CN111304694A - Method for directly electrolyzing scrap copper - Google Patents
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- CN111304694A CN111304694A CN201911106934.2A CN201911106934A CN111304694A CN 111304694 A CN111304694 A CN 111304694A CN 201911106934 A CN201911106934 A CN 201911106934A CN 111304694 A CN111304694 A CN 111304694A
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- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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Abstract
The invention discloses a method for directly electrolyzing scrap copper, which comprises the following steps: (1) adopting a non-conductive anode frame, wherein the anode frame takes a copper sheet as a conductive material, waste copper is loaded on two sides of the copper sheet, the non-conductive anode frame is supported on a conductive rod, a permanent stainless steel cathode plate is used as a cathode, and an acidic copper sulfate solution is used as an electrolyte; (2) adding gelatin, protein powder, thiourea, acitretin and an additive A into an electrolytic cell to serve as an electrolytic additive; (3) and electrolyzing, continuously dissolving the scrap copper in the non-conductive anode frame, and depositing on a stainless steel cathode to obtain the standard electrolytic copper of the A-level copper. The invention has the advantages that through the optimization improvement of the electrolytic additive and the control of the filtering quality of the electrolyte in the electrolytic process, and the adoption of the mode of double jet flow cooperating with bottom liquid inlet, the concentration polarization is eliminated, and the voltage of the electrolytic tank and the impurity content of electrolytic copper are greatly reduced, thereby improving the quality of the electrolytic copper product and improving the economic added value of the electrolytic product.
Description
Technical Field
The invention relates to the field of recycling of renewable resources, in particular to a method for directly electrolyzing scrap copper.
Background
The conventional method for producing the regenerated copper is to firstly smelt the scrap copper by a fire method to cast an anode plate and then to electrolyze and refine the scrap copper to form electrolytic copper. The pyrometallurgical smelting of scrap copper generally adopts a two-stage process, i.e. reduction smelting in a blast furnace or blowing in a converter is carried out, and then anode copper is refined in a reverberatory furnace. Numerous enterprises adopt simple production processes, such as cupola furnaces, small reverberatory furnaces and the like, to smelt and recover scrap copper, and most of the obtained products are blister copper (commonly called black copper); due to the backward technical equipment, the energy consumption is high, the resource recovery and utilization rate is low, and the environment is seriously polluted. It can be seen that the pyrometallurgical treatment of scrap copper has the following disadvantages: (1) the process flow is long, and smelting and refining processes are required; (2) the energy consumption is high and the cost is high; (3) the metal recovery rate is low, intermediate products such as smoke dust, metal-rich slag and the like can be generated in the pyrogenic process, and a small part of copper can be taken away by the intermediate products; (4) the environmental pollution is large and the labor condition is poor.
There is currently no large-scale production practice for direct electrolysis of scrap copper. The scrap copper direct electrolysis process can be classified into a frame anode electrolysis method and a cold-pressed anode electrolysis method according to the form of the anode used. The frame type anode electrolysis method has no essential difference from the traditional electrolysis, but the scrap copper is generally in fragment, fragment or mud-ash shape after being pretreated, an anode frame device and the scrap copper fragments to be refined filled in the anode frame device are required to be utilized to form a special frame type anode which is arranged in an electrolytic bath for electrolysis, the frame type anode can be divided into a conductive type anode frame and a non-conductive type anode frame according to the conductive condition of the frame type anode, wherein the conductive type anode frame is mostly made of stainless steel, titanium materials and the like, the manufacturing cost is high, the use cost is high, the popularization and the use are not facilitated, the non-conductive type anode frame is processed by plates such as plastics and the like, the general non-conductive type anode frame only plays a role in filling and supporting the scrap copper fragments of the anode, the conductivity is poor, the energy consumption of the electrolysis is high, and the purity of the; the cold-pressed anode electrolysis method is characterized by that instead of fire-refining and casting formed copper anode, the waste copper particles are made into anode copper integral polar plate by using forming press, and placed in acid-resisting microporous polyester fabric bag, then suspended in electrolytic bath to make electrolysis.
At present, the additives commonly used in copper electrolysis comprise gelatin, thiourea, avilamycin and the like. The gelatin plays two roles in the electrolytic process, namely, the gelatin is adsorbed on a high current density area on the surface of a cathode, the polarization value of the cathode is increased, and the prominent growth of crystals is inhibited; and secondly, the surface tension of the electrolyte is reduced, the wetting agent is used for preventing the copper cathode from having long pores, the smooth cathode copper is ensured to be obtained, and the voltage of the electrolytic bath is increased due to the excessive addition of the gelatin with larger molecular weight. The thiourea mainly plays roles of promoting cathode polarization and refining crystal grains in the electrolytic process. However, too high a concentration of thiourea reacts at the cathode to form copper sulfide, which roughens the surface of the deposit, produces streaks, embrittles the copper deposit and increases the sulfur content. The sulfur in thiourea is about 52-59% into the anode mud, 5-10% into the electrolytic copper, and the rest remains in the electrolyte as hydrolysis product. Therefore, excessive thiourea is added and accumulated in the electrolytic process, and may become a main factor of high impurities such as cathode copper sulfur and the like. The electrolytic process should pay attention to control the dosage of the electrolytic additives, particularly gelatin and thiourea, and seek the synergistic use of the gelatin and the low molecular weight gelatin to reduce the cell voltage of the electrolytic cell, and use the sulfur-free additive to replace or partially replace thiourea to reduce the content of impurities such as sulfur in electrolytic copper.
The floating anode mud in the copper electrolysis process is generated in the electrolysis process due to the fact that the content of As, Sb and Bi in the electrolyte is increased, and SbAsO4 and BiAsO4 are fine floccules. The floating anode mud is fine and not easy to settle, the floating anode mud is difficult to be removed by a filtering system, the existence of the floating anode mud directly influences the purity of the electrolyte, the content of cathode copper impurities is over standard due to capillary pore adsorption among cathode sediment crystals in the electrolytic process, and meanwhile, the floating anode mud is adhered to the surface of a cathode to become a crystallization center to finally increase anode mud particles on the surface of the cathode and influence the physical appearance quality of cathode copper. The electrolyte filtration should be strengthened in the electrolysis process, and the electrolyte quality is guaranteed in strict control of the suspended matter content in the liquid inlet and the overflow port of the electrolytic cell.
A direct electrolytic method for scrap copper, which uses a drilled plastic plate frame or a cast lead frame as an anode frame and a middle lead plate hung as a conductor, reported by Xiaoyangmen, Lanzhou non-ferrous metal smeltery in 'direct electrolytic refining of scrap copper' (non-ferrous metal (smelting part), 1975), wherein when the area of a central hole in an anode of the plastic plate frame is 30%, the cell voltage is 0.665V, the electrolytic copper grade is 99.953%, the current efficiency is 96.32%, and when the area of the central hole in the anode of the cast lead frame is 27%, the cell voltage is 0.55V, the electrolytic copper grade is 99.957%, and the current efficiency is 96.43%; because only one surface of the plastic plate frame and the cast lead frame is provided with holes and the lead plate is used as a conductor, the conductivity is poor, and when the method is used for directly electrolyzing the scrap copper, the cell voltage is high and the current efficiency is low. In the net rack combined anode basket device for direct electrolysis of impure copper, CN2732762 has proposed a net rack combined anode basket device for direct electrolysis of impure copper, which comprises a basket rack made of insulating laths, a corresponding polyester bag lined inside, insulating ropes woven on the basket rack, and an inner conductive electrode plate and an outer conductive electrode plate arranged on the net basket and communicated with the positive electrode of a power supply. The anode frame is adopted to directly electrolyze scrap copper mainly comprising a waste electric wire, a conventional electrolytic system and technical conditions are applied, the anode electric efficiency is more than 98%, the produced cathode copper meets the GB/T-467-; the test for preparing copper powder by direct electrolysis of red impure copper reported by the minister of science and technology, et al, in the preparation of copper powder by direct electrolysis of impure copper (hydrometallurgy, 1999-01), the anode adopts an epoxy glass fiber reinforced plastic frame, small holes are drilled around the anode, red impure copper and an anode conductive copper plate are placed inside, and the mass fraction of copper in the prepared copper powder is more than 99.5 percent; because neither of the two methods optimizes the filtering quality of the electrolytic additive and the electrolyte, the purity of the obtained electrolytic copper product is low.
Disclosure of Invention
The invention aims to solve the technical problems that the existing scrap copper electrolysis additive containing gelatin can cause the voltage of an electrolytic bath to rise, and containing thiourea can introduce sulfur impurities into electrolytic copper, thereby providing a method for directly electrolyzing scrap copper.
According to the invention, researches show that the additive can cause the precipitation of rough and impurity-mixed cathode copper, reduce the product grade and influence the tensile strength and the conductivity of electrolytic copper, whether the additive is excessive or insufficient, so that the reasonable use of the additive in the production process is very important. When the glue is excessive, the surface of the electrolytic copper is crystallized and rough; when the adhesive is insufficient, the electrolytic copper is soft, when the thiourea is excessive, the surface is longitudinally thick wick-shaped stripes and the sulfur content is too high, when the thiourea is insufficient, the crystallization compactness of the cathode surface is poor, and only when the additive is proper, the electrolytic copper is compact in crystallization, smooth and flat in surface and moderate in toughness. The determination of the additive ratio is determined according to various control process parameters of an electrolytic system per se, electrolyte liquidity and other data, which is one of the innovation points of the invention, namely a method for directly electrolyzing the scrap copper, wherein the additive component ratio and the electrolytic process condition are better matched.
The technical scheme of the invention is as follows: the direct scrap copper electrolyzing process includes the following steps: (1) adopting a non-conductive anode frame, wherein the anode frame takes a copper sheet as a conductive material, waste copper is loaded on two sides of the copper sheet, the non-conductive anode frame is supported on a conductive rod, a permanent stainless steel cathode plate is used as a cathode, and an acidic copper sulfate solution is used as an electrolyte; (2) adding a certain amount of gelatin, protein powder, thiourea, acitretin and an additive A into an electrolytic cell to serve as an electrolytic additive, wherein the additive A is one or a combination of more of polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyoxyethylene phenyl ether, polyoxyethylene naphthyl ether and the like; (3) at a current density of 180-2(ii) a The electrolysis temperature is 45-65 ℃; the same polar distance is 12 cm; the circulation speed of the electrolyte per unit cathode area is 25-50L/min2The electrolytic copper is electrolyzed, the suspended substance content of the liquid inlet and the overflow port of the electrolytic tank is controlled to be 5-10ppm and 10-15ppm respectively in the electrolytic process through filtration, scrap copper in the non-conductive anode frame is continuously dissolved, and electrolytic copper reaching the GB/T467-2010A level copper standard is obtained through deposition on a stainless steel cathode.
The improvement of the above scheme is that the electrolyte in step (2) enters the electrolytic cell through a first liquid inlet pipe, a second liquid inlet pipe and a third liquid inlet pipe, the liquid outlet of the first liquid inlet pipe is just opposite to the anode frame, the liquid outlets of the second liquid inlet pipe are two and respectively face to the two sides of the cathode plate, the third liquid inlet pipe is distributed at the bottom of the electrolytic cell, and the liquid outlets are uniformly arranged on the third liquid inlet pipe.
In the scheme, the aperture ratio of the non-conductive anode frame is 15% -30%.
The components of the electrolyte in the scheme are Cu40-55g/L, H2SO4180-200g/L, As2-8g/L, Sb0.2-0.5g/L, Bi0.2-0.5g/L and Cl0.05-0.1 g/L.
In the scheme, the dosage of the gelatin is 120-120 g/tCu, the dosage of the protein powder is 10-30g/tCu, the dosage of the thiourea is 80-120g/tCu, the dosage of the additive A is 20-30g/tCu, and the general dosage of the abamectin is 10-20 g/tCu.
The molecular weight of the protein powder in the scheme is 2000-4000.
The invention has the advantages that through the optimization improvement of the electrolytic additive and the control of the filtering quality of the electrolyte in the electrolytic process, and the adoption of the mode of double jet flow cooperating with bottom liquid inlet, the concentration polarization is eliminated, and the voltage of the electrolytic tank and the impurity content of electrolytic copper are greatly reduced, thereby improving the quality of the electrolytic copper product and improving the economic added value of the electrolytic product.
Drawings
FIG. 1 is a schematic view of an electrolytic cell of the present invention;
in the figure, 1, an anode frame, 2, a cathode plate, 3, a first liquid inlet pipe, 4, a second liquid inlet pipe, 5 and a third liquid inlet pipe.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below by combining the embodiment. 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 based on the embodiments in the present invention, without any inventive work, will be apparent to those skilled in the art from the following description.
Example 1
Scrap copper raw material composition (%): cu 95.71, Zn 0.079, Sn 0.00019, Sb 0.00016, Bi 0.0001, Pb0.00019 and As 0.00071. The anode frame 1 is a non-conductive anode frame, the copper sheet is a conductive material, and the opening rate of the conductive anode frame is 30%; electrolyte components: cu2+48g/L、H2SO4 190g/L、As 8g/L、Sb 0.3g/L、Bi 0.3g/L、Cl-0.05 g/L; current density 260A/m2(ii) a The electrolysis temperature is 60 ℃; the same polar distance is 12 cm; circulation speed of electrolyte per unit cathode area is 50L/min.m2(ii) a Electrolytic additive: the dosage of gelatin is 120g/tCu, the dosage of protein powder is 10g/tCu, the dosage of thiourea is 100g/tCu, the dosage of polyethylene glycol of additive A is 20g/tCu, and the dosage of avermectin is 15 g/tCu; the content of the suspended matters in the liquid inlet of the electrolytic cell is less than 5ppm and the content of the suspended matters in the overflow port is less than 10ppm in the electrolytic process. And electrolyzing under the conditions, continuously dissolving scrap copper in the anode frame, and depositing on a stainless steel cathode to obtain electrolytic copper reaching the GB/T467-2010A-grade copper (Cu-CATH-1) standard. The technological indexes under the electrolysis condition are as follows: cell voltage 0.45V, cathode electrical efficiency: 97.32%, DC power consumption: 389.88 kW.h/tCu. Cathode copper impurity element content (%): se0.0001, Te 0.00015, Bi 0.00014, Cr 0.00016, Mn 0.00001, Sb 0.00021, Cd0.00005, As0.00014, P0.0001, Pb 0.00029, S0.00148, Sn 0.0001, Ni 0.00029, Fe 0.00013, Si0.00039, Zn 0.00008, Co 0.00009 and Ag 0.00139.
Example 2
Scrap copper raw material composition (%): cu 95.34, Zn 0.058, Sn 0.27, Sb 0.0041, Bi 0.022, Pb 0.0021 and As 0.0031. The anode frame is a non-conductive anode frame, the copper sheet is a conductive material, and the opening rate of the conductive anode frame is 15%; electrolyte components: cu2+40g/L、H2SO4 180g/L、As 2g/L、Sb 0.2g/L、Bi 0.2g/L、Cl-0.08 g/L; current density 200A/m 2; the electrolysis temperature is 45 ℃; the same polar distance is 12 cm; the circulation speed of the unit cathode area of the electrolyte is 25L/min. m 2; electrolytic additive: the dosage of gelatin is 100g/tCu, the dosage of protein powder is 30g/tCu, the dosage of thiourea is 80g/tCu, the dosage of additive A polyvinyl alcohol is 30g/tCu, and the general dosage of avermectin is 10 g/tCu; the content of the suspended matters in the liquid inlet of the electrolytic cell is less than 10ppm and the content of the suspended matters in the overflow port is less than 15ppm in the electrolytic process. And electrolyzing under the conditions, continuously dissolving scrap copper in the anode frame, and depositing on a stainless steel cathode to obtain electrolytic copper reaching the GB/T467-2010A-grade copper (Cu-CATH-1) standard. The technological indexes under the electrolysis condition are as follows: the cell voltage is 0.42V, the cathode efficiency is 97.65 percent, and the direct current power consumption is 362.62 kW.h/tCu. Cathode copper impuritiesElement content (%): se0.00005, Te 0.0001, Bi 0.00005, Cr 0.0001, Mn0.00005, Sb 0.00011, Cd0.00005, As0.00005, P0.00005, Pb0.0001, S0.00046, Sn 0.00005, Ni 0.00006, Fe0.0001, Si0.0001, Zn 0.00014, Co 0.00005 and Ag 0.00118.
Example 3
Scrap copper raw material composition (%): cu 96.58, Zn 0.096, Sn 0.12, Sb 0.0087, Bi 0.015, Pb 0.0095 and As 0.0086. The anode frame is a non-conductive anode frame, the copper sheet is a conductive material, and the opening rate of the conductive anode frame is 25%; electrolyte components: cu2+55g/L、H2SO4 200g/L、As 5g/L、Sb 0.5g/L、Bi 0.5g/L、Cl-0.1 g/L; current density 220A/m 2; the electrolysis temperature is 65 ℃; the same polar distance is 12 cm; the circulation speed of the unit cathode area of the electrolyte is 35L/min. m 2; electrolytic additive: the dosage of gelatin is 110g/tCu, the dosage of protein powder is 20g/tCu, the dosage of thiourea is 120g/tCu, the dosage of additive A polyoxyethylene naphthyl ether is 25g/tCu, and the general dosage of avermectin is 20 g/tCu; the content of the suspended matters in the liquid inlet of the electrolytic cell is less than 8ppm and the content of the suspended matters in the overflow port is less than 12ppm in the electrolytic process. And electrolyzing under the conditions, wherein the scrap copper in the anode frame continuously dissolves copper and the stainless steel is deposited at the cathode to obtain electrolytic copper reaching the GB/T467-2010A-level copper (Cu-CATH-1) standard. The technological indexes under the electrolysis condition are as follows: the cell voltage is 0.43V, the cathode efficiency is 97.48 percent, and the direct current power consumption is 369.74 kW.h/tCu. Cathode copper impurity element content (%): se0.00005, Te 0.0001, Bi 0.00005, Cr 0.0001, Mn0.00005, Sb 0.0001, Cd0.00005, As0.00005, P0.00005, Pb0.0001, S0.00044, Sn 0.00005, Ni 0.00005, Fe0.0001, Si0.00012, Zn 0.0001, Co 0.00005, Ag 0.00101.
Example 4
Scrap copper raw material composition (%): cu 95.34, Zn 0.058, Sn 0.27, Sb 0.0041, Bi 0.022, Pb 0.0021 and As 0.0031. The anode frame is a non-conductive anode frame, the copper sheet is a conductive material, and the opening rate of the conductive anode frame is 25%; electrolyte components: cu2+50g/L、H2SO4 185g/L、As 3g/L、Sb 0.4g/L、Bi 0.3g/L、Cl-0.06 g/L; the current density is 180A/m 2; the electrolysis temperature is 55 ℃; the same polar distance is 12 cm; circulation rate per unit area of cathode of electrolyte 40L/min.m 2; electrolytic additive: the dosage of gelatin is 120g/tCu, the dosage of protein powder is 20g/tCu, the dosage of thiourea is 80g/tCu, the dosage of polyvinyl alcohol of additive A is 20g/tCu, the dosage of polyoxyethylene phenyl ether is 10g/tCu, and the total dosage of avermectin is 15 g/tCu; the content of the suspended matters in the liquid inlet of the electrolytic cell is less than 8ppm and the content of the suspended matters in the overflow port is less than 15ppm in the electrolytic process. And electrolyzing under the conditions, continuously dissolving scrap copper in the anode frame, and depositing on a stainless steel cathode to obtain electrolytic copper reaching the GB/T467-2010A-grade copper (Cu-CATH-1) standard. The technological indexes under the electrolysis condition are as follows: the cell voltage is 0.41V, the cathode efficiency is 98.02 percent, and the direct current power consumption is 358.37 kW.h/tCu. Cathode copper impurity element content (%): se0.00005, Te 0.0001, Bi 0.00003, Cr 0.0001, Mn0.00005, Sb 0.00008, Cd0.00005, As0.00005, P0.00005, Pb0.0001, S0.00051, Sn 0.00005, Ni 0.00005, Fe0.0001, Si0.0001, Zn 0.00008, Co 0.00005 and Ag 0.00095.
The invention directly electrolyzes the scrap copper, avoids the problem of high energy consumption and large pollution of the conventional pyrogenic process, and realizes the short-flow green utilization of the regenerated copper. The non-conductive anode frame is utilized, the copper sheet is taken as a conductive material, the manufacturing cost is low, the processing is convenient, and the direct current unit consumption in the electrolytic process is low; the albumen powder and the gelatin of low molecular weight use in coordination, further reduce electrolysis trough voltage, adopt the partial thiourea that replaces of novel additive, through the suspended solid content of microfiltration strict control electrolysis process electrolysis trough overflow mouth, reduce electrolytic copper's sulphur and other impurity content by a wide margin to promote electrolytic copper product quality.
As shown in figure 1, the liquid inlet mode of the electrolyte is changed into a distributed liquid inlet system, a first liquid inlet pipe 3 and a second liquid inlet pipe 4 can be distributed on the side wall of the electrolytic cell, liquid outlets are respectively opposite to an anode frame 1 and a cathode plate 2, wherein the liquid outlet of the first liquid inlet pipe is opposite to the anode frame, each anode frame corresponds to an opening, the liquid outlet of the second liquid inlet pipe inclines by 45 degrees to the cathode plate, and each cathode plate corresponds to two openings, so that the jet flow formed by the first liquid inlet pipe, the second liquid inlet pipe and the third liquid inlet pipe can promote the uniform distribution of the electrolyte, the concentration polarization is eliminated to a certain extent, and the voltage of the electrolytic cell is reduced.
Claims (6)
1. A method for directly electrolyzing scrap copper is characterized by comprising the following steps: it comprises the following steps: (1) adopting a non-conductive anode frame, wherein the anode frame takes a copper sheet as a conductive material, waste copper is loaded on two sides of the copper sheet, the non-conductive anode frame is supported on a conductive rod, a permanent stainless steel cathode plate is used as a cathode, and an acidic copper sulfate solution is used as an electrolyte; (2) adding a certain amount of gelatin, protein powder, thiourea, acitretin and an additive A into an electrolytic cell to serve as an electrolytic additive, wherein the additive A is one or a combination of more of polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyoxyethylene phenyl ether, polyoxyethylene naphthyl ether and the like; (3) at a current density of 180-2(ii) a The electrolysis temperature is 45-65 ℃; the same polar distance is 12 cm; the circulation speed of the electrolyte per unit cathode area is 25-50L/min2The electrolytic copper is electrolyzed, the suspended substance content of the liquid inlet and the overflow port of the electrolytic tank is controlled to be 5-10ppm and 10-15ppm respectively in the electrolytic process through filtration, scrap copper in the non-conductive anode frame is continuously dissolved, and electrolytic copper reaching the GB/T467-2010A level copper standard is obtained through deposition on a stainless steel cathode.
2. The method for direct electrolysis of scrap copper according to claim 1, wherein: electrolyte in step (2) gets into the electrolysis trough through first feed liquor pipe (3), second feed liquor pipe (4) and third feed liquor pipe (5), the liquid outlet of first feed liquor pipe is just to the positive pole frame, the liquid outlet of second feed liquor pipe has two and respectively moves towards the both sides at the negative plate, the third feed liquor pipe distributes in the electrolysis trough bottom, has evenly seted up the liquid outlet on it.
3. The method for direct electrolysis of scrap copper according to claim 1, wherein: the aperture ratio of the non-conductive anode frame is 15% -30%.
4. The method for direct electrolysis of scrap copper according to claim 1, wherein: the electrolyte comprises Cu40-55g/L and H2SO4180-200g/L，As2-8g/L，Sb0.2-0.5g/L，Bi0.2-0.5g/L，Cl0.05-0.1 g/L。
5. The method for direct electrolysis of scrap copper according to claim 1, wherein: the dosage of the gelatin is 100-120g/tCu, the dosage of the protein powder is 10-30g/tCu, the dosage of the thiourea is 80-120g/tCu, the dosage of the additive A is 20-30g/tCu, and the general dosage of the abamectin is 10-20 g/tCu.
6. The method for direct electrolysis of scrap copper according to claim 1, wherein: the molecular weight of the protein powder is 2000-4000.
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Cited By (2)
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| CN111826684A (en) * | 2020-07-31 | 2020-10-27 | 中华全国供销合作总社天津再生资源研究所 | Electrolytic tank and electrolytic system for producing copper powder by using scrap copper material |
| CN113235133A (en) * | 2021-05-21 | 2021-08-10 | 中国恩菲工程技术有限公司 | Copper electrolyte additive, copper electrolytic refining method and cathode copper |
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