JP3647362B2 - Apparatus and method for automatically cleaning liquid after copper removal - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention provides a post-decoppering solution for removing impurity metals such as copper, arsenic, antimony, bismuth and nickel, which increase in the circulating copper electrolyte when electrolytically purifying crude copper to produce high purity electrolytic copper. The present invention relates to an automatic liquid purification apparatus and a liquid purification method. In particular, by adding sodium hydrosulfide and / or sulfuric acid while controlling the supply amount in the system, a necessary amount of hydrogen sulfide is generated, and this hydrogen sulfide is used to supply a predetermined amount to a multi-stage sulfidation reaction tank. The present invention relates to an automatic liquid purification apparatus and a liquid purification method for a post-copper removal liquid that can efficiently and reliably produce a sulfide precipitate.
[0002]
[Prior art]
In copper electrolytic refining, since the amount of copper eluted from the anode is generally larger than the amount of copper deposited on the cathode, the concentration of copper in the electrolytic solution gradually increases. Increasing the copper concentration above a predetermined level prevents optimal electrolytic purification. On the other hand, impurities such as arsenic, bismuth, nickel and antimony contained in the copper anode are eluted into the electrolyte. When these impurity ion concentrations become high, they are deposited on the cathode to lower the quality of electrolytic copper. Nickel also raises the electrolysis voltage, and antimony also exhibits harmful effects such as floating due to hydrolysis. Therefore, it is important to purify the copper electrolytic circulating liquid that is extracted from the electrolytic cell and returned to the electrolytic cell after purification.
[0003]
As the liquid purification method, the copper electrolytic tail solution is concentrated by heating and the difference in solubility is utilized, copper is separated and removed as copper sulfate, and then the copper, arsenic, antimony and bismuth remaining in the solution are electrodeposited by electrolytic collection. Finally, a method of cooling the liquid and separating and removing nickel as nickel sulfate has been widely practiced. However, since this liquid purification method uses an electrolytic collection method for removing arsenic and antimony, there is a drawback that highly toxic arsine gas (AsH3) is generated during electrolysis. Furthermore, there is a disadvantage that the amount of power consumption during electrowinning is extremely large.
[0004]
In order to solve the above problem, the applicant of the present application disclosed in Japanese Patent Application Laid-Open No. 11-286797 by contacting hydrogen sulfide gas as shown in FIG. 2 to sulfidize copper, arsenic, antimony, and bismuth in the solution after decopperization. After separating and removing as a product and recovering copper, etc., the post-copper removal solution is divided into two parts, one is removed and returned to the recirculating copper removal solution in the liquid purification system, and the other post-copper removal solution is heated. Concentrate, then cool down and use the difference in solubility of nickel sulfate to remove a portion of the nickel as nickel sulfate and divide the solution after the copper removal again into two parts, one of which circulates in the copper electrolytic purification system Return the electrolyte and add sodium hydrosulfide to the other post-decoppering solution to generate hydrogen sulfide, and then contact this gas with the post-decoppering solution to be processed next. Used to separate and remove copper, arsenic, antimony, and bismuth as sulfides The law was proposed.
In this method, when hydrogen sulfide is generated, nickel sulfide is generated as a side reaction from the nickel content in the solution after copper removal, and can be separated and removed as sulfide.
[0005]
However, when industrially implementing the proposed method on a large scale, there is a problem that hydrogen sulfide is not stably generated. It was found that the generation of hydrogen sulfide is unstable, and if the amount of generated hydrogen sulfide is small, the sulfurization reaction is slow and it takes too much time to clean the liquid after decopperization. If too much hydrogen sulfide is generated, excessive hydrogen sulfide is generated, and it is necessary to store a large amount of highly toxic and expensive hydrogen sulfide gas, and an apparatus for that purpose must be provided.
[0006]
Therefore, the applicant of the present application proposes an apparatus and a method that enable further stable production of hydrogen sulfide by further improving in order to carry out the previously proposed method for purifying the copper-free solution on a large-scale industrial level. In this application, in order to carry out the liquid purification method at an industrial level, a hydrogen sulfide generation tank for generating hydrogen sulfide by bringing sodium hydrosulfide into contact with a solution after copper removal, Next, the hydrogen sulfide gas has at least a first-stage sulfidation reaction tank in contact with the liquid after copper removal, and a second-stage sulfidation reaction tank into which an overflow of the treatment liquid is introduced through a connecting pipe, A treatment apparatus for the post-copper removal solution, which is hermetically sealed, was proposed. The sulfurization reaction can be performed in multiple stages with multiple sulfuration reaction tanks, and the hydrogen sulfide-containing clean solution including the hydrogen sulfide generation tank can be isolated from the outside air in a sealed state. I was able to do it. In addition, a desulfurization hydrogen tank is also installed in which the hydrogen sulfide-containing waste liquid discharged from the hydrogen sulfide generation tank is brought into contact with the electrolytic solution after decopperization.
[0007]
According to this invention, in order to carry out the reaction stably in an individual technique for carrying out the liquid purification method at an industrial level, for example, in a hydrogen sulfide generation tank, a predetermined amount of hydrogen sulfide gas is stably stabilized. When this hydrogen sulfide gas is generated, sulfuric acid is consumed. However, in order to supply hydrogen sulfide gas stably, it is necessary to reduce the variation in sulfuric acid concentration in the hydrogen sulfide generation tank. In order to reduce the variation in sulfuric acid concentration, a technique has been established that can be managed by measuring the oxidation-reduction potential in the tank.
[0008]
[Problems to be solved by the invention]
However, in this application, there has been no proposal for an automatic liquid purification apparatus or a liquid purification method for a post-copper removal solution that can efficiently and reliably perform operation control at an industrial level, and there has been a demand for these. .
Accordingly, an object of the present invention is to meet the above-mentioned demand for the prior art, and to provide an automatic liquid purification apparatus for a post-copper removal liquid using hydrogen sulfide as a sulfide precipitation removing agent. An object of the present invention is to provide an automatic liquid purification method for a post-copper removal solution using hydrogen sulfide as a sulfide precipitation remover.
[0009]
[Means for Solving the Problems]
The first aspect of the present invention is the automatic operation of a post-copper removal solution using hydrogen sulfide as a sulfide precipitation remover (in the case of not undergoing copper removal electrolysis, a copper electrolytic tail solution; hereinafter referred to as “post-decopperization solution”). A liquid purification device comprising a hydrogen sulfide generation tank for generating hydrogen sulfide by contacting sodium hydrosulfide and sulfuric acid, a gas holder for storing the generated hydrogen sulfide, and hydrogen sulfide gas for copper, arsenic, antimony, bismuth and A plurality of sulfidation reaction tanks arranged in series in contact with the post-decopperization solution containing impurities such as nickel, and the hydrogen sulfide pressure in the gas holder are detected, and to the hydrogen sulfide generation tank of sodium hydrosulfide and / or sulfuric acid The first control device that can adjust the amount of hydrogen sulfide generated by adjusting the supply amount of hydrogen, and the supply amount of hydrogen sulfide to the sulfidation reaction tank of each stage are adjusted and present in the liquid after copper removal To control the formation of sulfide precipitates of impurities A control unit, and, the automatic solution purification device of copper removal after solution composed is constituted by a hydrodesulfurisation tank for the discharged hydrogen sulphide-containing waste liquid is contacted reacted with Datsudo solution after the hydrogen sulfide generation tank provide.
[0010]
According to a second aspect of the present invention, there is provided an automatic liquid purification apparatus for a post-decopperization liquid according to the first aspect, wherein the second control device measures the oxidation-reduction potential in the sulfurization reaction tank of each stage, thereby causing the sulfidation precipitation. The production amount of the product is detected, and based on this, the supply amount of hydrogen sulfide to the sulfurization reaction tank of each stage is adjusted.
[0011]
A second aspect of the present invention is an automatic liquid purification method for a post-copper removal solution using hydrogen sulfide as a sulfide precipitation remover, which automatically cleans the post-decopperization solution, including sodium hydrosulfide and / or sulfuric acid. The step of bringing both into contact with each other while controlling the supply amount of hydrogen and controlling the generation amount of hydrogen sulfide, and removing copper from the copper electrolysis tank into the uppermost sulfurization reaction tank of the multi-stage sulfurization reaction tank connected in series Sending the post-solution, supplying hydrogen sulfide while controlling the supply amount to each stage of the sulfidation reaction tank to generate sulfide precipitate, and removing the sulfide precipitate from the effluent from the most downstream sulfidation reaction tank And removing the hydrogen sulfide from the hydrogen sulfide-containing waste liquid by contact-reacting the hydrogen sulfide-containing waste liquid after generating hydrogen sulfide with the post-decopper-free liquid and removing the hydrogen sulfide from the hydrogen sulfide-containing waste liquid. An automatic liquid purification method for a post-solution is provided.
[0012]
The present invention described in claim 4 is the automatic solution purification method of copper removal after solution according to claim 3, wherein the sulphide precipitate generation step, by measuring the redox potential in the sulfurization reaction vessel of each stage It is characterized in that the amount of sulfide precipitate produced is detected, and the amount of hydrogen sulfide supplied to the sulfurization reaction tank in each stage is adjusted based on the detected amount.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an automatic liquid purification device and an automatic liquid purification method for a post-copper removal solution according to the present invention will be described in detail with reference to the drawings.
FIG. 1 is a block diagram of an embodiment of an automatic liquid purifier for post-copper removal liquid according to the present invention.
An automatic liquid purification apparatus for a post-copper removal liquid according to the present invention is an apparatus for removing a metal such as copper, arsenic, antimony, bismuth and nickel from the post-copper removal liquid and purifying the liquid.
[0014]
Before performing the cleaning with the apparatus of the present invention, by electrolytic extraction from a copper electrolytic tail solution containing impurities such as copper, arsenic, antimony, bismuth and nickel taken out from the electrolytic cell 60 periodically or as necessary. It is also possible to provide a copper removal electrolyzer 62 that separates and collects a part of copper in advance. According to this method, electrolytic copper having a purity of 99% or more can be obtained. Since the copper electrolytic tail liquid contains the largest amount of copper as a metal component, when the liquid is directly brought into contact with hydrogen sulfide gas, a large amount of copper sulfide is produced together with other sulfides. In this case, the consumption of hydrogen sulfide gas is large and the amount of sulfide is also large. It is advantageous if the copper is separated and recovered in advance by electrowinning, because this is no longer necessary. In the electrolytic solution after the treatment, usually, copper is about 5 to 20 g / liter, arsenic is about 1 to 10 g / liter, antimony is about 0.1 to 1 g / liter, nickel is about 5 to 20 g / liter, About 150 to 300 g / liter of free sulfuric acid is contained. Alternatively, the copper sulfate may be separated and recovered in advance by heating and concentrating the solution after copper removal.
[0015]
Next, the automatic liquid purification apparatus of the present invention is roughly divided into various liquid pipes 1 and gas pipes 2, and an electrolytic solution tank 3 for storing a liquid after copper removal from the copper removal electrolytic apparatus 62, A sodium hydrosulfide tank 4 for storing sodium hydrosulfide, a post-freezing liquid tank 5 for storing sulfuric acid after freezing, a hydrogen sulfide generation tank 6 for generating hydrogen sulfide by contacting sulfuric acid and sodium hydrosulfide, A gas holder 7 for hermetically holding the generated hydrogen sulfide, and the hydrogen sulfide gas in contact with a copper electrolytic tail solution, in the illustrated preferred embodiment, a solution after copper removal (hereinafter abbreviated as “solution after copper removal”). A plurality of sulfidation reaction tanks 10, 20, 30, 40 arranged in series, first control for adjusting the amount of hydrogen sulfide generated, and hydrogen sulfide to the sulfidation reaction tanks 10, 20, 30, 40 of each stage The control device 8 for performing the second control for adjusting the supply amount of sulfur, and the sulfurization in the final stage From the first liquid storage tank 50 in which the liquid discharged from the reaction tank 40 is stored, filter means such as a filter press for filtering sulfide from the liquid discharged from the first liquid storage tank 50, and the hydrogen sulfide generation tank 6 A desulfurized hydrogen tank 52 for contacting the discharged hydrogen sulfide-containing waste liquid with the post-decopperization liquid from the electrolyte tank 3, and a second liquid storage tank 54 for storing the purified liquid from the desulfurized hydrogen tank 52; And the filter 56 which filters the sulfide of the discharge liquid from the 2nd liquid storage tank 54 is comprised.
[0016]
Here, the hydrogen sulfide generation amount is adjusted by the control device 8 detecting the hydrogen sulfide pressure in the gas holder 7 and adjusting the supply amount of sodium hydrosulfide and / or sulfuric acid to the hydrogen sulfide generation tank 6. Do. In the preferred embodiment shown, the control device 8 adjusts the supply amount of sodium hydrosulfide and / or sulfuric acid to the hydrogen sulfide generation tank 6 by opening or closing either or both of the valves V1 and V2. .
[0017]
For example, the case where only the valve V2 is controlled to adjust the supply amount of sulfuric acid to the hydrogen sulfide generation tank 6 will be described more specifically.
The sulfuric acid concentration in the hydrogen sulfide generation tank 6 is controlled so that the opening / closing of the valve V2 is controlled by the control device 8, but the oxidation-reduction potential ORP is in the range of −80 to −120 mV. In order to accelerate the reaction, the liquid is heated to 60 ° C. by a heater in the tank, and the liquid is circulated and stirred by a pump. As the pump, a pump excellent in corrosion resistance, wear resistance and airtightness is recommended in consideration of presence of hydrogen sulfide and entrainment of a thriller. The hydrogen sulfide gas pressure corresponds to the sulfidation tank (depth 1000 mm) and is managed at a pressure of 0.008 to 0.012 MPa.
[0018]
In the hydrogen sulfide generation tank 6, when hydrogen sulfide is generated by the reaction and sulfuric acid is consumed, the oxidation-reduction potential decreases. When the oxidation-reduction potential in the tank drops, the control device 8 opens the valve V <b> 2 and supplies the frozen liquid in the frozen liquid tank 5 to the hydrogen sulfide generation tank 6. The liquid level is controlled within a predetermined level range in order to stabilize the gas pressure. When the filtrate rises to the upper limit of the liquid level, the filtrate is discharged from the tank and sent to the desulfurization hydrogen tank 52. The concentration of hydrogen sulfide in the discharged liquid was 0.3 g / liter. Since the pressure inside the tank is higher than the atmosphere, the liquid can be easily discharged by opening the discharge valve.
[0019]
In addition, the control device 8 detects the oxidation-reduction potential in each sulfidation reaction tank and adjusts the supply amount of hydrogen sulfide to the sulfidation reaction tanks 10, 20, 30, 40 in each stage, and the sulfidation reaction tanks in each stage. This is done by adjusting the amount of hydrogen sulfide supplied to 10, 20, 30, 40. In the illustrated preferred embodiment, the supply amount of hydrogen sulfide to the sulfidation reaction tanks 10, 20, 30, 40 of each stage is adjusted by controlling the opening and closing of the valves V3 to V6. In the above-described embodiment, these controls are performed by one control device 8, but may be performed by another control device.
[0020]
Next, removal of impurities such as copper, arsenic, antimony, bismuth and nickel in the sulfurization reaction tank will be described in detail with reference to FIG.
An example of four-stage treatment in the four sulfuration reaction tanks (10, 30, 50, 70) of FIG. The post-copper removal liquid from which a part of copper has been separated and removed is put into the first stage sulfurization reaction tank 10. The hydrogen sulfide gas generated in the hydrogen sulfide generation tank 6 is introduced from the bottom of the first sulfurization reaction tank 10 via the gas pipe 2a and reacts with the liquid after copper removal. The oxidation-reduction potential ORP is managed at 350 to 450 mV. In this oxidation-reduction potential range, copper mainly becomes sulfides selectively. In order to make the sulfidation rate proceed stably, the oxidation-reduction potential is an allowable range of about 10 mV with respect to a predetermined potential (hereinafter, “*” is used to indicate the allowable range. For example, in the above case, “ * Expressed as “10 mV”). This control is managed by the control device 8 operating the valve V3 installed in the hydrogen sulfide gas introduction pipe 2a to control the amount of hydrogen sulfide gas to be introduced.
[0021]
The post-copper removal liquid in the first stage sulfidation reaction tank 10 is stirred by a stirrer, and steam is blown from a steam introduction pipe (not shown) and heated to about 60 ° C. By heating, the reaction is promoted, the viscosity of the reaction solution is lowered, and the filterability of sulfide is improved. Moreover, in order to improve the effect of stirring by a stirrer, unevenness such as a baffle plate (not shown) may be provided on the sulfurization reaction tank wall.
[0022]
The liquid after the copper removal to the first sulfurization reaction tank 10 is continuously supplied, and the liquid after the sulfurization reaction overflows, and has the same configuration as the first sulfurization reaction tank 10 but a slightly smaller capacity second stage. To the sulfurization reaction tank 20. Hereinafter, similarly, the sulfidation reaction tank becomes smaller as it becomes later.
In addition, the supply amount of the liquid after the copper removal to the sulfurization reaction tank 10 is 78 liters / minute when the liquid is contained up to a depth of 650 mm in the sulfurization reaction tank having an inner diameter of 1100 mm and a depth of 1000 mm. On the other hand, hydrogen sulfide gas is supplied at a rate of about 100 liters / minute in four tanks. The amount of hydrogen sulfide gas required in the sulfidation reaction tank is determined by the amount of sulfide produced, and an amount increased by 5 to 10% of the theoretical amount necessary for the production of sulfide is required.
[0023]
In the present invention, the control device 8 is connected to the valves V1 and / or V2 installed in the liquid pipe 1a and / or the liquid pipe 1b so that the amount of hydrogen sulfide stored in the gas holder 7 is substantially constant. Controls opening and closing. In the illustrated preferred embodiment, hydrogen sulfide is controlled by controlling the opening and closing of the valve V2 installed in the liquid pipe 1b, that is, by adjusting the supply amount of the post-freezing electrolyte from the post-freezing liquid tank 5. The amount of hydrogen sulfide generated in the generation tank 6 is controlled. In the present invention, surplus hydrogen sulfide is not generated because the amount of hydrogen sulfide supplied to each of the sulfurization reaction tanks 10, 20, 30, and 40 is controlled. However, when surplus is generated, The hydrogen sulfide is exhausted from the exhaust pipe at the top of the sulfurization reactor, absorbed by caustic soda, concentrated to become sodium hydrosulfide and reused.
[0024]
The reaction solution overflowed from the first sulfurization reaction tank 10 and introduced into the second sulfurization reaction tank 20 is managed in the range of oxidation-reduction potential of 370 to 390 mV. At this redox potential, arsenic is mainly separated as a sulfide precipitate. In the second sulfidation reaction tank 20, the conditions such as addition of hydrogen sulfide, heating, and stirring are controlled in the same manner as in the first sulfidation reaction tank 10 except that the volume is slightly smaller than in the sulfidation reaction tank 10. The after liquor is discharged. Similarly, antimony sent from the second sulfurization reactor 20 to the third sulfurization reactor 30 is further sent to the fourth sulfidation reactor 40 in the final stage, and bismuth is separated as a sulfide precipitate. The sulfurized post-reaction liquid discharged from the fourth sulfidation reaction tank 40 is stored in the first liquid storage tank 50, and then sent to a filtering means such as a filter press, filtered by a conventional method, and sulfide. Is recovered. The filtrate contains nickel at a high purity, and crude nickel is separated by cooling and freezing it in a well-known manner.
[0025]
On the other hand, in the desulfurized hydrogen tank 52, a liquid after copper removal (copper concentration is 10 g / liter, arsenic concentration is 5 g / liter, nickel concentration is 15 g / liter, free sulfuric acid concentration is 240 g / liter) is connected to the liquid pipe 1c. And waste liquid containing hydrogen sulfide discharged from the hydrogen sulfide generation tank 6 through the liquid pipe 1d. The hydrogen sulfide in the waste liquid forms a sulfide with a metal element such as copper in the liquid after copper removal, and the hydrogen sulfide in the liquid is consumed. The waste liquid after the reaction is once stored in the second liquid storage tank 54 and then filtered by the filter 56, the sulfide is recovered, and the filtrate is returned to the electrolytic tank and reused.
In the above description, the case of using a four-stage sulfidation reaction tank has been described. However, if the oxidation-reduction potential is appropriately controlled, multistage treatment of two, three stages, five stages or more is possible.
[0026]
【Example】
A solution after copper removal which had been subjected to copper removal treatment in advance was used. The sulfurization reaction was a four-stage process. Concentrations of various metal elements in the electrolyte are 10 g / liter copper, 4.7 g / liter arsenic, 0.6 g / liter antimony, 0.3 g / liter bismuth, 16.0 g / liter nickel, 252 g / liter free sulfuric acid. was. The solution after removing copper (6000 liters) was introduced into the first sulfurization reactor. The operating conditions were as follows and operated for 7 hours.
Sulfurization reactor 10 20 30 40
Flow rate (l / min) 78 78 78 78
Redox potential (mV) 380 * 10 280 * 8 250 * 8 200 * 8
Temperature (℃) 60 60 60 60
Hydrogen sulfide amount (l / min) 50 * 5 20 * 5 20 * 5 10 * 5
Agitation (rpm) 280 280 280 280
[0027]
As a result of the above implementation, the concentrations of various metal elements contained in the effluent from the final stage sulfurization reactor 40 are copper 0 g / liter, arsenic 0.5 g / liter, antimony 0 g / liter, bismuth 0 g / liter, nickel It was 16.0 g / liter and free sulfuric acid 267 g / liter.
Thus, after the final stage sulfurization reactor 40, copper, arsenic, antimony, and bismuth excluding nickel were also in the form of sulfide precipitates and became separable.
High-purity nickel contained in the effluent from the final stage sulfidation reaction tank 40 was heated and concentrated, cooled and filtered to obtain 82 kg of nickel sulfate.
[0028]
A hydrogen sulfide generation tank 6 having a diameter of 450 mm and a depth of 1300 mm was used, and the liquid volume was set to a depth of 850 * 50 mm. The operating conditions were as follows and operated for 7 hours. Sodium hydrosulfide was supplied in the form of an aqueous solution.
Flowing electrolyte amount 0.5 liter / min Sodium hydrosulfide addition amount 250 g / min redox potential −100 * 5 mV
60 ° C
Hydrogen sulfide gas pressure 0.01 * 0.002MPa
Stirring rate 40 liters / minute Under the above conditions, 100 liters / minute of hydrogen sulfide was obtained. The reaction efficiency of hydrogen hydrosulfide was 98%.
[0029]
【The invention's effect】
Efficient and reliable generation of sulfide precipitates in a sulfidation reactor while controlling the amount of hydrogen sulfide generated by the copper electrolytic tail solution automatic cleaning device and the copper electrolytic tail solution automatic cleaning method of the present invention. Can do. In addition, the generation and management of highly toxic hydrogen sulfide and the supply to the sulfurization reaction tank can be performed from a separate control room, and a suitable environment for work safety can be created.
[Brief description of the drawings]
FIG. 1 is a block diagram of an embodiment of an automatic copper tail solution purifier according to the present invention.
FIG. 2 is a flowchart showing the flow of a liquid purification method disclosed in Japanese Patent Laid-Open No. 11-286797.
[Explanation of symbols]
1 Liquid piping 2 Gas piping 3 Electrolyte tank 4 Sodium hydrosulfide tank 5 Liquid tank after freezing 6 Hydrogen sulfide generation tank 7 Gas holder 8 Control device 10, 20, 30, 40 Sulfurization reaction tank 50 First liquid storage tank 52 Desulfurized hydrogen tank 54 Second storage tank 56 Filter 60 Electrolytic tank 62 Decopper electrolyzer

Claims (4)

An automatic liquid purification device for the post-copper removal liquid using hydrogen sulfide as a sulfide precipitation remover,
A hydrogen sulfide generation tank for generating hydrogen sulfide by contacting sodium hydrosulfide and sulfuric acid;
A gas holder for storing the generated hydrogen sulfide,
A plurality of sulfurization reaction tanks arranged in series, wherein the hydrogen sulfide gas is brought into contact with a post-decopperization solution containing impurities such as copper, arsenic, antimony, bismuth and nickel;
A first control device capable of adjusting a hydrogen sulfide generation amount by detecting a hydrogen sulfide pressure in the gas holder and adjusting a supply amount of sodium hydrosulfide and / or sulfuric acid to a hydrogen sulfide generation tank; ,
A second control device for adjusting the supply amount of hydrogen sulfide to the sulfurization reaction tank of each stage, and controlling the generation of sulfide precipitates of impurities present in the liquid after decopperization; and
A desulfurization hydrogen tank for contacting the hydrogen sulfide-containing waste liquid discharged from the hydrogen sulfide generation tank with a post-decoppering liquid; and
An automatic liquid purification device for the liquid after copper removal, which is configured to include: In the automatic liquid purification apparatus of the post-copper removal liquid according to claim 1,
The second control device detects the amount of sulfide precipitate generated by measuring the oxidation-reduction potential in each stage of the sulfurization reaction tank, and based on this, determines the amount of hydrogen sulfide supplied to the sulfurization reaction tank of each stage. An automatic liquid purification device for the liquid after copper removal, characterized by adjusting. An automatic liquid purification method for a post-copper removal liquid that automatically purifies the post-decopperization liquid using hydrogen sulfide as a sulfide precipitation remover,
A step of bringing hydrogen sulfide into contact with each other while controlling the supply amount of sodium hydrosulfide and / or sulfuric acid, and generating hydrogen sulfide by controlling the production amount;
After removing the copper-free copper from the copper electrolysis tank, the hydrogen sulfide is supplied to each stage of the sulfurization reaction tank while controlling the supply amount. Producing a sulfide precipitate;
Removing sulfurized sediment from the effluent from the most downstream sulfurization reactor; and
Removing hydrogen sulfide from the hydrogen sulfide-containing waste liquid by reacting the hydrogen sulfide-containing waste liquid after the generation of hydrogen sulfide with the liquid after the copper removal contact reaction;
A method for automatically purifying a solution after copper removal, comprising: In the automatic liquid cleaning method of the post-copper removal liquid according to claim 3 ,
The sulfide precipitate generation step detects the amount of sulfide precipitate generated by measuring the oxidation-reduction potential in each stage of the sulfurization reaction tank, and based on this, the amount of hydrogen sulfide supplied to each stage of the sulfurization reaction tank A method for automatically purifying a solution after decoppering, characterized by adjusting the pH.

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