CN108486606B - Method for recycling copper, selenium and tellurium in cyclone electrolysis step mode and product thereof - Google Patents
Method for recycling copper, selenium and tellurium in cyclone electrolysis step mode and product thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode and a product thereof. The method comprises the following steps of: placing the solution containing copper, selenium and tellurium ions and hydrochloric acid or sulfuric acid in a cyclone electrolytic reaction device for electrochemical reaction, sequentially adjusting the potential, and performing cyclone electrolytic reaction once when adjusting the potential each time to sequentially obtain solid mixtures of tellurium, copper and selenium; separation: and washing and drying the solid mixture to obtain the simple substances or oxides of copper, selenium and tellurium in sequence. The cathode adopted by the invention comprises the titanium sheet subjected to oxidation treatment, the surface molecules of the titanium sheet are in a net-shaped laminated structure, the specific surface area of the electrode is increased, the whole structure is compact and uniform, the titanium sheet can be better contacted with a solution compared with a stainless steel sheet used in the traditional cyclone electrolysis, the adsorption capacity is greatly improved, the purity of the obtained product is greatly improved, and the yield is also greatly improved.
Description
Technical Field
The invention belongs to the technical field of rare (non) metal recovery and pollutant treatment, and particularly relates to a method for recovering copper, selenium and tellurium in a cyclone electrolysis step mode and a product thereof.
Background
Copper is a non-ferrous metal having a very close relationship with humans, and is widely used in the fields of electricity, light industry, machine manufacturing, building industry, national defense industry and the like. Copper is a "green" metal, mainly because it has a low melting point and is easily remelted and remelted, so it is rather cheap to recycle. However, in China, a large amount of waste contains a large amount of copper, and how to recover the copper metal with the greatest effect is also a difficult problem.
Selenium is widely applied to the industrial fields of glass, ceramics, dyes, rubber, petrochemical industry, metallurgy, electroplating and the like, in particular to the high-tech industrial departments, such as the manufacture of semiconductor devices, photoelectric devices, selenium solar cells, laser devices, laser and infrared light guide materials and the like. With the continuous development of the scientific and technological level, people continuously and deeply know and research selenium. The important position of selenium in national economy is more and more prominent, the application of selenium in industrial and agricultural production and human health industry is more and more extensive, and the market demand is increased or not reduced. China is also one of the countries that rely on imported selenium products for a long time.
80% of the tellurium consumption is applied in the metallurgical industry: a small amount of tellurium is added into the steel and copper alloy, so that the cutting processing performance of the steel and copper alloy can be improved, and the hardness of the steel and copper alloy can be increased; tellurium is used as a carbide stabilizer in the white cast iron, so that the surface is firm and wear-resistant; a small amount of tellurium is added into the lead, so that the wear resistance, corrosion resistance and strength of the material can be improved, and the material can be used as a sheath on a submarine cable; the addition of tellurium to lead increases the hardness of the lead and can be used to make the plates of batteries and to print types. Tellurium is also used as an additive to petroleum cracking catalysts and also as a catalyst for the production of ethylene glycol. The high-purity tellurium can also be used as an alloy component of a thermoelectric material, a tellurium compound bismuth telluride is a good refrigeration material, tellurium and a plurality of tellurides are semiconductor materials, and an ultra-pure tellurium single crystal is a novel infrared material.
Selenium and tellurium are present in large quantities in the industry in anode sludge for electrowinning of refined copper, but the separation of the individual components is complicated and the separation efficiency is low, which does not meet the desired separation requirements, so that there is a need for better ways and methods to utilize the raw materials more efficiently in as short a period of time as possible, with the double effect of economy and efficiency.
Therefore, there is a need in the art for an efficient and environmentally friendly process that results in improved utilization of the same raw material, reduced cost, increased yield, and increased economic benefits.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art and provides a method for recycling copper, selenium and tellurium in a cyclone electrolysis step.
In order to solve the technical problems, the invention provides the following technical scheme: a method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode comprises the following steps,
and (3) cyclone electrolytic reaction: placing the solution containing copper, selenium and tellurium ions and hydrochloric acid or sulfuric acid in a cyclone electrolytic reaction device for electrochemical reaction, sequentially adjusting the potential, and performing cyclone electrolytic reaction once when adjusting the potential each time to sequentially obtain solid mixtures of tellurium, copper and selenium;
separation: and washing and drying the solid mixture to obtain the simple substances or oxides of copper, selenium and tellurium in sequence.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: the solution containing copper ions, selenium ions and tellurium ions is characterized in that the concentration of the hydrochloric acid or the sulfuric acid is 1M-4M.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: the rotational flow electrolysis reaction device comprises a rotational flow electrolytic cell, a working electrode and a counter electrode, wherein the rotational flow electrolytic cell is a normal-pressure electrolytic cell.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: the working electrode comprises a titanium sheet or a 316L-shaped stainless steel sheet which is subjected to oxidation treatment and has a high specific surface area, and the counter electrode is a graphite electrode.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: the cyclone electrolysis reaction is carried out at the temperature of 25-140 ℃.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: and in the cyclone electrolysis reaction, the time for carrying out the reaction by adjusting the potential each time is 4-8 h.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: the voltage of the cyclone electrolytic reaction during the tellurium electrolytic reaction is-0.18V to-0.25V.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: the voltage of the spiral-flow electrolysis reaction is-0.38V to-0.42V when the copper electrolysis reaction is carried out.
As a preferred scheme of the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis cascade, the method comprises the following steps: the voltage of the spiral-flow electrolysis reaction is-0.48V to-0.50V when the selenium electrolysis reaction is carried out.
As another aspect of the present invention, the present invention overcomes the deficiencies in the prior art and provides copper, selenium and tellurium, wherein: the purity of the copper is more than 90%, the purity of the selenium is more than 89%, and the purity of the tellurium is more than 92%.
The invention has the beneficial effects that:
(1) the cathode used in the method for recycling copper, selenium and tellurium in a cyclone electrolysis step manner is a titanium sheet subjected to oxidation treatment, and the surface molecules of the titanium sheet are in a net-shaped laminated structure, so that the specific surface area of an electrode is increased, the whole structure is compact and uniform, the titanium sheet can be better contacted with a solution compared with a stainless steel sheet used in the traditional cyclone electrolysis, the adsorption capacity is greatly improved, the purity of the obtained product is greatly improved, and the yield is greatly improved.
(2) The method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis step mode adopts normal pressure operation, has low reaction temperature (the reaction temperature is only 25 ℃ at the lowest), and reduces the reaction temperature compared with the traditional process, thereby reducing the energy consumption.
(3) According to the method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode, impurities are not introduced into a system from a reflection medium, so that subsequent separation is facilitated; the concentration of the used acid is greatly reduced, and the acid consumption is reduced;
(4) the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis step mode does not add any auxiliary material, and compared with the traditional process, the method has the advantages that the sewage discharge amount can be reduced by 20-50 wt%;
(5) the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis step mode has the advantages of high automation degree of cyclone electrolysis reaction operation, reduction of labor input, convenience for mass production, capability of bringing about good economic benefits and social benefits and good application prospect.
(6) The method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode provided by the invention utilizes the cyclone electrolysis method to carry out step recycling, and the obtained product is nano-micro powder, has good plasticity for subsequent application and processing, and is convenient for subsequent use.
(7) The method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode, provided by the invention, has the advantages that copper salt, selenium salt and tellurium salt are comprehensively treated in the same solution, convenience is brought to later engineering practice, the consumption of raw materials is reduced, and the reaction time and the consumption of equipment are reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
fig. 1 is a flow chart of a treatment process for step-wise recovery of copper, selenium and tellurium by cyclone electrolysis according to an embodiment of the present invention.
Fig. 2 is a graph of copper extraction over time as provided in example 1.
Fig. 3 is a graph of selenium extraction over time as provided in example 1.
Fig. 4 is a graph of the extraction rate of tellurium over time provided in example 1.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The electrochemical reaction process of the invention comprises the following chemical reactions:
Cu2++2e→Cu (1)
SeO3 2-+6H++4e-→Se+3H2O (2)
TeO3 2-+6H++4e-→Te+3H2O (3)
example 1:
a treatment method for separating copper, selenium and tellurium in a cyclone electrolysis step mode comprises the following steps:
(1) preparing materials: preparing a solution, wherein the concentration of copper ions is 1g/L, the concentration of selenium ions is 1g/L, the concentration of tellurium ions is 1g/L, and the concentration of hydrochloric acid in the solution is 1M;
(2) and (3) cyclone electrolytic reaction: putting the solution obtained in the step (1) into a liquid storage tank of a cyclone electrolysis device, then adjusting the potential to be-0.2V, reacting in the cyclone electrolysis device with a working electrode which is a titanium sheet with high specific surface area after oxidation treatment and a counter electrode which is a graphite electrode, wherein the reaction time is 8h, and the reaction temperature is adjusted to be 25 ℃; after the reaction is finished, the working electrode is replaced, the potential is adjusted to-0.4V, the reaction temperature is unchanged, and the reaction is carried out for 8 hours; after the reaction is finished, the working electrode is replaced, the potential is adjusted to-0.5V, the reaction is carried out at constant temperature, and the reaction time is 8 hours. The simple substances or oxides of tellurium, copper and selenium are collected on the replaced electrode titanium sheet in sequence.
The titanium electrode is processed in the following way: and (3) placing the titanium sheet into hydrofluoric acid for pickling for 1h to remove the oxide film on the surface of the titanium sheet. And cleaning and vacuum drying the titanium sheet after acid cleaning. Preparing a mixed solution of H2O2 and H2SO4 in a ratio of 1:3, and then placing the titanium sheet in the solution to react for 40min at the temperature of 80 ℃.
(3) Product separation: the product obtained in step (2) was collected, washed and dried in a stepwise manner, and the purity thereof was tested by XRD and EDS spectroscopy using a small amount of sample. The purity of copper was calculated to be 98%, selenium 99% and tellurium 98%. The yield of copper was 99%, the yield of selenium 98% and the yield of tellurium 98% were calculated by weighing.
Example 2:
a treatment method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode comprises the following steps:
(1) preparing a solution, wherein the concentration of copper ions is 2.5g/L, the concentration of selenium ions is 1.7g/L, the concentration of tellurium ions is 1g/L, and the concentration of hydrochloric acid is 4M;
(2) putting the prepared solution into a liquid storage tank of a cyclone electrolysis device, setting the temperature at 140 ℃, adjusting the potential to-0.22V, and reacting in the cyclone electrolysis device with a working electrode of titanium sheet with high specific surface area subjected to oxidation treatment and a counter electrode of graphite electrode for 4 hours; after the reaction is finished, the reaction electrode is replaced, the point position is adjusted to-0.41V, and the reaction is carried out for 4 h; and after the reaction is finished, replacing the electrode, adjusting the potential to-0.49V, and reacting for 4 hours. The simple substances or oxides of tellurium, copper and selenium are collected on the replaced electrode in turn.
The titanium electrode is processed in the following way: and (3) placing the titanium sheet into hydrofluoric acid for pickling for 1h to remove the oxide film on the surface of the titanium sheet. And cleaning and vacuum drying the titanium sheet after acid cleaning. Preparing a mixed solution of H2O2 and H2SO4 in a ratio of 1:3, and then placing the titanium sheet in the solution to react for 40min at the temperature of 80 ℃.
(3) And (3) separating, washing and drying the reaction product obtained in the step (2), taking a small amount of samples, testing the purity of each product by using XRD and EDS spectrum, and calculating to obtain the purities of copper, selenium and tellurium in the products, namely 95%, 94% and 92%. The yield of copper was 99%, the yield of selenium was 96% and the yield of tellurium was 97% by weighing calculation.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, the copper salt used was changed to copper sulfate, and the same measurement method was used to obtain copper, selenium and tellurium purities of 92%, 93% and 93% in this order, and yields of 97%, 96% and 96% in this order.
Example 3:
a treatment method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode comprises the following steps:
(1) preparing a solution, wherein the concentration of copper ions is 1.8g/L, the concentration of selenium ions is 1.8g/L, the concentration of tellurium ions is 1.5g/L, and the concentration of hydrochloric acid is 4M;
(2) putting the prepared solution into a liquid storage tank of a cyclone electrolysis device, setting the temperature to be 60 ℃, adjusting the potential to be-0.22V, and reacting in the cyclone electrolysis device with a working electrode which is a titanium sheet with high specific surface area after oxidation treatment and a counter electrode which is a graphite electrode for 8 hours; after the reaction is finished, the reaction electrode is replaced, the point position is adjusted to-0.41V, and the reaction is carried out for 8 h; and after the reaction is finished, replacing the electrode, adjusting the potential to-0.50V, and reacting for 8 h. The simple substances or oxides of tellurium, copper and selenium are collected on the replaced electrode in turn.
The titanium electrode is processed in the following way: and (3) placing the titanium sheet into hydrofluoric acid for pickling for 1h to remove the oxide film on the surface of the titanium sheet. And cleaning and vacuum drying the titanium sheet after acid cleaning. Preparing a mixed solution of H2O2 and H2SO4 in a ratio of 1:3, and then placing the titanium sheet in the solution to react for 40min at the temperature of 80 ℃.
(3) And (3) separating, washing and drying the reaction product obtained in the step (2), taking a small amount of samples, testing the purity of each product by using XRD and EDS spectrum, and calculating to obtain the purities of copper, selenium and tellurium in the products, wherein the purities of copper, selenium and tellurium are 96%, 94% and 95%. The yield of copper, selenium and tellurium was 97%, 96% and 94% respectively, calculated by weighing.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, the copper salt used was changed to copper sulfate, and the same measurement method was used to obtain copper, selenium and tellurium purities of 90%, 89% and 92% in this order, and yields of 97%, 93% and 92% in this order.
Example 4:
the procedure of example 1 was repeated except that the swirling-flow electrolytic reaction in step (2) was replaced with a normal electrolytic reaction.
The purity of each product was measured by XRD and EDS spectroscopy, and the purities of copper, selenium and tellurium in the products were calculated to be 68%, 54% and 49%. The yield of copper, selenium and tellurium was 78% by weight calculation.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, and the same measurement methods were used to obtain copper, selenium and tellurium purities of 63%, 50% and 45% in this order, and yields of 67%, 73% and 78% in this order.
Example 5:
the procedure of example 1 was repeated, except that the titanium sheet in the spiral-flow electrolytic cell of step (2) was replaced with a type 304 stainless steel sheet.
The purity of each product was measured by XRD and EDS spectroscopy, and the purities of copper, selenium and tellurium in the products were calculated to be 73%, 62% and 50%. The yield of copper was 93%, the yield of selenium was 90% and the yield of tellurium was 94% by weighing calculation.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, and the same measurement methods were used to obtain copper, selenium and tellurium purities of 70%, 63% and 54% in this order, and yields of 91%, 93% and 91% in this order.
Example 6:
the procedure of example 1 was repeated, except that the titanium plate in the spiral-flow electrolyzer of step (2) was replaced with a 321 type stainless steel plate.
The purity of each product is tested by XRD and EDS spectrum, and the purities of copper, selenium and tellurium in the products are calculated to be 95%, 96% and 92%. The yield of copper, selenium and tellurium was 97%, 95% and 93% by weight.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, and the same measurement methods were used to obtain copper, selenium and tellurium purities of 89%, 92% and 94% in this order, and yields of 97%, 96% and 93% in this order.
Example 7:
the procedure of example 1 was repeated, except that the titanium sheet having a high specific surface area after the oxidation treatment in the spiral-flow electrolytic cell of step (2) was replaced with a 316L-type stainless steel sheet.
The purity of each product was measured by XRD and EDS spectra of the obtained product, and the purities of copper, selenium and tellurium in the product were calculated to be 96%, 94% and 93%. The yield of copper, selenium and tellurium was 98%, 96% and 96% respectively, calculated by weighing.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, and the same measurement methods were used to obtain copper, selenium and tellurium purities of 95%, 92% and 94% in this order, and yields of 97%, 98% and 96% in this order.
Example 8:
the procedure of example 1 was repeated, except that the titanium sheet having a high specific surface area after the oxidation treatment in the spiral-flow electrolytic cell of step (2) was replaced with a type 201 stainless steel sheet.
The purity of each product was measured by XRD and EDS spectra of the obtained product, and the purities of copper, selenium and tellurium in the product were calculated to be 50%, 47% and 49%. The yield of copper, selenium and tellurium was 85%, 84% and 86% respectively, calculated by weighing.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, and the same measurement methods were used to obtain copper, selenium and tellurium purities of 68%, 61% and 71%, and yields of 84%, 86% and 87%, respectively.
Example 9:
a treatment method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode comprises the following steps:
(1) preparing a solution, wherein the concentration of copper ions is 2.5g/L, the concentration of selenium ions is 1.7g/L, the concentration of tellurium ions is 1g/L, and the concentration of hydrochloric acid is 4M;
(2) putting the prepared solution into a liquid storage tank of a cyclone electrolysis device, setting the temperature at 140 ℃, adjusting the potential to-0.22V, and reacting in the cyclone electrolysis device with a working electrode of 316L stainless steel and a counter electrode of graphite electrode for 4 hours; after the reaction is finished, the reaction electrode is replaced, the point position is adjusted to-0.41V, and the reaction is carried out for 4 h; and after the reaction is finished, replacing the electrode, adjusting the potential to-0.49V, and reacting for 4 hours. The simple substances or oxides of tellurium, copper and selenium are collected on the replaced electrode in turn.
(3) And (3) separating, washing and drying the reaction product obtained in the step (2), taking a small amount of samples, testing the purity of each product by using XRD and EDS spectrum, and calculating to obtain the purities of copper, selenium and tellurium in the products, namely 91%, 86% and 81%. The yield of copper was 99%, the yield of selenium was 96% and the yield of tellurium was 97% by weighing calculation.
Example 10:
a treatment method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode comprises the following steps:
(1) preparing a solution, wherein the concentration of copper ions is 2g/L, the concentration of selenium ions is 1.5g/L, the concentration of tellurium ions is 1.5g/L, and the concentration of hydrochloric acid is 4M;
(2) putting the prepared solution into a liquid storage tank of a cyclone electrolysis device, setting the temperature to be 90 ℃, adjusting the potential to be-0.2V for carrying out cyclone electrolysis reaction, and carrying out reaction in the cyclone electrolysis device with a working electrode of 316L type stainless steel and a counter electrode of graphite electrode for 8 hours; after the reaction is finished, the reaction electrode is replaced, the point position is adjusted to-0.4V, and the reaction is carried out for 8 h; and after the reaction is finished, replacing the electrode, adjusting the potential to-0.5V, and reacting for 8 h. The simple substances or oxides of tellurium, copper and selenium are collected on the replaced electrode in turn.
(3) And (3) separating, washing and drying the reaction product obtained in the step (2), taking a small amount of samples, testing the purity of each product by using XRD and EDS spectrum, and calculating to obtain the purities of copper, selenium and tellurium in the products, wherein the purities of copper, selenium and tellurium are 97%, 89% and 87%. The yield of copper, selenium and tellurium was 96%, 95% and 98% respectively, as calculated by weighing.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, the copper salt used was changed to copper sulfate, and the same measurement method was used to obtain copper, selenium and tellurium purities of 96%, 86% and 84% in this order, and yields of 95%, 94% and 97% in this order.
Example 11:
the procedure of example 1 was repeated, except that the titanium plate having a high specific surface area after the oxidation treatment in the spiral-flow electrolytic cell of step (2) was replaced with a common titanium plate.
The purity of each product was measured by XRD and EDS spectroscopy, and the purities of copper, selenium and tellurium in the products were calculated to be 86%, 84% and 87%. The yield of copper, selenium and tellurium was 91%, 90% and 89% by weight calculation.
The hydrochloric acid in this example was changed to sulfuric acid of the same concentration, and the same measurement methods were used to obtain copper, selenium and tellurium purities of 87%, 85% and 85% in this order, and yields of 89%, 90% and 92% in this order.
From this example, it is known that the efficiency of the conventional titanium sheet electrode in the cyclone electrolysis is inferior to that of the 316L stainless steel sheet electrode.
In conclusion, the method for separating copper, selenium and tellurium in a cyclone electrolysis step mode utilizes electrochemical direct reduction of the inner cathode of a cyclone electrolysis device to obtain products, the reaction shows that the copper, selenium and tellurium are sequentially separated from raw materials under mild conditions, the electrodes can be better contacted with a solution due to cyclone electrolysis, concentration polarization of the liquid is eliminated through high-speed rotation, and therefore high-purity nano-micro powder products can be obtained, and efficient utilization and purification of the copper, selenium and tellurium are achieved.
The working electrode (cathode) in the cyclone electrolyzer adopts a titanium sheet which is subjected to oxidation treatment and has high specific surface area, and the counter electrode (anode) adopts a graphite rod, so that the method can achieve the best effect.
The cathode used in the method for recycling copper, selenium and tellurium in a cyclone electrolysis step manner is a titanium sheet subjected to oxidation treatment, and the surface molecules of the titanium sheet are in a net-shaped laminated structure, so that the specific surface area of an electrode is increased, the whole structure is compact and uniform, the titanium sheet can be better contacted with a solution compared with a stainless steel sheet used in the traditional cyclone electrolysis, the adsorption capacity is greatly improved, the purity of the obtained product is greatly improved, and the yield is greatly improved. The method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis step mode adopts normal pressure operation, has low reaction temperature (the reaction temperature is only 25 ℃ at the lowest), and reduces the reaction temperature compared with the traditional process, thereby reducing the energy consumption. According to the method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode, impurities are not introduced into a system from a reflection medium, so that subsequent separation is facilitated; the concentration of the used acid is greatly reduced, and the acid consumption is reduced; the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis step mode does not add any auxiliary material, and compared with the traditional process, the method has the advantages that the sewage discharge amount can be reduced by 20-50 wt%; the method for recycling the copper, the selenium and the tellurium in the cyclone electrolysis step mode has the advantages of high automation degree of cyclone electrolysis reaction operation, reduction of labor input, convenience for mass production, capability of bringing about good economic benefits and social benefits and good application prospect. The method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode provided by the invention utilizes the cyclone electrolysis method to carry out step recycling, and the obtained product is nano-micro powder, has good plasticity for subsequent application and processing, and is convenient for subsequent use. The method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode, provided by the invention, has the advantages that copper salt, selenium salt and tellurium salt are comprehensively treated in the same solution, convenience is brought to later engineering practice, the consumption of raw materials is reduced, and the reaction time and the consumption of equipment are reduced.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (2)
1. A method for recycling copper, selenium and tellurium in a cyclone electrolysis step mode is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
and (3) cyclone electrolytic reaction: placing a solution containing copper, selenium and tellurium ions and hydrochloric acid or sulfuric acid in a rotational flow electrolytic reaction device for electrochemical reaction, wherein the concentration of the hydrochloric acid or the sulfuric acid is 1M, the concentration of the copper ions is 1g/L, the concentration of the selenium ions is 1g/L and the concentration of the tellurium ions is 1g/L, sequentially adjusting the potential, performing rotational flow electrolytic reaction once every time the potential is adjusted, the voltage during the tellurium electrolytic reaction is-0.2V, the voltage during the copper electrolytic reaction is-0.4V, and the voltage during the selenium electrolytic reaction is-0.50V, and sequentially obtaining a tellurium, copper and selenium solid mixture;
separation: washing and drying the solid mixture to obtain simple substances or oxides of copper, selenium and tellurium in sequence;
wherein the rotational flow electrolysis reaction is carried out at the temperature of 25 ℃, and the time for carrying out the reaction by adjusting the potential each time is 8 hours; the cyclone electrolytic reaction device comprises a cyclone electrolytic tank, a working electrode and a counter electrode, wherein the working electrode comprises one or more of a titanium sheet with a high specific surface area, a 316L-shaped stainless steel sheet and a 321-shaped stainless steel sheet which are subjected to oxidation treatment, and the counter electrode is a graphite electrode.
2. The method for cascade recovery of copper, selenium and tellurium by cyclone electrolysis as claimed in claim 1, wherein: the rotational flow electrolytic bath is a normal pressure electrolytic bath.
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| CN112210790B (en) * | 2020-09-17 | 2022-01-11 | 中南大学 | Treatment method of copper anode slime copper separating liquid |
| CN114892221A (en) * | 2022-05-09 | 2022-08-12 | 惠州市华盈科技有限公司 | Cyclone electrolysis method for manufacturing cathode copper sheet |
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