WO2017052021A1

WO2017052021A1 - Apparatus for collecting useful metal ions from aqueous solution and method for collecting useful metal ions using same

Info

Publication number: WO2017052021A1
Application number: PCT/KR2016/004655
Authority: WO
Inventors: 류태공; 김병규; 정강섭; 류정호; 홍혜진; 박인수
Original assignee: 한국지질자원연구원
Priority date: 2015-09-21
Filing date: 2016-05-03
Publication date: 2017-03-30
Also published as: KR101602459B1

Abstract

The present invention relates to an apparatus for collecting useful metal ions from an aqueous solution and a method for collecting useful metal ions using the same, and provides an apparatus for collecting useful metal ions and a method for collecting useful metal ions using the same, the apparatus comprising: an adsorption/desorption reaction tank having at least one ion-collecting column for adsorbing metal ions in a supplied aqueous solution; a washing water storage tank having washing water stored therein, which is supplied to the ion-collecting column onto which the metal ions are adsorbed; and an extracted-solution storage tank having an extracted solution stored therein, which is supplied to the ion-collecting column to elute the adsorbed metal ions. The present invention is environmentally-friendly since the present invention reuses washing water frequently used in a process of adsorbing, desorbing, and collecting metal ions in an aqueous solution without discharging the washing water to the outside, thereby achieving a continual supply of washing water. In addition, the present invention can collect useful metal ions through an integrated process, thereby remarkably reducing energy required for collecting ions.

Description

Apparatus for recovering useful metal ions from aqueous solution and method for recovering useful metal ions using the same

The present invention relates to an apparatus for recovering a useful metal ion from an aqueous solution and a method for recovering a useful metal ion using the same. More specifically, the present invention relates to a useful metal ion recovery apparatus for recovering metal ions from an aqueous solution in which metal ions are dissolved, in particular, a low salt lake having a low concentration of ions, an etchant generated in an industry, and a method for recovering useful metal ions using the same. will be.

The waste liquid generated during the chemical process contains a catalyst. Most of these catalysts are valuable metals. In order to recover these useful metals in the form of metals and recycle them in the waste liquid, recovery processes through wet or dry processes are used.

However, existing metal ion recovery methods have problems of cost increase in recovery process by using expensive extractant and reducing agent, environmental pollution and by-products caused by the generation of large amount of secondary by-products when reducing metal ions recovered from waste liquid to metal form. Has a reprocessing problem. In addition, the recovery rate of the useful metal is low, and by recovering the useful metal in a complicated recovery process, there is a disadvantage in that the efficiency in the process is very low.

In the wet extraction process applied as a conventional metal ion recovery process, there is a problem of accumulating corrosive or toxic leach liquors generated in an alkali treatment process for removing impurities, for example, for precipitation and separation of impurities. have.

On the other hand, in the case of the adsorption process is applied to the adsorption / recovery of the specific metal ions dissolved in the aqueous solution has a problem that the adsorption efficiency ion selectivity is lowered depending on the type of specific ion. In order to overcome this problem, a process of removing ions that have not been adsorbed by using the washing water is performed. In this case, a large amount of washing water is required, and the used washing water is discharged to the outside of the system. There are disadvantages.

However, when the washing water is not used, impurities other than the specific metal ions are introduced, and thus, a post-treatment process using chemicals is required, similar to the wet extraction process, so that the problem of deteriorating process efficiency remains.

In order to solve these problems, it is necessary to develop an eco-friendly, energy-saving integrated recovery process system that can improve the existing ion adsorption process.

In order to solve the above problems, the present invention can be reused by circulating without washing the discharged water, and useful metal ion recovery apparatus for adsorbing and recovering metal ions dissolved in an aqueous solution through an integrated process, and the same. An object of the present invention is to provide a useful metal ion recovery method.

The present invention to achieve the above object is an adsorption-desorption reaction tank having at least one ion recovery column for adsorbing metal ions in the supplied aqueous solution; A washing water storage tank in which washing water supplied to the ion recovery column to which metal ions are adsorbed is stored; And it provides a useful metal ion recovery apparatus comprising a leaching liquid storage tank is stored in the leaching liquid to elute the adsorbed metal ions to the ion recovery column.

In this case, the useful metal ion recovery device may further include a first circulation passage for supplying the aqueous solution discharged through the ion recovery column back to the ion recovery column.

In addition, the CDI module for deionizing the solution discharged from the aqueous solution or the washing water passing through the ion recovery column; And a second circulation passage for communicating the ion recovery column with the CDI module to introduce the solution into the CDI module, wherein the solution passing through the CDI module is supplied to the wash water storage tank or the ion recovery column. It is done.

The apparatus may further include a third circulation passage through which the leachate discharged through the ion recovery column is introduced into the leachate storage tank.

In addition, it characterized in that it further comprises a discharge passage for discharging the leaching liquid containing metal ions eluted from the ion recovery column to the ion recovery tank.

In addition, the common flow path to which the first to third circulation flow path is communicated; And a discharge valve for selectively communicating any one of the common channel and the discharge channel with the ion recovery column.

The ion recovery column may further include: a column housing having an inlet through which the aqueous solution is introduced and an outlet disposed on an opposite side of the inlet; And an adsorbent disposed inside the column housing in a state surrounded by a filter or a porous mesh to adsorb metal ions in the aqueous solution, wherein the column housing includes a plurality of branch passages that branch the flow path of the introduced aqueous solution. By passing through the adsorbent in the aqueous solution is a branched state.

Further, the washing water is supplied to the ion recovery column to wash the ion recovery column, or the leachate is supplied to the ion recovery column to elute ions adsorbed on the ion recovery column, and then remains in the ion recovery column. It may further include a flushing unit for supplying the washing water or air for removing the leaching liquid to the ion recovery column.

In addition, the CDI module electrically adsorbs ions in the solution introduced into the inside or desorbs the adsorbed ions into the solution, and removes the ions desorbed from the CDI module to the wash water stored in the wash water reservoir to the CDI And a washing water discharge passage for discharging the washing water supply channel to be supplied to the module, and the washing water discharged to the ion recovery column after being supplied to the CDI module and discharged to the ion recovery column.

On the other hand, the present invention (a) adsorbing the metal ion in the aqueous solution by permeating the aqueous solution to the ion recovery column for adsorbing the metal ions in the aqueous solution; (b) supplying deionized wash water to the ion recovery column to remove ions not adsorbed to the ion recovery column from the ion recovery column; And (c) supplying the leachate to the washed ion recovery column to elute the adsorbed metal ions, and then introducing the leachate containing the eluted metal ions into the leachate storage tank. Provide a recovery method.

At this time, the useful metal ion recovery method is a deionized by supplying the solution discharged through the ion recovery column to the CDI module between the step (a) and the step (b) after deionization, And storing the wash water generated by ionization in a wash water reservoir.

In addition, between step (b) and step (c), the washing water is deionized by supplying the discharged solution through the ion recovery column to the CDI module, and then the washing water generated by deionization of the solution is washed. It further comprises the step of storing in the reservoir.

In addition, (d) supplying the washing water to the ion recovery column characterized in that it further comprises the step of removing the leachate remaining in the ion recovery column.

In addition, (e) repeating the steps (a) to (d) to concentrate the recovery metal ions contained in the leaching solution; And (f) discharging the leachate containing the concentrated metal ions into the ion recovery tank.

In addition, in the step (d), the washed water containing the leachate discharged from the ion recovery column is introduced into the CDI module to be deionized, and the deionized wash water is supplied to the ion recovery column or the wash water storage tank.

The present invention can be continuously supplied by reusing the washing water often used in the process of adsorption, desorption and recovery of the metal ions in the aqueous solution without being discharged to the outside environment-friendly, it is possible to recover the useful metal ions through an integrated process to recover the ion There is an effect that can significantly reduce the energy required for.

1 is a schematic diagram of a useful metal ion recovery apparatus according to a preferred embodiment of the present invention.

Figure 2 is a cross-sectional view of the ion recovery column provided in the adsorption-desorption reaction tank of the useful metal ion recovery apparatus according to a preferred embodiment of the present invention.

3 is a graph comparing seawater flow rate through the ion recovery column of FIG. 2 with a conventional ion recovery reaction column.

4 is a view showing a circulation path of the washing water in the useful metal ion recovery apparatus according to a preferred embodiment of the present invention.

Figure 5 is a schematic diagram of a CDI module provided in the useful metal ion recovery apparatus according to a preferred embodiment of the present invention.

FIG. 6 is an enlarged view of a portion 'A' of FIG. 5.

Figure 7 is a flow chart for explaining the useful metal ion recovery method using the useful metal ion recovery apparatus according to a preferred embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. First, in adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are used as much as possible even if displayed on different drawings. In addition, detailed description is abbreviate | omitted when it is judged that it may obscure the summary of this invention. In addition, preferred embodiments of the present invention will be described below, but the technical idea of the present invention may be implemented by those skilled in the art without being limited or limited thereto.

Hereinafter, a useful metal ion recovery apparatus 100 according to a preferred embodiment of the present invention will be described with reference to FIG.

The useful metal ion recovery apparatus 100 according to a preferred embodiment of the present invention is for recovering metal ions from an aqueous solution in which the useful metal ions are dissolved, such as low salt lake or an industrial by-product etching solution.

Specifically, the useful metal ion recovery apparatus 100 according to the preferred embodiment of the present invention has an adsorption and desorption reaction tank having at least one ion recovery column 140 (see FIG. 4) for adsorbing metal ions dissolved in the supplied aqueous solution. 130, the wash water storage tank 210 in which the wash water supplied to the ion recovery column 140 in which the metal ions are adsorbed is stored, and the leachate storage tank 320 in which the leachate is supplied to the ion recovery column 140 to elute the adsorbed metal ions. ). The apparatus further includes flow paths constituting a flow path of a solution such as an aqueous solution containing ions, washing water, and a leachate, and a valve and a pump installed on the flow path.

The aqueous solution in which the metal ions are dissolved is stored in the aqueous solution storage tank 110 and then introduced into the ion recovery column 140 through an inflow passage 120 communicating with the ion recovery column 140 of the adsorption-desorption reaction tank 130. .

In this case, an inflow valve 122 may be installed between the aqueous solution storage tank 110 and the inflow passage 120 to allow or block the inflow of the aqueous solution into the inflow passage 120.

The inflow valve 122 serves to switch the flow path in which the solution is introduced into the inflow passage 120 from the wash water storage tank 210 and the leachate storage tank 320. In other words, the inlet valve 122 is installed at the contact point of the passages through which the solution is discharged from the aqueous solution reservoir 110, the washing water storage tank 210, and the leachate storage tank 320, and any one of the flow paths is transferred to the inflow passage 120. Perform the function of communicating.

In addition, the inlet flow passage 120, the main pump 125 for supplying the solution introduced into the inlet flow passage 120 to the adsorption-desorption reaction tank 130 and pressurized so that the solution is circulated through a designated path, and the adsorption and reaction reactor 130 The opening and closing valve 127 is disposed at the front end of the) to open and close the flow path communicated from the inflow passage 120 to the ion recovery column 140.

The solution discharged from the adsorption-desorption reaction tank 130 is introduced into any one of the first to third circulation passages (170, 180, 190) and the discharge passage (200).

To this end, a common flow path 162 through which the first to third

circulation flow paths

170, 180, and 190 are communicated is disposed at the rear end of the adsorption-desorption reaction tank 130, and the common flow path 162 between the common flow path 162 and the discharge flow path 200. ) And a discharge valve 160 for selectively communicating any one of the flow path of the discharge path (200) and the ion recovery column (140).

In addition, open /

close valves

172, 182, and 192 are installed in the first to

third circulation passages

170, 180, and 190, respectively, so that any one of the common passage 162 and the first to

third circulation passages

170, 180, and 190 may be selectively communicated with each other.

The first circulation passage 170 passes through the ion recovery column 140 and finishes the adsorption process of the metal ions, so that the discharged aqueous solution may be supplied to the ion recovery column 140 again in common with the inflow passage 120. 162).

By allowing the aqueous solution discharged through the first circulation passage 170 to flow back into the ion recovery column 140, the target metal ions remaining in the aqueous solution can be resorbed, thereby improving the efficiency in the adsorption process. Will be.

The second circulation passage 180 is an ion recovery column 140 in which an aqueous solution discharged after the adsorption process is completed in the ion recovery column 140 and a process of eluting the adsorbed metal ions by inputting the adsorption process or leachate are completed. The washing water discharged after being supplied to the ion recovery column 140 for washing is introduced into the CDI module 230.

To this end, the second circulation passage 180 is connected to the common passage 162 and the CDI module 230 to form a flow passage such that the ion recovery column 140 and the CDI module 230 communicate with each other.

The CDI module 230 deionizes the solution discharged in the state containing ions after the aqueous solution or washing water introduced for the adsorption process or the washing process in the ion recovery column 140 passes through the ion recovery column 140. . The deionized solution in the CDI module 230 is stored in the washing water storage tank 210 or discharged to the inflow passage 120 through the washing water discharge passage 224 and then supplied to the ion recovery column 140 to be used again as the washing water. do.

The third circulation passage 190 concentrates the metal ions to be recovered by introducing the leachate discharged through the ion recovery column 140 into the leachate storage tank 320 to elute the metal ions adsorbed to the ion recovery column 140. The leachate is circulated without release to the outside until

To this end, the third circulation passage 190 is installed between the common passage 162 and the leachate reservoir 320.

The discharge passage 200 communicates between the discharge valve 160 and the ion recovery tank 340 to discharge the leachate containing the metal ions eluted from the ion recovery column 140 to the ion recovery tank 340.

When the metal ions contained in the leachate are concentrated to a certain level while repeating the adsorption and desorption (separation) process of the metal ions to be recovered, the discharge valve 160 is connected to communicate with the ion recovery column 140 and the discharge passage 200. The leachate containing the recovery target metal ions is stored in the ion recovery tank 340.

On the other hand, after the washing water is supplied to the ion recovery column 140 to wash the ion recovery column 140, or the leachate is supplied to the ion recovery column 140 to elute the ions adsorbed to the ion recovery column 140 In order to remove the washing water or the leachate remaining in the ion recovery column 140, the air is supplied to the ion recovery column 140, for this purpose, a flushing unit 330 for supplying air to the front end of the adsorption and desorption reaction tank 130 is Can be installed.

In addition, flow paths connecting the washing water storage tank 210 and the leachate storage tank 320 to the inflow valve 122 and the washing water discharge passage 224 may be provided with opening / closing

valves

212, 226, 322 to control the opening and closing states of the flow passages.

Figure 2 is a cross-sectional view of the ion recovery column provided in the adsorption and desorption reaction tank of the useful metal ion recovery apparatus according to a preferred embodiment of the present invention, Figure 3 is a conventional ion recovery to change the seawater flow rate through the ion recovery column of FIG. This is a graph compared to the aqueous reaction column.

Hereinafter, the ion recovery column 140 provided in the adsorption-desorption reaction tank 130 will be described in more detail with reference to FIGS. 2 and 3.

The ion recovery column 140 has an adsorbent 150 for adsorbing metal ions therein, and the metal ion is supplied to the adsorbent 150 in the process of passing through the adsorbent 150 by supplying an aqueous solution containing the metal ions to be recovered. To be adsorbed. At this time, according to the type and size of the adsorbent 150 in the ion recovery column 140 using a pump at normal pressure and pressure to supply an aqueous solution.

Specifically, the ion recovery column 140 is a column housing 142 having a water inlet 144 through which the aqueous solution containing the metal ions to be recovered flows and an outlet 146 disposed on the opposite side of the water inlet 144, and a water permeability. The adsorbent 150 is disposed inside the column housing 142 in a state surrounded by the filter 152 or the porous mesh to adsorb metal ions in the aqueous solution.

At this time, the column housing 142 is provided with a plurality of branch passages 148 for branching the flow path of the introduced aqueous solution to pass through the adsorbent 150 in a branched state of the aqueous solution.

In the conventional reaction column for ion recovery, the internal pressure is excessively increased by the aqueous solution introduced at high pressure, so that the housing is damaged or the aqueous solution cannot be introduced into the column due to the internal and external pressure difference. There is a problem that the reaction area of the aqueous solution and the adsorbent is limited by the restricted flow path.

In the present invention, by providing the branch flow path 148 in the ion recovery column 140 as described above to prevent the pressure inside the column housing 142 is concentrated or excessively raised in a portion, the introduced aqueous solution is adsorbent 150 By adhering uniformly to, the adsorption efficiency of metal ions was improved.

This effect was also proved experimentally as shown in Figure 3, 'reaction column 1' of Figure 3 is a conventional ion recovery column, 'reaction column 2' is the ion recovery column 140 of the present invention. .

Each reaction column was supplied with seawater at a pressure of 5㎏f / ㎠ using a diaphragm pump, and the internal pressure of the reaction columns was 1 ~ 1.5㎏f / ㎠, and the change in the flow rate of the seawater with the reaction time was observed. It was.

As a result, as shown in FIG. 3, it is observed that the pressure rise in the ion recovery column 140 and the reaction column 2 of the present invention in which the branch flow path 148 is formed is suppressed, and the flow rate decrease of the seawater supplied to the inside occurs little. It became. As a result, when the aqueous solution is supplied to the ion recovery column 140 in which the branch passage 148 is formed, it can be seen that the solution supply interruption phenomenon in the ion recovery column 140 due to the pressure increase is suppressed.

The adsorption and desorption reactor 130 further includes a discharge pump 156 equipped with a pressure gauge on the outlet 146 side of the ion recovery column 140 in order to facilitate the flow of the solution passing through the ion recovery column 140. It may be provided (see Fig. 4), through which pressure can be easily discharged to the outlet 146 by observing the pressure change inside the ion recovery column 140 and controlling the pump.

On the other hand, the column housing 142 may be formed as a prefabricated to have an adsorbent 150 therein, it is preferable to maintain the interior tightly through the sealing member 154 such as a gasket or packing in the assembly portion. Do.

In addition, the adsorbent 150 for adsorbing metal ions and the leachate for eluting the metal ions adsorbed to the adsorbent 150 may be provided in various kinds according to the metal ions to be recovered.

For example, when zeolite A is used as the adsorbent 150 to adsorb strontium (Sr) ions, the adsorbed strontium ions may be desorbed using sodium chloride (NaCl) solution or ammonia water (NH ₄ OH). In the case of using an ion exchange resin as the adsorbent 150 to adsorb boron (B) ions, the adsorbed boron ions may be desorbed using a weak hydrochloric acid (HCl) solution as a leaching solution. In addition, when lithium manganese oxide is used as the adsorbent 150 to adsorb lithium (Li) ions, a weak hydrochloric acid (HCl) solution may be used as a leaching solution.

4 is a view showing a circulation path of the washing water in the useful metal ion recovery apparatus according to a preferred embodiment of the present invention. For reference, FIG. 4 illustrates that two ion recovery columns 140 are provided in the adsorption-and-desorption reaction tank 130, and the solution discharged from the ion recovery column 140 is transferred to the CDI module through the second circulation channel 180. Only the flow path flowing into the 230 is shown separately.

Hereinafter, the circulation path for reuse of the washing water will be described in more detail with reference to FIG. 4.

The CDI module 230 serves to adsorb ions in a solution electrically introduced into or desorb the adsorbed ions into the solution.

In detail, the CDI module 230 adsorbs ions in a solution such as washing water or an aqueous solution introduced into the second circulation passage 180 to deionize the solution so that the deionized solution can be used again as the washing water. . At this time, the deionized washing water is stored in the washing water storage tank 210, or is discharged to the inflow passage 120 through the washing water discharge passage 224.

When the adsorption performance of the CDI module 230 is excessively absorbed and the adsorption performance is lowered, the electricity applied to the CDI module 230 is reversed to desorb the adsorbed ions, and the washing water stored in the washing water storage tank 210 is supplied as the washing water supply flow path. By supplying the CDI module 230 through 222, ions are discharged into the introduced wash water to remove ions that have been adsorbed in the CDI module 230.

At this time, the solution containing the ions desorbed from the CDI module 230 is discharged to the inflow passage 120 through the washing water discharge passage 224. By doing so, the recovery target metal ions present in the desorbed ions can be adsorbed in the ion recovery column 140, thereby improving the recovery efficiency of the metal ions.

Here, it is possible to install an auxiliary pump 220 for supplying the washing water to the CDI module 230 on the supply passage 222.

On the other hand, as shown in Figure 4 in the adsorption-desorption reaction tank 130, a plurality of ion recovery column 140, the flow path and the valve communicating with the front and rear ends of each ion recovery column (140a, 140b), that is, the opening and closing valve 127a 127b),

discharge valves

160a and 160b, and

common flow paths

162a and 162b may be installed.

At this time, the adsorbent 150 provided in each ion recovery column 140 may be made of a material capable of adsorbing different kinds of ions so as to adsorb and recover a plurality of ions.

5 is a schematic view of a CDI module provided in the useful metal ion recovery apparatus according to a preferred embodiment of the present invention, Figure 6 is an enlarged view 'A' part of FIG.

Hereinafter, the CDI module 230 will be described in more detail with reference to FIGS. 5 and 6.

The CDI module 230 includes a plurality of channels 240 including a first electrode part 250 for electrically adsorbing negative ions and a second electrode part 260 for electrically adsorbing positive ions, respectively, arranged in parallel. In the channel 240 of the electricity is configured to be applied separately.

In addition, a non-conductor 280 that electrically insulates each of the channels 240 is interposed between the plurality of channels 240 arranged in parallel.

As described above, the channels 240 that are insulated by the non-conductor 280 to form an independent flow path have a channel housing 290 provided with inlets 292 and outlets 294 at the inlet and outlet sides of the flow path, respectively. Is connected as an enemy.

In addition, each channel 240 may be separately supplied with electricity to perform a process independent of the process proceeding in the other channel 240. For this purpose, the CDI module 230 includes a power supply unit 300. do.

At this time, the power supply unit 300 is preferably implemented as a multi-channel power supply (multi-channel power supply) that can apply electricity to each channel 240 individually.

As the electricity is applied to each channel 240 by the power supply unit 300 as described above, the adsorption and desorption process of ions may be simultaneously performed in one CDI module 230, and thus, the washing water may be smoothly supplied. Will be.

On the other hand, each channel 240 forms a flow path through which the liquid is permeated, and electrically adsorbs or desorbs (separates) ions contained in the permeate solution.

In detail, the first electrode part 250 of the channel 240 includes a current collector plate 252 to which electricity is applied, an active carbon layer 254 coated on the current collector plate 252, and an anion attached to the active carbon layer 254. An exchange membrane 256 is provided.

In addition, the second electrode unit 260 may include a current collector plate 262 to which electricity is applied, an active carbon layer 264 coated on the current collector plate 262, and a cation exchange membrane 266 attached to the active carbon layer 264. Equipped.

In this case, the anion exchange membrane 256 and the cation exchange membrane 266 of the first electrode portion 250 and the second electrode portion 260 are disposed to face each other, and the first electrode portion 250 and the second electrode portion 260 are disposed to face each other. ) Is a permeable layer 270 that electrically insulates the first electrode portion 250 and the second electrode portion 260 and transmits a liquid.

The permeable layer 270 may be formed of any material as long as it is a material capable of moving a fluid by forming a gap between the two

electrode parts

250 and 260. For example, a nylon material having a gap having a size of 30 to 300 mesh (mesh) may be used. It can be formed from a nonwoven fabric.

Hereinafter, a method of recovering useful metal ions from an aqueous solution using the useful metal ion recovery device 100 of the present invention described above with reference to FIG. 7 will be described.

First, the aqueous solution in which the metal ions are dissolved from the aqueous solution storage tank 110 is permeated into the ion recovery column 140 so that the adsorption process of the metal ions to be recovered may proceed in the ion recovery column 140 of the adsorption and desorption reaction tank 130. (S10).

At this time, the metal ions in the aqueous solution passing through the ion recovery column 140 is adsorbed by reacting with the adsorbent 150.

The aqueous solution discharged from the ion recovery column 140 is deionized by flowing into the CDI module 230 through the second circulation passage 180 and stores the washing water generated after deionization in the washing water storage tank 210 (S20). ).

At this time, the aqueous solution having completed the adsorption process while passing through the ion recovery column 140 is introduced into the common flow path 162 through the discharge valve 160, and then sent to the first circulation flow path 170 so as to return to the ion recovery column. The adsorption process may be repeatedly performed by introducing into the 140.

Thereafter, the washing water stored in the washing water 210 or the deionized washing water in the CDI module 230 is supplied to the ion recovery column 140 to remove other ions and impurities other than the recovery target ions that are not adsorbed to the ion recovery column 140. A washing process for removing from the ion recovery column 140 is performed (S30).

The solution discharged after washing the ion recovery column 140, that is, the solution discharged through the ion recovery column 140, is supplied to the CDI module 230, deionized, and then washed with the deionized water. Stored in the reservoir 210 (S40).

At this time, after the washing of the ion recovery column 140 by the washing water is completed, air may be supplied to the ion recovery column 140 through the flushing unit 330 to remove the washing water remaining in the ion recovery column 140. .

After the ion adsorption and washing process in the ion recovery column 140 is completed, the leachate is supplied from the leach solution tank 320 to the ion recovery column 140 to elute the adsorbed metal ions (S50), and the eluted metal ions. The leaching liquid containing the same is introduced again into the leaching liquid storage tank through the third circulation passage 190 (S60).

At this time, after the elution of the metal ions by the leaching solution is completed, the leachate remaining in the ion recovery column 140 may be removed by supplying air to the ion recovery column 140 through the flushing unit 330.

Thereafter, the washing water is supplied to the ion recovery column 140 to perform a washing process to remove the leachate remaining in the ion recovery column 140 (S70), and is discharged from the ion recovery column 140 containing the leachate The washing water is deionized by flowing into the CDI module 230 (S80).

By repeatedly performing the steps S10 to S80 as described above, the metal ions to be recovered in the leachate are concentrated (S90), and when the metal ions are concentrated to an appropriate level, the leachate containing the concentrated metal ions is discharged through the discharge passage 200. The useful metal ions are recovered by discharging to the recovery tank 340 (S100).

As described above, the useful metal ion recovery method using the useful metal ion recovery device 100 of the present invention is very efficient because the metal ion can be recovered through an integrated process, and the aqueous solution and pre-stored washing water supplied to the device are highly efficient. As it can be continuously used without being discharged to the outside, there is an advantage of being eco-friendly and economical.

The above description is merely illustrative of the technical idea of the present invention, and various modifications, changes, and substitutions may be made by those skilled in the art without departing from the essential characteristics of the present invention. will be. Accordingly, the embodiments disclosed in the present invention and the accompanying drawings are not intended to limit the technical spirit of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by the embodiments and the accompanying drawings. The scope of protection of the present invention should be interpreted by the claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims

An adsorption-desorption reaction tank having at least one ion recovery column for adsorbing metal ions in the supplied aqueous solution;

A washing water storage tank in which washing water supplied to the ion recovery column to which metal ions are adsorbed is stored; And

A leach storage tank in which a leach solution is supplied to the ion recovery column to elute the adsorbed metal ions;

A first circulation passage through which the aqueous solution discharged through the ion recovery column is supplied to the ion recovery column again;

A CDI module for deionizing the solution discharged from the aqueous solution or the wash water through the ion recovery column; And

And a second circulation passage for communicating the ion recovery column with the CDI module to introduce the solution into the CDI module.

The solution passing through the CDI module is useful metal ion recovery apparatus characterized in that it is supplied to the wash water storage tank or the ion recovery column.
The method of claim 1,

Useful metal ion recovery apparatus further comprises a third circulation passage for introducing the leachate discharged through the ion recovery column into the leachate storage tank.
The method of claim 2,

Useful metal ion recovery apparatus further comprises a discharge passage for discharging the leaching liquid containing metal ions eluted from the ion recovery column to the ion recovery tank.
The method of claim 3,

A common passage through which the first to third circulation passages communicate; And

Useful metal ion recovery device further comprises a discharge valve for selectively communicating any one of the common passage and the discharge passage to the ion recovery column.
The method of claim 1,

The ion recovery column

A column housing having an inlet through which the aqueous solution is introduced and an outlet on the opposite side of the inlet; And

A sorbent disposed inside the column housing surrounded by a filter or a porous mesh to adsorb metal ions in the aqueous solution,

The column housing is provided with a plurality of branch passages for branching the flow path of the aqueous solution introduced useful metal ion recovery apparatus, characterized in that the aqueous solution is passed through the adsorbent in a branched state.
The method of claim 1,

The washing water is supplied to the ion recovery column to wash the ion recovery column, or the leachate is supplied to the ion recovery column to elute the ions adsorbed to the ion recovery column, the residue remaining in the ion recovery column Useful metal ion recovery apparatus further comprises a flushing unit for supplying the washing water or air for removing the leaching liquid to the ion recovery column.
The method of claim 1,

The CDI module electrically adsorbs ions in the solution introduced into the inside or desorbs the adsorbed ions into the solution,

A washing water supply passage for supplying the washing water stored in the washing water storage tank to the CDI module to remove ions desorbed from the CDI module;

Useful metal ion recovery apparatus further comprises a washing water discharge passage for discharging the washing water discharged to the ion recovery column after being supplied to the CDI module and discharged to the ion recovery column.
(a) permeating the aqueous solution to an ion recovery column for adsorbing the metal ions in the aqueous solution to adsorb the metal ions in the aqueous solution;

(b) supplying deionized wash water to the ion recovery column to remove ions not adsorbed to the ion recovery column from the ion recovery column; And

(c) supplying a leachate to the washed ion recovery column to elute adsorbed metal ions, and then introducing the leachate containing the eluted metal ions into the leachate reservoir,

Between step (a) and step (b)

The useful metal further comprises the step of supplying the solution discharged through the ion recovery column to the CDI module and deionizing the aqueous solution, and storing the washing water generated by deionization of the solution in a wash water storage tank. Ion recovery method.
The method of claim 8,

Between step (b) and step (c)

Supplying the solution discharged through the ion recovery column to the CDI module to deionize the washing water, and then storing the washing water generated by deionization of the solution in a washing water storage tank. Ion recovery method.
The method of claim 8,

(d) supplying the washing water to the ion recovery column to remove the leachate remaining in the ion recovery column.
The method of claim 10,

(e) repeating steps (a) to (d) to concentrate the recovered metal ions contained in the leachate; And

(f) useful metal ion recovery method further comprising the step of discharging the leachate containing the concentrated metal ion to the ion recovery tank.
The method of claim 10,

In step (d)

The washed water containing the leaching liquid discharged from the ion recovery column is introduced into the CDI module and deionized, and the deionized wash water is supplied to the ion recovery column or the wash water storage tank.