JPS6030746B2 - Method and device for selective recovery of metals from leachate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering metals from an aqueous solution, and more particularly to a method and apparatus for selectively recovering metals from a leachate.

The present invention is most useful for the recovery of nonferrous metals, rare metals, and precious metals in the hydrometallurgy of nonferrous metals, and is also useful for the recovery of rare earth elements from liquids produced by natural and artificial leaching.

The present invention enables co-precipitation of several metal hydroxides by strictly controlling the pH of the medium without using alkali as a reactant, thereby recovering metals from wastewater of an engraving factory. It can be used to extensively purify wastewater from non-ferrous and ferrous smelting processes, or to purify water from any source.

As is well known, there are various ore bodies that contain significant amounts of useful components that can only be accessed by leaching.

The leachate contains gold, iron, copper, zinc, cadmium and other metals, and the concentration of metals in the leachate varies by a fraction of an order of magnitude. Generally, the leachate contains silica particles in suspension and the concentration of humic acid is relatively high. The liquid produced by natural or artificial leaching is
Examples include wastewater from dew plating and etching plants, wastewater from nonferrous smelting plants, especially smelting plants, and also mine wastewater or fluids produced in battery, storage, autoclaving, and bacterial leaching processes. included.

In recent years, the total amount of leachate has increased, the need has arisen to process ore bodies that are not economically advantageous to conventional hydrometallurgical processes, and the need has arisen to reprocess various secondary raw materials.

Methods well known in the prior art include the electrolytic recovery of non-ferrous metals from concentrated solutions of these metals.

This method is carried out by providing a reactor with an anode and a cathode.
A constant field is created in the reactor to deposit non-ferrous metals on the cathode. Also, many leachates have relatively low concentrations.

Such a liquid has a low conductivity, and on the other hand, the amount of power consumed for electrolysis is large. Therefore, it is not economically advantageous to recover metals from these leachates by electrolysis. As is well known in the art, there are recovery methods that use iron scrap as a metal precipitant to precipitate copper from the leachate.

This precipitation method is... Place an iron shoulder over the leaking bottom of the reactor. This reactor has straight or curved inclined grooves,
Use a rotating drum or tapered container. This process is carried out as follows.

The leachate from the pre-settling tank is fed by gravity to the reactor, allowing the liquid to flow freely into the reactor.

Due to the interaction between the iron shoulder and copper, copper is precipitated from the leachate as precipitated steel, and iron is eluted into the liquid. This precipitation reaction is
It is based on the difference in ionization potential between copper and the metal from which it is precipitated.

In the ionization series, metals with a more negative potential than copper can precipitate copper from solution. The copper precipitation reaction is
It is shown by the following chemical formula.

C〆10Me→Cu10Me2〆The most commonly used metal is iron shoulder.

Under actual manufacturing conditions, besides precipitation of copper, the following reactions also occur: ga e3 10 Fe → Snake e 2 2 2 H ++ Fe → Fe 2 10 days 2 ↑ ga e 3 10 Cu → ga e 2 10 Cu 20 Cu + 2 H ++ 1/2 Q → Cze + 10 days 20 Fe+ is 11 1/2 Q → Fe 2 10 days 20 These side reactions not only reduce the extent of copper precipitation, but also considerably increase the consumption of precipitant compared to the theoretically required amount (0.874 k9 of iron per ton of copper).

As the reaction progresses, the concentration of free acid decreases, while at pH 2.5-4.0 conditions are formed for the hydrolysis of trivalent iron and aluminum salts normally present in mine waters.

That is, 2Me2 (S04) 30 Cape 20 one side Me (O
H) S04↓12 LS04Me2 (S04) 30 thin 20
12Me(OH)3↓2S04 These insoluble products create additional kinetic difficulties for copper precipitation.

The precipitation rate of copper and the nature of the solids produced are most influenced by the liquid composition, the nature of the precipitant, temperature and hydration conditions.

Thus, as the steel content in the liquid increases, the precipitation rate increases. When the copper content is as high as 20 m/s, it forms a dense precipitate and is difficult to separate from the iron shoulder. The design of the precipitation apparatus is determined by the contact time of the reactants, the liquid feed rate, and the reactor volume per unit of recovered steel.

The values of these parameters are all related to the copper content in the processing solution. The most important value is the reactor volume per unit of metal produced. In order to properly dissipate the liquid, it is desirable to have sufficient contact time and a relatively high flow rate. There are two types of equipment for recovering copper using this precipitation method. In other words, whether to arrange the reactors in a straight line or in a staggered manner. The latter is less cumbersome and inexpensive to operate, but it is difficult to increase the volume of liquid when needed. The precipitation method has a simple equipment design, requires little capital investment, and has low operating costs.

However, a large amount of iron shoulder is used for copper precipitation.

Iron shoulders are relatively expensive and not always available. Most of the shoulders obtained from iron plates have different coatings and require cutting, hammering and other pretreatment before use, which increases the overall cost. Furthermore, if the treatment solution is a product obtained by leaching arsenic-containing ore, there is a risk that extremely toxic hydrogen arsenide will be generated by the following reaction.
Bait e+day 3As03 13th day 2S04-ASH3↑10gae
S04 13th 20 When aluminum is included in the iron shoulder, hydrogen arsenide is generated even more intensely.

2A evening + sun 3AS〇30 milk day 2S〇4→ASH3↑10A
Evening 2 (S04) 30 is 20 The recovery level of copper is affected by trivalent iron.

For this purpose, trivalent iron is reduced to divalent iron with pyrotin Fe7S8, which increases the production cost. Furthermore, in addition to copper, the leachate contains dissolved zinc and other useful components.

The precipitation process only recovers a portion of the copper. After neutralization, all other components are discharged into a reservoir and allowed to settle. The sedimentation liquid contains significant amounts of inorganic salts and is therefore unsuitable for use. Furthermore, part of the copper and all of the zinc is lost during the precipitation process. Ion exchange methods are also known for copper recovery.

The process is carried out in a reactor with an eagle frame machine and a bed of ion exchange resin. This process is performed as follows.

A specified amount of the leachate is placed in a reactor containing the ion-exchanged resin, and the liquid and resin are mixed, entraining the copper with the resin.

Next, the solid consisting of copper and resin is separated from the liquid, and the abbreviated acid (
Process with Day○○4). The copper is transferred to an acid solution and the resin is recycled for repeated use. Copper is easily recovered with sulfonated phenol formaldehyde resin from ammonia solution.

This reaction proceeds as follows. Cry R+ is 31st day (NH
4) 2R(NH4)2R+[Cu(N is)2]21[
Cu(NH3)2]R+ is 410[Cu(NH3)2]
]R+QS04→[Cu(NH3)2]S04 Toka 2R
where the ratio R is a sulfonated anion exchange resin.

The recent development of high-grade ion exchange resins has made it possible to use lower concentrations of sulfuric acid and improve copper recovery.

Since copper can be concentrated in an acid solution by ion exchange treatment, copper can be economically advantageously recovered by electrolysis.

However, in all these operations, a portion of the resin is lost, increasing the cost of copper recovery in ion exchange methods.

Extraction methods for recovering copper from leachate are also known in the prior art.

The method and apparatus are similar to those described above.

The only difference is that an extractant is used instead of ion exchange≠sword resin. The extractant consists of a water-insoluble organic liquid that can be ionized. Ion exchange is performed with an organic water-retaining diluent. A liquid phase ion exchange system is thus formed,
Continuous manufacturing process arrangement is possible. Liquid phase ion exchange has many advantages.

While processing steps such as milling serve only one purpose, liquid phase ion exchange can perform several steps, including: '1' Transfer valuable metals from the leachate to other easily processed solutions.

■ After leaching, valuable metals are concentrated from the dilute solution and transferred to other solutions.

'3' Or selective extraction of impurities to separate valuable metals from impurities.

{4} Selective extraction or re-extraction of one or more elements from the organic phase to separate useful components of the leachate.

'5} Immediate re-extraction and no further processing to obtain the final product.

This method relates to an electrowinning method for treating acidic leachates.

Aliphatic monocarboxylic acids are used as extractants. It is readily available, inexpensive, and can be used indefinitely. The components of the liquid are extracted in the form of hydroxide. However, the extraction method has not been widely applied commercially because it requires processing a large volume of leachate, a large volume of extractant, and a large floor area of the equipment. In the prior art, methods for extracting gold from gold-bearing ores are known. The main process of smelting gold-containing ores and millet is:
This is a cyanidation method in which gold is selectively leached with a weak solution of alkaline cyanide.

As a method that can compete with these treatment methods, the leaching process with thiourea acidic solution is promising from an economic and safety point of view.

In addition to artificial leaches, which are the main source of gold production throughout the world, the processing of liquors obtained from natural leaching of alloy ores, especially copper-zinc ores, is economically promising.

This process is carried out in a reactor containing reactants. After the gold from the ore has been brought into solution, it is concentrated, for example in the classic cyanide process, to deposit the gold on zinc dust. However, the advantages of the sorption-extraction method achieved in recent years can effectively apply the extraction, sorption and ion exchange methods in gold hydrometallurgy. Under conditions of continuous processing of large volumes of alloy liquid, the most effective gold sorbents are activated carbon and ion exchange resins. Activated carbon is useful for sorption of gold not only from cyanide solutions but also from acidic solutions.

It is also promising to use naturally occurring coal shale with high surface activity as a gold precipitant. However, the sorption recovery of gold by activated carbon has a low capacity for precious metals, low mechanical strength, and therefore a large loss of adsorbent, a large amount of activated carbon needs to be instantaneously supplied to the reactor, and There are no simple and inexpensive sorbents to sorb gold. Compared to activated carbon,
Synthetic ionic resins have substantially higher sorption capacity and mechanical strength, so they can be used repeatedly.

Processes for recovering zinc from zinc solutions are also known in the prior art.

The basic hydrometallurgical process for producing zinc is the electrolysis of an acidic solution obtained by treating zinc ore with sulfuric acid.

Approximately 45% of the total amount of zinc in the world is produced by this method. Zinc concentration at least 20 pm/pm, acid concentration 3
It is economically advantageous to electrolyze zinc solutions at ~15%.

For example, recovering zinc from a dilute solution obtained from mine wastewater requires twice as much power per unit of metal weight. The electrolytic recovery equipment for zinc is similar to the equipment for the copper recovery process described above.

Recovery of zinc from natural and artificial leachates is carried out using methods similar to those used for copper recovery.

Thus, ion exchange methods are used to recover zinc from textile and pulp industry effluents. The zinc concentration in these effluents is approximately 1 night/sleeve, which value corresponds to the zinc content of mine effluents. Zinc is recovered by sorption on a polystyrene-type enteric ion exchange resin containing active sulfone groups.

Mother R〆Z〆〆〆〆〆ZnR+2日〆〆〆〆〆〈ZnR+日 04→ZnS04 〆日2R After desorbing the zinc, the solution contains 12-14% of zinc sulfate and an excess of sulfuric acid 2S0 of 48%.

This solution can be advantageously used as it is for electrolytic recovery in Azono. In the prior art, methods for purifying water containing metal ions are known (French Patent No. 2 148 730, 19
(See 73 Kings February 26). This method teaches the recovery of metals as oxides, hydroxides and sulfides. The process is carried out in a reactor having a cathode and an anode.

The space between the electrodes is filled with activated carbon. Since in this method the anode is not isolated from the cathode, the products of the anode and cathode mix with each other, impeding the possibility of selective recovery of metals and increasing power consumption. The apparatus for carrying out this method has an anode and a cathode in a reactor, and the space between the electrodes is filled with activated carbon.

The bottom of the cathode has a number of pores with a diameter smaller than the size of the activated carbon particles, through which only metal oxides, hydroxides and sulfides enter a specific settling tank and settle there.
However, this device cannot selectively recover metals from solution.

Since the cathode is not isolated from the anode, the products formed at the cathode and anode mix vigorously with each other. This loss is high because the product does not settle for a long time and contains contaminated activated carbon. Additionally, gases generated during operation of the device are lost by venting to the atmosphere. As the liquid flows downward in this device, solids accumulate at the bottom of the device, increasing the hydraulic resistance of the reactor, reducing productivity and increasing power consumption.
As a result, this device cannot be applied to a process for selective recovery of metals from leachates, while simultaneously producing useful by-products with low power consumption. The aim of the invention is to overcome the above-mentioned drawbacks.

The present invention provides a method and apparatus for the selective recovery of metals from leachate, whereby various metals are sequentially recovered as hydroxides by PH, useful by-products and pure water are separated, and waste in metal recovery is The purpose is to eliminate the occurrence of electricity and reduce power consumption.

The above object of the present invention is to provide a method for selective recovery of metals from leachate, in which a space 5 generating a constant electric field is divided into an anode region 6 and a cathode region 7, and the leachate to be treated is simultaneously passed through these regions. Then, by applying external electric and magnetic fields in the cathode region 7, the pH of the leachate is maintained in the range of 1 to 14, and the leachate supply rate and pH change rate are appropriately selected to correspond to the p-law in the above range. This can be achieved by a selective metal recovery method that sets conditions for selective recovery of various metal oxides and hydroxides at a precipitation pH of .

The present method of selectively recovering metals from a leachate by applying an electric field to the space between the electrodes does not require filling this space with activated carbon to achieve its purpose. The method chosen as a prototype works as an electrode in which activated carbon is dispersed, and the current efficiency can be increased to more than 100%. At the same time, the presence of activated carbon in the space between the electrodes makes this method undesirable and disadvantageous for the treatment of concentrated solutions. The method of the present invention differs significantly from this prototype method in that the present invention does not use activated carbon as a special purpose charge in the cathode region;
This is achieved by using the metal as a dispersion medium, which is formed when separating the metal as a hydroxide.

The upper limit of the pH range, i4, was chosen because all metals are converted from the leachate to the hydroxide state before the pH is increased to 14. No leachate with a pH lower than 1 is known. In order to achieve the above objectives of the present invention, it is not sufficient to maintain the pH within a certain range. The external electric field and the rate of supplying leaching fluid to the cathode and anode regions separately can be selected to force the high pressure catholyte in the cathode region through the pores of the diaphragm into the anode region at a given porosity of the diaphragm. is necessary. The optimal delivery rate of exudate is dependent on the porosity of the corneal membrane. On the other hand, the composition of the electrolyte changes depending on the supply rate of the leachate to the anode chamber and the circulation rate to the cathode chamber, and thereby the direct current potential required to precipitate metal ions in the electrolyte also changes. Therefore, depending on the porosity of the diaphragm, the feed rate and circulation rate of the leachate can be selected accordingly, thereby minimizing the DC potential.
At the same time, the rate of supplying the leachate to the anode region is such that at this rate the anolyte does not migrate to the cathode region, and under the influence of the excess pressure in the cathode region, the catholyte leaches into the anode region, so that the conductivity of the cathode region is reduced. It is necessary to set a total supply rate that compensates for the decrease in energy consumption.

By choosing the actual feed rate of leachate to the anode and cathode regions to be compatible with the strength of the external electric and magnetic fields, selective recovery of metals from the fluid, whether in high or low concentrations, can be achieved. High productivity can be achieved with minimal power consumption. The criteria for obtaining the desired effect are the rate of change of stiffness and the rate of change of temperature in the cathode region. Selective recovery of metals by the method of the invention requires special equipment, which allows the rate of separate delivery of liquid through the anode and cathode regions to be matched to the strength of the external electric and magnetic hot water. As a result, power consumption can be minimized without filling the cathode region of the device with activated carbon.

The device selected as a prototype cannot adequately select such conditions to achieve the objectives of the present invention. Since the cathode space is isolated from the anode space, the device generates hydroxide ions in the cathode space, which combine with metal ions from the leachate through a chemical reaction to remove the barely dissolved hydroxide. It forms and precipitates.

This metal hydroxide passes through the cathode space in the form of a suspension and is subjected to the effects of external electric and magnetic fields. While moving in the solvent flow, the suspended particles acquire a triboelectric potential under the action of friction and become electrically charged. This charged microscopic particle is
During the movement, it interacts with the electric and magnetic fluid and moves towards the reactor wall, increasing the rate of particle intermixing and agglomeration. The suspension moves particularly strongly towards the reactor wall.

This is because there are a considerable amount of silica particles with a large area in the liquid.
This is also due to the presence of a large amount of iron ions that aggregate under the influence of a weak magnetic field to form a magnetic suspension. If the concentration of suspended particles in the liquid is quite high, the moving suspension creates a medium field formed by the moving particles and the total solvent by means of the triboelectric potential. This field moves the medium along with the external field to move the medium in an effective field that affects the reactions that exchange charge and heat within the medium. As a result, the above phenomenon creates conditions in which co-precipitation of metals due to hydrate-forming forces, which are closely related to the pH value, can be minimized. Furthermore, these conditions allow for the selective sequential recovery of various metals, with p-laws producing hydrates of the various metals. At the same time, purified water is obtained which contains useful products such as hydrogen, oxygen, commercial sulfuric acid solutions and soluble sulfates. These by-products can be used for industrial purposes, thus eliminating waste generation.

Additionally, the simultaneous passage of process leachate through the anode and cathode regions eliminates the possibility of acidic anolyte penetration into the catholyte, thereby reducing the cost of selective metal recovery.

It is recommended that the leachate be passed through the anode and cathode regions simultaneously.

This allows the pH to be uniform throughout the reactor.

At the same time, excess acidic anolyte is removed from the anolyte region to prevent the possibility of anolyte entering the catholyte through the cornea. This also reduces energy consumption and improves the selectivity of metal recovery. It is desirable to pass the aqueous chloride solution through the anode region at the same time as the leachate passes through the cathode region.

This first increases the conductivity of the anode region, and the second
First, gaseous chlorine is generated at the anode, and the chlorine is partially dissolved in the anolyte to consume heat and improve thermal conditions to avoid heat loss.

Third, since the anode is made of carbon or graphite, it is virtually unbreakable and has a long lifespan. Fourth, the consumption of anolyte is surprisingly low. All of these work together to reduce power consumption and make the process more economically efficient.
It is preferable to use a sylvinite solution as the aqueous chloride solution.

Sylvinite is naturally occurring and inexpensive, thus substantially lowering production costs and improving processing selectivity.

The use of silpinite solution significantly reduces anolyte consumption, reduces power consumption and increases productivity. It is recommended to pass an aqueous sulfate solution through the anode area.

This increases electrical conductivity in the anode region, reduces heat loss, increases productivity and also reduces power consumption.

It is desirable to use a sodium sulfate aqueous solution as the sulfate aqueous solution.

It is the cheapest naturally occurring sulfate salt and is highly soluble in water, making the process for selective recovery of metals from leachate even cheaper. Preferably, a magnetic field is applied to the treated solution.

As suspended particles move toward the vessel's edge, flocculation is promoted, reducing reaction completion time, reducing power consumption, and increasing process productivity.

If the leachate contains gold, it is desirable to fill the cathode region with activated carbon.

This allows the gold to be absorbed into the activated carbon before the iron hydroxide precipitates.

In this case the current efficiency exceeds 100%. This is because the activated carbon particles act as an additional electrode with a very large surface area. The object of the present invention is to provide an apparatus for selectively recovering metals from a leachate, which includes a reactor in which a cathode 2 and an anode 3 are arranged coaxially, as shown in FIG. The anode region 6 is divided by a diaphragm 4 into an anode region 6 located in the outer compartment 11 and a cathode region 7 located in the outer compartment 11. The cathode region 7 is provided with a catholyte supply port 49 and a discharge port 31 as well as cathode gas discharge ports 15 and 82; , a metal selective recovery device having a first circuit having a pump 54 and a feed port 49, which circuit has a second circuit returning to the first circuit via a settling tank 77 and a pump 78. I can do it. Another object of the present invention is to provide an apparatus for selectively recovering metals from a leachate, which includes a reactor in which a cathode and an anode are arranged coaxially as shown in FIG. Socket tube 29 located in the upper compartment of
The upper chamber 10 and the lower chamber 11 are electrically insulated from each other, and a diaphragm 4 is shared between the cathode 2 and the anode 3 in the lower chamber 11. A cylindrical manifold 8 which is axially mounted and divides the working space 5 of the reactor 1 into an anode region 6 and a cathode region 7 and a circulation pump 54 communicates with the reactor 1 to promote the formation of a solid phase. A device 52 for measuring the pH of the medium through the electromagnetic flocculator 34 and the reactor 1, and a pump 78 for returning the solution from the settling tank 77 to the reactor 1. Sedimentation tank 7
This can be achieved by a metal selective recovery device from leachate consisting of 7.

Because of the presence of the diaphragm, the cathode space is isolated from the anode space and the device produces hydroxide ions in the anode space.

Furthermore, since the reactions in the anodic and cathodic regions occur separately, the anolyte does not intermix with the catholyte.

As a result, the possibility of selective recovery of metals is created. The anode and cathode spaces of the reactor are separated from each other by a diaphragm, so that the anode and cathode gases are
This allows for supplementary information.

These gases are not lost and do not pollute the environment. Furthermore, these gases can be used in various industrial applications. Since there is a diaphragm and manifold separating the anode space from the cathode space, the feed rate of the solution that is fed separately to the anode and cathode spaces can be selected, and the strength of the external tortoise and magnetic fields can be adjusted such that the rate of change of the mother is maximal. can be selected to minimize power consumption.

The presence of the electromagnetic concentrator promotes the formation of a solid phase circulating in the cathode space, facilitating the progress of electrochemical reactions at the cathode and reducing power consumption.

Sekigates are recommended to coaxially attach the diaphragm to the center of the upper and lower chambers of the manifold.

This arrangement attaches the anode to the cathode in such a way that the potential is evenly distributed over the entire surface of the cathode.

This also eliminates side reactions with additional consumption of power. It is recommended that the diaphragm be mounted with a sealing gasket that does not allow gases and leachates produced by metal recovery to pass through the entrance in the lower chamber of the manifold.

This avoids the risk of overflowing the more acidic anolyte into the less acidic catholyte, reduces power consumption, and prevents the cathode and anode gases from mixing with each other, resulting in a more pure form. You can get it at

Also, the cathode is installed in the lower chamber of the manifold, the lower chamber is provided with a discharge pipe for taking out gas from the cathode region of the reactor, the anode is installed in the upper chamber of the manifold, and the upper chamber is provided with a gas discharge pipe from the anode region of the reactor. It is recommended that an inlet tube be provided.

This allows gases to be collected separately from the anode and cathode regions to avoid industrial gas loss and prevent environmental pollution.

It is recommended that the anode be mounted in the upper chamber of the manifold with a sealing gasket to avoid leakage of anode gas.

To treat leachates with low concentrations of dissolved metals, a magnetic condenser can be mounted directly at the bottom of the reactor so that it can be threaded through the reactor, making the overall selective metal recovery apparatus more compact.

Furthermore, the solid phase formation rate is increased to facilitate electrochemical reactions at the cathode and reduce power consumption. In order to treat leachates with high concentrations of dissolved metals, it is desirable to connect a magnetic concentrator to the lower part of the reactor to allow them to pass through.

This eliminates the risk of clogging of the coagulator and improves the productivity of the device that selectively recovers high-concentration metals in the leachate.

It is also desirable that the cathode be located coaxially with the anode, that the diaphragm be made of the same material as the reactor, and that the reactor be electrically connected.

This facilitates the deposition of the solid phase and the progress of the electrochemical reaction at the cathode, thereby reducing power consumption.

It is recommended to make holes in the cathode.

This allows rapid averaging of pH and temperature throughout the volume of the device.

When flowing leachate or sulfate solutions through the anode, it is desirable to provide the anode with a vibrator. A vibrator powerfully separates anode gas bubbles from the anode surface. As a result, the rate of chemical reactions at the anode increases and power consumption decreases. It is recommended that the magnetic concentrator consists of a helical coiled tube of dielectric material and is located between the terminals of the magnetic field source. This increases the rate of aggregation. When recovering metals from leachates with low concentrations of dissolved metals, it is recommended that a box of dielectric material of the magnetic concentrator be placed between the terminals of the magnetic field source and filled with magnetic material.

As the exudate passes through the filling material, it is not only affected by the external magnetic field but also by the magnetic field of the filling material itself. Due to the action of these magnetic fields, the liquid moving relative to the fill material changes in concentration of suspended and dissolved compounds formed as a result of the metal recovery process. The concentration increases in the immediate vicinity of the filler and decreases with distance from it. As the concentration increases around the filler, the agglomeration rate also increases. The present invention mechanizes and automates the selective recovery of metals from the leachate and has the advantage of not polluting the environment as it eliminates manufacturing waste, neutralization steps and open cycle non-waste.

Furthermore, since a large amount of purified water is obtained in the selective recovery of metals from leachate, it can be used as industrial water.

For a better understanding of the invention, the drawings are attached. FIG. 1 is an explanatory diagram of the entire apparatus for selective recovery of metals from leachate according to the present invention.

The reactor 1 has a cathode 2 and an anode 3 arranged coaxially along the axis a-a. An axis a coaxially exists between the cathode 2 and the anode 3.
-a, a diaphragm 4 is installed, which divides the working space 5 of the reactor 1 into an anode region 6 and a cathode region 7.
Due to the presence of this diaphragm 4, the selective recovery device for metals from the leachate generates hydroxide ions in the cathode region 7, and when the hydrate formation pH' is reached, the hydroxide ions are removed from the leachate by a chemical reaction. Combines with metal ions to form a meltable solid hydroxide. As a result, hydroxides form in the cathode region 7, depending on the pH value, forming precipitates of hydroxides of the various metals present in the leachate. Certain metal hydroxides precipitate out separately from other metals remaining in solution at certain pH values, allowing selective recovery of these metals from the leachate. The precipitate thus obtained can be used industrially and at the same time useful products and purified water can be obtained. The reactor 1 has a cylindrical manifold 8 mounted coaxially on its upper part.

This manifold 8 (FIG. 2) is separated by an insulating spacer 9 into an upper chamber 10 and a lower chamber 11, which prevents intermixing of the gases produced during metal separation from the leachate, thereby separating the gases. It can be recovered and used in industry to prevent environmental pollution. Casing 12 of lower chamber 11 of manifold 8 springs 1
3 screw onto reactor 1.

The sealing gasket 14 seals between the lower chamber 11 of the manifold 8 and the reactor 1 to eliminate leakage of leachate and cathode gas from the cathode region 7 of the reactor 1. An opening is made in the casing 12 of the lower chamber 11 and a discharge pipe 15 is installed to collect the cathode gas from the cathode region 7 of the reactor.

In this casing 12 of the lower chamber 11 there is a gateway along the axis a-a, in which the hollow cylindrical cathode 2 is placed.

The cathode 2 is rigidly connected to a casing 12 in the lower chamber of the manifold 8, and the cathode 2 and the casing 12 are made of the same metal. An insulating spacer 9 is rigidly mounted within the cylindrical cathode 2 coaxially therewith. The membrane 4 is secured in this space 9 by a sealing gasket 16 . The central opening □ in the upper part of the spacer 9 has a screw 17 by which a clamping ring 18 is attached to the spacer 9, and this ring 18 is connected to the cylinder 19. This clamping ring 18 or locking ring is attached to the cylinder 19 so as to seal the gasket 16 to prevent intermixing of the anolyte and catholyte and to prevent the catholyte from the cathode region 7 to the anode region 6 of the reactor 1. Gas leaching is prevented, thereby improving the selectivity of metal recovery from the leachate and reducing power consumption. The casing 21 of the upper chamber 10 of the manifold 8 is attached to the casing 12 of the lower chamber 11 of the manifold 8 with two screws.

Casing 12 in the lower chamber 11 and casing 21 in the upper chamber 10
A gas impermeable insulating gasket 22 is provided between the
Prevent anode gas from leaking into the atmosphere. A closure is raised inside the casing 21 of the upper chamber 10 along the shafts 9-9, and the odd-shaped washer 23 is inserted therein. This washi 23
is attached to the upper chamber 10 of the manifold 8 by screws 24. The washer 23 opens a threaded entrance 25 into which the cylindrical anode 3 is inserted. Anode 3 with irregularly shaped washer 23
For installation, seal gasket 26 and nut 27
is mounted coaxially with the cathode 2 and diaphragm 4 along the axis a-a to uniformly distribute the potential across the cathode surface and improve the selectivity of metal recovery.

The anode 3 has a central entrance 28 over its entire length, from which the anolyte is supplied to the anode region 6 of the reactor 1 . The sealing gasket 26 seals the anode region 6 of the reactor 1 in the metal recovery reaction.
It does not allow the gas generated during the process to pass through. A discharge pipe 29 is attached to the casing 21 of the upper chamber 10 of the manifold 8 with its opening raised.

These tubes 29 bottle and remove anode gas from the anode region 6 of the reactor 1. This minimizes the loss of anode gas and prevents environmental pollution. The anode gas can further be used for various industrial purposes. An opening 30 is provided in the casing 21 in the upper chamber 10 of the manifold 8 to remove the anolyte from the anode region 6 of the reactor 1 . In the upper part of the reactor 1, below the screw 13 and with a closure above the upper end of the cathode 2, a drain pipe 31 is installed to remove liquid from the cathode region 7 of the reactor 1.

A magnetic concentrator 34 is attached directly to the lower part of the reactor 1 by screws 32 and a sealing gasket 33 impermeable to leachate (FIG. 3).

A cylindrical permanent magnet 39 is attached to the outside of the casing 35 of the magnetic concentrator 34, and the bottom plate 3 made of a non-magnetic material is attached to this.
6. Attach with thrust ring 37 and screw 38.

A skeleton 41 in which a wire 42 is wound around the internal space of a permanent magnet 39
Attach the coil 40 having the following properties. The coil 40 is connected to an AC power source (not shown) through a terminal (not shown). A recess 43 is provided on the inner surface of the casing 35 of the magnetic concentrator 34, and a net 45 with a ring 44 is installed in the recess 43.

This silk 45 is permeable to exudates and metal suspensions, but
Activated carbon particles are impermeable. A ring 47 is rigidly attached to a recess 46 located below the bottom plate 36 on the inner surface of the casing 35 of the magnetic concentrator 34 at the lower part of the casing 35 of the magnetic concentrator 34, and a mesh separator 48 is rigidly attached to this ring 47. Attach to. Magnetic concentrator 34 below silk separator 48
A conduit 49 is attached to the lower part 35 of the magnetic concentrator 34.
The casing 35 of the reactor 1 is integrated with the casing 35 of
supply to. The magnetic concentrator 34 is attached by screws 32 and sealing gaskets 33 to the lower part of the casing 51 of the reaction medium wind measuring device 62 and connected to the inlet pipe 49 and the conduit 5.
3 to a circulation pump 54 (FIG. 1), which in turn is connected to the reactor by a conduit 53 and a control valve 55.

The cathode 2 is located coaxially with the anode 3 and the cornea 4,
There are holes in it.

For this purpose, the openings 57 are uniformly raised over the entire surface of the cathode 2.
It promotes pH uniformity within the reactor 1, promotes the reaction of recovering metals as hydrates, and improves the exchange of heat generated in recovering metals from liquids, reducing power consumption. Vibrator 58 (Figure 4) and anode adapter lead 59
can be attached to the anode 3 above the nut 27.

On the other hand, on the outside of the casing 12 (FIG. 2) in the lower chamber 11 of the manifold 8, a cathode conductor 60 is welded to the center of the two conduits 15 (FIG. 4). As mentioned above, the magnetic concentrator 34 is at the bottom of the reactor 1, while the magnetic concentrator 61 is outside the reactor 1. This magnetic concentrator 61 (FIG. 5) consists of two U-shaped magnets 62, an insert 63 of European magnetic material and a helical tube 64 of dielectric material. The upper tube 65 (FIG. 5) of the magnetic concentrator 61 is connected to the conduit 53 (FIG. 1) and the medium p
It is connected to the reactor through an H measuring device 52. The lower pipe 66 (FIG. 6) of the magnetic concentrator 61 is connected to the reactor 1 through the circulation pump 54 and the control valve 56 of the conduit 53. The magnetic concentrator 34 (FIG. 3) fills a dielectric material box with a magnetic material filler 67 (FIG. 3), and fills the space 50 of the magnetic concentrator 34 with a magnetic filler 67 (FIG. 3).
This promotes the agglomeration of iron from dilute solution.

The apparatus for recovering metals from solution includes a system 68 (FIG. 1) for displacing the anolyte.

This system 68 has valves 69 and 70, or a discharge valve 71 and a pump 72, by means of which the vacuum in the anode region 6 in the reactor 1 is controlled. A water pressure gauge 73 is installed between the medium mother measuring device 52 and the reactor 1, and is connected to the reactor 1 by a conduit 53.
Connect with 1. The conduit 53 between the circulation pump 54 and the magnetic condenser 61 is connected to an inlet valve 74 which in turn is connected to a conduit having a circulation valve 75 and a discharge valve 76, which in turn is connected to a settling tank 77. do.

This settling tank 77 is connected via a pump 78 to a circulation valve 75 and to a conduit 53, and has a discharge valve 79 at the bottom of the tank 77 for discharging the suspension into a vessel 8. This device has a supply pipe 81 for introducing liquid into the system, and a system of conduits 82 and 83 for gas discharge pipes 29 and 15 of manifold 8 (FIG. 2).
It is also connected to a gas manifold (not shown).

The apparatus for selective recovery of metals from leachate of the present invention operates as follows. Valves 75 and 76 are closed and valve 74 is opened to supply liquid from conduit 81 which enters reactor 1 from conduit 53 via circulation pump 54 and control valve 55 and also from magnetic concentrator 61 and medium pH. Enter the measuring device 52.

When the pressure gauge 73 reaches the index, the valve 74 is closed.
The anolyte replacement system 68 fills the anode space 6 of the reactor 1 with liquid.

For this purpose, valves 69 and 70 are opened and liquid is supplied to the anode region 6 of the reactor 1. Excess anolyte from the anodic region 6 of the reactor 1 is pumped by a pump 72 to the anodic region 6 of the reactor 1.
is taken out under slightly reduced pressure. Circulation pump 54 is then energized and the rate at which the liquid in reactor 1 circulates through conduit 53, pH measurement device 52, and magnetic condenser 61 is controlled by control valve 55. A recorder and a detector (not shown) are used to measure the medium pH.
a controlled direct current source, not shown, which is provided in the measuring device 52 and which applies a potential between the cathode 2 and the anode 3 of the reactor 1 when it begins to exhibit a constant value corresponding to the initial characteristic of the circulating fluid; Apply voltage to the anode adapter lead from the

The values of temperature, voltage and current in reactor 1 are recorded by the control device. Under constant operating conditions of the device, the pH vs. time relationship within the reactor follows an S-shaped curve, which consists of three distinct regions: initial, main operation, and terminal.

The terminal region of pH versus time corresponds to the rate of pH change within the reactor away from the pH of metal hydrate formation.

Using a leachate or a sulfate solution or a sodium sulfate solution as the anolyte, the following reactions occur in the cathode region 7 and anode region 6 of the reactor 1: Cathode area 72 ratio○12e→ratio↑120H- 1/2Q+day 2012e→illustration H- Anode region 6 2nd day 20→0214 day 114e When using a chloride solution or Silvinati solution as the anolyte The following reaction occurs.

Cathode region 7 2LO + 2e → ↑ 120H - Anode region 6 2 Koso - → C So 2 ↑ 12e C So 2 10 ratio 0 HC + HOC Once that value is reached, the rate of pH change decreases and a plateau appears in the pH vs. time curve.

This flat region corresponds to the region where hydroxide ions combine with metal ions to form a soluble hydroxide and form a suspension through liquid circulation. Therefore, the device of the present invention acts as a hydroxide ion generating device in the reactor 1, and the hydroxide ions combine with metal ions to generate hardly soluble hydroxide. Suspended particles circulating in a liquid are charged and acquire a triboelectric potential due to friction between the particles and solvent molecules, particularly water molecules.

Thus, as the concentration of a suspension in a liquid increases, the suspended particles, solvent molecules and solute substances collectively acquire a triboelectric potential and a magnetic moment of their own. They characterize this bond as a specific material medium that moves relative to external electrical and magnetic fields. These fields, which occur in this material medium under the influence of the circulation, cooperate with external fields to form specific effective fields that influence the movement of the medium itself and the reactions at the cathode. This availability is most pronounced due to the significant humic acid, suspended silica and iron content in the leachate. The strength of such fields increases as the concentration of the substance in the leachate increases. When a charged medium is circulated against electromagnetic and magnetic fields, the density of the medium increases at the wall interface and decreases with increasing distance from the wall.

Therefore, a solid phase is strongly formed in the magnetic concentrators 34 and 61 of the present invention, which is more dense at the interface and facilitates the electrochemical reaction on the cathode 2. The reaction in the reactor 1 stops from the moment the mother-to-time relationship passes through the S-shaped flat region.

For this purpose, the voltage applied to the anode 3 is cut off, and the anolyte replacement system 6 is
8 and stop the circulation pump. Valves 74 and 75 are closed and valve 70 is opened to remove reactor 1, conduit 53, circulation pump 54, medium pH measuring device 52 and magnetic concentrator 61.
The suspended solids in the tank are discharged into the sedimentation tank 77, and then the valve 76
Close. Through conduit 81 and valve 74, the apparatus is filled with water and flushed. Washing water flows from the device through valve 74 and conduit 8.
1, and is discharged to a receiving tank (not shown). Water is periodically removed from the receiver to prepare the acid solution for leaching. The settled suspension is discharged through valve 79 to storage tank 801 and the clarified solution from settling tank 77 is sent by pump 78 through open valve 75 to reactor 1, conduit 53, magnetic concentrator 61 and medium pH measuring device 52. Thereafter, the above treatment is performed to begin recovering other metals from the liquid. To minimize anolyte consumption, minimize power consumption, and maximize selectivity, perform the following operations.

Circulation pump 54, control valve 75 and pressure gauge 73 determine the rate of circulation of liquid through the device.

Using the medium pH measurement device 52, at any particular voltage applied to the anode 3, the rate of pH change in the solvent is recorded over time over the starting region of the curve pH time. Next, using the anolyte replacement system 68 and pump 72,
A reduced pressure is created in the anode region 6 of the reactor 1, and since the pressure in the cathode region 5 of the reactor 1 is high, this forces the catholyte from the cathode region 5 through the holes in the waist 4 into the anode region 6 of the reactor 1. , the rate is such that no increase in the voltage of the anode 3 is recognized. By changing the voltage applied to the anode 3, the reactor 1
Measure the value of the current through the reactor 1 such that the rate of change of temperature within the reactor 1 is minimal. The anolyte supply rate is then adjusted by the anolyte replacement system 68 to maximize the rate of change of pH in the cathode region of the reactor 1. Example 1 The leachate contains 0.832 kg of iron/0.096 kg of copper/
Gono, aluminum 0.3 kg/me and zinc 0.676
k9/m, had an initial pH of 2.65 and an initial conductivity of 0.517 Mho/m, and was injected as a catholyte into an apparatus having a reactor.

The same leachate was used as the anolyte. This equipment selectively recovered the above metals as hydroxides. In order to comprehensively recover iron, aluminum, copper and zinc, the pH of the solution was adjusted to 2.
The power per treatment liquid was changed from 65 to 8, and the power was 138.2.
consumed kWh.

Example 2 The leachate contains iron 0.73k9/ and copper 0.082k9/
So, aluminum is 0.32k9 and zinc is 0.52k9.
/, the first - is 3.05, the first conductivity is 0.5
1 Mho/m, and this was injected as a catholyte into a selective recovery device for metals from a leachate having a reactor.

Sodium chloride-potassium chloride (1:1) as anolyte
A 20% solution of was used.

This equipment selectively recovered the above metals as hydroxides. In order to recover all metals as hydroxides, the pH of the liquid is
3.0 mu) to 8, and the power consumption was 12.4 kWh/. At this time, as by-products, 3k9/ml of chlorine, 0.08k9/ml of hydrogen, 0.07ml/ml of commercial hypochlorite solution, 0.85ml/ml of water containing soluble sulfate 5.2k9/ml. Obtained. Although the consumption rate of the anolyte was 0.7 w/m, no consumption of the anode material was detected. Example 3 The leachate contains 0.832k9/l of iron, 0.096k9/l/l of copper, 0.3k9/l of aluminum, and 0.3k9/l of zinc. Contains 676k9/m, initial pH is 2.65, initial conductivity is 0.517
It was Mho/m.

This was injected into the apparatus described in Example 1. A sodium sulfate solution with a concentration of 30k9 was used as the anolyte. All metals were recovered as hydroxides with a mottling range of 2.8-8. The power consumption was 30 kWh/, and the consumption rate of the anolyte was 0.5 kWh/me.

Example 4 The leachate contains iron 0.73k9/, copper 0.082k9/,
Aluminum 0.3k9/, zinc 0.52k9/, initial pH 3.05, initial conductivity 0.51
It was 7 Mho/m.

This was injected into the apparatus described in Example 2. 3. Determine the area of spots.
All metals were selectively recovered as 05-8. At this time, the power is 18. Bulb Wh/of 30% sodium sulfate solution 0.
Consumed /servant at 15. 3 of the following composition as a dry solid
Seed precipitates were obtained. By-products were hydrogen, oxygen, purified water 0.85/m, and commercial sulfuric acid 0.15/m, and the anode material consumption/dry solids was 0.15 t/t.

Example 5 The leachate contained 0.81 k9/l of iron, 0.29 k9/l of copper, 0.3 kg/l of aluminum, 0.73 k9/l of zinc, and had an initial pH of 3.0.

This was injected into the apparatus described in Example 2 and the pH ranged from 3 to
8 and all metals were recovered as hydroxides. At this time, 39.1 kWh of electric power and 0.15 liters of 30% sodium sulfate solution were consumed. Three types of precipitates having the following compositions were obtained as dry solids. As a by-product, hydrogen,
Oxygen, commercial sulfuric acid 0.15/elbow and purified water 0.85
So/obtained obedience.

The amount of consumption of anode material/dry solids was 0.15 t/t. Example 6 The leachate contained 0.02 kg/l of copper and 7.0 kg/l of zinc.
It contained 6k9/〆, and the initial pH was 5.

This was injected into the apparatus described in Example 2. A 20% solution of sodium chloride-potassium chloride (1:1) was used as the anolyte, and one precipitate was obtained at a pH range of 5 to 8.
The composition of the dried precipitate was 0.16% copper and 6% zinc.
It was 4%. Electric power/dry solids 4100k for this recovery
Wh/t and 0.07〆/〆 of anolyte were consumed. Hydrogen, chlorine, commercially available subboxal chlorate and purified water were obtained as created organisms.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of the selective recovery device for metals from leachate of the present invention, FIG. 2 is a partially sectional side view of the reactor of the present invention, and FIG. FIG. 4 is a side view of a reactor of the invention equipped with a vibrator, and FIG. 5 is a helical magnetic concentrator attached to the bottom of the reactor of the invention. FIG. 6 is a plan view of the magnetic concentrator of FIG. 5; FIG. 7 is an explanatory diagram of the main parts of the apparatus for selectively recovering metals from leachate according to the present invention. 1...Reactor, 2...Cathode, 3.
... Anode, 4... Diaphragm, 5... Operating space of reactor,
6... Anode region, 7... Cathode region, 8... Cylindrical manifold, 9... Insulating spacer, 10... Upper chamber, 11 Lower chamber, 15... Taking out gas from the cathode region. Discharge pipe, 16, 26... Sealing gasket, 28... Anolyte supply closure, 29... Discharge pipe for removing gas from the anode region, 30... Opening hole for discharging the anolyte from the anode region. 3
1... Discharge pipe for taking out the leachate from the cathode area, 34...
・Magnetic concentrator, 35... Box-shaped body of dielectric material, 52...
・Medium pH measuring device, 54...Circulation pump, 58...
- Vibrator, 64... Spiral coil tube, 67... Filler of electromagnetic material, 77... Sedimentation tank, 78... Ponfu〇. Autumn Z Gu Gaibo〆Me GZ Bon GJ Buddha G〆Hada fortune telling and others 7

Claims (1)

[Scope of Claims] 1. A method for selectively recovering metals from a leachate containing various metals in an electrolytic cell having an anode chamber and a cathode chamber electrically separated by a porous diaphragm, comprising: The leachate to be treated or an anolyte consisting of an aqueous sulfate solution or an aqueous chloride solution is passed into the anode chamber 6 and at the same time the leachate is passed into the cathode chamber 7.
through which a DC potential is applied to these electrolytes,
By selecting the rate of supply of anolyte to the anolyte chamber 6 and the rate of circulation of leachate to the cathode chamber 7 such that this DC potential is minimized for a given porous diaphragm, a catholyte containing an oxide or hydroxide to maintain the pH of the leachate at a pH at which one of the various metals precipitates as an oxide or hydroxide, and such that the oxide or hydroxide coagulates. A method for selective recovery of metals, characterized by applying a magnetic field to. 2. The method of claim 1, wherein the exudate is passed simultaneously through each of the anode chamber 6 and the cathode chamber 7. 3. The method according to claim 1, wherein the chloride aqueous solution is caused to flow into the anode chamber 6 at the same time as the leachate is passed through the cathode chamber 7. 4 Using sylvinite solution as the chloride aqueous solution,
A method according to claim 3. 5. The method according to claim 1, wherein the leaching solution is passed through the cathode compartment 7 and, at the same time, the sulfate aqueous solution is passed through the anode compartment 6. 6. The method according to claim 5, wherein a sodium sulfate solution is used as the sulfate aqueous solution. 7. The method according to any one of claims 1 to 6, wherein a variable magnetic field is further applied to the catholyte that has been electrolyzed and treated with a magnetic field. 8. The method according to any one of claims 1 to 7, wherein the cathode chamber 7 is filled with activated carbon in a method for selectively recovering metal from a leachate containing gold. 9. Comprising a reactor with coaxially arranged cathode and anode,
This is an apparatus for selective recovery of metals from a leachate, in which a reactor is divided into an anode chamber 6 and a cathode chamber 7 by a diaphragm 4, and the anode chamber 6 has an anolyte supply inlet 28 and an outlet 30, The cathode chamber 7 is provided with a catholyte supply port 49 and a catholyte discharge port 31, and a cathode gas discharge port 15, 82.
It has a first circuit with a measuring device 52, a magnetic concentrator 34, 61, a pump 54 and a feed port 49, which has a first circuit which returns to the first circuit via a settling tank 77 and a pump 78. A metal selective recovery device having two circuits connected to each other. 10 Apparatus for the selective recovery of metals from leachate, comprising a reactor with a cathode and an anode arranged coaxially, having a cylindrical manifold 8 located in the upper section of the reactor, the manifold 8 having: It has a socket pipe 29 and a leachate supply port 28 and a discharge port 30, electrically insulating the upper chamber 10 and lower chamber 11 from each other, and providing a diaphragm 4 between the cathode 2 and the anode 3 in the lower chamber 11. Coaxially installed reactor 1
The operating space 5 is divided into an anode chamber 6 and a cathode chamber 7, and in addition to this manifold 8, a magnetic concentrator 34 is connected to the circulation pump 54 and the reactor 1 to promote the formation of the solid phase. a device 52 for measuring the pH of the medium in communication with the magnetic concentrator 34 and the reactor 1; and a settling tank 77 in communication with a pump 78 for returning the solution from the settling tank 77 to the reactor 1.
10. The device according to claim 9, comprising: 11. The device according to claim 10, wherein an opening is provided in the center of the upper chamber 10 and lower chamber 11 of the manifold 8, and the diaphragm 4 is attached coaxially. 12. The device according to claim 11, wherein the diaphragm 4 is attached to the opening of the lower chamber 11 of the manifold 8 by a sealing gasket 16 that does not allow permeation of gases generated during metal recovery and leachate. 13 Discharge pipe 15 for taking out gas from the cathode chamber 7 of the reactor 1
Attach the cathode 2 to the lower chamber 11 of the manifold 8 having
11. The apparatus according to claim 10, wherein the anode 3 is attached to the upper chamber 10 of a manifold 8 having a discharge pipe 29 for attaching gas from the anode chamber 6 of the reactor 1. 14. Apparatus according to claim 10, in which the anode 3 is attached to the upper chamber 10 of the manifold 8 by means of a sealing gasket 26. 15. The magnetic concentrator 34 is directly attached to the lower part of the reactor 1 in order to communicate with the reactor 1.
The device described in item 0. 16. The apparatus according to claim 10, wherein the magnetic concentrator 34 is connected to the lower part of the reactor 1 to communicate with the reactor 1. 17. The cathode 2 and the anode 3 are located coaxially, and the diaphragm 4 is made of the same material as the reactor 1 and is electrically connected to the reactor 1. The device described in any of the above. 18 Claims 10 to 1 in which holes are formed in the cathode 2
The device according to any of paragraph 7. 19. The device according to any one of claims 10 to 18, wherein the anode 3 has a vibrator 58. 20. Apparatus according to any of claims 10 to 19, wherein the magnetic concentrator 34 consists of a helical coiled tube 64 of dielectric material and is located between the terminals of the magnetic field source. 21. Any one of claims 10 to 20, wherein the magnetic concentrator 34 consists of a box-shaped body 35 made of dielectric material, filled with a magnetic material filler 67, and placed between the terminals of the magnetic field source. The device described in.