KR20080027911A - Metal recovery method and apparatus - Google Patents

Abstract

A method for recovering them from a liquid to be treated, such as waste liquids containing heavy metals such as Ni (nickel), Cu (copper), Sn (tin), In (indium), Ga (gallium), and the like as valuable metal bodies or alloys. With regard to the device and the device, only the target metal can be recovered from the liquid to be treated, such as waste liquid, as a valuable metal substance or alloy, and it is less likely to contain impurities other than the metal to be recovered. An object of the present invention is to provide a high-purity recovery method and apparatus.

A precipitation metal having a greater ionization tendency than that of the metal to be recovered is added to the liquid to be treated containing the metal to be recovered in an ionic state, and the metal to be recovered in the liquid to be treated is precipitated due to a difference in ionization tendency. It deposits on the surface of the metal for metal, and after that, the said metal to be collect | recovered is peeled and collect | recovered from the said metal for precipitation by a peeling means, It is characterized by the above-mentioned.

Description

Recovery method and apparatus of metal {PROCESS FOR RECOVERY OF METALS AND EQUIPMENT THEREFOR}

The present invention relates to a method for recovering a metal and a device thereof, and more particularly, to a waste liquid containing heavy metals such as Ni (nickel), Cu (copper), Sn (tin), In (indium), Ga (gallium) and the like. The present invention relates to a method and an apparatus for recovering them from a treating liquid as a single metal or alloy as valuables.

In general, various types of metals may be contained in the industrial waste liquid, and it has been attempted to recover them as metals which are valuables. For example, the waste liquid of a plating factory contains Ni, Cu, Zn, etc., the waste liquid of a semiconductor manufacturing factory contains Cu, Ga, etc., and the waste liquid of a liquid crystal manufacturing factory contains In etc. If recoverable as an alloy, these metals can also be reused.

As a treatment technique of waste liquid for recovering heavy metals, conventionally, agglomeration precipitation treatment using a chemical agent, coprecipitation treatment, and the like have been generally employed. When the concentration is low, metals are removed using an adsorbent. As a metal recovery from the waste plating solution, there is a method in which iron scrap is added to the waste plating solution to recover a metal to be recovered, such as Cu, by a cementation method. For example, there exists an invention which concerns on following patent document 1 as a technique using co-precipitation process.

Patent Document 1: Japanese Unexamined Patent Publication No. 2002-126758

However, in the flocculation precipitation treatment using a chemical agent, there is a problem that precipitates of hydroxide are generated as sludge. In addition, in a method in which iron scrap is added to a waste plating solution to precipitate Cu or the like by the cementation method, the precipitation reaction is terminated when the deposited Cu covers the iron scrap surface, so that the coated iron with Cu is recovered. Therefore, only the target metal cannot be recovered as the recovery target metal. In addition, there is a problem that only a low recovery rate and low purity can be obtained.

Disclosure of the Invention

Problems to be Solved by the Invention

This invention is made | formed in order to solve such a problem, and can collect only the target metal as a valuable substance metal or alloy from the to-be-processed liquids, such as waste liquid, and it is less likely to contain impurities other than the metal to be recovered, An object of the present invention is to provide a recovery method and apparatus having a high recovery rate and high purity of the metal to be recovered.

Means to solve the problem

The present invention has been made to solve such a problem, and a precipitation metal having a greater ionization tendency than that of the recovery target metal is added to the processing liquid containing the recovery target metal in an ionic state, and the above-mentioned difference is caused by the difference in ionization tendency. A metal recovery method comprising depositing a recovery target metal contained in a liquid to be treated on the surface of the precipitation metal, and then peeling and recovering the recovery target metal from the precipitation metal by a peeling means. to provide. In the recovery method of such a metal, while the to-be-processed liquid which the metal to collect | recovered is contained in the ion state flows into a reactor main body, you may add the metal for precipitation in the reactor main body.

As means for peeling the metal to be recovered from the metal for deposition, means for vibrating the metal for precipitation by ultrasonic waves, means for agitating the metal for precipitation by an electromagnet, and colliding a plurality of metals for precipitation, air jet or water Means for stirring the metal for deposition by means of a jet, means for forming a normal part in the reactor body, blowing gas into the normal part to stir the metal for precipitation, and a flow path for circulating and transporting the liquid to be treated and the metal for precipitation in the reactor body And means for stirring the precipitation metal by forming a pump outside the reactor body and circulating and transporting the liquid to be treated and the metal for precipitation.

As the precipitation metal, for example, metal particles are used. It is preferable that the average particle diameter of this metal particle is 0.1-8 mm, It is more preferable that it is 0.5-6 mm, It is further more preferable that it is 1.0-2.0 mm.

When a metal particle is aluminum, it is preferable that it is 1.5-5.5 mm in average particle diameter. Moreover, when a metal particle is zinc, it is preferable that it is 1.5-4.0 mm in average particle diameter.

When the to-be-processed liquid containing the metal to be recovered in an ionic state flows into the reactor main body, it is preferable that the to-be-processed liquid flows in from the lower part of the reactor main body and flows out from the upper part of the reactor main body.

When the liquid to be treated flows into the reactor body, the reactor body may be configured so that the cross-sectional area of the reactor body increases upward. Moreover, you may selectively collect | recover 2 or more types of collection object metal with 2 or more types of different precipitation metals by the reactor body of multiple stages. Moreover, you may collect | recover the peeled collection object metal with a filter.

In addition, when nitrate ion is contained in the to-be-processed liquid other than the metal to be recovered in an ionic state, a chlorine ion source may be added to the to-be-processed liquid together with the metal for precipitation. In this case, while the liquid to be treated is introduced into the adjusting tank, a source of chlorine ions is added to the adjusting tank, and then the liquid to be treated in the adjusting tank is introduced into the reactor body, and the precipitation metal is introduced into the reactor body. You may add. In addition, when adding such a chlorine ion source, you may add to the to-be-processed liquid which is a stock solution, and to process again the process liquid after collect | recovering the metal to collect | recover from a precipitation metal.

In addition, the present invention flows in the to-be-processed liquid containing the metal to be recovered in an ionic state, and adds a precipitation metal having a higher ionization tendency than the metal to be recovered, and thus the to-be-treated liquid And a reactor body for performing a metal precipitation reaction for depositing a recovery target metal contained in the surface on the surface of the precipitation metal, and peeling means for peeling from the precipitation metal to recover the precipitated recovery target metal. Provided is a metal recovery apparatus.

In such a metal recovery apparatus, as a means for peeling a metal to be recovered from a metal for precipitation, a means for vibrating the metal for precipitation by ultrasonic waves, a metal for precipitation by an electromagnet, and a plurality of metals for precipitation Means for impinging, means for agitating the metal for precipitation by an air jet or water jet, means for forming a normal part in the reactor body, and blowing gas into the normal part to stir the metal for deposition, the liquid to be treated and the metal in the reactor body A flow path and a pump for circulating and transporting particles are formed outside the reactor body, and means for stirring the precipitation metal by circulating and transporting the liquid to be treated and the metal for precipitation are employed.

The reactor body is configured such that, for example, the inflow portion of the liquid to be processed is disposed at the lower portion thereof, the liquid flow portion is disposed at the upper portion thereof, and the processing liquid flows into the reactor body from the inflow portion and flows out from the liquid discharge portion. It is.

The reactor body may be configured such that its cross-sectional area increases upward. Moreover, you may arrange the reactor main body of multiple stages. Moreover, you may arrange | position a filter for collect | recovering the peeled collection object metal at the rear end of a reactor main body.

Moreover, you may form the adjustment tank which accommodates the to-be-processed liquid which contains the recovery target metal in an ionic state, and contains the nitrate ion, and adds and adjusts a chlorine ion source in the front end of a reactor main body. Moreover, you may form the conveyance flow path which adds the process liquid after collect | recovering the metal to collect | recovery from the metal for precipitation to the to-be-processed liquid which is a stock solution, and processes again.

Effects of the Invention

In the present invention, as described above, a precipitation metal having an ionization tendency larger than that of the metal to be recovered is added to the liquid to be treated containing the metal to be recovered in an ionic state, and the treatment liquid is different depending on the difference in ionization tendency. The metal to be recovered contained in the metal is precipitated on the surface of the precipitation metal, and thereafter, it is a method of peeling and recovering the metal to be recovered from the metal for precipitation by the peeling means, and therefore, to some extent on the surface of the metal for precipitation. By peeling the grown recovery object metal with a peeling means, the surface of the metal can be exposed to a new metal surface at all times, so that the reaction rate can be maintained, thereby increasing the recovery efficiency of the recovery object metal.

In particular, in the case of using metal particles having an average particle diameter of 0.1 to 8 mm as the metal for precipitation, for example, the total surface area of the metal for precipitation for metal precipitation reaction is increased compared to the method of using scrap of iron, and the precipitation reaction rate is increased. Is improved, and the recovery efficiency of the metal to be recovered is further increased.

Moreover, when the to-be-processed liquid flows into the reactor main body and the metal particle of the average particle diameter of 0.1-8 mm which is the metal for precipitation is added in the reactor main body, metal particle can be made to flow preferably in the reactor main body, and precipitation will occur. The peeling effect of the metal to be recovered from the molten metal can be further improved.

In addition, when the reactor body is configured such that the liquid to be treated flows in from the lower portion of the reactor body and flows out from the upper portion of the reactor body and the cross-sectional area of the reactor body is increased upward, the flow rate of the liquid to be processed in the reactor body is increased. The velocity gradually decreases, and the metal particles, which are precipitation metals whose particle diameters are reduced by the metal precipitation reaction and the like above, can be maintained in the reactor body without unexpectedly overflowing in the upper portion of the reactor body in which the cross-sectional area increases.

The liquid to be treated flows in from the lower side of the reactor body, and the metal to be recovered precipitates in the precipitated metal when passing through the reactor body, so that the portion of the metal to be recovered in the liquid to be treated increases toward the top of the reactor body. As the concentration decreases and the particle diameter of the metal particles, which are precipitated metals, decreases as described above, fine metal particles are present in the upper portion of the reactor main body, and the rate of upward flow of the liquid to be treated gradually decreases, thereby decreasing the particle size of the metal particles. Since it is recognized that the number increases, the total surface area of the metal particles increases as the upper portion of the reactor main body increases, and as a result, the reaction rate of the metal precipitation reaction improves, and the recovery also occurs on the upper portion of the reactor main body in which the concentration of the metal to be recovered becomes lower. There is an effect that the target metal can be efficiently recovered and processed.

In the case where a plurality of reactor bodies are formed in a plurality of stages, and a filter is formed at a rear stage thereof, when two or more kinds of metals are contained in the target liquid to be treated, for example, some kind of metal in the reactor body of the first stage is used. Precipitates and recovers the metal with the first stage filter, and in the reactor body of the second stage, it is possible to precipitate other metals and recover the other metal with the second stage filter. There is an effect that two or more kinds of metals to be recovered can be selectively recovered from the treatment liquid.

In addition, when the liquid to be treated which contains nitrate ions in addition to the metal to be recovered in the ionic state, especially the metal to be recovered, is indium (In), the metal precipitation reaction using the difference in the ionization tendency as described above does not occur. In some cases, by adding a chlorine ion source to the liquid to be treated in addition to the metal for precipitation, despite the presence of nitrate ions in the liquid to be treated, the presence of the chloride ion source causes the metal to be recovered, such as In, to be deposited in the precipitation metal. It is possible to precipitate preferably, and it is possible to recover In more easily than conventional methods by peeling In from the metal for deposition by the peeling means.

As described above, when nitrate ions are present in the liquid to be treated, although In cannot be deposited on the metal for deposition, the reason for the precipitation of In becomes possible by adding a chlorine ion source to the liquid to be treated is as follows. I think. In other words, In is recognized that the presence of nitrate ions at a certain concentration changes the form in the solution, whereby the standard reduction potential of In is lower than a value generally considered, while Al constituting the precipitation metal And the standard reduction potential of Zn also increase, and it is thought that the potential difference between In, which is a recovered metal, and Al, Zn, which is a precipitation metal, becomes small, and it is difficult to reduce precipitation of In. Therefore, when chloride or hydrochloric acid, such as sodium chloride or potassium chloride, is added as a chlorine ion source, In forms a chloro complex, and the standard reduction potential lowered by nitrate ions rises again, whereby the It is thought that reduction precipitation becomes possible.

As another reason, the presence of nitrate ions in the liquid to be treated changes the potential of In and becomes a region at a stable potential-pH degree as In ions, whereby a reduction reaction by Al, which is a precipitation metal, is less likely to occur. It is also considered that the addition of Cl ions changes to a region at a stable potential-pH degree as the In metal, and the reduction reaction by Al, which is a metal for precipitation, is likely to occur.

In addition, the nitrate ions in the solution react with Al or Zn constituting the metal for precipitation to form nitrogen dioxide or nitrogen monoxide to be released as a gas.

In addition, in the case where the treatment liquid after the indium is recovered and recovered from the liquid to be treated by the metal for deposition is added to the liquid to be treated as a stock solution, and further treated, chlorine ions remain in the treatment liquid after the indium recovery. As a result, chlorine ions are reused. As a result, the amount of the chlorine ion source to be added can be reduced, and further, the treatment cost can be reduced.

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

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

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

4 is a schematic cross-sectional view of a metal recovery apparatus of another embodiment.

5 is a schematic plan view of an inflow chamber in the metal recovery apparatus of another embodiment.

6 is a cross-sectional view taken along the line A-A of FIG. 5.

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

FIG. 8 is a schematic plan view of a slide board with an electromagnet used in the embodiment of FIG. 7.

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

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

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

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

It is a schematic front view of the metal collection | recovery apparatus of other embodiment.

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

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

16 is a graph showing test results.

(Explanation of the sign)

1, 1a, 1b, 1c: reactor body

11a, 11b, 11c, 11d: ultrasonic oscillator

12: electromagnet

17, 18, 19: filter

25: Trade Department

32: Euro

33: pump

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described according to drawing.

(Embodiment 1)

As shown in FIG. 1, the metal recovery device of the present embodiment includes a vertically long reactor body 1. This embodiment demonstrates the case where waste liquid is used as a to-be-processed liquid. As shown in the drawing, the reactor main body 1 is composed of a reactor upper part 2, a reactor intermediate part 3, and a reactor lower part 4, and extends through the extension parts 5 and 6, respectively. . Each of the reactor upper part 2, the reactor middle part 3, and the reactor lower part 4 is formed with the same width, the cross-sectional area of the reactor upper part 2 is formed larger than the cross-sectional area of the reactor middle part 3, The cross-sectional area of the reactor intermediate part 3 is formed larger than the cross-sectional area of the reactor lower part 4. As a result, it is comprised so that the cross-sectional area of the reactor main body 1 as a whole may discontinuously increase upwards. In addition, the extending parts 5 and 6 are formed in a wide tapered shape upward.

In the lower part of the reactor lower part 4, the substantially conical inflow chamber 7 for inflowing the waste liquid to process is provided, and the inflow pipe 8 is formed in the lower part. Although not shown in the inlet pipe 8, a check valve is formed. Moreover, the upper chamber 9 is formed in the upper part of the reactor upper part 2, and the discharge pipe | tube 10 for discharging the collect | recovered flake shape and particulate form metal is formed in the side part. The upper chamber 9 is a part for discharging the metal recovered by the discharge pipe 10, and recovers to cause a so-called cementation reaction (metal precipitation reaction) based on the difference between the metal to be recovered and the ionization tendency. It is also a part for injecting a precipitation metal (metal particle) having a larger ionization tendency than the target metal. In practice, the cementation reaction of the precipitation metal and the metal to be recovered takes place in the entire reactor body 1.

And the waste liquid which flows in from the inflow pipe 8 until it reaches the discharge pipe 10 is comprised so that the waste liquid rises in a vertical direction, and forms a fluidized bed by metal particles. In addition, the ultrasonic oscillators 11a, 11b, 11c as the peeling means for peeling the metal to be recovered which are deposited on the metal particles introduced by the cementation reaction as the metal contained in the waste liquid include the upper part of the reactor 2 and the middle of the reactor. It is provided in the part 3 and the reactor lower part 4, respectively.

In the present embodiment, particles of zinc (Zn) are used as the metal particles to be introduced. As the waste liquid to be used, for example, a metal surface treatment plant waste liquid containing metal ions such as copper (Cu) and tin (Sn) is used. In this case, Cu and Sn are recovered as a metal. Although the average particle diameter of the metal particle | grains thrown in can use the metal particle of 0.1-8 mm, in this embodiment, an average particle diameter of 2 mm is used. In addition, an average particle diameter is measured by the image analysis method, JIS Z 8801 sieving test method, etc.

And the method of recovering metal by the metal collection | recovery apparatus which consists of such a structure is demonstrated, First, the waste liquid to be processed flows into the reactor main body 1 from the inflow pipe 8 through the inflow chamber 7. In one side, metal particles (Zn particles) for generating a cementation reaction are introduced from the upper chamber 9. In the reactor body 1, the introduced waste liquid rises in the vertical direction, while the waste liquid and the metal particles introduced from the upper chamber 9 are in a flow state so as to form a fluidized bed.

And so-called cementation reaction is generated based on the difference in the ionization tendency of metals, such as Cu and Sn, contained in the waste liquid, and Zn which is the injected metal particle. When this is explained in more detail, the reduction reaction of each metal ion is as following Formula (1)-(3), and the standard electrode potential (E °) of each metal ion is shown to each.

Zn ^{2 +} + 2e → Zn... (1) -0.76V

Cu ^{2 ++} 2e → Cu. (2) + 0.34V

Sn ^{2 +} + 2e → Sn. (3) -0.14V

(1) to (3), as is apparent from, Cu ^{2 +,} compared to the Sn ^{+ 2,} the standard reduction potential of the Zn ^{2 +} is the smallest. In other words, the ionization tendency of Zn is the largest compared with Cu and Sn. Accordingly, in a flow state such as the state, the ionization tendency is greater Zn is a Zn ^{2 +,} and eluted in the waste liquid (the above (1) expression and opposite reaction), Cu ^{2 +} with it were contained in the waste liquid, Sn ^{+ 2} is a Cu, Sn, is deposited on the surface of Zn particles.

After the metals of Cu and Sn are precipitated on the surface of the Zn particles by this cementation reaction, the ultrasonic wave oscillators 11a, 11b, 11c are operated. By operating the ultrasonic oscillators 11a, 11b, 11c, the ultrasonic waves oscillated from the ultrasonic oscillators 11a, 11b, 11c impart a vibration force and stirring force to the Zn particles in which Cu and Sn are precipitated. Each metal of Cu and Sn which precipitated by this will forcibly peel from Zn particle | grains. In this case, the ultrasonic oscillators 11a, 11b, 11c may be operated continuously, but if operated continuously, the ultrasonic oscillator may generate heat, which may make it difficult to operate the ultrasonic oscillator for a long time. In addition, when the ultrasonic oscillator is operated continuously, the precipitated metals (Cu, Sn) are grown and peeled sequentially before they become a certain size, and as a result, there is a fear that a precipitated metal of a certain size may not be obtained. . In this regard, when the ultrasonic oscillator is operated intermittently, there is little risk of unexpected peeling until the precipitated metal becomes somewhat large, so that the separated metal is easily separated. Therefore, it is preferable to perform the operation | movement of the ultrasonic wave oscillator 11a, 11b, 11c intermittently. Intermittent operation in this case is performed by 2 second ON, 8 second OFF, etc., for example.

Thus peeled Cu and Sn are discharged | emitted from the upper chamber 9 through the discharge pipe 10 to the exterior of the reactor main body 1, and it is collect | recovered as a recovery object metal (alloy of Cu and Sn in this embodiment). It will be recovered. In this case, in this embodiment, since a particulate material is used as a metal thrown in to precipitate a recovery object metal, it is a metal for generating a cementation reaction compared with the case where a scrap of zinc is thrown in, for example ( The surface area of Zn) increases, and the rate of precipitation reaction of Cu and Sn is improved.

And after the precipitation of the metal which has grown to some extent is confirmed, by the forced peeling by the above-mentioned ultrasonic vibration, a new metal surface (surface of Zn particle | grains) can always be exposed and reaction rate can be maintained. Moreover, compared with the method of injecting the scrap of zinc conventionally performed, there exists very few impurities other than Cu and Sn in the peeling collect | recovery object metal.

In addition, the particle diameter at the time of the metal particles consisting of Zn includes a reactor body (1) to flow in, since the Zn ^{2 +} are eluted by cementation reactions as described above, the injection of the metal particles charged into the upper chamber 9, the initial Is probably reduced over time. As a result, if the reactor cross section is the same from the lower part of the reactor to the upper part of the reactor, the waste liquid rises inside the reactor main body 1 at a substantially same upstream speed, so that the particle diameter decreases toward the upper part and the smaller metal particles become smaller. There is a risk of overflowing from 1) unexpectedly.

However, in this embodiment, since the cross-sectional area of the reactor main body 1 is formed so that it may become discontinuously larger as it goes upward, the speed | rate of the upflow of the waste liquid in the reactor main body 1 will gradually decrease. Therefore, the metal particles whose particle diameter is reduced by the cementation reaction or the like as described above are more likely to be retained in the reactor body 1 without unexpectedly overflowing out of the reactor body at the upper portion of the reactor body 1 with increasing cross-sectional area. .

Moreover, when the waste liquid flows in from the lower side of the reactor main body 1 and passes through the inside of the reactor main body 1, metals, such as Cu and Sn which are collection objects, are made to the metal particle which consists of Zn by a cementation reaction. In order to precipitate, the concentration of the metal to be recovered in the waste liquid decreases toward the upper portion of the reactor body 1.

In the present embodiment, however, fine metal particles are present in the upper portion of the reactor main body 1, and it is recognized that the number of metal particles increases by gradually decreasing the speed of the upstream flow of the waste liquid, so that the upper portion of the reactor main body 1 The larger the total surface area of the metal particles. As a result, since the reaction rate (efficiency of the metal to be recovered) of the cementation reaction is improved, the metal to be recovered can be efficiently recovered even from the upper part of the reactor main body 1 in which the concentration of the metal to be recovered becomes lower. It will be possible.

(Embodiment 2)

In the present embodiment, the structure of the reactor main body 1 is different from that in the first embodiment. That is, in this embodiment, as shown in FIG. 2, the whole peripheral surface of the reactor main body 1 is formed so that it may become taper upward, and it is comprised so that the cross-sectional area of the reactor main body 1 may continuously increase upward. This is different from the case of Embodiment 1 in which the cross-sectional area of the reactor body 1 is discontinuously increasing upward.

Since it is not discontinuous and it is comprised so that a cross-sectional area may continuously increase upwards, in this embodiment, it is divided and comprised like reactor upper part 2, reactor intermediate part 3, and reactor lower part 4 like Embodiment 1. It is not.

However, the point where the ultrasonic wave oscillators 11a, 11b, 11c are formed at three points from the top to the bottom of the reactor body 1 is common to the first embodiment. Therefore, also in this embodiment, similarly to the first embodiment, the effect of forcibly peeling off the recovery target metal deposited on the metal particles is obtained by the ultrasonic waves oscillated from the ultrasonic oscillators 11a, 11b, 11c. .

In addition, although it is different whether it is discontinuous or continuous, since it is comprised so that a cross-sectional area may increase upward, since it is common to Embodiment 1, also in this embodiment, the fine metal particle whose particle diameter was reduced is replaced with the reactor main body (1). The effect of preventing the overflow of the reactor main body unexpectedly from flowing out of the reactor main body, and the effect of efficiently recovering the recovery target metal at the upper part of the reactor main body 1 having a low concentration of the recovery target metal. will be.

(Embodiment 3)

Although the reactor main body 1 of this embodiment is common with the said Embodiments 1 and 2 in that it is vertically long, as shown to FIG. 3 and FIG. 4, it is formed so that the cross-sectional area may become the same in the upper and lower sides, and in this respect It differs from the said Embodiment 1, 2 comprised so that a cross-sectional area may increase upward.

Also in this embodiment, while the inflow chamber 7 is formed in the lower side of the reactor main body 1 similarly to the said Embodiment 1, the upper chamber 9 is formed in the upper side of the reactor main body 1. Although the shape is different from Embodiment 1 which was formed in substantially conical shape. That is, the upper chamber 9 is formed in a shallow cylindrical shape as shown in FIG. 3 and FIG. 4, and the inflow chamber 7 is shown in FIG. 5 and FIG. It is formed in the shape which consists of the side cylinder parts 21 and 21 formed in left and right communication with the center cylinder part 20. As shown in FIG.

In this embodiment, the inflow pipes 8 and 8 are formed in the front end side of the side cylinder part 21 and 21 of the said inflow chamber 7, respectively. In the side cylinder portions 21 and 21 of the inflow chamber 7, the baffles 22 and 23 are formed in two rows in the vertical direction, so that the liquid to be treated introduced from the inflow pipes 8 and 8 is blocked. The plates 22 and 23 are configured so that the flow is disturbed.

Moreover, as shown in FIG. 4, the upper chamber 9 is comprised from the inner cylinder 9a and the outer cylinder 9b, and as shown in the figure, the upper cylinder 9a is fitted outside in the upper part of the reactor main body 1, The chamber 9 is attached to the reactor body 1. Moreover, the discharge pipe 10 is a lower part of the upper chamber 9, and is attached in the position between the said inner cylinder 9a and the outer cylinder 9b. As a result of this structure, the to-be-processed liquid which distribute | circulates the inside of the reactor main body 1 upward flows between the outer cylinder 9b and the inner cylinder 9a from the upper opening part of the inner cylinder 9a, and the said discharge pipe 10 From the outside.

Moreover, the metal particle for generating a cementation reaction is thrown in from the upper opening part of the inner cylinder 9a. Then, the liquid to be processed flows up in the vertical direction while the waste liquid introduced from the inflow pipe 8 of the inflow chamber 7 reaches the discharge pipe 10 of the upper chamber 9 while flowing by the metal particles. It is comprised so that the cementation reaction of the metal thrown in and the recovery object metal generate | occur | produces in the reactor main body 1 is common to Embodiment 1, 2 mentioned above.

Moreover, also in this embodiment, the ultrasonic oscillator is employ | adopted as the peeling means which peels the recovery object metal precipitated in the metal particle by the cementation reaction as a metal contained in waste liquid. That is, in this embodiment, four ultrasonic oscillators 11a, 11b, 11c, and 11d are attached to the outer circumferential surface of the reactor main body 1. These four ultrasonic oscillators 11a, 11b, 11c, 11d are all mounted on the reactor body 1 at an angle of about 45 degrees with respect to the horizontal plane, of which two ultrasonic oscillators 11a, 11c are identical. Direction, and the other two ultrasonic oscillators 11b and 11d are mounted so as to face in opposite directions.

Also in this embodiment, waste liquid is used as a to-be-processed liquid, As the waste liquid, waste liquid of the metal surface treatment plant containing metal ions, such as Cu and Sn, similar to the said Embodiment 1, etc. are used, for example. In this case, particles of Zn are used as metal particles to be introduced in the same manner as in Embodiment 1, and Cu and Sn are recovered as metals.

And when metal is collect | recovered by the metal collection | recovery apparatus of this embodiment, waste liquid flows in into the reactor main body 1 from the inflow pipe 8 through the inflow chamber 7 first. In this case, the inflow chamber 7 is constituted by the central cylinder portion 20 and the side cylinder portions 21 and 21 as described above, and the side cylinder portions 21 and 21 are provided with obstruction plates 22 and 23. Since two rows are formed in the longitudinal direction, the waste liquid flowing in from the inflow pipes 8 and 8 mounted in the transverse direction with respect to the side barrel portion 21 does not flow into the transverse direction at once, but rather in the longitudinal direction. It flows into the center cylinder part 20 alternately flowing up and down inside the side cylinder part 21 along 22 and 23, and is flowed upward from the center cylinder part 20 toward the reactor main body 1. As shown in FIG. Therefore, the waste liquid flowing in from the inflow pipes 8 and 8 is disturbed by the obstruction plates 22 and 23, and is in a state where it is easy to flow upward in the reactor main body 1 without generating a drift. Moreover, if necessary, what put glass or ceramic balls in the cylindrical basket can be provided in the inflow chamber 7, for example, and it becomes possible to prevent drift more reliably by this.

The action of the so-called cementation reaction, the stirring by the ultrasonic oscillator, the peeling action of the metal, etc., based on the difference in the ionization tendency of the metals such as Cu and Sn contained in the waste liquid and Zn which is the metal particles to be introduced, are carried out as described above. It is the same as a form, and the detailed description is abbreviate | omitted.

(Embodiment 4)

In the present embodiment, as a means for peeling the recovered recovery target metal from the metal particles, a means for stirring using an electromagnet is used instead of the means for vibrating with the ultrasonic wave oscillated by the ultrasonic oscillators of the first to third embodiments. Doing. That is, in embodiment, the slide board 13 provided with the electromagnet 12 as shown in FIG. 8 can lift up and down freely to the guide rail 14 formed in the side of the reactor main body 1 as shown in FIG. It is mounted so that. The slide board 13 has the space part 15 in the center, as shown in FIG. 8, and is arrange | positioned so that the reactor main body 1 may be inserted in the space 15, and the reactor main body 1 may be surrounded. . In addition, the reactor main body 1 is not shown in FIG. Moreover, in this embodiment, the reactor main body 1 is formed so that a horizontal cross section may become rectangular shape, and in this point, the cross section is circular, ie, the said Embodiment 1 thru | or 3 in which the reactor main body 1 was formed in the cylindrical shape, and Different.

And as shown by the arrow 16 of FIG. 7, by moving up and down alternately, while stirring the metal particle in the reactor main body 1, many metal particles collide with each other, and the metal precipitated from the metal particle is thereby made. It is forcibly peeled off. The electromagnets 12 are alternately applied, for example, at regular intervals, such as 2 seconds, and the vertical movement of the slide board 13 is performed intermittently or continuously. Although the means for peeling the recovery object metal precipitated from the metal particles is different, also in this embodiment, the recovery object metal can be preferably peeled off and recovered from the metal particles. In addition, the iron particle which is a magnetic substance is used for the metal particle used in the case of this embodiment.

In addition, 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 of Cu or Sn and the standard electrode potential are as shown in the above formulas (2) and (3), and the value of the standard electrode potential is smaller than that of Cu or Sn, so that the ionization tendency of Fe is Since it is larger than the tendency to ionize, it can apply to the waste liquid containing Cu and Sn also in this embodiment.

(Embodiment 5)

In this embodiment, as shown in FIG. 9, two reactors are arrange | positioned and it differs from the case of Embodiment 1-4 which consists of only one reactor in that point. That is, in this embodiment, the filter 17 is formed in the front end of the reactor main body 1b of the 2nd stage as the rear end of the reactor main body 1a of the 1st stage, and is the rear end side of the reactor main body 1b of the 2nd stage. The filter 18 is formed in the filter. As a filter, a cartridge filter, a drum filter, etc. are used, for example. In addition, it is also possible to use solid-liquid separation means, such as a belt press and a filter press, instead of a filter.

In the present embodiment, for example, when Cu and Sn are contained in the target waste liquid, Fe particles are introduced into the reactor body 1a of the first stage, and Cu is deposited on the Fe particles to filter the first stage filter ( 17), Cu is collect | recovered, Zn particle | grains are thrown into the reactor main body 1b of a 2nd stage | paragraph, Sn can be precipitated in the Zn particle | grains, and Sn can be collect | recovered by the filter 18 of a 2nd stage | paragraph.

In this case, from the numerical values of the standard electrode potentials shown in the above formulas (2), (3) and (4), both Cu and Sn have a smaller ionization tendency than Fe, but the difference in the ionization tendency is less than that of Fe and Sn. The difference between and Cu is much larger, and therefore, in the reactor body 1a in the first stage, Cu preferentially precipitates in the Fe particles. On the other hand, from the numerical values of the standard electrode potentials shown in the above formula (1), the ionization tendency of Zn is larger than the ionization tendency of Cu and Sn, and therefore, in the reactor body 1b of the second stage, both Cu and Sn must be deposited on the Zn particles. However, since Cu is already precipitated in the Fe particles of the reactor body 1a in the first stage, Sn is mainly precipitated in the Zn particles in the reactor body 1b in the second stage. However, the residue of Cu which did not precipitate in Fe particle in the reactor main body 1a of 1st stage | paragraph precipitates in Zn particle | grains in the reactor main body 1b of 2nd stage | paragraph.

As described above, in this embodiment, there is an advantage that two kinds of metals can be selectively recovered from the waste liquid using two different kinds of metal particles. Moreover, although it does not describe the means which peels the collect | recovered recovery metal from a metal particle, it does not specifically limit, The method of using the above-mentioned ultrasonic oscillator, the method of stirring using an electromagnet, the other thing mentioned later Method can be used.

Embodiment 6

In this embodiment, as shown in FIG. 10, three reactors are arrange | positioned, and from that point, it is different from the case of Embodiment 1-4 which consists of only one reactor, and Embodiment 5 in which two reactors were arrange | positioned. . In this embodiment, the filter 17, the filter 18, and the filter 19 are formed in the rear end side of these three reactor main body 1a, the reactor main body 1b, and the reactor main body 1c. In the present embodiment, Fe particles are introduced from the reactor body 1a in the first stage and Zn particles are introduced from the reactor body 1b in the second stage, as in the fifth embodiment. In the reactor body 1c in the third stage, Aluminum (Al) particles are added.

When this embodiment is applied to the waste liquid containing Cu and Sn similarly to the said Embodiment 5, Cu reactor precipitates in Fe particle similarly to Embodiment 5 in the reactor main body 1a of 1st stage | paragraph, and the 1st stage filter ( 17) Cu is collect | recovered, Sn also precipitates in Zn particle | grains also in the reactor main body 1b of 2nd stage | paragraph, and Sn is collect | recovered by the filter 18 of 2nd stage | paragraph.

However, in the third stage reactor main body 1c, an unexpected action occurs from the fifth embodiment. That is, Fe eluted by the cementation reaction in the reactor body 1a in the first stage as described above, and Zn eluted by the cementation reaction in the reactor body 1b in the second stage are the reactor body 1c in the third stage. Precipitates on Al particles that are added to the particles.

Explaining this in more detail, the reduction reaction of Al ions and the standard electrode potential are shown in the following equation (5).

Al ^{3 +} + 3e → Al... (5) -1.66V

The Fe particles introduced from the reactor body 1a of the first stage and the Zn particles introduced from the reactor body 1b of the second stage are made of a metal having a larger ionization tendency than the metal to be recovered as described above, but (1), ( From the comparison of the numerical values of the standard electrode potentials shown in Equations 4 and 5, it is clear that the ionization tendency of Al is greater than that of Fe and Zn. Therefore, Fe eluted from the reactor body 1a of the first stage and Zn eluted from the reactor body 1b of the second stage are both precipitated to Al particles in the reactor body 1c of the third stage. Then, Al particles can be recovered as an alloy of Fe—Zn.

Therefore, operations such as flocculation and precipitation of Fe and Zn eluted in the reactor main body 1a of the first stage and the reactor main body 1b of the second stage, respectively, are unnecessary, and the amount of sludge generation can be suppressed. In addition, although Al is eluted from the reactor body 1c of the 3rd stage | paragraph, since the amount of sludge generate | occur | produces since the trivalent Al becomes less elution amount than divalent Zn and Fe, the specific gravity of Al can also be reduced and sludge weight can be reduced. There is no case. Also in this embodiment, it does not specifically limit about the means which peels the collect | recovered recovery metal from a metal particle.

(Embodiment 7)

In the present embodiment, as a means for peeling the precipitated recovery object metal from the metal particles, stirring is performed by means of vibrating with ultrasonic waves oscillated by the ultrasonic oscillators of the first to third embodiments and the electromagnet of the fourth embodiment. Instead of the means, a means using a so-called air lift action that blows and agitates a gas such as air is employed. That is, in this embodiment, as shown in FIG. 11, the normal part 25 is provided in the substantially center of the reactor main body 1, and the gas inflow pipe 26 is connected to the lower part of the normal part 25. As shown in FIG. . The gas inlet 27, which is one end opening of the gas inlet pipe 26, is protruded to the outside of the reactor body 1, and the other end opening 28 of the gas inlet pipe 26 is the ordinary part. It is in communication with 25. Moreover, the obstruction plate 30 is formed below the lower opening part 29 of the normal part 25.

In this embodiment, the reactor main body 1 is formed in substantially cylindrical shape similarly to the said Embodiment 3, and the inflow chamber 7 is formed in the lower part of the reactor main body 1 similarly to the said Embodiments 1-3. The upper chamber is formed in the upper portion. 11, although the discharge pipe 10 is shown, the upper chamber is not shown. In the present embodiment, particles of Al or Zn are used as the metal particles to be introduced. As the waste liquid to be used, waste liquid of a flat panel display (FPD) manufacturing plant containing indium (In) ions is used. In this case, In is recovered as a metal.

As above-mentioned, the average particle diameter of the metal particle to add can use the metal particle of 0.1-8 mm, but when metal particle is Al, it is preferable that it is 1.5-5.5 mm, and when it is Zn, it is 1.5-4.0 mm. It is preferable. This is because when the Zn particles exceed 4.0 mm and when the Al particles exceed 5.5 mm, the flow rate required for flowing these particles increases and the amount of gas intake increases. On the other hand, since the particle size of the metal particles gradually decreases due to the cementation reaction, when the original particle size of the metal particles is small, the metal particles may flow out from the reactor body 1 together with the treatment liquid as described above. Although it is the same, from this viewpoint, in the case of Zn particle | grains or Al particle | grains, it is preferable that it is 1.5 mm or more.

In the following, a method for recovering metal by the metal recovery apparatus of the present embodiment will be described. First, waste liquid is introduced into the reactor main body 1 through the inflow chamber 7 in the same manner as in each of the above embodiments. The metal particle is thrown in from the. In addition, gas is introduced into the normal portion 25 via the gas inflow pipe 26. Thereby, the specific gravity of the mixed part of the gas and water in the normal part 25 falls, and a liquid presses up with a gas.

As described above, the gas flows into the normal part 25 and flows upward, so that the liquid to be processed in the normal part 25 also flows upward. Thus, although the to-be-processed liquid flows through the inside of the normal part 25, since the pressure difference generate | occur | produces inside and outside the normal part 25, the flow rate of a to-be-processed liquid also changes inside and outside the normal part 25, As a result, the metal particles are stirred in the reactor main body 1, and In precipitated on the surface of the metal particles is peeled off.

In this case, since In, which is a recovery target metal in the present embodiment, is precipitated in a sponge form, the adhesion to metal particles such as Zn is worse than that of Cu and Sn of the first embodiment, and thus, the above embodiment. Even if it does not employ the means for forcibly peeling off by ultrasonic vibrations such as 1 to 3, or the means for forcibly peeling off using an electromagnet as in the fourth embodiment, as in the present embodiment, the stirring means using only the air lift action, In can be peeled from the metal particles relatively easily. That is, In can be recovered by a device having a simple and low energy means.

And a so-called cementation reaction is generated based on the difference in the ionization tendency of In contained in the waste liquid with Zn or Al which is the injected metal particles. When this is explained in more detail, the reduction reaction of In ion is as following Formula, and the standard electrode potential (E degrees) is also shown.

In ^{3 +} + 3e → In... (6) -0.34V

The 1, 5, 6, as is apparent from the formula, compared to ^{3 +} In, Zn ^{+ 2} or less, the standard reduction potential of the Al ^3+. In other words, the ionization tendency of Zn and Al is large compared with In. Therefore, a large Zn or Al ionization tendency is a Zn ^{2 +} or Al ^{3 +,} and eluted in the waste liquid, the In ^{3 +} with it were contained in the waste liquid are the In, it is precipitated on the surface of the Zn or a particle . After In is precipitated on the surface of the Zn particles or Al particles by such a cementation reaction, In precipitated by stirring using the air lift action as described above is separated from the Zn particles or Al particles, and the separated In is discharged. It is discharged to the outside of the reactor main body 1 via 10, and it is collect | recovered.

In addition, in this embodiment, since the baffle plate 30 is formed below the lower opening part 29 of the normal part 25, the water flow of the waste liquid which flows in from the inflow chamber 7 directly to the normal part 25. It is preferably prevented that the flow rate of the liquid to be processed in the ordinary portion 25 is extremely high because it does not flow into the baffle plate 30.

Embodiment 8

In this embodiment, air jet agitation or water jet agitation is employed as a means for peeling a metal to be recovered from metal particles, and is different from the above Embodiments 1 to 7 in this respect. That is, in this embodiment, as shown in FIG. 12, the jet stirring jet port 31 is attached to the circumferential surface part of the reactor main body 1, and air or water is jetted from the jet stirring jet port 31, and a reactor is carried out. It is comprised so that a fine bubble may generate | occur | produce in the main body 1. As shown in FIG. That is, air jet agitation means dispersing gas such as air to generate fine bubbles, and water jet agitation means generating fine bubbles by ejecting a liquid such as water.

Since the shape of the reactor main body 1, the inflow chamber 7, and the structure in which the discharge pipe | tube 10 are formed are the same as that of Embodiment 7, the description is abbreviate | omitted. Moreover, since the kind of metal particle | grains thrown in, the kind of waste liquid used as an object, the action of a cementation reaction, etc. are the same as that of the said Embodiment 7, the detailed description is abbreviate | omitted. In this embodiment, gas or water (for example, processing liquid), such as air, is ejected from the jet stirring jet port 31 to generate turbulence in the reactor main body 1, and the turbulent flow causes the reactor main body 1 to flow. The metal particles in the inside are stirred, whereby In precipitated on the surface of the metal particles is peeled off.

Also in this embodiment, since In which is a recovery target metal is inferior in adhesion to metal particles such as Zn, the means for forcibly peeling off by ultrasonic vibrations as in the first to third embodiments and the electromagnet as in the fourth embodiment are Even if no means for forcibly peeling off is used, In can be relatively easily peeled off from the metal particles only by means of air jet or water jet agitation. That is, In can be recovered by a device having a simple and low energy stirring means.

(Embodiment 9)

In this embodiment, the means by a solid-liquid transport pump stirring is employ | adopted as a means which peels a recovery object metal from a metal particle, and differs from the said Embodiments 1-8 in this point. That is, in this embodiment, as shown in FIG. 13, the flow path 32 and the pump 33 which circulate and transport the to-be-processed liquid and metal particle in the reactor main body 1 are formed in the exterior of the reactor main body 1, And a means for stirring the metal particles by circulating and transporting the liquid to be treated and the metal particles in the flow passage 32 and the reactor main body 1 by the pump 33.

Since the shape of the reactor main body 1, the structure in which the inflow chamber 7 and the discharge pipe 10 are formed are the same as in the above-mentioned Embodiments 7, 8, the description is omitted. Moreover, since the metal particle to be thrown in, the kind of waste liquid used as an object, and the effect | action of a cementation reaction are also the same as that of the said Embodiment 7, 8, the detailed description is abbreviate | omitted.

In this embodiment, the to-be-processed liquid flows out from the reactor main body 1 to the flow path 32 by the pump 33, and it circulates through the flow path 32, and is conveyed to the reactor main body 1 again. As a result, the metal particles in the reactor body 1 are stirred, whereby In precipitated on the surface of the metal particles is peeled off.

Also in this embodiment, since In which is a precipitated metal is inferior in adhesiveness to metal particles such as Zn, a means for forcibly peeling off by ultrasonic vibrations as in the first to third embodiments, or an electromagnet as in the fourth embodiment is used. In this case, the In can be relatively easily peeled from the metal particles by means of the degree of stirring only the solid-liquid transport pump using the pump 33 or the flow path 32 without employing a means for forcibly peeling off. That is, In can be recovered by a device having a simple and low energy means.

Embodiment 10

The indium recovery apparatus of this embodiment is equipped with the reactor main body 1, the adjustment tank 42, and the filter 43, as shown in FIG. The reactor main body 1 is for depositing In from the waste liquid (to-be-processed liquid) by a cementation reaction (metal precipitation reaction), as described later, and the adjusting tank 42 has chlorine ions (Cl ⁻ ) in the waste liquid before it. It is for adjusting the concentration of chlorine ions in the liquid to be treated by adding a circle, and the filter 43 is for separating and recovering In precipitated in the reactor body 1. Moreover, the separated process liquid is comprised so that it can convey to the said adjustment tank 42, and the flow path for it is formed between the filter 43 and the adjustment tank 42. As shown in FIG. Moreover, the flow path from the adjustment tank 42 to the reactor main body 1, and the flow path from the reactor main body 1 to the filter 43 are also formed. In FIG. 14, the pump etc. which circulate the to-be-processed liquid are not shown in figure.

This embodiment demonstrates the case where waste liquid is used as a to-be-processed liquid. Since the structure of the reactor main body 1 is the same as that of the said Embodiment 1, the detailed description is abbreviate | omitted.

In the present embodiment, particles of zinc (Zn) or aluminum (Al) are used as the metal particles to be introduced. As the waste liquid to be used, for example, a cleaning waste liquid of an aluminum target material containing ions of In and containing nitrate ions (N0 ₃ ⁻ ), or an etching waste liquid of FPD using nitric acid is used.

Then, when the described method for recovering indium by a system for recovering indium consisting of such a configuration, first, supplying a process subject to the waste liquid in the adjusting tank 42, an ion chlorine in the adjusting tank 42 (Cl ^-) cause sodium chloride or Add a chloride, such as potassium chloride. Indium forms a hydroxide precipitate when the pH is increased, so the pH is adjusted to 1.5 or less in advance so as not to form a precipitate. When the pH is too low, the reaction with the precipitation metal to be used is accelerated to generate H ₂ , NO, and NO ₂ gases, which unnecessarily consumes the precipitation metal, so the pH is preferably 0.5 or more.

Moreover, when pH is higher than the said range, it is preferable to adjust pH by hydrochloric acid, and when pH is lower than the said range, it is preferable to adjust pH by adding alkali, such as NaOH.

Next, the to-be-processed liquid adjusted by adding chloride in this way flows into the reactor main body 1 from the inflow pipe 8 through the inflow chamber 7. On the other hand, metal particles (Zn or Al particles) for generating a cementation reaction are introduced from the upper chamber 9. In the reactor body 1, the introduced waste liquid rises in the vertical direction, while the metal particles introduced from the upper chamber 9 are in a fluidized state to form a fluidized bed.

And a so-called cementation reaction is generated based on the difference in the ionization tendency of In contained in the waste liquid with Zn or Al which is the injected metal particles.

In more detail this, the reduction reaction in (1) described above for each metal ion, (5), as is apparent from (6) expression, as compared to In ^{3 +,} Zn ^{2 +} and Al standard ^{3 +} Small reduction potential.

In other words, the ionization tendency of Zn and Al is large compared with In. Accordingly, in a flow state such as the state, the ionization tendency is greater Zn or Al is eluted is a Zn ^{2 +} or Al ^{3 +} waste liquid, is In ^{3 +} is the In with it were contained in the waste solution Precipitates on the surface of the particles of Zn or Al.

In this case, since the nitrate ions (NO ₃ ⁻ ) are contained in the waste liquid, there is a possibility that the standard reduction potential of In is lowered, and the standard reduction potential of Al or Zn may be raised, and In and Al Or the potential difference of Zn becomes small, and there exists a possibility that reduction precipitation of In may become difficult. However, in this embodiment, since the to-be-processed liquid is supplied to the adjustment tank 42 previously, and the chlorine ion (Cl <^-> ) source is added, when the to-be-processed liquid flows into the reactor main body 1, Cl ⁻ ) forms a chloro complex of In, whereby the standard reduction potential of In is raised again, and as a result, precipitation of In on the surface of the particles of Zn or Al is not inhibited.

Since the operation | movement, peeling process, etc. which generate other cementation reaction are the same as each said embodiment, the description is abbreviate | omitted.

(Other Embodiments)

Moreover, in the said embodiment, about the case where it applies to the waste liquid of the metal surface treatment plant containing Cu and Sn ion as waste liquid (to-be-processed liquid), the case where it is applied to the cleaning waste liquid of an aluminum target material, the etching waste liquid of FPD, etc. Although it demonstrated, the kind of waste liquid made into object is not limited to this, It can apply to the waste liquid of a plating factory, the waste liquid of a semiconductor manufacturing factory, the waste liquid of a liquid crystal manufacturing factory, etc. In the present invention, the waste liquid is mainly used as the liquid to be treated. However, the metal to be recovered is brought into contact with a liquid other than the waste liquid, for example, a metal-containing solid waste by dissolving and ionizing the metal to be recovered. It can apply to the obtained aqueous solution.

Therefore, the kind of metal to be recovered is not limited to Cu, Sn, In of the embodiment, and for example, Ni, Ga, Zn or the like may be used as the recovery target metal. It doesn't matter.

Moreover, although the average particle diameter of the metal particle was made into about 2 mm in the embodiment, the average particle diameter of the metal particle is not limited to the embodiment. However, it is preferable that it is 0.1-8 mm. If it is less than 0.1 mm, the cementation reaction may not necessarily be preferably performed, and there is a possibility that recovery of the recovery target metal peeled from the metal particles may not be easily performed. The number of metal particles that can be maintained at is reduced, and as a result, the total surface area of the metal particles is reduced, which may lower the efficiency of the precipitation reaction, and it is necessary to increase the flow rate in order to make the metal particles flow, thereby requiring the required reaction time. This is because the reactor needs to be enlarged (reactor height is high) in order to maintain it. From this viewpoint, it is more preferable that it is 0.5-6 mm. Moreover, in order to make the fluidity | liquidity and reactivity in a reactor main body favorable, and to hold | maintain in a reactor main body easily, it is more preferable that it is the range of 1.0-2.0 mm.

In addition, the average particle diameter of a metal particle is measured by the image analysis method, the JIS Z 8801 sieving test method, etc. as mentioned above. As for the measurement of the average particle diameter by the image analysis method, the millet track JPA by Nikkiso Corporation is used, for example. In addition, in the JIS sieving test method, when it is set as the range of an average particle diameter of 1-2 mm, the metal particle used as a nominal dimension 2000 micrometer sieve or less and 1000 micrometer sieve or more is used, for example.

In addition, the uniformity of the metal particles is preferably less than 5 from the viewpoint of processing efficiency and operation control. Here, the uniformity of the metal particles is a transmittance curve formed by particle size distribution measurement or sieving, etc. (a percentage of the total sample mass of the mass of particles smaller than any particle diameter, that is, a curve drawn for any particle diameter, a cumulative cumulative curve is also called. ) Is a value obtained by dividing the body weight 60% particle diameter by the body weight 10% particle size. It represents the width of the particle size distribution.

In addition, in each said embodiment, although the metal particle used the metal single body, an alloy may be sufficient. As the alloy, an iron-aluminum alloy, a calcium-silicon alloy, or the like can be used.

Moreover, in the said Embodiment 1, 2, since the cross-sectional area of the reactor main body 1 was formed so that it might become large upwards, although the preferable effector was obtained as mentioned above, it is essential for this invention to form the reactor main body 1 in this way. It is not a condition. Like Embodiment 3, 7, 8, and 9, the cross section of the reactor main body 1 is the same, and it may form so that the whole may be substantially cylindrical.

Moreover, the means which peels a precipitation metal from a metal particle is not limited to each means of the said Embodiments 1-9, Means other than these may be sufficient.

Moreover, in the said Embodiment 10, although chlorides, such as sodium chloride and potassium chloride, were used as a chlorine ion source to add, hydrochloric acid can also be used without being limited to these chlorides. However, when hydrochloric acid is used, the acid concentration of the to-be-processed liquid becomes high, the dissolution reaction of the metal used for precipitation is accelerated | stimulated, and hydrogen gas is generated. Since this leads to an increase in unnecessary consumption of the metal for precipitation, an increase in the amount of hydrogen gas generated, and further an increase in running costs, it is preferable to use the chloride of the tenth embodiment as the chlorine ion source.

On the other hand, when the reduction precipitation reaction of In proceeds by adding a chlorine ion source, the metal ion to be used dissolves and hydrogen gas is also generated. Therefore, H ⁺ in the solution is consumed and the pH of the liquid to be treated is increased. do. When the pH is greater than about 1.5, In in the treated liquid becomes a hydroxide and precipitates and precipitates, so that addition of an acid is necessary to lower the pH. In this case, it is preferable to add hydrochloric acid.

In addition, in the said Embodiment 10, since the processing liquid after use was conveyed to the adjustment tank 42 as shown in FIG. 14, the chlorine ion source remaining in the processing liquid was added to the to-be-processed liquid (waste liquid). As a result, a desirable effect of reducing the amount of additional chloride required for the next In recovery process has been obtained. It is not an essential condition for the invention. In addition, in the said embodiment, although the adjustment tank 42 for adding a chlorine ion source was formed separately from the reactor main body 1, it is not limited to this, It can also adjust by adding a chlorine ion source directly to the reactor main body 1.

Moreover, although the metal particle was used as a metal for precipitation of each said embodiment, it is not limited to this, The thing which processed the metal wire or the metal wire in the mesh form, the plate-shaped metal, etc. may be used.

(Example 1)

Zn was used as a metal particle, and the copper sulfate solution was used as a simulated to-be-processed liquid for a test. As a test apparatus, as shown in FIG. 14, two tanks 34 and 35, two pumps 36 and 37, and a bug filter 38 besides the reactor main body 1 in which the ultrasonic oscillator 11 was provided in the center. ) And an apparatus in which the flow paths 39, 40, 41 for connecting them are formed.

The pH of the copper sulfate solution was 5, the initial concentration was 65.5 mg / L, the amount of the treatment liquid was 70L, and the target liquid was treated with respect to metal particles having an average particle diameter of 0.05 mm, 1 mm, 2 mm, 5 mm, and 10 mm. The test was performed by supplying the test apparatus shown in FIG. The test results are shown in Tables 1 to 5 and FIG. 16.

As is apparent from Tables 1 to 5 and FIG. 16, when metal particles having an average particle diameter of 1 mm, 2 mm, and 5 mm are employed, copper which is a precipitated metal as compared with the case of employing 0.05 mm or 10 mm metal particles. The removal rate of (Cu) was good.

(Example 2)

A nitric acid solution in which indium was dissolved was prepared as a simulation liquid of the waste liquid. The simulation liquid used what melt | dissolved In in 400 mg / L in 2.8% nitric acid solution. This was put into a 1 L beaker, and 50 g of sodium chloride was added first, and the In alloy recovery process was started using Al metal particles having an average particle diameter of 2 mm by the image analysis method. H ₂ gas and mainly NO ₂ gas were generated with the treatment. With the treatment, H ⁺ becomes H ₂ gas and is consumed, and the pH rises. Therefore, the pH in the solution is measured by a pH meter, and the stirring treatment is performed for 120 minutes to prevent the particles from flowing by adding hydrochloric acid so that the pH does not exceed 1.5. It was done. The In alloy precipitated on the Al metal particles was sponge-like and agglomerated and agglomerated during the agitation treatment, so that it could be easily peeled and recovered by ultrasonic treatment. The sonication was performed once every 2 minutes and for 2 seconds each. In this regard, the obtained In alloy was in the range of several 100 µm to several mm. In such a large mass, it is possible to recover with an inexpensive filter such as a bag filter.

1L of a fresh stock solution (indium-containing nitric acid solution) is added to the liquid after the treatment, and 25 g of sodium chloride is added to start the treatment, thereby enabling the treatment in the same process as described above. Therefore, the amount of chloride added can be reduced, and the treatment cost could be reduced.

As a result of the test under the above conditions, a very good result was obtained with a recovery rate of In from the solution of 95%.

(Example 3)

Zn metal particles were used in place of the Al metal particles of Example 2, and others were tested under the same conditions. Also in the present Example, the favorable result that In recovery was 90% was obtained.

(Comparative Example 1)

The same treatment was performed by adding only Al metal particles to the simulation solution prepared in Example 2 without adding sodium chloride. In addition, since nitrate ion and a part of Al metal particle react, since pH became 1.5 or more, pH was adjusted using sulfuric acid. The solution was stirred for 120 minutes, but no precipitation of In alloy was observed on the Al metal particle surface.

(Comparative Example 2)

Zinc metal particles were used in place of the Al metal particles of Comparative Example 1, and the others were tested under the same conditions. In this comparative example, the precipitation of In was not seen.

Claims (31)

A precipitation metal having a greater ionization tendency than that of the metal to be recovered is added to the liquid to be treated containing the metal to be recovered in an ionic state, and the metal to be recovered in the liquid to be treated is precipitated due to a difference in ionization tendency. Precipitating on the surface of the metal for metal, and then peeling and recovering the said metal to be recovered from the metal for deposition by a peeling means, it is recovered. The method of claim 1, A method for recovering a metal in which a liquid to be treated containing a metal to be recovered in an ionic state flows into the reactor body, and a metal for precipitation is added to the reactor body. The method according to claim 1 or 2, A method for recovering metal, wherein the means for peeling the metal to be recovered from the metal for precipitation is a means for vibrating the metal for precipitation by ultrasonic waves. The method according to claim 1 or 2, A method for recovering metal, wherein the means for peeling the metal to be recovered from the metal for precipitation is a means for stirring the metal for precipitation by an electromagnet to collide with a plurality of metals for precipitation. The method according to claim 1 or 2, A method for recovering metal, wherein the means for peeling the metal to be recovered from the metal for precipitation is a means for stirring the metal for precipitation by air jet or water jet. The method of claim 2, A method for recovering metal, wherein the means for peeling the metal to be recovered from the metal for deposition forms a normal portion in the reactor body, and blows gas into the ordinary portion to stir the metal for precipitation. The method of claim 2, The means for peeling the metal to be recovered from the metal for deposition forms a flow path and a pump for circulating and transporting the liquid to be treated and the metal for deposition in the reactor main body to the outside of the reactor main body. A metal recovery method, which is a means for stirring the precipitation metal by circulating and transporting. The method according to any one of claims 1 to 7, The metal recovery method is a metal particle whose average particle diameter is 0.1-8 mm. The method according to any one of claims 1 to 7, The metal recovery method is a metal particle whose average particle diameter is 0.5-6 mm. The method according to any one of claims 1 to 7, The metal recovery method is a metal particle whose average particle diameter is 1.0-2.0 mm. The method according to any one of claims 1 to 7, A method for recovering metal, wherein the metal for deposition is aluminum, and the metal for precipitation is metal particles having an average particle diameter of 1.5 to 5.5 mm. The method according to any one of claims 1 to 7, The metal recovery method is zinc, and the metal for precipitation is a metal particle | grain with an average particle diameter of 1.5-4.0 mm. The method according to any one of claims 2 to 12, A method for recovering metal, wherein the liquid to be treated flows in from the bottom of the reactor body and flows out of the top of the reactor body. The method of claim 13, A method for recovering metal, wherein the reactor main body is configured such that the cross-sectional area of the reactor main body increases upward. The method according to any one of claims 2 to 14, A method for recovering a metal, wherein two or more kinds of metals to be recovered are selectively recovered by two or more different kinds of precipitation metals by a plurality of reactor bodies. The method according to any one of claims 1 to 15, A metal recovery method for recovering a peeled recovery target metal with a filter. The method according to any one of claims 1 to 16, A method for recovering a metal, in which a nitrate ion is contained in a liquid to be treated in addition to a metal to be recovered in an ionic state, and a chlorine ion source is added to the liquid to be treated together with the precipitation metal. The method of claim 17, The recovery of the metal which flows a to-be-processed liquid into an adjustment tank, adds a chlorine ion source to the adjustment tank, next introduces the to-be-processed liquid in the adjustment tank into a reactor main body, and adds a metal for precipitation in the reactor main body. Way. The method of claim 17 or 18, A method for recovering a metal, in which a treatment liquid after recovering a metal to be recovered from a metal for precipitation is added to an object to be treated as a stock solution and treated again. The object to be recovered containing the metal to be recovered in an ionic state is added, and a precipitation metal having a greater ionization tendency than the metal to be recovered is added, and the object to be recovered is contained in the object to be treated by the difference in ionization tendency. A reactor body for performing a metal precipitation reaction for depositing a metal on the surface of the precipitation metal, and peeling means for peeling from the precipitation metal to recover the precipitated recovery target metal. Recovery device for metals. The method of claim 20, A device for recovering metal, wherein the means for peeling the metal to be recovered from the metal for precipitation is a means for vibrating the metal for precipitation by ultrasonic waves. The method of claim 20, A device for recovering metal, wherein the means for peeling the metal to be recovered from the metal for precipitation is a means for stirring the metal for precipitation with an electromagnet to collide with a plurality of metals for precipitation. The method of claim 20, A device for recovering metal, wherein the means for peeling the metal to be recovered from the metal for precipitation is a means for stirring the metal for precipitation by air jet or water jet. The method of claim 20, A means for separating a metal to be recovered from a metal for deposition forms a normal portion in the reactor body, and blows gas into the ordinary portion to stir the metal for precipitation. The method of claim 20, A means for peeling the metal to be recovered from the precipitation metal forms a flow path and a pump for circulating and transporting the liquid to be treated and the metal particles in the reactor body outside the reactor body, and circulates the liquid to be treated and the metal for precipitation. And a device for recovering metal, which is a means for stirring the precipitation metal by transporting. The method according to any one of claims 20 to 25, A metal having an inflow portion of the liquid to be processed at the lower part of the reactor body and having a liquid outflow portion at the upper portion of the reactor body, wherein the processing liquid flows into the reactor body from the inflow portion and flows out of the liquid outflow portion. Recovery device. The method of claim 26, An apparatus for recovering metal, wherein the reactor body is configured such that the cross-sectional area of the reactor body increases upward. The method according to any one of claims 20 to 27, The metal collection | recovery apparatus in which the reactor main body of several stages is arrange | positioned. The method according to any one of claims 20 to 28, The metal collection | recovery apparatus which the filter for collect | recovering the metal to collect | recovered which peeled at the rear end of a reactor main body is arrange | positioned. The method according to any one of claims 20 to 29, An apparatus for recovering metal, wherein an adjustment tank for containing a metal to be recovered in an ion state and containing a liquid to be treated containing nitrate ions and adding and adjusting a source of chlorine ions is formed at the front end of the reactor body. The method of claim 30, An apparatus for recovering metal, in which a conveying flow path is formed in which a processing liquid after recovering a metal to be recovered from a metal for precipitation is added to a liquid to be treated as a stock solution and processed again.

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