CN112626340A - Treatment method of copper anode plate washing slag - Google Patents

Treatment method of copper anode plate washing slag Download PDF

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CN112626340A
CN112626340A CN202011439144.9A CN202011439144A CN112626340A CN 112626340 A CN112626340 A CN 112626340A CN 202011439144 A CN202011439144 A CN 202011439144A CN 112626340 A CN112626340 A CN 112626340A
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anode plate
copper
washing slag
copper anode
oxygen
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CN112626340B (en
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董广刚
刘士祥
魏栋
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Yanggu Xiangguang Copper Co Ltd
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Yanggu Xiangguang Copper Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/462—Sulfates of Sr or Ba
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention relates to the technical field of treatment of copper anode plate washing slag, in particular to a treatment method of copper anode plate washing slag. The processing method comprises the following steps: A) mixing the copper anode plate washing slag, a sulfuric acid solution and an oxidant, and performing presoaking to obtain a presoaking solution; B) carrying out oxygen pressure acid leaching on the pre-leaching solution to obtain a leaching solution; C) carrying out filter pressing on the leachate obtained in the step B) to obtain barium sulfate; D) extracting the filter pressing liquid obtained by filter pressing; E) and carrying out electrodeposition on the extracted raffinate to obtain copper. The invention solves the problems that the cost of returning the washing slag of the copper anode plate to the furnace is high, the production is influenced by barium sulfate in the washing slag of the copper anode plate, the barium sulfate cannot be recycled and the like, and creatively provides a process for recovering copper from the washing slag of the copper anode plate to prepare high-purity copper powder and separating the barium sulfate.

Description

Treatment method of copper anode plate washing slag
Technical Field
The invention relates to the technical field of treatment of copper anode plate washing slag, in particular to a treatment method of copper anode plate washing slag.
Background
When the copper anode plate is cast, in order to prevent the copper mold from adhering to the anode plate, a layer of release agent is usually coated on the copper mold before casting. In copper smelting production, barium sulfate is generally used as a release agent of a copper anode plate. Barium sulfate has the following characteristics: the melting point is high; the property is stable and does not react with acid and alkali; fine particles and large specific surface area, and is easy to adhere to a copper mould. After the anode plate is cast and molded and demoulded, the anode plate is cooled and cooled in a circulating water tank usually. At the moment, the release agent, the copper oxide powder, the cuprous oxide, the elemental copper and the like which are adhered to the anode plate sink to the bottom of the circulating water tank to form the washing slag of the copper anode plate. In actual production, the copper anode plate washing slag is usually returned to the furnace for treatment and copper recovery. However, because the melting point of barium sulfate in the washing slag of the copper anode plate is high, a large amount of wrapped elementary copper or cuprous oxide can easily enter the slag during smelting and slagging, the quantity of the smelting slag is increased, the direct yield of copper is reduced, and the furnace return treatment cost of the washing slag of the copper anode plate is greatly increased. Moreover, when the barium sulfate is returned to the furnace for treatment, the barium sulfate is lost along with the smelting slag, and the barium sulfate cannot be recycled.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for treating copper anode plate washing slag, which solves the problems that the cost of returning the copper anode plate washing slag to a furnace is high, the production of barium sulfate in the copper anode plate washing slag is affected, and the barium sulfate cannot be recycled.
The invention provides a treatment method of copper anode plate washing slag, which comprises the following steps:
A) mixing the copper anode plate washing slag, a sulfuric acid solution and an oxidant, and performing presoaking to obtain a presoaking solution;
B) carrying out oxygen pressure acid leaching on the pre-leaching solution to obtain a leaching solution;
C) carrying out filter pressing on the leachate obtained in the step B) to obtain barium sulfate;
D) extracting the filter pressing liquid obtained by filter pressing;
E) and carrying out electrodeposition on the extracted raffinate to obtain copper.
Preferably, before mixing the copper anode plate washing slag, the sulfuric acid solution and the oxidant in the step a), the method further comprises:
and (4) finely grinding the washing slag of the copper anode plate, and sieving the washing slag with a 100-mesh sieve.
Preferably, in the step A), the washing slag of the copper anode plate comprises elemental copper, copper oxide, barium sulfate and silicate;
in the anode plate washing slag, the content of copper element is 40 wt% -60 wt%, and the content of barium element is 20 wt% -30 wt%.
Preferably, in the step a), the mixing the copper anode plate washing slag, the sulfuric acid solution and the oxidant comprises:
adding the washing slag of the copper anode plate into a sulfuric acid solution, and then adding an oxidant into the obtained mixed solution;
the concentration of the sulfuric acid solution is 260-360 g/L;
the mass ratio of the sulfuric acid solution to the copper anode plate washing slag is 4-5: 1;
the oxidant is selected from hydrogen peroxide;
the mass ratio of the hydrogen peroxide to the copper element in the copper anode plate washing slag is 2-4: 1.
preferably, in the step A), the presoaking temperature is 60-80 ℃, and the presoaking time is 2-3 h.
Preferably, the step B) of subjecting the pre-leach solution to an oxygen pressure acid leach comprises:
a) placing the pre-immersion liquid in a reaction container, introducing steam to heat the pre-immersion liquid, stopping steam when the temperature of the pre-immersion liquid rises to 80-100 ℃, and introducing oxygen once, wherein the flow rate of oxygen once is 30-50 Nm3/h；
b) Stopping introducing oxygen when the pressure in the reaction container rises to 8-10 bar or the temperature rises to 150-180 ℃, and then starting pressure relief;
c) after the pressure in the reaction container is decompressed to 3bar, oxygen is introduced for the second time; the flow rate of the secondary oxygen introduction is 20-40 Nm3/h；
d) When the pressure in the reaction container reaches 8-10 bar again, the reaction is complete, and the operation can be finished to obtain a leaching solution;
when the pressure in the reaction container does not reach 8-10 bar and the temperature reaches 150-180 ℃, indicating that the reaction is still continued, and carrying out oxygen introduction for three times; the third oxygen introduction operation is consistent with the second oxygen introduction operation.
Preferably, in the step C), the filter pressing adopts acid and alkali resistant filter cloth with the mesh size not less than 400.
Preferably, in the step D), the extraction is a P204 extraction method;
the parameters of the P204 extraction method comprise:
the volume fraction of P204 is 20-40%, the saponification rate of P204 is 50-70%, and the pH value of the pressure filtrate for extraction is 0.2-0.8;
the volume ratio of the extracted organic phase to the aqueous phase is 1: 1;
the extraction is carried out under the condition of stirring, the temperature of the extraction is room temperature, and the time is 3-5 min.
Preferably, in the step D), the method of electrodeposition is a high-density electrodeposition method;
the parameters of the electrodeposition include:
the current density is 800-2000A/m2The powder scraping period is 3-10 h, and the electrodeposition time is 3-6 d.
Preferably, in the step D), after the electrodeposition, the method further comprises the steps of discharging from a tank, washing with water and drying;
the number of washing times is 2-3.
The invention provides a treatment method of copper anode plate washing slag, which comprises the following steps: A) mixing the copper anode plate washing slag, a sulfuric acid solution and an oxidant, and performing presoaking to obtain a presoaking solution; B) carrying out oxygen pressure acid leaching on the pre-leaching solution to obtain a leaching solution; C) carrying out filter pressing on the leachate obtained in the step B) to obtain barium sulfate; D) extracting the filter pressing liquid obtained by filter pressing; E) and carrying out electrodeposition on the extracted raffinate to obtain copper. The invention solves the problems that the cost of returning the washing slag of the copper anode plate to the furnace is high, the production is influenced by barium sulfate in the washing slag of the copper anode plate, the barium sulfate cannot be recycled and the like, and creatively provides a process for recovering copper from the washing slag of the copper anode plate to prepare high-purity copper powder and separating the barium sulfate.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a treatment method of copper anode plate washing slag, which comprises the following steps:
A) mixing the copper anode plate washing slag, a sulfuric acid solution and an oxidant, and performing presoaking to obtain a presoaking solution;
B) carrying out oxygen pressure acid leaching on the pre-leaching solution to obtain a leaching solution;
C) carrying out filter pressing on the leachate obtained in the step B) to obtain barium sulfate;
D) extracting the filter pressing liquid obtained by filter pressing;
E) and carrying out electrodeposition on the extracted raffinate to obtain copper.
In certain embodiments of the present invention, the copper anode plate slag includes elemental copper, copper oxide, barium sulfate, and silicate. In some embodiments of the invention, the anode plate washing slag contains 40 wt% to 60 wt% of copper element and 20 wt% to 30 wt% of barium element. In some embodiments of the invention, the main chemical components of the copper anode plate washing slag are shown in table 1.
TABLE 1 main chemical composition of anode plate washing slag
Figure BDA0002821691900000041
In some embodiments of the present invention, the concentration of the sulfuric acid solution is 260-360 g/L. In certain embodiments, the concentration of the sulfuric acid solution is 280g/L or 330 g/L.
In some embodiments of the invention, the mass ratio of the sulfuric acid solution to the copper anode plate washing slag is 4-5: 1. in certain embodiments, the mass ratio of the sulfuric acid solution to the copper anode plate washing slag is 5: 1 or 4: 1.
in certain embodiments of the present invention, the oxidizing agent is selected from hydrogen peroxide.
In some embodiments of the invention, the mass ratio of the hydrogen peroxide to the copper element in the copper anode plate washing slag is 2-4: 1. in some embodiments, the mass ratio of the hydrogen peroxide to the copper element in the copper anode plate washing slag is 2: 1 or 3: 1.
the method comprises the steps of mixing the copper anode plate washing slag, the sulfuric acid solution and the oxidant, and performing presoaking to obtain a presoaking solution.
In some embodiments of the present invention, before mixing the copper anode plate washing slag, the sulfuric acid solution and the oxidant, the method further comprises:
and (4) finely grinding the washing slag of the copper anode plate, and sieving the washing slag with a 100-mesh sieve.
The method of refining is not particularly limited by the present invention, and a refining method known to those skilled in the art may be used.
In certain embodiments of the invention, the refined undersize is mixed with a sulfuric acid solution and an oxidizer and the oversize is again refined.
In certain embodiments of the present invention, mixing the copper anode plate wash sludge, the sulfuric acid solution, and the oxidizing agent comprises:
adding the washing slag of the copper anode plate into a sulfuric acid solution, and then adding an oxidant into the obtained mixed solution.
In some embodiments of the invention, the temperature of the pre-soaking is 60-80 ℃, and the pre-soaking time is 2-3 h. In certain embodiments, the temperature of the pre-soak is 70 ℃ or 80 ℃. In certain embodiments, the time of pre-soak is 2h or 3 h.
And after obtaining the pre-leaching solution, carrying out oxygen pressure acid leaching on the pre-leaching solution to obtain a leaching solution.
In certain embodiments of the invention, subjecting the pre-leach to an oxygen pressure acid leach comprises:
a) placing the pre-immersion liquid in a reaction container, introducing steam to heat the pre-immersion liquid, stopping steam when the temperature of the pre-immersion liquid rises to 80-100 ℃, and introducing oxygen once, wherein the flow rate of oxygen once is 30-50 Nm3/h；
b) Stopping introducing oxygen when the pressure in the reaction container rises to 8-10 bar or the temperature rises to 150-180 ℃, and then starting pressure relief;
c) after the pressure in the reaction container is decompressed to 3bar, oxygen is introduced for the second time; flow rate of secondary oxygen supply20 to 40Nm3/h；
d) When the pressure in the reaction container reaches 8-10 bar again, the reaction is complete, and the operation can be finished to obtain a leaching solution;
when the pressure in the reaction container does not reach 8-10 bar and the temperature reaches 150-180 ℃, indicating that the reaction is still continued, and carrying out oxygen introduction for three times; the third oxygen introduction operation is consistent with the second oxygen introduction operation.
In step a):
in certain embodiments of the invention, the steam is stopped when the temperature of the pre-dip rises to 85 ℃ or 90 ℃.
In certain embodiments of the invention, the flow rate of one oxygen pass is 35Nm3H or 40Nm3/h。
In step b):
in certain embodiments of the invention, the oxygen feed is stopped when the pressure in the reaction vessel rises to 8bar or 10 bar.
In step c):
in certain embodiments of the invention, the flow rate of the second oxygen aeration is 25Nm3H or 30Nm3/h。
In step d):
in some embodiments of the invention, when the pressure in the kettle reaches 8.5bar and the temperature is 120 ℃, the operation is finished to obtain the leaching solution.
In some embodiments of the invention, when the temperature in the kettle stably rises to 140 ℃, the temperature does not rise any more, the pressure still rises continuously, and the operation is stopped when the pressure rises to 10bar, so as to obtain the leaching solution.
In the invention, the third oxygen introduction operation is consistent with the second oxygen introduction operation, namely: the operation steps of the third oxygen introduction can be repeated according to the steps of the second oxygen introduction.
In certain embodiments of the invention, the oxygen pressure acid leach is conducted in an autoclave.
And after obtaining the leaching solution, carrying out filter pressing on the leaching solution to obtain barium sulfate.
In certain embodiments of the invention, the pressure filtration is performed using a plate and frame filter press.
In some embodiments of the invention, an acid and alkali resistant filter cloth of no less than 400 mesh is used for filter pressing.
In some embodiments of the present invention, the filter residue obtained by pressure filtration is barium sulfate. In some embodiments of the invention, the obtained filter residue can be returned to the anode casting position for reuse after being washed with water and dried twice.
And extracting the filter pressing liquid obtained by filter pressing.
In certain embodiments of the invention, the extraction is a P204 extraction.
In certain embodiments of the present invention, the parameters of the P204 extraction process include:
the volume fraction of P204 is 20-40%, the saponification rate of P204 is 50-70%, and the pH value of the pressure filtrate for extraction is 0.2-0.8.
In certain embodiments of the invention, the volume fraction of P204 is 20% or 30%. In certain embodiments of the invention, the saponification rate of P204 is 60% or 70%. In certain embodiments of the invention, the pH of the press filtrate from which the extraction is conducted is 0.4 or 0.6.
In certain embodiments of the invention, the volume ratio of the extracted organic phase to the aqueous phase is 1: 1.
in certain embodiments of the invention, the extraction is performed under agitation.
In some embodiments of the present invention, the temperature of the extraction is room temperature, and the time is 3-5 min. In certain embodiments, the time of extraction is 3min or 5 min.
And after extraction is finished, performing electrodeposition on the extracted raffinate to obtain copper.
In certain embodiments of the invention, the method of electrodeposition is high density electrodeposition.
In some embodiments of the invention, the parameters of the electrodeposition include:
the current density is 800-2000A/m2The powder scraping period is 3-10 h, and the electrodeposition time is 3-6 d.
In certain embodiments of the invention, the current density of the electrodeposition is 1200A/m2Or 1500A/m2。
In certain embodiments of the invention, the scraping period of the electrodeposition is 8 hours or 6 hours.
In some embodiments of the invention, the time of electrodeposition is 6d or 5 d.
In some embodiments of the invention, after the electrodeposition, the method further comprises draining, washing with water and drying.
In some embodiments of the present invention, the number of the water washing is 2 to 3. In certain embodiments, the number of water washes is 2.
The method of drying is not particularly limited in the present invention, and a method of drying known to those skilled in the art may be used.
The invention solves the problems that the cost of returning the washing slag of the copper anode plate to the furnace is high, the production is influenced by barium sulfate in the washing slag of the copper anode plate, the barium sulfate cannot be recycled and the like, and creatively provides a process for preparing high-purity copper powder by recovering copper from the washing slag of the copper anode plate and separating the barium sulfate to be used as a release agent for continuous use.
In the invention: (1) the copper oxide slag is finely ground, the particle size of the material after fine grinding is small, the reaction speed can be accelerated, and the leaching rate and the operation efficiency are improved. (2) The presoaking can be carried out simultaneously with the oxygen pressure leaching, the reaction time of the oxygen pressure leaching is shortened, and the operation efficiency is improved. (3) Acid leaching is carried out under oxygen pressure, the leaching process is strengthened, so that copper in the slag is leached out as completely as possible, and the recovery rate of copper is improved; so that impurities such as iron, zinc and the like are completely leached and are completely separated from barium sulfate in the slag, and the purity of the barium sulfate is improved; the separated barium sulfate can be returned to the casting position to be used as a release agent for continuous use. (4) The impurities are removed by extraction, so that impurities such as iron, zinc and the like in the pickle liquor can be removed deeply, and the foundation is laid for preparing high-purity copper powder by an electrodeposition method. (5) The copper powder is prepared by a high-density electrodeposition method, copper in the slag is directly converted into high-purity copper powder, the added value of the product is improved, and a new process is explored for treating the copper oxide slag.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In order to further illustrate the present invention, the following will describe the treatment method of the copper anode plate washing slag in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
The main chemical components of the copper anode plate washing slag in the embodiment are shown in the table 2.
Table 2 Main chemical composition of copper anode plate washing slag in example
Figure BDA0002821691900000071
Example 1
(1) And (3) taking a proper amount of copper anode plate washing slag for fine grinding, sieving by using a 100-mesh/square sieve, conveying the undersize product to a pre-leaching tank for acid liquor pre-leaching, and returning the oversize product to the fine grinding treatment again.
(2) Adding the undersize into a sulfuric acid solution in a pre-soaking tank, adding hydrogen peroxide into the obtained mixed solution, and pre-soaking at 70 ℃ for 2 hours to obtain a pre-soaking solution; the concentration of the sulfuric acid solution is 280 g/L; the mass ratio of the sulfuric acid solution to the copper anode plate washing slag is 5: 1; the mass ratio of the hydrogen peroxide to the copper element in the anode plate washing slag is 2: 1.
(3) placing the pre-immersion liquid in a high-pressure kettle, introducing steam to heat the pre-immersion liquid, stopping steam when the temperature of the pre-immersion liquid rises to 85 ℃, and introducing oxygen once, wherein the flow rate of oxygen once is 35Nm3H; stopping introducing oxygen when the pressure in the kettle rises to 8bar, and then starting pressure relief; after the pressure in the kettle is decompressed to 3bar, oxygen is introduced for the second time; the flow rate of the secondary oxygen introduction is 25Nm3H; when the pressure in the kettle reaches 8.5bar, the temperature is 120 ℃, and the operation is finished to obtain the leaching solution.
(4) Filter pressing the leached pulp by a plate-and-frame filter press, wherein the filter press adopts acid-base resistant filter cloth with the mesh size of not less than 400, and the copper sulfate solution in the filtrate contains 48g/L of copper, 0.16g/L of iron and 0.13g/L of zinc; the barium sulfate content in the filter residue is 98.4%, and the silicon dioxide content is 1.5%. The filter residue, namely the barium sulfate, is washed and dried twice and then returns to the anode casting position for reuse.
(5) And extracting the filter pressing liquid obtained by filter pressing by adopting P204. The volume fraction of P204 was 20%, the saponification rate of P204 was 60%, and the pH of the press filtrate subjected to extraction was 0.4; the volume ratio of the extracted organic phase to the aqueous phase is 1: 1; the extraction reaction temperature is 25 ℃, and the stirring is carried out for 3 min. The copper content of the raffinate is 47.64g/L, the iron content is 4mg/L, the zinc content is 3mg/L, and the impurities such as arsenic, antimony, bismuth and the like are all less than 1 mg/L.
(6) And preparing copper powder from the extracted raffinate by a high-density electrodeposition method. Current density 1200A/m2The powder scraping period is 8 hours; and discharging the steel wire from the groove after being electrified for 6 d. And washing the copper powder twice by using deionized water, and then drying. The apparent density of the prepared copper powder is 1.9g/cm3The mass fraction of the particle size of 200 mesh or less was 98.6%. The chemical composition of the copper powder prepared is shown in table 3.
Table 3 chemical composition of copper powder prepared in example 1
Composition (I) Cu Fe Pb As Sb Bi O
Content, wt% 99.9 0.005 0.01 0.0006 0.0008 0.0011 0.05
Composition (I) Ni Sn Zn S Cl Moisture content Sum of impurities
Content, wt% 0.0008 0.0005 0.0019 0.0022 0.001 0.025 0.0989
Example 2
(1) And (3) taking a proper amount of copper anode plate washing slag for fine grinding, sieving by using a 100-mesh/square sieve, conveying the undersize product to a pre-leaching tank for acid liquor pre-leaching, and returning the oversize product to the fine grinding treatment again.
(2) Adding the undersize into a sulfuric acid solution in a pre-soaking tank, adding hydrogen peroxide into the obtained mixed solution, and pre-soaking at 80 ℃ for 3 hours to obtain a pre-soaking solution; the concentration of the sulfuric acid solution is 330 g/L; the mass ratio of the sulfuric acid solution to the copper anode plate washing slag is 4: 1; the mass ratio of the hydrogen peroxide to the copper element in the anode plate washing slag is 3: 1.
(3) placing the pre-immersion liquidIntroducing steam into autoclave, heating the prepreg, stopping steam when the temperature of prepreg rises to 90 deg.C, introducing oxygen once with flow rate of 40Nm3H; stopping introducing oxygen when the pressure in the kettle rises to 10bar, and then starting pressure relief; after the pressure in the kettle is decompressed to 3bar, oxygen is introduced for the second time; the flow rate of the secondary oxygen introduction is 30Nm3H; when the temperature in the kettle stably rises to 140 ℃, the temperature does not rise any more, the pressure still rises continuously, and the operation is stopped when the pressure rises to 10bar, so as to obtain the leaching solution.
(4) Filter pressing the leached pulp by a plate-and-frame filter press, wherein the filter press adopts acid-base resistant filter cloth with the mesh size of not less than 400, and the copper sulfate solution in the filtrate contains 62g/L of copper, 0.18g/L of iron and 0.14g/L of zinc; the barium sulfate content in the filter residue is 98.6 percent, and the silicon dioxide content is 1.3 percent. The filter residue, namely the barium sulfate, is washed and dried twice and then returns to the anode casting position for reuse.
(5) And extracting the filter pressing liquid obtained by filter pressing by adopting P204. The volume fraction of P204 was 30%, the saponification rate of P204 was 70%, and the pH of the press filtrate subjected to extraction was 0.6; the volume ratio of the extracted organic phase to the aqueous phase is 1: 1; the extraction reaction temperature is 35 ℃, and the stirring is carried out for 5 min. The raffinate contains 61.52g/L copper, 3mg/L iron, 3mg/L zinc, and less than 1mg/L arsenic, antimony, bismuth and other impurities.
(6) And preparing copper powder from the extracted raffinate by a high-density electrodeposition method. Current density 1500A/m2The powder scraping period is 6 hours; and discharging the steel strip after 5d of electrification. And washing the copper powder twice by using deionized water, and then drying. The apparent density of the prepared copper powder is 1.98g/cm3The mass fraction of the particle size of 200 mesh or less was 98.5%. The chemical composition of the copper powder prepared is shown in table 4.
Table 4 chemical composition of copper powder prepared in example 2
Composition (I) Cu Fe Pb As Sb Bi O
Content, wt% 99.89 0.0052 0.014 0.0005 0.0007 0.0010 0.055
Composition (I) Ni Sn Zn S Cl Moisture content Sum of impurities
Content, wt% 0.0008 0.0006 0.0016 0.0021 0.001 0.028 0.1105
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A treatment method of copper anode plate washing slag comprises the following steps:
A) mixing the copper anode plate washing slag, a sulfuric acid solution and an oxidant, and performing presoaking to obtain a presoaking solution;
B) carrying out oxygen pressure acid leaching on the pre-leaching solution to obtain a leaching solution;
C) carrying out filter pressing on the leachate obtained in the step B) to obtain barium sulfate;
D) extracting the filter pressing liquid obtained by filter pressing;
E) and carrying out electrodeposition on the extracted raffinate to obtain copper.
2. The treatment method according to claim 1, wherein before mixing the copper anode plate washing slag, the sulfuric acid solution and the oxidant in the step A), the method further comprises the following steps:
and (4) finely grinding the washing slag of the copper anode plate, and sieving the washing slag with a 100-mesh sieve.
3. The treatment method as claimed in claim 1, wherein in the step A), the copper anode plate washing slag comprises elemental copper, copper oxide, barium sulfate and silicate;
in the anode plate washing slag, the content of copper element is 40 wt% -60 wt%, and the content of barium element is 20 wt% -30 wt%.
4. The treatment method as claimed in claim 1, wherein the mixing of the copper anode plate washing slag, the sulfuric acid solution and the oxidant in the step a) comprises:
adding the washing slag of the copper anode plate into a sulfuric acid solution, and then adding an oxidant into the obtained mixed solution;
the concentration of the sulfuric acid solution is 260-360 g/L;
the mass ratio of the sulfuric acid solution to the copper anode plate washing slag is 4-5: 1;
the oxidant is selected from hydrogen peroxide;
the mass ratio of the hydrogen peroxide to the copper element in the copper anode plate washing slag is 2-4: 1.
5. the process according to claim 1, wherein in the step A), the temperature of the pre-soaking is 60 to 80 ℃, and the time of the pre-soaking is 2 to 3 hours.
6. The process according to claim 1, characterized in that the step B) of subjecting the pre-dip to an oxygen pressure acid leaching comprises:
a) placing the pre-immersion liquid in a reaction container, introducing steam to heat the pre-immersion liquid, stopping steam when the temperature of the pre-immersion liquid rises to 80-100 ℃, and introducing oxygen once, wherein the flow rate of oxygen once is 30-50 Nm3/h；
b) Stopping introducing oxygen when the pressure in the reaction container rises to 8-10 bar or the temperature rises to 150-180 ℃, and then starting pressure relief;
c) after the pressure in the reaction container is decompressed to 3bar, oxygen is introduced for the second time; the flow rate of the secondary oxygen introduction is 20-40 Nm3/h；
d) When the pressure in the reaction container reaches 8-10 bar again, the reaction is complete, and the operation can be finished to obtain a leaching solution;
when the pressure in the reaction container does not reach 8-10 bar and the temperature reaches 150-180 ℃, indicating that the reaction is still continued, and carrying out oxygen introduction for three times; the third oxygen introduction operation is consistent with the second oxygen introduction operation.
7. The treatment method according to claim 1, wherein in the step C), an acid and alkali resistant filter cloth with the size of not less than 400 meshes is adopted for filter pressing.
8. The process according to claim 1, wherein in step D), the extraction is a P204 extraction;
the parameters of the P204 extraction method comprise:
the volume fraction of P204 is 20-40%, the saponification rate of P204 is 50-70%, and the pH value of the pressure filtrate for extraction is 0.2-0.8;
the volume ratio of the extracted organic phase to the aqueous phase is 1: 1;
the extraction is carried out under the condition of stirring, the temperature of the extraction is room temperature, and the time is 3-5 min.
9. The process according to claim 1, wherein in step D), the method of electrodeposition is a high-density electrodeposition method;
the parameters of the electrodeposition include:
the current density is 800-2000A/m2The powder scraping period is 3-10 h, and the electrodeposition time is 3-6 d.
10. The process of claim 1, wherein step D), after electrodeposition, further comprises draining, washing with water and drying;
the number of washing times is 2-3.
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