CN113818047B - Method for recovering copper from reclaimed copper smelting fly ash - Google Patents

Method for recovering copper from reclaimed copper smelting fly ash Download PDF

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CN113818047B
CN113818047B CN202111138197.1A CN202111138197A CN113818047B CN 113818047 B CN113818047 B CN 113818047B CN 202111138197 A CN202111138197 A CN 202111138197A CN 113818047 B CN113818047 B CN 113818047B
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fly ash
copper
electrolyte
reclaimed
copper smelting
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CN113818047A (en
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舒建成
雷天涯
陈梦君
伍海萍
王蓉
邓亚玲
文利伟
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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    • 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
    • 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
    • C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
    • 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

Abstract

The invention discloses a method for recovering copper from reclaimed copper smelting fly ash, which solves the technical problems of complex process, long time consumption and high energy consumption of the method for recovering copper from reclaimed copper smelting fly ash in the prior art. The method for recovering copper from reclaimed copper smelting fly ash comprises the following steps: placing the reclaimed copper smelting fly ash in an anode chamber of an electrolytic cell; proportionally adding electrolyte into the electrolytic cell, wherein the electrolyte is alkaline electrolyte and comprises NH 3 ·H 2 O、NH 4 Cl and Cu 2+ (ii) a And (3) carrying out electrolytic reaction on the reclaimed copper smelting fly ash in an electrolytic bath in a stirring state, and collecting a cathode product after the electrolytic reaction is finished. The invention relates to a method for recovering copper from reclaimed copper smelting fly ash, wherein NH is added into electrolyte 3 ·H 2 O、NH 4 Cl is beneficial to the formation of a copper ammonia complex, and can also keep the electrolyte within a certain pH range, thereby improving the recovery efficiency of copper; compared with the prior art, the method of the invention also has the advantages of shortening the reaction time, reducing the energy consumption and being simple and convenient to operate.

Description

Method for recovering copper from reclaimed copper smelting fly ash
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for recovering copper from reclaimed copper smelting fly ash.
Background
Copper has good conductivity, corrosion resistance and ductility, so that the copper is widely applied to the fields of electricity, light industry, building industry, mechanical manufacturing, national defense industry and the like. In 2020, the yield of refined copper in China is 1002.5 ten thousand tons, which accounts for about 42.6% of the global yield. In 10 months before 2020, the apparent consumption of refined copper in China reaches 1217.89 ten thousand tons, which accounts for about 60% of the global consumption. The consumption is reduced due to the influence of epidemic situations in 2020, and is expected to rise again in 2021.
In recent years, the shortage and consumption of copper resources in our country are large, and the demand for copper needs to be met by means of reclaimed copper to a great extent. With the development of the secondary copper smelting industry, the environmental problems are increasing. The reclaimed copper smelting fly ash is residue generated in the melting process of refined copper solid waste, contains heavy metals such as copper, zinc, lead and the like, and can cause pollution to the environment if directly stacked in the environment without being treated, thereby influencing the growth and development of animals and plants and influencing the physical and mental health of human beings. Therefore, the method has very important economic benefits and social benefits for recovering the heavy metals in the reclaimed copper smelting fly ash, and can realize resource utilization of reclaimed copper while improving the environment.
The method for recovering copper from reclaimed copper smelting fly ash at home and abroad mainly comprises a pyrogenic process and a wet process. Among them, pyrometallurgy is to melt recycled copper melting fly ash in an incinerator, but additional energy consumption and pollution such as dioxin are generated during the melting process. The hydrometallurgy is that useful components in the reclaimed copper smelting fly ash are transferred into acidic or alkaline solution, and then the leached solution is purified and enriched, so that the target metal or compound in the purified solution is extracted and recovered.
At present, relatively few researches on the recovery of copper from reclaimed copper smelting fly ash are carried out at home and abroad, wherein in a patent with publication number of CN102212701A, a method for recovering metallic copper and zinc from copper smelting ash is disclosed, and the metallic copper is produced by leaching, selective extraction, back extraction and electrodeposition, so that the operation is easy, but the flow is complex. In the patent publication No. CN112609082A, a method for preparing high-purity cathode copper from copper-containing soot and acidic waste liquid is disclosed, in which medium leaching, low leaching, copper extraction and copper electrolysis are adopted to obtain a cathode copper plate with a copper content of more than 99.99%, but the treatment process before electrolysis is complicated and takes a long time. In the patent with publication number CN109735700A, a method for recovering copper and zinc elements in copper soot by microwave reduction roasting and sulfuric acid leaching is disclosed, wherein the leaching rate of copper and zinc by microwave reduction roasting and sulfuric acid leaching can reach 95%, the production cost is relatively low, but the energy consumption is high (the roasting temperature is high and the time is long). In the patent with publication number CN108034830B, a method for comprehensively recovering valuable metals in copper smelting soot is disclosed, and magnetic separation, acid leaching, intermediate leaching, reduction, low leaching and electrodeposition are adopted to obtain cathode pure copper, so that the arsenic content in acid leaching slag is reduced, but the process is relatively complicated.
Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide a method for recovering copper from reclaimed copper smelting fly ash with a simple process.
Disclosure of Invention
One of the purposes of the invention is to provide a method for recovering copper from reclaimed copper smelting fly ash, which solves the technical problems of complex process, long time consumption and high energy consumption of the method for recovering copper from reclaimed copper smelting fly ash in the prior art. The technical effects that can be produced by the preferred technical scheme of the invention are explained in detail in the following.
In order to realize the purpose, the invention provides the following technical scheme:
the invention discloses a method for recovering copper from reclaimed copper smelting fly ash, which comprises the following steps: placing the reclaimed copper smelting fly ash in an anode chamber of an electrolytic bath; proportionally adding an electrolyte into the electrolytic cell, wherein the electrolyte is an alkaline electrolyte and comprises NH 3 ·H 2 O、NH 4 Cl and Cu 2+ (ii) a And (3) carrying out electrolytic reaction on the reclaimed copper smelting fly ash in an electrolytic bath in a stirring state, and collecting a cathode product after the electrolytic reaction is finished.
According to a preferred embodiment, NH is present in the electrolyte 3 ·H 2 The concentration of O is 0.3-2.8 mol/L. Preferably, NH is present in the electrolyte 3 ·H 2 The concentration of O was 2.0 mol/L.
According to a preferred embodiment, NH is present in the electrolyte 4 The concentration of Cl is 0.1-0.4 mol/L. Preferably, NH is present in the electrolyte 4 The Cl concentration was 0.4 mol/L.
According to a preferred embodiment, Cu is in the electrolyte 2+ From CuSO 4 ·5H 2 O。
According to a preferred embodiment, Cu is in the electrolyte 2+ The concentration of (A) is 5-20 g/L. Preferably, in the electrolyteCu 2+ The concentration of (2) is 20 g/L.
According to a preferred embodiment, the electrolyte is added in an amount at least satisfying: the content of the reclaimed copper smelting fly ash in the electrolyte is 50-125 g/L. Preferably, the electrolyte is added in an amount at least satisfying: the content of the reclaimed copper smelting fly ash in the electrolyte is 50 g/L.
According to a preferred embodiment, the recycled copper smelting fly ash is subjected to electrolytic reaction in an electrolytic cell at a current density of 10-18mA/cm 2 . Preferably, the current density of the electrolytic reaction of the reclaimed copper smelting fly ash in the electrolytic bath is 18mA/cm 2 。
According to a preferred embodiment, the electrolysis time of the recycled copper smelting fly ash in the electrolytic bath is 0.5-1.5 h. Preferably, the electrolysis time of the electrolytic reaction of the reclaimed copper smelting fly ash in the electrolytic bath is 1.5 h.
According to a preferred embodiment, the anode and cathode compartments of the cell are separated by a double layer of acid and alkali resistant filter cloth.
According to a preferred embodiment, the anode plate of the electrolytic cell is a DSA electrode plate or a graphite electrode plate; the cathode plate of the electrolytic bath is a DSA electrode plate, a titanium plate or a copper plate. Preferably, the anode plate is a DSA electrode plate, and the cathode plate is a titanium plate.
The method for recovering copper from reclaimed copper smelting fly ash provided by the invention at least has the following beneficial technical effects:
the invention relates to a method for recovering copper from reclaimed copper smelting fly ash, which comprises the steps of placing the reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, adding electrolyte into the electrolytic cell in proportion, carrying out electrolytic reaction on the reclaimed copper smelting fly ash in the electrolytic cell under the stirring state, and collecting a cathode product after the electrolytic reaction is finished, thus obtaining a copper product, such as copper foil or copper powder. The invention relates to a method for recovering copper from reclaimed copper smelting fly ash, wherein electrolyte comprises NH 3 ·H 2 O、NH 4 Cl and Cu 2+ Adding NH into the electrolyte 3 ·H 2 O、NH 4 Cl not only provides the ligand NH 3 Is favorable for the formation of copper ammonia complex, can also be used as a buffer solution,the electrolyte can be kept in a certain pH range, and the formation of a copper ammonia complex is further facilitated, so that the recovery efficiency of copper can be improved. On the other hand, the method for recovering copper from reclaimed copper smelting fly ash can simultaneously carry out leaching and electrodeposition of copper in reclaimed copper smelting fly ash in the same device, and realize the recovery of copper from reclaimed copper smelting fly ash in one step. The method for recovering copper from reclaimed copper smelting fly ash solves the technical problems of complex process, long consumed time and high energy consumption of the method for recovering copper from reclaimed copper smelting fly ash in the prior art.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The method for recovering copper from reclaimed copper smelting fly ash according to the present invention will be described in detail with reference to examples 1 to 15 and comparative examples 1 to 6.
Example 1
(1) Weighing 5kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 1mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 10mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 85.22%, and the current efficiency is 20.48%.
Example 2
(1) Weighing 5kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 1.0mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 15mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 88.34 percent, and the current efficiency is 22.18 percent.
Example 3
(1) Weighing 5kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 1.0mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 91.15%, and the current efficiency is 24.27%.
Example 4
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 1.0mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 95.11%, and the current efficiency is 12.37%.
Example 5
(1) Weighing 4kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 1.0mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 92.78%, and the current efficiency is 24.07%.
Example 6
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 0.3mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 93.74%, and the current efficiency is 4.53%.
Example 7
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 96.22%, and the current efficiency is 28.74%.
Example 8
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.8mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 96.68 percent, and the current efficiency is 32.89 percent.
Example 9
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 5g/L Cu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 96.68 percent, and the current efficiency is 38.02 percent.
Example 10
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 10g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 97.00 percent, and the current efficiency is 63.86 percent.
Example 11
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 20g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 97.93%, and the current efficiency is 98.72%.
Example 12
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 20g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 0.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 92.24%, and the current efficiency is 76.31%.
Example 13
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 20g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1 hour.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 94.51%, and the current efficiency is 88.82%.
Example 14
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.1mol/L NH 4 Cl and 20g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 96.04%, and the current efficiency is 89.27%.
Example 15
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.2mol/L NH 4 Cl and 20g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 96.35%, and the current efficiency is 92.96%.
Comparative example 1
(1) Weighing 5kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 1mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 30mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 77.91%, and the current efficiency is 30.60%.
Comparative example 2
(1) Weighing 1kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 1.0mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 95.13%, and the current efficiency is 6.66%.
Comparative example 3
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 3mol/L NH 3 ·H 2 O and 0.4mol/L NH 4 Cl, stirring with magnetic stirring water bath, switching on power supply, and controlling current density at 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 96.82%, and the current efficiency is 23.69%.
Comparative example 4
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 25g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 95.40%, and the current efficiency is 86.43%.
Comparative example 5
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 20g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 3 hours.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 97.78%, and the current efficiency is 77.16%.
Comparative example 6
(1) Weighing 2kg of dried reclaimed copper smelting fly ash, placing the weighed reclaimed copper smelting fly ash into an anode chamber of an electrolytic cell, and selecting a DSA plate and a titanium plate as an anode plate and a cathode plate of the electrolytic cell respectively. Adding 40L of prepared electrolyte into an electrolytic cell, wherein the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、1.0mol/L NH 4 Cl and 20g/LCu 2+ (Cu 2+ From CuSO 4 ·5H 2 O), stirring by a magnetic stirring water bath, switching on a power supply, and controlling the current density to be 18mA/cm 2 And electrolyzing for 1.5 h.
(2) After the electrolytic reaction is finished, a cathode product can be obtained from the cathode plate, and is washed by deionized water, dried, collected and weighed; and (4) washing the anode slag by using deionized water, drying, collecting and weighing, and collecting and storing the electrolyte.
(3) And (3) completely digesting the dried cathode product and the dried anode slag, measuring digestion solutions of the cathode product and the anode slag and the concentration of copper in the electrolyte, and calculating to obtain: the recovery rate of Cu in the reclaimed copper smelting fly ash is 95.26%, and the current efficiency is 86.14%.
The following conclusions can be obtained by analyzing the above examples 1 to 15 and comparative examples 1 to 6:
(1) analysis of examples 1 to 3 and comparative example 1 revealed that: the current density is 10-18mA/cm 2 When the range is increased, the recovery rate and the current efficiency of Cu are gradually increased; when the current density increased to 30mA/cm 2 However, the recovery rate of Cu is remarkably decreased although the current efficiency is increased, which indicates that the anode side reaction is increased when the current density is high, and the leaching of copper is not facilitated. Therefore, the method for recovering copper from reclaimed copper smelting fly ash has the current density not greater than 30mA/cm 2 Preferably, the current density is 18mA/cm 2 。
(2) Analysis of examples 3 to 5 and comparative example 2 revealed that: when the solid-liquid ratio (the content of reclaimed copper smelting fly ash in the electrolyte) is changed within the range of 50-125g/L, the recovery rate of Cu is reduced along with the increase of the solid-liquid ratio, and the current efficiency is increased along with the increase of the solid-liquid ratio; when the solid-liquid ratio is reduced to 25g/L, the recovery rate of Cu is increased, but the current efficiency is obviously reduced, which shows that when the solid-liquid ratio is smaller, less copper enters the electrolyte, and the deposition at the cathode is not facilitated. Therefore, in the method for recovering copper from reclaimed copper smelting fly ash, the solid-to-liquid ratio cannot be less than 25g/L, and the solid-to-liquid ratio is preferably 50 g/L.
(3) Analysis of examples 4, 6 to 8 and comparative example 3 revealed that: NH 3 ·H 2 When the O concentration is increased within the range of 0.3-2.8mol/L, the recovery rate and the current efficiency of Cu are gradually increased; when NH is generated 3 ·H 2 When the O concentration is increased to 3mol/L, the recovery rate of Cu is not obviously increased, but the current efficiency is obviously reduced, which indicates that NH 3 ·H 2 When the concentration of O is larger, the cathode generates side reaction to oxidize the cathode copper and the oxide is NH 3 ·H 2 O dissolves, resulting in a decrease in current efficiency. Thus, the present invention is a process for recovering copper, NH, from reclaimed copper smelting fly ash 3 ·H 2 O concentration not greater than 3mol/L, preferably NH 3 ·H 2 The O concentration is 2 mol/L.
(4) Analysis of examples 7, 9 to 11 and comparative example 4 revealed that: adding Cu to electrolyte 2+ (Cu 2+ From CuSO 4 ·5H 2 O), current efficiency can be significantly improved. Cu 2+ When the concentration is increased within the range of 5-20g/L, the recovery rate and the current efficiency of Cu are gradually increased; when Cu 2+ When the concentration is increased to 25g/L, the recovery rate of Cu is reduced, the current efficiency is obviously reduced, and the indication of Cu is that 2+ When the concentration is higher, the cathode Cu can generate a reverse dissolution phenomenon, which is not beneficial to leaching of copper. Thus, the present invention is a method for recovering copper from reclaimed copper smelting fly ash, Cu 2+ The concentration of Cu is not more than 25g/L, preferably Cu 2+ The concentration was 20 g/L.
(5) Analysis of examples 11 to 13 and comparative example 5 revealed that: when the electrolysis time is increased within the range of 0.5-1.5h, the recovery rate and the current efficiency of Cu are gradually increased; when the electrolysis time is increased to 3h, the recovery rate of Cu is reduced, the current efficiency is obviously reduced, which shows that the electrolysis time is longer, and the concentration of copper ammonia ions in the cathode area is continuously reduced, so that the recovery rate of Cu and the current efficiency are reduced. Therefore, in the method for recovering copper from reclaimed copper smelting fly ash, the electrolysis time cannot be more than 3h, and the preferred electrolysis time is 1.5 h.
(6) Analysis of examples 11, 14, 15 and comparative example 6 revealed that: NH 4 When the Cl concentration is increased within the range of 0.1-0.4mol/L, the recovery rate and the current efficiency of Cu are gradually increased; when NH is generated 4 When the Cl concentration is increased to 1mol/L, the recovery rate of Cu is reduced, the current efficiency is obviously reduced, and the NH is shown 4 When the Cl concentration is high, side reactions occur in the anode. Thus, the present invention is a process for recovering copper, NH, from reclaimed copper smelting fly ash 4 Cl concentration not greater than 1mol/L, preferably NH 4 The Cl concentration was 0.4 mol/L.
(7) The invention relates to a method for recovering copper from reclaimed copper smelting fly ash, which is characterized in that in an electrolytic tank with a DSA plate as an anode plate and a titanium plate as a cathode plate, the solid-to-liquid ratio is 50g/L, and the electrolyte comprises the following components: 2.0mol/L NH 3 ·H 2 O、0.4mol/L NH 4 Cl and 20g/L Cu 2+ (Cu 2+ From CuSO 4 ·5H 2 O) and the current density is 18mA/cm 2 And under the condition of electrolysis for 1.5h, the recovery rate of Cu in the reclaimed copper smelting fly ash reaches 97.93%, and the current efficiency is 98.72%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. A method for recovering copper from reclaimed copper smelting fly ash is characterized by comprising the following steps:
placing the reclaimed copper smelting fly ash in an anode chamber of an electrolytic bath;
proportionally adding an electrolyte into the electrolytic cell, wherein the electrolyte is an alkaline electrolyte and comprises NH 3 ·H 2 O、NH 4 Cl and Cu 2+ ；
And (3) carrying out electrolytic reaction on the reclaimed copper smelting fly ash in an electrolytic bath in a stirring state, and collecting a cathode product after the electrolytic reaction is finished.
2. The method of recovering copper from reclaimed copper smelting fly ash of claim 1, wherein the NH in the electrolyte 3 ·H 2 The concentration of O is 0.3-2.8 mol/L.
3. The method of recovering copper from reclaimed copper smelting fly ash of claim 1, wherein the NH in the electrolyte 4 The concentration of Cl is 0.1-0.4 mol/L.
4. The method of recovering copper from reclaimed copper smelting fly ash of claim 1, wherein the Cu in the electrolyte 2+ From CuSO 4 ·5H 2 O。
5. The method of recovering copper from reclaimed copper smelting fly ash of claim 4, wherein the Cu in the electrolyte 2+ The concentration of (A) is 5-20 g/L.
6. The method for recovering copper from reclaimed copper smelting fly ash according to any one of claims 1 to 5, wherein the electrolyte is added in an amount at least sufficient to: the content of the reclaimed copper smelting fly ash in the electrolyte is 50-125 g/L.
7. The method for recovering copper from reclaimed copper smelting fly ash according to any one of claims 1 to 5, wherein the reclaimed copper smelting fly ash is subjected to an electrolysis reaction in an electrolysis cell at a current density of 10-18mA/cm 2 。
8. The method for recovering copper from reclaimed copper smelting fly ash according to any one of claims 1 to 5, wherein the electrolysis time for the electrolytic reaction of the reclaimed copper smelting fly ash in the electrolysis cell is 0.5-1.5 h.
9. The method for recovering copper from reclaimed copper smelting fly ash of claim 1 wherein the anode and cathode compartments of the electrolytic cell are separated by a double layer of acid and alkali resistant filter cloth.
10. The method of recovering copper from reclaimed copper smelting fly ash according to claim 1, wherein the anode plates of the electrolytic cell are DSA electrode plates or graphite electrode plates; the cathode plate of the electrolytic bath is a DSA electrode plate, a titanium plate or a copper plate.
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