of the rotating shaft 23.

As shown in FIG. 3, the rotating body 25 is provided at the lower end of the rotating shaft 23, and the lower end of the outer cylinder 31 of the rotating shaft 23 and the rotating body 25 are fixed so as not to rotate relative to each other. Further, the passage 22 in the rotating shaft and the connecting hole 25A provided on the upper surface of the rotating body 25 are provided so as to be connected to each other. The lower surface of the communication hole 25A is closed, and a plurality of communication holes 25B are formed on the side surface thereof. The number of communication holes 25B is provided so as to be the same as the number of passages in the rotating body, which will be described later, and in the present embodiment, two are provided.
The rotating body passage 24 projects radially outward from the center of the rotating body 25, and one end thereof is connected to the communication hole 25A. Further, the other end of the passage 24 in the rotating body on the outer side in the radial direction is connected to the passage 27 in the bubble generating medium provided in the bubble generating medium 26.

The bubble generating medium 26 is made of a carbon-based porous material, and has a large number of fine holes 26A having a diameter of several μm to several tens of μm as shown in FIG. 6 (b). Further, the bubble generating medium 26 is a conductor, and the bubbles generated from the bubble generating medium 26 are negatively charged. In other words, a negative charge is charged by adding free electrons to the hyperfine bubbles when passing through the bubble generation medium 26, which is a conductor. This negative charge prevents the bubbles from repelling each other and coalescing into large bubbles.
The carbon-based porous material is a composite material containing only carbon or carbon and ceramic, and is an inorganic material.

Further, the bubble generating medium 26 is formed in a plate shape (substantially streamlined in cross section) so that the wall thickness at the head portion in the rotation direction (arrow direction in FIG. 5) is thick and the wall thickness at the end portion in the rotation direction is thin. .. The bubble generating medium 26 can be rotated and fixed in the vertical direction, whereby the inclination angle of the bubble generating medium 26 can be freely changed.
For example, when the bubble generating medium 26 is tilted downward, a slurry containing an acid in contact with the lower surface of the bubble generating medium 26 flows downward on the lower side of the bubble generating medium 26, so that the liquid is directed downward. A flow occurs, and on the upper side of the bubble generating medium 26, a slurry containing an acid flows along the upper surface of the bubble generating medium 26, so that a downward liquid flow is generated. As a result, the bubble generating medium 26 can be rotated to generate a downward liquid flow, and the slurry containing the acid can be agitated.
Even when a downward liquid flow is generated, if it is a normal bubble, it once sinks downward and then rises upward again, so it is necessary to apply a large pressure to send the bubble downward. However, according to the present embodiment, the ultrafine bubbles can be easily sent downward only by causing a downward liquid flow by utilizing the property that the buoyancy of the ultrafine bubbles is small.

The bubble generating medium 26 is provided with a passage 27 in the bubble generating medium. The bubble generation medium inner passage 27 is provided inside the bubble generation medium 26, bends from the middle part of the bubble generation medium 26 in the lateral direction, and is provided up to the middle part of the bubble generation medium 26 in the longitudinal direction. One end of the passage 27 in the bubble generating medium is connected to the passage 24 in the rotating body. Each connecting portion of the rotating shaft passage 22, the communication hole 25A, the communication hole 25B, the rotating body passage 24, and the bubble generating medium passage 27 is sealed to prevent the liquid from entering the inside.

Next, a method of generating ultrafine bubbles by the ultrafine bubble generator 12 will be described.
First, the rotating shaft 23 is driven. Specifically, the rotary joint 33 driven by a power source (not shown) rotates to rotate the outer cylinder 31 to rotate the rotating shaft 23. When the rotating shaft 23 rotates, the rotating body 25 provided at the lower end of the rotating shaft 23 rotates.
Next, the gas is pumped by the compressor 21. The gas pumped by the compressor 21 is sent to the passage 22 in the rotating shaft.
The gas sent to the passage 22 in the rotating shaft is sent to the passage 24 in the rotating body through the communication hole 25A and the communication hole 25B. The air sent to the inside passage 24 of the rotating body is sent to the passage 27 in the bubble generation medium, and the fine holes 26A having a diameter of several μm to several tens of μm provided in the bubble generation medium 26 from the passage 27 in the bubble generation medium. Through, it becomes ultrafine bubbles and is released into the liquid. The ultrafine bubbles released into the liquid are the flow created between the rotating bubble generating medium 26 and the surrounding liquid at the moment when they are released on the surface of the bubble generating medium 26 (in the direction of the arrow in FIG. 6A). Flow) separates it from the surface. With this configuration, the ultrafine bubbles generated later and the ultrafine bubbles generated from the surrounding holes 26A do not coalesce and move into the liquid independently.

The metal contained in the ore is oxidized by the oxidizing agent supplied into the reaction vessel 11 as ultrafine bubbles and leached into the acid. In addition, impurities, fine ores, and the like are deposited as slag in the reaction vessel 11. The deposited slag is pulled out from the pull-out port 11B and discharged. The leachate from which the slag has been removed is treated by solvent extraction or the like to further separate impurities, and the desired metal is obtained by recovering the metal from the liquid containing the metal oxide from which the impurities have been removed by electrowinning using an insoluble electrode. It becomes possible to smelt.

As described above, the metal is leached from the ore by spraying an acid on the crushed ore containing the metal into a slurry, and the metal is collected from the liquid containing the metal oxide by electrolytic sampling using an insoluble electrode. In the wet smelting apparatus 1 for recovering the above, the crushed ore is put into an acid, and the reaction tank 11 is leached by oxidizing the metal contained in the ore, and the gas is supplied as ultrafine bubbles inside the reaction tank 11. The ultrafine bubble generator 12 includes a bubble generating medium 26 formed of a carbon-based porous material, and the bubble generating medium 26 is arranged in the reaction vessel 11. Is to be done.
With this configuration, the gas that has become ultrafine bubbles is widely distributed in the liquid without moving above the reaction vessel 11 due to its nature, and there is an opportunity to come into contact with the metal contained in the ore. As it increases, the oxidation of the contained metal is promoted. Further, even in a strongly acidic and high temperature environment in the reaction vessel 11, the bubble generating medium 26 is formed of carbon-based porous material, so that it does not deteriorate and maintenance is improved. Further, by supplying the oxidizing agent as ultrafine bubbles into the slurry containing the acid, the dissolution efficiency of the gas becomes 80% or more, and the chance of contact with the metal contained in the ore increases. Oxidation is promoted.

Further, the ultrafine bubble generator 12 includes a compressor 21 which is a pumping means for pumping gas, a rotating shaft 23 provided with a passage 22 in a rotating shaft communicating with the compressor 21 in the center, and a rotating shaft 23 on the rotating shaft 23. At least one rotating body 25, which is provided so as to be non-rotatable and has a rotating body passage 24 communicating with the rotating shaft passage 22, and the bubble generating medium 26 communicates with the rotating body passage 24 and communicates with the rotating body. It is fixed at 25.
With this configuration, even in the liquid of the reaction tank 11 having a high viscosity, it is possible to efficiently generate ultrafine bubbles by rotating the bubble generating medium 26 fixed to the rotating body 25. Further, by rotating the rotating body 25 and the bubble generating medium 26, a downward liquid flow is generated, and the ultrafine bubbles can be easily sent downward by utilizing the property that the buoyancy of the ultrafine bubbles is small. Therefore, ultrafine bubbles having a small particle size can be generated by a simple method.

<Second embodiment>
Further, as another embodiment, it is also possible to provide an ultrafine bubble generator 112 having a plurality of rotating bodies 125 on the upper and lower sides. As shown in FIGS. 7 to 9, as compared with the first embodiment, the ultrafine bubble generator 112 is provided with a plurality of rotating bodies 125 on the rotating shaft 23. Here, since the configuration of the rotating body 125 is the same as the configuration of the rotating body 25 of the first embodiment, the description thereof will be omitted. Further, since the parts having the same numbers as those of the first embodiment have the same configuration as that of the first embodiment, the description thereof will be omitted.

As shown in FIG. 9, the rotating shaft inner passage 122 is provided inside the outer cylinder 31 and the inner cylinder 32 of the rotating shaft 23, and one passage 141 is provided for one rotating body 125. .. In this embodiment, three rotating bodies 125 are provided, and three corresponding passages 141 are provided. A pressure regulating valve 142 is provided in the middle of each passage 141. The pressure regulating valve 142 is composed of a solenoid valve and is connected to the control device 150.
Further, each passage 141 is provided with a flow rate sensor 151. The flow rate sensor 151 is a means for measuring the flow rate of the gas flowing in the passage 141, and is connected to the control device 150.

The rotating body 125 is provided at the upper part, the middle part, and the lower part of the rotating shaft 23. The rotating body 125 is fixed to the outer cylinder 31 of the rotating shaft 23 so as not to rotate relative to the outer cylinder 31. Further, the passage 22 in the rotating shaft and the communication hole 125A provided at the center of the plane of the rotating body 125 are provided so as to be connected to each other. The lower surface of the communication hole 125A is closed, and a plurality of communication holes 125B are provided on the side surface thereof.
The rotating body passage 124 protrudes outward in the radial direction from the center of the rotating body 125, and one end thereof is connected to the communication hole 125B. Further, the other end of the passage 124 in the rotating body on the outer side in the radial direction is connected to the passage 127 in the bubble generating medium provided in the bubble generating medium 126.

The rotating body passage 124 has a communication hole projecting from the center of the rotating body 125 to the outside in the radial direction, and one end thereof is connected to the communication hole 125B. Further, the other end of the passage 124 in the rotating body on the outer side in the radial direction is connected to the passage 127 in the bubble generating medium provided in the bubble generating medium 126.

Regarding the pressure in the passage 141, the control device 150 controls the pressure of the passage 141 connected to the lower rotating body 125 so as to be larger than the pressure of the passage 141 connected to the upper rotating body 125. In the reaction vessel 11, since the liquid pressure is higher in the lower part than in the upper part, it is necessary to increase the pressure for ejecting the gas as the liquid pressure is arranged in the lower part. Therefore, by forming the pressure of the passage 141 connected to the lower rotating body 125 to be larger than the pressure of the passage 141 connected to the upper rotating body 125, the ultrafineness depends on the depth at which the rotating body 125 is arranged. It is possible to eliminate the difference in the amount of bubbles generated.

Next, a method of generating ultrafine bubbles by the ultrafine bubble generator 112 will be described.
First, the rotating shaft 23 is driven. Specifically, the rotary joint 33 driven by a power source (not shown) rotates to rotate the outer cylinder 31 to rotate the rotating shaft 23. When the rotating shaft 23 rotates, the rotating body 125 provided at the middle portion and the lower end of the rotating shaft 23 rotates.
Next, the gas is pumped by the compressor 21. The gas pumped by the compressor 21 is sent to each passage 141 provided in the passage 22 in the rotating shaft. Here, the control device 150 controls the pressure of the passage 141 connected to the lower rotating body 125 so as to be larger than the pressure of the passage 141 connected to the upper rotating body 125.
The gas sent to each passage 141 is sent to the rotating body passage 124 through the communication hole 125A and the communication hole 125B. The air sent to the rotating body passage 124 is sent to the bubble generation medium passage 127, and the air is provided from the bubble generation medium passage 127 to the bubble generation medium 126 through fine holes having a diameter of several μm to several tens of μm. Through it, it becomes ultrafine bubbles and is released into the liquid. The ultrafine bubbles released into the liquid are separated from the surface by the flow generated between the rotating bubble generation medium 126 and the surrounding liquid at the moment when the bubbles are released to the surface of the bubble generation medium 126. With such a configuration, it moves into the liquid independently without being combined with the ultrafine bubbles generated later and the ultrafine bubbles generated from the surrounding holes.

The metal contained in the ore is oxidized by the oxidizing agent supplied into the reaction vessel 11 as ultrafine bubbles and leached into the acid. In addition, impurities, fine ores, and the like are deposited as slag in the reaction vessel 11. The deposited slag is pulled out from the pull-out port 11B and discharged. The leachate from which the slag has been removed is treated by solvent extraction or the like to further separate impurities, and the desired metal is obtained by recovering the metal from the liquid containing the metal oxide from which the impurities have been removed by electrowinning using an insoluble electrode. It becomes possible to smelt.

Further, the flow rate sensor 151 detects the flow rate of the gas flowing in each passage 141, and when the flow rate of the gas becomes equal to or less than a predetermined value, the control device 150 adjusts the opening degree of the pressure adjusting valve 142. The flow rate of the gas flowing in each passage 141 is controlled to be uniform.

As described above, the metal is leached from the ore by spraying an acid on the crushed ore containing the metal into a slurry, and the metal is collected from the liquid containing the metal oxide by electrolytic sampling using an insoluble electrode. In the wet smelting apparatus 1 for recovering the above, the crushed ore is put into an acid, and the reaction tank 11 is leached by oxidizing the metal contained in the ore, and the gas is supplied as ultrafine bubbles inside the reaction tank 11. The ultrafine bubble generator 112 includes a bubble generating medium 126 formed of a carbon-based porous material, and the bubble generating medium 126 is arranged in the reaction vessel 11. Is to be done.
With this configuration, the gas that has become ultrafine bubbles is widely distributed in the liquid without moving above the reaction vessel 11 due to its nature, and there is an opportunity to come into contact with the metal contained in the ore. As it increases, the oxidation of the contained metal is promoted. Further, even in a strongly acidic and high temperature environment in the reaction vessel 11, the bubble generating medium 126 is formed of carbon-based porous material, so that it does not deteriorate, so that maintainability is improved. Further, by supplying the oxidizing agent as ultrafine bubbles into the slurry containing the acid, the dissolution efficiency of the gas becomes 80% or more, and the chance of contact with the metal contained in the ore increases. Oxidation is promoted.

<Third Embodiment>
Further, as another embodiment, as shown in FIGS. 10 and 11, it is also possible to provide an ultrafine bubble generator 312 outside the reaction vessel 11. The ultrafine bubble generator 312 includes a circulation passage 301 and a bubble generation medium 302 provided in the circulation passage 301. Here, since the parts having the same numbers as those in the first embodiment have the same configuration as those in the first embodiment, the description thereof will be omitted.

The circulation passage 301 is a passage for circulating the liquid in the reaction tank 11, and the pump 303 is provided in the middle of the circulation passage 301. Further, the bubble generating medium 302 is provided inside the circulation passage 301. The bubble generating medium 302 is configured to have a spindle shape with a cone-shaped tip on the downstream side, and as shown in FIG. 11, an internal space 302A is provided inside the bubble generating medium 302. Further, the bubble generating medium 302 is formed of a carbon-based porous material. The bubble generating medium 302 has fine holes 302B having a diameter of several μm to several tens of μm. A compressor 304, which is a pumping means, is connected to the internal space 302A of the bubble generating medium 302.

The bubble generating medium 302 is formed so that the liquid flows along the surface, and in the present embodiment, the bubble generating medium 302 is provided so that the longitudinal direction of the bubble generating medium 302 is parallel to the flow of the liquid in the circulation passage 301. ing.

Next, a method of generating ultrafine bubbles by the ultrafine bubble generator 312 will be described.
First, the pump 303 is driven to generate a liquid flow in the circulation passage 301. Next, the gas is pumped by the compressor 304. The gas pumped by the compressor 304 is sent to the internal space 302A.
The gas sent to the internal space 302A passes through fine holes 302B having a diameter of several μm to several tens of μm, becomes ultrafine bubbles, and is discharged into the liquid. The ultrafine bubbles released into the liquid are separated from the surface by the liquid flow in the circulation passage 301 at the moment when the bubbles are released to the surface of the bubble generation medium 302. With such a configuration, the ultrafine bubbles generated later and the ultrafine bubbles generated from the peripheral holes 302B do not coalesce and move into the liquid independently.

The metal contained in the ore is oxidized by the oxidizing agent supplied into the reaction vessel 11 as ultrafine bubbles and leached into the acid. In addition, impurities, fine ores, and the like are deposited as slag in the reaction vessel 11. The deposited slag is pulled out from the pull-out port 11B and discharged. The leachate from which the slag has been removed is treated by solvent extraction or the like to further separate impurities, and the desired metal is obtained by recovering the metal from the liquid containing the metal oxide from which the impurities have been removed by electrowinning using an insoluble electrode. It becomes possible to smelt.

As described above, the metal is leached from the ore by spraying an acid on the crushed ore containing the metal into a slurry, and the metal is collected from the liquid containing the metal oxide by electrolytic sampling using an insoluble electrode. In the wet smelting apparatus 1 for recovering the above, the crushed ore is put into an acid, and the reaction tank 11 is leached by oxidizing the metal contained in the ore, and the gas is supplied as ultrafine bubbles inside the reaction tank 11. The ultrafine bubble generator 312 includes a bubble generating medium 302 formed of a carbon-based porous material, and the bubble generating medium 302 is located outside the reaction vessel 11. It is to be placed.
With this configuration, the gas that has become ultrafine bubbles is widely distributed in the liquid without moving above the reaction vessel 11 due to its nature, and there is an opportunity to come into contact with the metal contained in the ore. As it increases, the oxidation of the contained metal is promoted. Further, even in a strongly acidic and high temperature environment in the reaction vessel 11, the bubble generating medium 302 is formed of carbon-based porous material, so that it does not deteriorate, so that maintainability is improved. Further, by supplying the oxidizing agent as ultrafine bubbles into the slurry containing the acid, the dissolution efficiency of the gas becomes 80% or more, and the chance of contact with the metal contained in the ore increases. Oxidation is promoted.

<Fourth Embodiment>
Further, as another embodiment, it is also possible to provide the bubble generating medium 426 separately from the rotating body 425 and to provide the ultrafine bubble generating device 412 in which the bubble generating medium 426 is fixed in the reaction tank 11.
As shown in FIG. 12, the ultrafine bubble generator 412 includes a compressor 21, a rotating shaft 423, and at least one or more rotating bodies 425 provided so as to be non-rotatable relative to the rotating shaft 423. , A bubble generating medium 426 which is in the vicinity of the rotating body 425 and is fixed in the reaction tank 11. Here, since the parts having the same numbers as those in the first embodiment have the same configuration as those in the first embodiment, the description thereof will be omitted.

The pumping means is a device for pumping gas to the bubble generating medium 426, and is composed of a compressor 21 in the present embodiment. The gas to be pumped is a gas used as an oxidant, such as air, oxygen, ozone or hydrogen peroxide.
The rotating shaft 423 is a member that is rotated by the driving means, and is a cylindrical member that is rotatably configured by the driving means.
The driving means is a means for driving the rotating shaft 423, and more specifically, the driving means is composed of a motor 433 for driving the rotating shaft 23. In the present embodiment, the motor 433 and the drive shaft 423 are connected via a power transmission means such as a gearbox (not shown).

A plurality of rotating bodies 425 are provided on the rotating shaft 423. In this embodiment, three rotating bodies 425 are provided. The rotating body 425 is provided at the upper part, the middle part, and the lower part of the rotating shaft 423. The rotating body 425 is fixed to the rotating shaft 423 so as not to rotate relative to the rotating shaft 423.
Rotating blades 431 are provided on the outer side of the rotating body 425 in the radial direction. The rotary vane 431 is a member for agitating the liquid in the reaction vessel 11, and is formed in the shape of a propeller in the present embodiment. The rotating body 425 and the rotating blade 431 are made of a carbon-based porous material. The carbon-based porous material is a composite material containing only carbon or carbon and ceramic, is an inorganic material, and has fine pores having a diameter of several μm to several tens of μm.

The bubble generating medium 426 is fixed to the wall surface of the reaction tank 11 at a position substantially intermediate between the rotating body 425 and the rotating body 425 in the vertical direction. Two bubble generating media 426 are provided in the vertical direction.
The bubble generating medium 426 is formed in a ring shape, and an internal space 426A is provided inside the bubble generating medium 426. Further, the bubble generating medium 426 is formed of a carbon-based porous material. The bubble generating medium 426 has fine holes 426B having a diameter of several μm to several tens of μm. A compressor 21, which is a pumping means, is connected to the internal space 426A of the bubble generating medium 426.

Next, a method of generating ultrafine bubbles by the ultrafine bubble generator 412 will be described.
First, the rotating shaft 423 is driven to generate a liquid flow. Specifically, the rotation shaft 423 is rotated by driving the motor 433. When the rotating shaft 423 rotates, a plurality of rotating bodies 425 provided at the middle portion and the lower end of the rotating shaft 423 rotate. As the rotating body 425 rotates, the rotating blades 431 provided on the outer side of the rotating body 425 in the circumferential direction rotate. As the rotary blade 431 rotates, the liquid is agitated and a liquid flow is generated. In the present embodiment, a liquid flow that is agitated toward the lower side of the rotary blade 431 is generated. Next, the gas is pumped by the compressor 21. The gas pumped by the compressor 21 is sent to the internal space 426A.
The gas sent to the internal space 426A becomes ultrafine bubbles and is discharged into the liquid through fine holes 426B having a diameter of several μm to several tens of μm. The ultrafine bubbles released into the liquid are separated from the surface by the liquid flow in the reaction tank 11 at the moment when they are released to the surface of the bubble generation medium 426. Specifically, as shown in FIG. 13, the liquid flow generated by the rotation of the upper rotary vane 431 flows from the upper side to the lower side, and further flows along the surface of the bubble generation medium 426. With such a configuration, it moves into the liquid independently without being combined with the ultrafine bubbles generated later and the ultrafine bubbles generated from the peripheral holes 426B.

The metal contained in the ore is oxidized by the oxidizing agent supplied into the reaction vessel 11 as ultrafine bubbles and leached into the acid. In addition, impurities, fine ores, and the like are deposited as slag in the reaction vessel 11. The deposited slag is pulled out from the pull-out port 11B and discharged. The leachate from which the slag has been removed is treated by solvent extraction or the like to further separate impurities, and the desired metal is obtained by recovering the metal from the liquid containing the metal oxide from which the impurities have been removed by electrowinning using an insoluble electrode. It becomes possible to smelt.

As described above, the metal is leached from the ore by spraying an acid on the crushed ore containing the metal into a slurry, and the metal is collected from the liquid containing the metal oxide by electrolytic sampling using an insoluble electrode. In the wet smelting apparatus 1 for recovering the above, a reaction tank 11 in which crushed ore is put into an acid and leached by oxidizing a metal contained in the ore, and a gas is supplied as ultrafine bubbles inside the reaction tank 11. The ultrafine bubble generator 412 is provided with a compressor 21, a rotating shaft 423, and a rotating shaft 423 that are non-rotatable relative to the rotating shaft 423. The rotating body 425 and the bubble generating medium 426 which is in the vicinity of the rotating body 425 and is fixed in the reaction tank 11 are provided.
With this configuration, the gas that has become ultrafine bubbles is widely distributed in the liquid without moving above the reaction vessel 11 due to its nature, and there is an opportunity to come into contact with the metal contained in the ore. As it increases, the oxidation of the contained metal is promoted. Further, even in a strongly acidic and high temperature environment in the reaction tank 11, the bubble generating medium 426, the rotating body 425 and the rotating blade 431 are formed of carbon-based porous material, so that they do not deteriorate, so that maintenance is performed. Improves sex. Further, by supplying the oxidizing agent as ultrafine bubbles into the slurry containing the acid, the dissolution efficiency of the gas becomes 80% or more, and the chance of contact with the metal contained in the ore increases. Oxidation is promoted.

11 Reaction tank 12 Ultra-fine bubble generator 21 Compressor (pressure feeding means)
22 Passage in the rotating shaft 23 Rotating shaft 23
24 Rotating body passage 25 Rotating body 26 Bubble generating medium 27 Bubble generating medium Inner passage 31 Outer cylinder 32 Inner cylinder 33 Rotary joint

Claims (2)

A hydrometallurgical device that recovers metal from a liquid containing metal ions by electrowinning using an insoluble electrode by spraying acid on a slurry made by crushing the ore containing metal to leach metal ions from the ore. In
A reaction tank in which crushed ore is put into acid and leached by oxidizing the metal contained in the ore.
An ultrafine bubble generator that supplies gas as ultrafine bubbles inside the reaction vessel is provided.
The ultrafine bubble generator is
A bubble generation medium, which is a conductor formed of a carbon-based porous material,
A pumping means that pumps gas and
A rotating shaft provided with a passage in the rotating shaft communicating with the pumping means in the central portion,
A plurality of rotating bodies provided so as to be non-rotatable relative to the rotating shaft and having a passage in the rotating body communicating with the passage in the rotating shaft.
The bubble generating medium communicates with the passage in the rotating body and is fixed to the rotating body.
The ultrafine bubble generator is
A pressure adjusting valve for adjusting the pressure of the gas pumped from the pumping means, and
A control device for controlling the opening degree of the pressure adjusting valve is provided.
The control device is a hydrometallurgical device that controls the pressure of the gas in the rotating body at the lower part to be higher than the pressure of the gas in the rotating body at the upper part. The bubble generating medium is
It is formed in a streamlined cross-sectional view so that the wall thickness at the beginning in the rotation direction is thick and the wall thickness at the end in the rotation direction is thin.
The wet smelting apparatus according to claim 1.

Images