WO2007004664A1 - Process for recovery of metals and equipment therefor - Google Patents

Abstract

The invention relates to a process for recovering heavy metals such as nickel (Ni), copper (Cu), tin (Sn), indium (In), and gallium (Ga) as valuable simple substances or alloys from a raw effluent (such as wastewater) containing them and equipment for the recovery and aims at providing a process for recovery by which only objective metals can be recovered as valuable simple substances or alloys little containing impurity metals from a raw effluent such as wastewater with high recovery and at high purity; and equipment for the recovery. The process is characterized by incorporating a raw effluent containing objective metals in the form of ions with a precipitating metal having an ionization tendency higher than those of the objective metals, making the objective metals contained in the raw effluent deposit on the surface of the precipitating metal by utilizing the difference between both in ionization tendency, and then scaling the objective metals from the precipitating metal by a scaling means to recover them.

Description

 Specification

 Metal recovery method and apparatus

 Technical field

 [0001] The present invention relates to a metal recovery method and apparatus, and more particularly, a waste liquid containing heavy metals such as Ni (nickel), Cu (copper), Sn (tin), In (indium), and Ga (gallium). The present invention relates to a method and an apparatus for recovering, as an alloy, a metal simple substance that is a valuable material from a liquid to be processed. Background art

 [0002] In general, industrial waste liquids may contain various metals, and attempts have been made to recover them as simple metals that are valuable resources. For example, the METSUKI factory effluent contains Ni, Cu, Zn, etc., the semiconductor manufacturing factory effluent contains Cu, Ga, etc., and the liquid crystal manufacturing factory effluent contains In etc. If it can be recovered as an alloy, these metals can be reused.

 [0003] Conventionally, coagulation sedimentation treatment and coprecipitation treatment using chemicals are generally adopted as waste liquid treatment technology to recover heavy metals. When the concentration is low, metals are removed using an adsorbent. It is also done. There is also a method for recovering metals from waste metal liquids, in which iron scrap is introduced into the waste metal liquid and the metals to be recovered such as Cu are recovered by the cementation method. For example, there is an invention according to Patent Document 1 below as a technique using coprecipitation

[0004] Patent Document 1: Japanese Patent Laid-Open No. 2002-126758

 [0005] However, in the coagulation sedimentation treatment using a chemical, there is a problem in that it is generated as a precipitate sediment of hydroxide. In addition, in a method in which iron scrap is introduced into the waste plating solution and Cu is deposited by the cementation method, the precipitation reaction ends when the deposited Cu covers the surface of the iron scrap, and the iron is coated with Cu. It will be recovered, and only the target metal cannot be recovered as the target metal. In addition, there is a problem that the recovery rate is low and the purity is low, and it is impossible to obtain the strength.

 Disclosure of the invention

Problems to be solved by the invention [0006] The present invention has been made to solve such a problem, and only a target metal can be recovered as a valuable metal element or alloy from a liquid to be treated such as a waste liquid. It is another object of the present invention to provide a recovery method and apparatus having a high recovery rate with a low possibility of containing impurities other than the recovery target metal and a high purity of the recovery target metal.

 Means for solving the problem

 [0007] The present invention has been made to solve such problems, and the liquid to be treated containing the metal to be recovered in an ion state has a higher ionization tendency than the metal to be recovered. Then, a deposition metal is added, and the collection target metal contained in the liquid to be treated is deposited on the surface of the deposition metal due to a difference in ionization tendency, and then the collection target is separated from the deposition metal by a peeling means. Provided is a method for recovering a metal, characterized by peeling and recovering the metal. In such a metal recovery method, the liquid to be processed containing the metal to be recovered in an ionic state may flow into the reactor main body, and the deposition metal may be added to the reactor main body.

 [0008] Precipitation metal force As means for separating the metal to be collected, means for vibrating the metal for precipitation by ultrasonic waves, means for agitating the metal for precipitation by an electromagnet and causing a large number of metals for precipitation to collide with each other , Means for stirring the metal for precipitation by air jet or water jet, means for providing a cylindrical part in the reactor main body, and means for stirring the metal for precipitation by blowing gas into the cylindrical part, A channel and a pump for circulating and transporting the deposition metal are provided outside the reactor main body, and means for stirring the deposition metal by circulating and transporting the liquid to be treated and the deposition metal are employed. be able to.

 [0009] As the deposition metal, for example, metal particles are used. The average particle size of the metal particles is preferably 0.1 to 8 mm, more preferably 0.5 to 6 mm. 1.0 to

2. More preferably, it is Omm.

[0010] When the metal particles are aluminum, the average particle size is preferably 1.5 to 5.5 mm. When the metal particles are zinc, the average particle size is preferably 1.5 to 4. Omm.

[0011] The metal to be collected is contained in an ionic state !, and the liquid to be treated flows into the reactor body In this case, it is preferable that the liquid to be treated is configured to flow into the lower force of the reactor main body and to flow out of the upper portion of the reactor main body.

 [0012] Further, when the liquid to be treated flows into the reactor main body, the reactor main body may be configured so that the cross-sectional area of the reactor main body increases upward. Further, two or more kinds of metals to be collected may be selectively recovered by using two or more different kinds of deposition metals by using a multi-stage reactor body. Further, the separated metal to be collected may be collected with a filter.

 [0013] Further, in the case where nitrate ions are contained in the liquid to be treated in addition to the metal to be recovered in an ionic state, a chlorine ion source may be added to the liquid to be treated together with the deposition metal. In this case, the liquid to be treated flows into the adjustment tank and a chlorine ion source is added to the adjustment tank. Then, the liquid to be treated in the adjustment tank flows into the reactor main body and the reactor main body. A metal for precipitation may be added inside. Furthermore, when such a chlorine ion source is added, the processing liquid after recovering the metal to be recovered from the deposition metal may be added to the liquid to be processed which is the stock solution, and then processed again. .

 [0014] In addition, the present invention flows in a liquid to be collected containing the metal to be recovered in an ionic state, and adds a deposition metal having a higher ionization tendency than the metal to be recovered. Due to the difference, a reactor main body for performing a metal precipitation reaction for precipitating the metal to be collected contained in the liquid to be treated on the surface of the metal for precipitation, and for collecting the deposited metal to be collected should be collected. There is provided a metal recovery device comprising a peeling means for peeling off a metal force.

[0015] In such a metal recovery apparatus, as a means for separating the recovery target metal from the deposition metal, means for vibrating the deposition metal by ultrasonic waves, stirring the deposition metal with an electromagnet, Means for colliding the metal with each other, means for stirring the metal for precipitation by air jet or water jet, means for providing a cylindrical part in the reactor body, and stirring the metal for precipitation by blowing gas into the cylindrical part In addition, a flow path and a pump for circulating and transporting the liquid to be treated and the metal particles in the reactor main body and a pump are provided outside the reactor main body, and the liquid to be treated and the metal for deposition are circulated and transported for the deposition. A means for stirring the metal is employed. [0016] For example, the reactor main body has an inflow portion for the liquid to be processed in the lower portion thereof, and has a liquid outflow portion in the upper portion, and the inflow portion force the liquid to be processed flows into the reactor main body, and the liquid outflow portion Configured to flow out of

 [0017] Further, the reactor main body may be configured such that its cross-sectional area increases upward. Further, a plurality of reactor bodies may be provided. In addition, a filter for recovering the separated metal to be recovered may be disposed after the reactor body.

 [0018] Sarakuko, a recovery tank containing a liquid to be treated containing a metal to be collected in an ionic state and containing nitrate ions, and adjusting by adding a chlorine ion source, You may provide in the front | former stage side. Furthermore, a return flow path may be provided in which the processing liquid after recovering the metal to be recovered from the deposition metal is added to the liquid to be processed which is the stock solution and the processing is performed again.

 The invention's effect

 [0019] As described above, the present invention adds a deposition metal having a higher ionization tendency than the metal to be recovered to the liquid to be recovered in which the metal to be recovered is contained in an ionic state. The recovery target metal contained in the liquid to be treated is deposited on the surface of the deposition metal due to the difference between the two, and then the recovery target metal is stripped from the deposition metal by a stripping means and recovered. For this reason, the recovery target metal that has grown to some extent on the surface of the depositing metal is peeled off by the stripping means, so that the new metal surface can always be exposed and the reaction rate can be maintained. This has the effect of increasing efficiency.

 [0020] In particular, when metal particles having an average particle size of 0.1 to 8 mm are used as the deposition metal, for example, the total surface area of the deposition metal for the metal deposition reaction as compared with a method using iron scrap. This increases the precipitation reaction rate and further increases the recovery efficiency of the metal to be recovered.

[0021] When the liquid to be treated flows into the reactor main body and metal particles with an average particle size of 0.1 to 8 mm, which is a metal for precipitation, are added to the reactor main body, Thus, the metal particles can be suitably flowed, and the separation effect of the metal to be recovered from the deposition metal can be further improved. [0022] Further, when the reactor main body is configured so that the liquid to be treated flows in from the lower part of the reactor main body and the upper force of the reactor main body flows out and the cross-sectional area of the reactor main body increases upward, the reactor main body In the reactor main body, the cross-sectional area of the metal particles, which is a metal for precipitation whose particle size is reduced by the metal precipitation reaction as described above, gradually decreases. At the top, it can be held in the reactor body without inadvertent overflow.

 [0023] In addition, the liquid to be treated flows into the lower side of the reactor main body, and when passing through the reactor main body, the recovery target metal is deposited on the deposited metal, and thus the liquid to be treated is directed toward the upper part of the reactor main body. As the concentration of the metal to be recovered in the liquid to be treated decreases and the particle size of the deposited metal particles decreases as described above, finer metal particles are present in the upper part of the reactor body, and further, Since it is recognized that the number of metal particles increases as the upward flow velocity of the liquid gradually decreases, the total surface area of the metal particles increases toward the top of the reactor body, and as a result, the reaction rate of the metal precipitation reaction increases. As a result, the recovery target metal can be efficiently recovered even in the upper part of the reactor body where the concentration of the recovery target metal is lower.

 [0024] Further, when a reactor body having a plurality of stages is provided, and a filter is provided at the subsequent stage, in the case where two or more kinds of metals are contained in the liquid to be treated, for example, the first stage Reactor body deposits some metal and collects it with the first stage filter, while the second stage reactor body deposits other metal and the second stage filter collects the other metal. This makes it possible to selectively recover two or more types of metals to be recovered from the liquid to be treated using two or more different types of deposited metals.

[0025] Further, in the case of a liquid to be treated containing nitrate ions in addition to the metal to be recovered in an ionic state, particularly the metal power to be recovered, S indium (In), the above difference in ionization tendency was used. Force that metal precipitation reaction may not occur suitably In addition to the metal for precipitation, a chlorine ion source is added to the liquid to be treated. Even though nitrate ions are present in the liquid to be treated, the chlorine Due to the presence of the ion source, it becomes possible to suitably deposit a metal to be recovered such as In on the deposition metal, and by separating the deposition metal force In by the stripping means, compared to the conventional method. In can be collected easily. [0026] When nitrate ions are present in the liquid to be treated as described above, the chlorine ion source can be added to the liquid to be treated, even though In cannot be deposited on the deposition metal. The reason why precipitation is possible is considered as follows. In other words, it is recognized that the presence of nitrate ions at a certain concentration in In changes the form in the solution, thereby lowering the standard reduction potential of In below the normally considered value, The standard reduction potential of A1 and Zn constituting the metal for the metal also rises, and the potential difference between the recovered metal In and the precipitation metals Al, Zn, etc. becomes smaller, making it difficult to reduce the In precipitation. Not considered a force. Therefore, when a chloride salt such as sodium chloride or potassium salt or hydrochloric acid was added as a chlorine ion source, In formed a black-opened complex, and the standard reduction potential that had been lowered by nitrate ion increased again. However, it seems that it will be possible to reduce and deposit In on the metal for precipitation.

 [0027] Another reason is that the potential of In changes due to the presence of nitrate ions in the liquid to be treated and becomes a stable potential in the pH diagram as In ions. The power of the reduction reaction caused by the addition of the C1 ion changes to a region in the potential-pH diagram that is stable as an In metal, and the reduction reaction due to the precipitation metal A1 tends to occur. It is also possible to meet.

 [0028] Furthermore, nitrate ions in the solution react with A1 and Zn constituting the deposition metal to form nitrogen dioxide and nitric oxide, which are released as a gas.

 [0029] In addition, when the treatment liquid after depositing and collecting indium by the deposition metal is added to the treatment liquid that is the stock solution and the treatment is performed again, chlorine is added to the treatment liquid after the indium recovery. Since ions remain, the result is that the remaining chlorine ions are reused. As a result, the amount of added chlorine ion source can be reduced, and the processing cost can be reduced. And there is an effect.

 Brief Description of Drawings

FIG. 1 is a schematic front view of a metal recovery apparatus as one embodiment.

 FIG. 2 is a schematic front view of a metal recovery apparatus according to another embodiment.

 FIG. 3 is a schematic perspective view of a metal recovery apparatus according to another embodiment.

FIG. 4 is a schematic sectional view of a metal recovery apparatus according to another embodiment. FIG. 5 is a schematic plan view of an inflow chamber in a metal recovery apparatus according to another embodiment.

 FIG. 6 is a cross-sectional view taken along line AA in FIG.

 FIG. 7 is a schematic front view of a metal recovery apparatus according to another embodiment.

 FIG. 8 is a schematic plan view of a slide board provided with an electromagnet used in the embodiment of FIG.

 FIG. 9 is a schematic block diagram of a metal recovery apparatus according to another embodiment.

 FIG. 10 is a schematic block diagram of a metal recovery apparatus according to another embodiment.

 FIG. 11 is a schematic front view of a metal recovery apparatus according to another embodiment.

 FIG. 12 is a schematic front view of a metal recovery apparatus according to another embodiment.

 FIG. 13 is a schematic front view of a metal recovery apparatus according to another embodiment.

 FIG. 14 is a schematic block diagram of an indium recovery apparatus as one embodiment.

 FIG. 15 is a schematic block diagram showing a test apparatus of an example.

 FIG. 16 is a graph showing test results.

 Explanation of symbols

[0031] 1, la, lb, lc ... Reactor body

 11a ゝ l ib ゝ 11c ゝ l id… Ultrasonic oscillator

 12 Electromagnet 17, 18, 19 Filter

 25 · · · Tube part 32 · · · Channel

 33 ·· 'Pump

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

 (Embodiment 1)

[0033] As shown in Fig. 1, the metal recovery apparatus of the present embodiment is provided with a vertically long reactor main body 1. In the present embodiment, the case where waste liquid is used as the liquid to be treated will be described. As shown in the figure, the reactor main body 1 includes a reactor upper part 2, a reactor intermediate part 3, and a reactor lower part 4, which are connected via connecting parts 5 and 6, respectively. Reactor upper part 2, reactor intermediate part 3, and reactor lower part 4 are each formed to have the same width, but the cross-sectional area of reactor upper part 2 is larger than the cross-sectional area of reactor intermediate part 3, and The cross-sectional area is larger than the cross-sectional area of the reactor bottom 4 It is. As a result, as a whole, the cross-sectional area of the reactor main body 1 is configured to increase discontinuously with upward force. Note that the continuous portions 5 and 6 are formed in a tapered shape that is wide upward.

 [0034] Below the reactor lower part 4, a substantially conical inflow chamber 7 for introducing the waste liquid to be treated is provided, and an inflow pipe 8 is provided further below. Although not shown, the inflow pipe 8 is provided with a check valve. Further, an upper chamber 9 is provided on the upper side of the upper part 2 of the reactor, and a discharge pipe 10 for discharging the recovered flaky or particulate metal is provided on the side thereof. The upper chamber 9 is a part for discharging the metal recovered by such a discharge pipe 10, and based on the difference in the tendency to ionize with the metal to be recovered, a so-called cementation reaction ( It is also the part where the metal for precipitation (metal particles), which has a higher ionization tendency than the metal to be recovered, is used to cause the (metal precipitation reaction). Actually, the cementation reaction between the deposition metal and the metal to be recovered occurs in the entire reactor body 1.

 [0035] The waste liquid flowing in from the inflow pipe 8 reaches the discharge pipe 10 so that the waste liquid rises in the vertical direction and forms a fluidized bed of metal particles. Furthermore, the ultrasonic oscillator l la, l ib is a metal contained in the waste liquid and serves as a stripping means for stripping the metal to be collected deposited on the metal particles introduced by the cementation reaction. 11c are provided in the upper part 2 of the reactor, the middle part 3 of the reactor, and the lower part 4 of the reactor, respectively.

 In this embodiment, zinc (Zn) particles are used as the metal particles to be charged. As the target waste liquid, for example, a metal surface treatment factory waste liquid containing metal ions such as copper (Cu) and tin (Sn) is used. In this case, Cu and Sn are recovered as metal. The average particle size of the metal particles to be introduced is a force that can use metal particles of 0.1 to 8 mm. In this embodiment, the average particle size is 2 mm. The average particle diameter is measured by an image analysis method or an IS Z 8801 screening test method.

[0037] Then, a method of recovering metal by using a metal recovery device having such a structural force will be described. First, waste liquid to be treated is introduced into the reactor main body 1 from the inflow pipe 8 through the inflow chamber 17. Flow into. On the other hand, cementation from the upper chamber 9 Metal particles (Zn particles) are added to cause the reaction. In the reactor main body 1, while the waste liquid that has flowed in rises in the vertical direction, the waste liquid and the metal particles introduced from the upper chamber 9 enter a fluidized state so as to form a fluidized bed.

 [0038] Then, a so-called cementation reaction is caused based on a difference in ionization tendency between metals such as Cu and Sn contained in the waste liquid and Zn as the charged metal particles. This will be explained in more detail. The reduction reaction of each metal ion is represented by the following equations (1) to (3), and the standard electrode potential (E °) of each metal ion is shown respectively.

[0039] Zn ²⁺ + 2e → Zn… hi) —0. 76V

Cu ²⁺ + 2e → Cu--(2) + 0.34V

Sn ²⁺ + 2e → Sn--(3) —0.14V

[0040] As apparent from the above (1) to (3), the standard reduction potential of Zn ²⁺ is the smallest compared to Cu ²⁺ and Sn ²⁺ . In other words, the ionization tendency of Zn is the largest compared to Cu and Sn. Therefore, in the fluidized state as described above, Zn with a high ionization tendency becomes Zn ²⁺ (reaction opposite to the above formula (1)) and is eluted in the waste liquid and is contained in the waste liquid along with it. Cu ²⁺ and Sn ²⁺ that have been deposited become Cu and Sn, and are deposited on the surface of the Zn particles.

[0041] Then, after the Cu and Sn metals are deposited on the surface of the Zn particles by such a cementation reaction, the ultrasonic oscillators lla, ib, and 11c are operated. By operating the ultrasonic oscillators l la, l ib, and 11c, the ultrasonic waves generated from the ultrasonic oscillators l la, l ib, and 11c vibrate to the Zn particles on which the Cu and Sn are deposited. A force and a stirring force are applied, and the precipitated Cu and Sn metals are forcibly separated from the Zn particle force. In this case, the ultrasonic oscillators l la, l ib, and 11c can be operated continuously. When the ultrasonic oscillator is operated continuously, the ultrasonic oscillator generates heat, and the ultrasonic oscillator is operated for a long time. May be difficult. In addition, when the ultrasonic oscillator is operated continuously, the deposited metal (Cu, Sn) is peeled off before it grows to a certain size, and as a result, a deposited metal with a certain size is obtained. There is a risk of not. In this regard, when the ultrasonic oscillator is operated intermittently, there is little risk of inadvertent peeling until the deposited metal becomes large to some extent, so that the separated metal can be easily separated. Therefore, it is preferable to operate the ultrasonic oscillators 11a, l ib and 11c intermittently. The intermittent operation in this case is For example, 2 seconds ON, 8 seconds OFF, etc.

[0042] Cu and Sn peeled in this way are discharged from the upper chamber 9 through the discharge pipe 10 to the outside of the reactor body 1 and collected metal (in this embodiment, Cu and Sn). It will be collected as a combination. In this case, in the present embodiment, since the metal used for depositing the metal to be collected is in the form of particles, for example, compared to the case where zinc scrap is introduced, the cementate is used. The surface area of the metal (Zn) for causing the Chillon reaction is increased, and the rate of the Cu and Sn precipitation reaction is improved.

 [0043] Then, after precipitation of the metal that has grown to some extent is recognized, the forced removal by ultrasonic vibration as described above always exposes a new metal surface (Zn particle surface), and the reaction rate is increased. Can be maintained. In addition, compared to the conventional method of throwing in zinc scrap, the separated metals to be collected have very few impurities other than Cu and Sn.

[0044] In addition, since the metal particles made of Zn flow in the reactor main body 1 and Zn ²⁺ is eluted by the above-described cementation reaction, the metal particles put into the upper chamber 9 are initially charged. The particle size in inevitably decreases with time. As a result, if the reactor cross-section up to the top of the reactor is the same, the waste liquid will rise in the reactor body 1 at the same upward flow rate. There is a risk that the metal particles will overflow from the reactor body 1 inadvertently.

 However, in this embodiment, the cross-sectional area of the reactor main body 1 is formed so as to increase discontinuously as the upward force is increased in the present embodiment. Therefore, the waste liquid in the reactor main body 1 is increased. The upward flow velocity gradually decreases. Therefore, as described above, the metal particles whose particle size has decreased due to the cementation reaction, etc., in the reactor body 1 without inadvertently overflowing outside the reactor body at the top of the reactor body 1 where the cross-sectional area increases. Is more likely to be retained.

[0046] In addition, when the waste liquid flows into the lower side of the reactor main body 1 and passes through the reactor main body 1, it is converted into metal particles that also have Zn force due to the cementation reaction, Cu, Sn, etc. to be recovered. As the amount of the metal is deposited, the concentration of the target metal in the waste liquid decreases as the force toward the top of the reactor body 1 increases.

 [0047] However, in the present embodiment, finer metal particles exist in the upper part of the reactor body 1, and the number of metal particles increases as the upward flow velocity of the waste liquid gradually decreases. As can be seen, the total surface area of the metal particles increases toward the top of the reactor body 1. As a result, the reaction rate of the cementation reaction (efficiency of precipitation of the target metal) is improved, and the target metal is efficiently recovered even in the upper part of the reactor body 1 where the concentration of the target metal is lower. The collection process can be performed.

 [0048] (Embodiment 2)

 In the present embodiment, the structure of the reactor main body 1 is different from that of the first embodiment. That is, in the present embodiment, as shown in FIG. 2, the entire peripheral surface of the reactor main body 1 is formed to be tapered upward, and the cross-sectional area of the reactor main body 1 is continuously increased upward. It is configured as follows. In this respect, the cross-sectional area of the reactor body 1 increases discontinuously upwards, which is different from the case of the first embodiment.

 [0049] Since the cross-sectional area that is not discontinuous is configured to continuously increase upward, the reactor upper part 2, the reactor intermediate part 3, as in Embodiment 1, If the reactor is divided into four parts as shown in the lower part of the reactor,

 [0050] However, the ultrasonic oscillators l la, l ib and 11c are provided in three places from the upper part to the lower part of the reactor main body 1 in common with the first embodiment. Therefore, in the present embodiment, as in the first embodiment, the recovery target metal deposited on the metal particles is forcibly forced by the ultrasonic waves oscillated from the ultrasonic oscillators lla, ib, and 11c. The effect of being able to peel off is obtained.

[0051] Further, although there is a difference between discontinuous and force continuous, the cross-sectional area is configured to increase upward, and in common with Embodiment 1, Therefore, even in the present embodiment, the fine metal particles having a reduced particle size are retained at the upper part of the reactor main body 1, and the effect of preventing inadvertent overflow from the reactor main body and the object to be collected This means that the recovery target metal can be efficiently recovered at the upper part of the reactor body 1 where the metal concentration is low. [0052] (Embodiment 3)

 The reactor body 1 of this embodiment is the same as that of Embodiments 1 and 2 in that it is vertically long. However, as shown in FIGS. 3 and 4, the reactor body 1 is formed so that the cross-sectional area is the same at the top and bottom. In this respect, this embodiment is different from Embodiments 1 and 2 in which the cross-sectional area is increased upward.

 [0053] Also in the present embodiment, as in the first embodiment, an inflow chamber 7 is provided on the lower side of the reactor body 1, and an upper chamber 9 is provided on the upper side of the reactor body 1. However, the shape is different from that of Embodiment 1 which is formed in a substantially conical shape. That is, the upper chamber 9 is formed in a shallow cylindrical shape as shown in FIGS. 3 and 4, and the inflow chamber 7 is formed with a central cylindrical portion 20 as shown in FIGS. The central cylinder part 20 is formed in a shape including side cylinder parts 21 and 21 provided on the left and right sides in communication with the central cylinder part 20.

 In the present embodiment, the inflow pipes 8 and 8 are provided on the distal end sides of the side tube portions 21 and 21 of the inflow chamber 7, respectively. The side cylinders 21 and 21 of the inflow chamber 7 are provided with two baffle plates 22 and 23 in the vertical direction, and the liquid to be treated flowing in from the inflow pipes 8 and 8 is blocked by these baffles. The flow is disturbed by the plates 22 and 23.

 Further, the upper chamber 9 is composed of an inner cylinder 9a and an outer cylinder 9b as shown in FIG. 4, and the inner cylinder 9a is externally fitted to the upper part of the reactor main body 1 as shown in FIG. As a result, the upper chamber 9 is attached to the reactor body 1. The discharge pipe 10 is attached to the lower portion of the upper chamber 9 at a position between the inner cylinder 9a and the outer cylinder 9b.

 As a result of this configuration, the liquid to be treated that flows upward in the reactor body 1 overflows from the upper opening of the inner cylinder 9a between the outer cylinder 9b and the inner cylinder 9a, and is discharged from the discharge pipe 10. It will be discharged to the outside.

[0056] Further, the metal particles for causing the cementation reaction are also supplied with the force of the upper opening of the inner cylinder 9a. Then, while the waste liquid flowing in from the inflow pipe 8 of the inflow chamber 7 reaches the discharge pipe 10 of the upper chamber 9, the fluid to be treated rises in the vertical direction to form a fluidized bed of metal particles. The point that the cementation reaction between the input metal and the metal to be recovered occurs in the whole reactor body 1 is that Common to states 1 and 2.

 Furthermore, also in the present embodiment, an ultrasonic oscillator is employed as a stripping means for stripping the metal to be collected, which is a metal contained in the waste liquid and deposited on the metal particles by the cementation reaction. Yes. That is, in the present embodiment, four ultrasonic oscillators l la, l ib, l lc, and l id force are attached to the outer peripheral surface of the reactor main body 1. These four ultrasonic oscillators l la, l lb, l lc, and id are all the forces attached to the reactor body 1 at an angle of about 45 degrees with respect to the horizontal plane. The ultrasonic oscillators l la and 11c are attached in the same direction, and the other two ultrasonic oscillators l lb and l id are attached so as to face in opposite directions.

 Also in this embodiment, waste liquid is used as the liquid to be treated, and as the waste liquid, for example, the same metal waste treatment liquid containing metal ions such as Cu and Sn as in Embodiment 1 is used. It is done. In this case, Zn particles are used as the metal particles to be charged in the same manner as in Embodiment 1, and Cu and Sn are recovered as metals.

 [0059] When the metal is recovered by the metal recovery apparatus of the present embodiment, first, the waste liquid flows from the inflow pipe 8 into the reactor body 1 through the inflow chamber 17. In this case, the inflow chamber 17 is composed of the central cylindrical portion 20 and the side cylindrical portions 21 and 21 as described above, and the side cylindrical portions 21 and 21 are provided with two baffle plates 22 and 23 vertically. Since the waste liquid that flows in from the inflow pipes 8 and 8 that are mounted sideways to the side tube portion 21 does not flow in the horizontal direction at once, the baffle plate that is provided in the vertical direction. The gas flows into the central cylindrical portion 20 while flowing alternately up and down in the side cylindrical portion 21 along the lines 22 and 23, and the force of the central cylindrical portion 20 is also directed upward to the reactor body 1 and flows upward. Therefore, the waste liquid flowing in from the inflow pipes 8 and 8 is disturbed by the baffle plates 22 and 23, and can easily flow upward in the reactor main body 1 without causing drift. If necessary, for example, a cylindrical basket containing glass or ceramic balls can be installed in the inflow chamber 17, which can prevent drifting more reliably. It becomes.

[0060] Contained in waste liquid !, the action of so-called cementation reaction based on the difference in ionization tendency between metals such as Cu and Sn and the metal particles Zn to be added, ultrasonic The action of stirring and metal peeling by the oscillator is the same as in the above embodiment, and the detailed explanation thereof is as follows. Omitted.

 [Embodiment 4]

 In this embodiment, instead of the means for vibrating with ultrasonic waves oscillated by the ultrasonic oscillators of the above-described Embodiments 1 to 3 as means for peeling the deposited metal to be collected by metal particle force, stirring is performed using an electromagnet. The means to do is adopted. That is, in this embodiment, the slide board 13 having the electromagnet 12 as shown in FIG. 8 is mounted on the guide rail 14 provided on the side of the reactor main body 1 as shown in FIG. Has been. As shown in FIG. 8, the slide board 13 has a space portion 15 in the center, and is disposed so as to surround the reactor body 1 by inserting the reactor body 1 into the space portion 15. The figure

In FIG. 8, the reactor body 1 is not shown. In the present embodiment, the reactor main body 1 is formed so that the horizontal cross section is rectangular, and in this respect, the cross section is circular, that is, the reactor main body 1 is formed in a cylindrical shape. Is different.

 Then, as indicated by arrows 16 in FIG. 7, the metal particles in the reactor main body 1 are agitated by alternately moving up and down, and a large number of metal particles collide with each other, thereby The metal particle force also forcibly separates the deposited metal. The electromagnet 12 is applied alternately at regular intervals such as 2 seconds, and the vertical movement of the slide board 13 is performed intermittently or continuously. Metal particle force Although the means for separating the deposited metal to be collected is different, the metal to be collected can be suitably separated from the metal particles and recovered in this embodiment as well. The metal particles used in this embodiment are iron particles that are magnetic materials.

 [0063] The reduction reaction of iron (Fe) ions and the standard electrode potential are as follows.

Fe ²⁺ + 2e → Fe · '· (4) —0.44V

 On the other hand, the reduction reaction and standard electrode potential of Cu and Sn are as shown in the above formulas (2) and (3). The standard electrode potential is smaller in Fe than Cu and Sn. Since the ionization tendency is larger than the ionization tendency of Cu and Sn, this embodiment can be applied to waste liquid containing Cu and Sn.

[Embodiment 5] In the present embodiment, as shown in FIG. 9, two reactors are provided, and this is different from the first to fourth embodiments in which only one reactor is used. That is, in this embodiment, the filter 17 is provided after the first-stage reactor main body la and before the second-stage reactor main body lb, and further, the filter is provided after the second-stage reactor main body lb. One 18 is provided. For example, a cartridge filter or a drum filter is used as the filter. Moreover, it is also possible to use solid-liquid separation means such as a belt press and a filter press in place of the filter.

[0065] In this embodiment, for example, when Cu and Sn are contained in the target waste liquid, Fe particles are introduced into the first-stage reactor main body la, and Cu is precipitated on the Fe particles. Cu is recovered by the second stage filter 17, Zn particles are put into the second stage reactor body lb, Sn is precipitated on the Zn particles, and Sn is recovered by the second stage filter 18. It becomes possible.

 [0066] In this case, from the numerical values of the standard electrode potentials indicated by the above formulas (2), (3), and (4), both Cu and Sn have a smaller ionization tendency than Fe. The difference in the habit is that the difference between Fe and Cu is much larger than the difference between Fe and Sn. Therefore, in the first stage reactor body la, Cu preferentially precipitates on Fe particles. It becomes. On the other hand, from the numerical value of the standard electrode potential shown in the above equation (1), the ionization tendency of Zn is larger than the ionization tendency of Cu and Sn. Therefore, in the second reactor body lb, both Cu and Sn are Zn. The force that must be deposited on the particles Cu has already deposited on the Fe particles in the first-stage reactor body la, so in the second-stage reactor body lb, Sn mainly precipitates on the Zn particles. It is. However, the remaining Cu residue that did not precipitate on the Fe particles in the first-stage reactor body la precipitates on the Zn particles in the second-stage reactor body lb.

 [0067] Thus, the present embodiment has an advantage that two types of metal can be selectively recovered from the waste liquid using two different types of metal particles. Further, although means for peeling the deposited metal to be recovered also with the metal particle force is not described, it is not particularly limited. The method using the ultrasonic oscillator described above, the method of stirring using an electromagnet, Other methods described can be used.

[Embodiment 6] In this embodiment, as shown in FIG. 10, three reactors are arranged, and in this respect, only one reactor is used in Embodiments 1 to 4, or two reactors are arranged. This is different from the case of Form 5. In the present embodiment, the three reactor bodies la, one reactor body lb, and the filter 17, the filter 18, and the filter 19 are provided on the rear stage side of the reactor body lc. In the present embodiment, as in the fifth embodiment, the force in which Fe particles are charged in the first-stage reactor main body la and the Zn particles are charged in the second-stage reactor main body lb In the third-stage reactor main body lc, Aluminum (A1) particles are charged.

 [0069] When this embodiment is applied to a waste liquid containing Cu and Sn as in the fifth embodiment, Cu is deposited on Fe particles in the first-stage reactor main body la as in the fifth embodiment. Then, Cu is recovered by the first-stage filter 17, and Sn is also precipitated in the Zn particles in the second-stage reactor main body lb as in Embodiment 5, and Sn is recovered by the second-stage filter 18.

 [0070] However, in the third-stage reactor main body lc, an unexpected action occurs from the fifth embodiment. That is, as described above, Fe eluted by the cementation reaction in the first-stage reactor main body la and Zn eluted by the cementation reaction in the second-stage reactor main body lb are input to the third-stage reactor main body lc. Deposited on the A1 particles.

 This point will be described in more detail. The reduction reaction of the A1 ion and the standard electrode potential are represented by the following formula (5).

Al ³⁺ + 3e → Al--(5) — 1. 66V

 The Fe particles introduced in the first-stage reactor body la and the Zn particles introduced in the second-stage reactor body lb are made of a metal that has a higher ionization tendency than the target metal as described above. From the comparison of the numerical values of the standard electrode potentials expressed by Eqs. (1), (4), and (5), it is clear that the ionic tendency of A1 is larger than that of Fe and Zn. Therefore, Fe eluted from the first-stage reactor body la and Zn eluted from the second-stage reactor body lb are both deposited on A1 particles by the third-stage reactor body lc. The A 1 particles can be recovered as an Fe—Zn alloy.

[0072] Therefore, the work of coagulating and precipitating Fe and Zn eluted in the first-stage reactor main body la and the second-stage reactor main body lb, respectively, becomes unnecessary, and the amount of sludge generated can be suppressed. Is possible. In the third-stage reactor body lc, the power at which A1 elutes The amount of sludge generated does not increase because the amount of elution is less than that of divalent Zn and Fe, and the specific gravity of A1 is light and the sludge weight can be reduced. Also in this embodiment, there is no particular limitation on the means for peeling off the metal to be collected, which is a metal particle force.

[0073] (Embodiment 7)

 In the present embodiment, as means for peeling the deposited metal to be collected by metal particle force, means for vibrating with ultrasonic waves oscillated by the ultrasonic oscillators of Embodiments 1 to 3 above and the electromagnet of Embodiment 4 are used. Instead of agitation means, a means utilizing a so-called air lift action, in which a gas such as air is blown and agitated, is employed. That is, in the present embodiment, as shown in FIG. 11, a cylindrical part 25 is provided at the approximate center of the reactor body 1, and a gas inflow pipe 26 is connected to the lower part of the cylindrical part 25. A gas inlet 27, which is an opening on one end side of the gas inlet pipe 26, protrudes outside the reactor body 1, and an opening 28 on the other end side of the gas inlet pipe 26 communicates with the tubular portion 25. Has been. Further, a baffle plate 30 is provided below the lower opening 29 of the cylindrical portion 25.

 In the present embodiment, the reactor main body 1 is formed in a substantially cylindrical shape as in the third embodiment, and the inflow chamber is placed under the reactor main body 1 in the same manner as in the first to third embodiments. 7 is provided, and an upper chamber is provided in the upper part. However, in FIG. 11, the discharge pipe 10 does not show the force upper chamber shown. In this embodiment, A1 or Zn particles are used as the metal particles to be charged. As the target waste liquid, flat “panel” display (FPD) manufacturing waste liquid containing indium (In) ions is used. In this case, In is recovered as a metal.

[0075] As described above, the average particle diameter of the metal particles to be added can be 0.1 to 8 mm. When the metal particles are A1, the average particle diameter is preferably 1.5 to 5.5 mm. In the case of Zn, it is preferably 1.5 to 4. Omm. In the case of Zn particles exceeding 4. Omm, and in the case of A1 particles exceeding 5.5 mm, the flow velocity necessary to make these particles flow increases and also the force to increase the amount of gas blown. . On the other hand, since the particle size of the metal particles gradually decreases due to the cementation reaction, if the initial particle size of the metal particles is small, As described above, there is a possibility that metal particles may flow out of the reactor body 1 together with the treatment liquid. From this point of view, it is preferable that the particle size is 1.5 mm or more in the case of Zn particles or A1 particles.

 Then, a method of recovering metal by the metal recovery apparatus of the present embodiment will be described. First, similarly to the above-described embodiments, first, the waste liquid flows into the reactor main body 1 through the inflow chamber 17, and the upper part The best of the chamber is charged with metal particles. In addition, gas is caused to flow into the cylindrical portion 25 via the gas inflow pipe 26. As a result, the specific gravity of the mixed portion of the gas and water in the cylindrical portion 25 decreases, and the liquid is pushed up together with the gas.

 [0077] In this way, by flowing the gas into the cylindrical portion 25 and causing it to flow upward, the liquid to be treated in the cylindrical portion 25 also flows upward. As described above, the liquid to be treated flows through the inside of the cylindrical portion 25, but a pressure difference is generated between the inside and the outside of the cylindrical portion 25, so that the flow rate of the liquid to be treated is also the inside and outside of the cylindrical portion 25. As a result, the metal particles are agitated in the reactor main body 1 and the In deposited on the surface of the metal particles is peeled off.

 In this case, since In that is a metal to be collected in this embodiment is deposited in a sponge shape, adhesion to metal particles such as Zn as compared to Cu and Sn in Embodiment 1 and the like is increased. Therefore, even if the means for forcibly separating by the ultrasonic vibration as in Embodiments 1 to 3 and the means for forcibly separating using an electromagnet as in Embodiment 4 are not adopted, this embodiment is implemented. Even if the stirring means simply uses the air lift action as in the embodiment, the metal particle force of In can be separated relatively easily. That is, it is possible to recover In with an apparatus having simple and low energy means.

 [0079] Then, a so-called cementation reaction is caused based on a difference in ionization tendency between In contained in the waste liquid and Zn or A1 as the charged metal particles. To explain this in more detail, the reduction reaction of In ions is as follows, and the standard electrode potential (E °) is also shown.

In ³⁺ + 3e → In · '· (6) —0.34V

[0080] As can be seen from the above formulas (1), (5), and (6), the standard quasi-reduction potentials of Zn ²⁺ and Al ³⁺ are smaller than those of In ³⁺ . In other words, the ionization tendency of Zn and A1 is greater than that of In. For this reason, Zn and A1, which have a large ionization tendency, become Zn ²⁺ or Al ³⁺ in the waste liquid. It elutes, and In ³⁺ contained in the waste liquid becomes In and precipitates on the surface of Zn and A1 particles. After precipitation of In on the surface of the Zn particles or A1 particles by such a cementation reaction, the In force n particles or A1 particles separated by stirring using the air lift action as described above are peeled off. The peeled In is discharged to the outside of the reactor body 1 through the discharge pipe 10 and collected.

 In this embodiment, since the baffle plate 30 is provided below the lower opening 29 of the cylindrical portion 25, the water flow of the waste liquid flowing in from the inflow chamber 17 is directly applied to the cylindrical portion 25. When the baffle plate 30 that does not flow in is hit, the flow rate of the liquid to be treated in the cylindrical portion 25 is preferably prevented from becoming extremely high.

 (Embodiment 8)

 In this embodiment, air jet agitation or water jet agitation is adopted as means for separating the metal to be collected from the metal particles, and this is different from the above-described Embodiments 1 to 7. That is, in the present embodiment, as shown in FIG. 12, the jet stirring jetting tool 31 is attached to the peripheral surface portion of the reactor main body 1, and air or water is jetted from the jet stirring jetting tool 31 so that the inside of the reactor main body 1 It is configured to generate fine bubbles. That is, air jet agitation means that a gas such as air is ejected to generate fine bubbles, and water jet agitation means that a liquid such as water is ejected to generate fine bubbles. .

 [0083] The shape of the reactor main body 1 and the configuration in which the inflow chamber 7 and the discharge pipe 10 are provided are the same as those in the seventh embodiment, and a description thereof will be omitted. Further, since the metal particles to be input, the type of waste liquid to be used, and the action of the cementation reaction are the same as those in the seventh embodiment, detailed description thereof will be omitted. In the present embodiment, a gas such as air or water (for example, treatment liquid) is ejected from the jet stirring jetting tool 31 to generate turbulent flow in the reactor main body 1, and the turbulent flow causes the reactor main body 1 to Thus, the metal particles are agitated, so that the In deposited on the surface of the metal particles is peeled off.

[0084] Also in this embodiment, since the recovery target metal In has poor adhesion to metal particles such as Zn, it is forcibly removed by ultrasonic vibration as in Embodiments 1 to 3 above. Even if the means for separating and the means for forcibly separating using the electromagnet as in Embodiment 4 are not adopted, the metal particle force is relatively reduced by means of simply performing air jet or water jet stirring. It can be easily peeled off. That is, it is possible to recover In with a device having a simple and low energy stirring means.

[Embodiment 9]

 In the present embodiment, as a means for separating the metal to be collected from the metal particles, a means by solid-liquid transport pump agitation is adopted, which is different from the above-described Embodiments 1 to 8. That is, in this embodiment, as shown in FIG. 13, a flow path 32 for circulating and transporting the liquid to be treated and the metal particles in the reactor main body 1 and the pump 33 are provided outside the reactor main body 1. Further, means for stirring the metal particles by circulating and transporting the liquid to be treated and the metal particles through the flow path 32 and the reactor main body 1 by the pump 33 is adopted.

[0086] The shape of the reactor main body 1 and the configuration in which the inflow chamber 7 and the discharge pipe 10 are provided are the same as those in Embodiments 7 and 8 described above, and thus the description thereof is omitted. Further, since the metal particles to be introduced, the type of waste liquid to be used, and the action of the cementation reaction are the same as those in Embodiments 7 and 8, detailed description thereof will be omitted.

 [0087] In the present embodiment, the liquid to be treated is discharged from the reactor main body 1 to the flow path 32 together with the metal particles by the pump 33, circulates through the flow path 32, and is returned to the reactor main body 1 again. As a result, the metal particles in the reactor main body 1 are agitated, whereby In deposited on the surface of the metal particles is peeled off.

 [0088] Even in this embodiment, since the deposited metal In has poor adhesion to metal particles such as Zn, it is forced by ultrasonic vibration as in Embodiments 1 to 3 above. Even if the means for peeling off to the outside and the means for forcing peeling using the electromagnet as in Embodiment 4 are not employed, the means for simply stirring the solid-liquid transport pump using the pump 33 and the flow path 32 can be used. In, the metal particle force can be peeled off relatively easily. That is, it is possible to recover In with a device having simple and low energy means.

 [Embodiment 10]

As shown in FIG. 14, the indium recovery apparatus of the present embodiment has a reactor body 1 and a control unit. It is equipped with a regulating tank 42 and a filter 43. As will be described later, the reactor main body 1 is used for precipitating In from the waste liquid (liquid to be treated) by a cementation reaction (metal precipitation reaction). the Cl ^_) source is added Caro is for adjusting the chloride ion concentration in the liquid to be treated, the filter 43 is for the in, which is deposited in the previous SL reactor body 1 separated and recovered. The separated processing liquid is configured to be able to be returned to the adjustment tank 42, and a flow path for that purpose is provided between the filter 43 and the adjustment tank 42. A flow path from the adjustment tank 42 to the reactor main body 1 and a flow path from the reactor main body 1 to the filter 43 are also provided. FIG. 14 shows a pump for circulating the liquid to be treated.

 In the present embodiment, a case where waste liquid is targeted as the liquid to be treated will be described. Since the structure of the reactor main body 1 is the same as that of the first embodiment, detailed description thereof is omitted.

 In this embodiment, zinc (Zn) or aluminum (A1) particles are used as the metal particles to be charged. The target waste liquid includes, for example, cleaning waste liquid of aluminum target materials containing In ions and nitrate ions (NO-), or nitric acid.

 Three

 The used FPD etching waste liquid is used.

[0092] A method for recovering indium by such an indium recovery apparatus having a constitutional power will be described. First, waste liquid to be treated is supplied to the adjustment tank 42, and chlorine ions (Cl_) are supplied to the adjustment tank 42. Add salt such as sodium salt or potassium salt. Since indium forms a hydroxide precipitate when the pH increases, the pH should be adjusted to 1.5 or less in advance so as not to form a precipitate. In addition, if the pH is too low, the reaction with the deposition metal used is promoted, and H, NO, NO gas is generated and no deposition metal is used.

 twenty two

 The pH is preferably 0.5 or more because it is consumed wastefully.

[0093] It is preferable to adjust the pH with hydrochloric acid when the pH is higher than the above range, and adjust the pH by adding an alkali such as NaOH when the pH is lower than the above range. .

Next, the liquid to be treated which has been adjusted by adding salt and soot in this manner flows from the inflow pipe 8 into the reactor main body 1 through the inflow chamber 7. On the other hand, metal particles (Zn or A1 particles) are introduced from the upper chamber 9 to cause a cementation reaction. The In the reactor main body 1, the waste liquid that has flowed in rises in the vertical direction, while the metal particles introduced from the upper chamber 9 enter a fluidized state so as to form a fluidized bed.

[0095] Then, a so-called cementation reaction is caused based on a difference in ionization tendency between In contained in the waste liquid and Zn or A1 as the charged metal particles.

Explaining this in more detail, the reduction reaction of each metal ion is Zn ²⁺ as compared with In ³⁺ , as is clear from the above-mentioned formulas (1), (5) and (6). The standard reduction potential of Al ³⁺ is small.

In other words, the ionization tendency of Zn and A1 is larger than that of In. Therefore, in the state of fluidization as described above, the ionization tendency is large 大 き Zn, A1 force ¾n ²⁺ or ヽ becomes Al ³⁺ and is eluted in the waste liquid, and it is also contained in the waste liquid! As In ³⁺ becomes In, it precipitates on the surface of Zn and A1 particles.

 [0098] In this case, nitrate ions (NO ") are contained in the waste liquid.

 Three

 The quasi-reduction potential may decrease, and the standard reduction potential of A1 or Zn may increase, and the potential difference between In and A1 or Zn may be reduced, making it difficult to reduce In. However, in this embodiment, since the liquid to be processed is supplied to the adjustment tank 42 in advance and the chlorine ion (cr) source is added, when the liquid to be processed flows into the reactor main body 1. In addition, chloride ion (CD forms a black mouth complex which causes the standard reduction potential of In to rise again, and as a result, the precipitation of In on the surface of Zn and A1 particles is inhibited. There is nothing to do.

 [0099] The other effects of causing a cementation reaction, the peeling step, and the like are the same as those in the above embodiments, and thus the description thereof is omitted.

 [0100] (Other Embodiments)

In the above embodiment, the waste liquid (treatment liquid) is applied to the waste liquid of a metal surface treatment plant containing Cu and Sn ions, the cleaning waste liquid of an aluminum target material, the FPD etching waste liquid, etc. Although the case has been described, the type of waste liquid to be applied is not limited to this, and it can also be applied to METSUKI factory waste liquid, semiconductor manufacturing factory waste liquid, liquid crystal manufacturing factory waste liquid, and the like. Further, in the present invention, the main purpose is to use a waste liquid as a liquid to be treated, but a liquid to be treated other than the waste liquid, for example, a metal-containing solid waste. It can be applied to an aqueous solution obtained by bringing chemicals such as acid into contact with waste to dissolve and ionize the metal to be recovered.

 Therefore, the types of metals to be collected are not limited to Cu, Sn, and In in the embodiment, and for example, Ni, Ga, Zn, etc. can be used as the metals to be collected. Does not matter.

 [0101] In this embodiment, the average particle diameter of the metal particles is not limited to that of the embodiment. However, it is desirable to be 0.1 to 8mm. When the thickness is less than 1 mm, the cementation reaction is not necessarily performed favorably, and there is a possibility that the recovery of the metal to be recovered which has been separated by the metal particle force may not be easily performed. The number of metal particles that can be held in the reactor body decreases, and as a result, the total surface area of the metal particles may decrease and the efficiency of the precipitation reaction may decrease.In addition, the flow rate must be increased in order to cause the metal particles to flow. This is because it is necessary to enlarge the reactor (reactor height) in order to maintain the necessary reaction time. From this viewpoint, the thickness is more preferably 0.5 to 6 mm. Further, in order to improve the fluidity and reactivity in the reactor body and to facilitate the holding in the reactor body, the force is more preferably in the range of 1.0 to 2. Omm.

 [0102] The average particle diameter of the metal particles is measured by the image analysis method, the JIS Z 8801 screening test method, etc. as described above. For example, Millitrack JPA manufactured by Nikkiso Co., Ltd. is used for the measurement of the average particle diameter by the image analysis method. In addition, in the JIS sieving method, when the average particle diameter is in the range of 1 to 2 mm, for example, 1000 / z m sieve V is used under a nominal size of 2000 m sieve, and the upper metal particles are used.

 [0103] Further, the uniformity of the metal particles is preferably less than 5 from the viewpoint of power treatment efficiency, operation control, and the like. Here, the uniformity of the metal particles refers to a transmittance curve formed by particle size distribution measurement or sieving or the like (the percentage of the mass of particles smaller than a certain particle size relative to the total sample mass, that is, the transmittance The value obtained by dividing the 60% particle size under the screen by the 10% particle size under the screen. It represents the width of the particle size distribution.

[0104] Furthermore, in each of the above embodiments, the metal particles used a single metal, but even if it is an alloy. Good. As the alloy, iron-aluminum alloy, calcium-silicon alloy, or the like can be used.

 [0105] Furthermore, in Embodiments 1 and 2, since the cross-sectional area of the reactor main body 1 is formed so as to increase toward the top, the force that provides the above preferable effect is obtained. Forming the body 1 is not an essential condition for the present invention. As in the third, seventh, eighth, and ninth embodiments, the reactor main body 1 can be formed so that the cross-sectional area is the same and the entire body is substantially cylindrical.

 [0106] Furthermore, the means for peeling the deposited metal from the metal particles is not limited to the means of Embodiments 1 to 9, but may be other means.

[0107] Furthermore, in Embodiment 10 described above, force using a salted product such as sodium chloride or potassium salt as a source of added chlorine ions is not limited to such a salted product, and hydrochloric acid is used. It is also possible. However, when hydrochloric acid is used, the acid concentration of the liquid to be treated increases, so that the dissolution reaction of the metal for precipitation to be used is accelerated and hydrogen gas is generated. This leads to an increase in the consumption of unnecessary deposition metal and an increase in the amount of hydrogen gas generated, which in turn leads to an increase in running cost. It is preferable to use things.

 [0108] On the other hand, if the reduction and precipitation reaction of In proceeds by adding a chlorine ion source, the metal ions used will be dissolved and hydrogen gas will also be generated, so H + in the solution will be consumed and the liquid to be treated PH increases. If the pH is higher than about 1.5, In in the liquid to be treated becomes a hydroxide and precipitates, so an acid addition is required to lower the pH. In such a case, it is preferable to add hydrochloric acid.

[0109] In the above embodiment 10, as shown in FIG. 14, since the used processing liquid is returned to the adjustment tank 42, the liquid to be processed which is the chlorine ion source stock solution remaining in the processing liquid As a result, the amount of additional salt and salt required for the next In recovery process can be reduced! Acquired force It is not an essential condition for the present invention to return the treatment liquid and reuse the chlorine ion source as in the above embodiment. Further, in the above embodiment, the adjustment tank 42 for adding the chlorine ion source is provided separately from the reactor main body 1, but this is not limiting, and the chlorine It is also possible to adjust by adding an on-source.

 [0110] Further, although metal particles are used as the deposition metal in each of the above embodiments, the present invention is not limited to this.

A metal wire, a metal wire processed into a mesh shape, a plate-like metal, or the like may be used. Example

 [0111] (Example 1)

 Zn was used as the metal particles, and a copper sulfate solution was used as a simulated liquid to be tested. As shown in Fig. 14, as the test equipment, in addition to the reactor main body 1 with the ultrasonic oscillator 11 in the center, two tanks 34, 35, two pumps 36, 37, bag filter 38 and this An apparatus provided with flow paths 39, 40, and 41 for connecting them was used.

[0112] The pH of the copper sulfate solution is 5, the initial concentration is 65.5 mg / L, the amount of treatment liquid is 70 L, and the liquid to be treated is applied to metal particles with average particle diameters of 0.05 mm, lmm, 2 mm, 5 mm, and 10 mm. The test was performed by supplying the test equipment shown in Fig. 15 in a circulating manner. The test results are shown in Tables 1 to 5 and Fig. 16.

 [0113] As is clear from Tables 1 to 5 and FIG. 16, when metal particles with an average particle size of 1 mm, 2 mm, and 5 mm are used, compared to when 0.05 and 10 mm metal particles are used. And the removal rate of copper (Cu), the deposited metal, was good.

 [0114] [Table 1]

 0 .0 5 mm

[0115] [Table 2] (Average particle size 1 mm)

 [0116] [Table 3]

 (Average particle size 2 mm)

 [0117] [Table 4]

(Average particle size 5 mm)

 Processing time (mi n) Cu concentration (mg / L) Cu removal rate (%)

0. 0 65. 5 0

1. 0 58. 2 1 1

2. 0 47. 7 27

3. 0 41. 4 37

5. 0 33. 6 49

10. 0 22. 8 65

20. 0 10. 1 85 [0118] [Table 5]

 (Average particle size 10 mm)

[0119] (Example 2)

 A nitric acid solution in which indium was dissolved was prepared as a simulation solution of the waste liquid. The simulated solution used was a 2.8% nitric acid solution in which In was dissolved at a concentration of 400mgZL. This was put into a 1 L beaker, 50 g of sodium chloride was first added, and In alloy recovery processing was started using A1 metal particles with an average particle diameter of 2 mm by image analysis. H gas and mainly NO with treatment

 2 2 Gas was generated. Since H + is consumed as H gas with the treatment, the pH rises.

 2

 Therefore, the pH in the solution was measured with a pH meter, and hydrochloric acid was added so that the pH did not exceed 1.5, and stirring was performed for 120 minutes so that the particles did not flow. The In alloy deposited on the A1 metal particles was in the form of a sponge and aggregated during the stirring process to form a large lump, which could be easily peeled and collected by ultrasonic treatment. Sonication was performed once every 2 minutes for 2 seconds each. By the way, the obtained In alloy was about several hundreds of meters to several millimeters in size. Such a large lump can be recovered even with an inexpensive filter such as a knock filter.

 [0120] By adding 1 L of a new stock solution (indium-containing nitric acid solution) to the solution after the above treatment and adding 25 g of sodium chloride, the treatment can be performed in the same process as described above. Therefore, the amount of chloride added can be reduced, and the processing cost can be reduced.

[0121] As a result of the test under the conditions as described above, the recovery rate of In from the solution was 95%, and a very good result was obtained. [0122] (Example 3)

 A test was conducted under the same conditions as above except that Zn metal particles were used instead of the Al metal particles in Example 2 above. Also in this example, a good result with an In recovery rate of 90% was obtained.

[0123] (Comparative Example 1)

 The same treatment was performed by adding only A1 metal particles to the simulated solution prepared in Example 2 above without adding sodium chloride sodium. Since nitrate ions and some of the A1 metal particles reacted, the pH reached 1.5 or higher, and the pH was adjusted using sulfuric acid. The force of stirring the solution for 120 minutes. No precipitation of In alloy was observed on the surface of the A1 metal particles.

[0124] (Comparative Example 2)

 The test was performed under the same conditions except that zinc metal particles were used instead of the A1 metal particles in Comparative Example 1 above. Even in this comparative example, the precipitation of In was strong.

Claims

The scope of the claims  [1] A deposition metal having a higher ionization tendency than the metal to be recovered is added to the liquid to be processed in which the metal to be recovered is contained in an ionic state, and is contained in the liquid to be processed due to a difference in ionization tendency. A metal recovery method comprising: depositing a metal to be collected on the surface of the metal for precipitation, and then separating and collecting the metal to be collected from the metal for precipitation by a peeling means.  [2] The target metal is contained in an ionic state! 2. The method for recovering a metal according to claim 1, wherein the liquid to be treated flows into the reactor main body, and a deposition metal is added to the reactor main body.  [3] The method for recovering a metal according to claim 1 or 2, wherein the means for separating the metal to be recovered from the metal for precipitation is a means for vibrating the metal for precipitation by ultrasonic waves.  [4] Metal force for precipitation The metal recovery method according to claim 1 or 2, wherein the means for separating the metal to be recovered is a means for stirring the metal for precipitation with an electromagnet and causing a large number of metals for precipitation to collide with each other. .  [5] Metal force for precipitation The method for recovering a metal according to claim 1 or 2, wherein the means for peeling the metal to be collected is a means for stirring the metal for precipitation by an air jet or a water jet.  [6] Precipitation metal force The means for separating the metal to be collected is a means in which a cylindrical portion is provided in the reactor body, and a gas is blown into the cylindrical portion to stir the deposition metal. Metal recovery method.  [7] Precipitation metal force The means for separating the metal to be collected is provided outside the reactor body with a flow path and a pump for circulating and transporting the liquid to be treated in the reactor body and the metal for deposition. 3. The method for recovering a metal according to claim 2, which is means for stirring the metal for precipitation by circulating and transporting the liquid and the metal for precipitation.  [8] The method for recovering a metal according to any one of [1] to [7], wherein the metal for precipitation is metal particles having an average particle diameter of 0.1 to 8 mm. [9] The method for recovering a metal according to any one of [1] to [7], wherein the metal for precipitation is metal particles having an average particle diameter of 0.5 to 6 mm. [10] The method for recovering a metal according to any one of [1] to [7], wherein the metal for precipitation is metal particles having an average particle diameter of 1.0 to 2. Omm. [11] The method for recovering a metal according to any one of [1] to [7], wherein the metal for precipitation is aluminum, and the metal for precipitation is metal particles having an average particle diameter of 1.5 to 5.5 mm. 12. The method for recovering a metal according to any one of claims 1 to 7, wherein the depositing metal is zinc, and the depositing metal is a metal particle having an average particle diameter of 1.5 to 4. Omm. 13. The method for recovering a metal according to any one of claims 2 to 12, wherein the liquid to be treated flows into the lower force of the reactor main body and flows out of the upper force of the reactor main body. 14. The method for recovering a metal according to claim 13, wherein the reactor main body is configured such that the cross-sectional area of the reactor main body increases upward. [15] The method for recovering a metal according to any one of [2] to [14], wherein two or more kinds of metals to be recovered are selectively recovered with two or more different kinds of depositing metals by means of a plurality of reactor bodies.  [16] The method for recovering a metal according to any one of [1] to [15], wherein the separated metal to be recovered is recovered with a filter.  [17] The nitrate ion is contained in the liquid to be treated in addition to the metal to be recovered in an ionic state, and a chlorine ion source is added to the liquid to be treated together with the deposition metal. Metal recovery methods.  [18] The liquid to be treated flows into the adjustment tank and a chlorine ion source is added to the adjustment tank, and then the liquid to be treated in the adjustment tank flows into the reactor main body and is deposited in the reactor main body. The method for recovering a metal according to claim 17, wherein a metal is added.  [19] The method for recovering a metal according to claim 17 or 18, wherein the processing liquid after recovering the metal to be recovered from the depositing metal is added to the liquid to be processed which is a stock solution and the processing is performed again. [20] A treatment liquid containing a metal to be collected in an ionic state is introduced, and a deposition metal having a larger ionization tendency than the metal to be collected is added, and the treatment target is treated according to a difference in ionization tendency. A reactor main body for performing a metal precipitation reaction for depositing the metal to be collected contained in the liquid on the surface of the metal for precipitation, and for separating the metal force for precipitation to recover the deposited metal to be collected. A peeling means. Metal collection device to collect.  21. The metal recovery apparatus according to claim 20, wherein the means for separating the metal to be recovered from the metal for precipitation is a means for vibrating the metal for precipitation by ultrasonic waves. [22] The metal recovery apparatus according to claim 20, wherein the means for separating the metal to be recovered is a means for stirring the metal for precipitation with an electromagnet and causing a large number of metals for precipitation to collide with each other.  [23] The metal recovery apparatus according to [20], wherein the means for separating the metal to be recovered is a means for stirring the metal for precipitation by an air jet or a water jet.  [24] The metal force for precipitation is a means for separating the metal to be collected by providing a cylindrical portion in the reactor main body and stirring the precipitation metal by blowing a gas into the cylindrical portion. Metal recovery equipment.  [25] Precipitation metal force The means for separating the metal to be collected is provided with a liquid to be treated in the reactor body and a flow path for circulating and transporting the metal particles and a pump outside the reactor body, and the liquid to be treated 21. The metal recovery apparatus according to claim 20, wherein the metal for precipitation is a means for stirring the metal for precipitation by circulating and transporting the metal for precipitation.  [26] The inflow portion of the liquid to be treated is provided at the lower part of the reactor main body, the liquid outflow portion is provided at the upper part of the reactor main body, and the inflow portion force the liquid to be treated flows into the reactor main body, from the liquid outflow portion 26. The metal recovery device according to any one of claims 20 to 25, wherein the metal recovery device is configured to flow out.  27. The metal recovery device according to claim 26, wherein the reactor main body is configured such that the cross-sectional area of the reactor main body increases upward. [28] The metal recovery device according to any one of [20] to [27], wherein a plurality of reactor bodies are provided.  [29] The metal recovery device according to any one of [20] to [28], wherein a filter for recovering the metal to be recovered which is peeled off is disposed downstream of the reactor main body! /. [30] The metal to be collected is contained in an ionic state and nitrate ions are contained. The adjustment tank that contains the liquid to be treated and is adjusted by adding a chlorine ion source is located on the front side of the reactor body. 30. The metal recovery device according to claim 20, wherein the metal recovery device is provided in the above. 31. The metal recovery apparatus according to claim 30, wherein a return flow path is provided so that the processing liquid after recovering the metal to be recovered from the deposition metal is added to the liquid to be processed which is a stock solution and then processed again. .