Roasting regenerated copper in zinc hydrometallurgy cuprous dechlorination
By calcining treatment, the copper oxide generates copper oxide and evaporates chlorine, which solves the problems of chloride ion corrosion and cost increase in wet zinc smelting, and realizes low energy consumption, short process, and high dechlorination rate technology, and improves the quality and market competitiveness of recycled copper.
Patent Information
- Application Number
- CN202510046108.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-13
- Publication Date
- 2025-04-15
AI Technical Summary
During the wet zinc smelting process, chloride ion corrodes the equipment, increases the consumption cost of anode plates, and causes the product zinc ingots to exceed the standard. The existing copper-chlorine removal method produces salts that do not meet the industrialization standards, resulting in an increase in costs.
The chlorine removal is removed by roasting treatment, and the copper oxide is oxideed to form copper oxide and evaporate chlorine gas, thereby achieving the purpose of chlorine removal. The roasting temperature is 600-800℃, a time of 2-3 hours, and no auxiliary materials are added, achieving low energy consumption, short process and high dechlorination rate.
It greatly reduces energy consumption and environmental pollution, and the recycled copper obtained is purer in quality, has better market competitiveness, and realizes low-cost resource treatment of chloride ions.
Smart Images
Figure CN119824239A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of hydrometallurgical metallurgy, and particularly relates to a method for roasting and regenerating copper in the process of removing chlorine from cuprous zinc in hydrometallurgy. Background Art
[0002] In hydrometallurgical zinc smelting, the ore powder contains chloride ions. The chloride ions entering the solution will corrode the equipment and the electrolytic anode plate, which will cause a high equipment damage rate, increase the cost of anode plate consumption, and the lead content of the product zinc ingot exceeds the standard. Therefore, it is necessary to dechlorinate the leaching solution of hydrometallurgical zinc smelting to reduce the chloride ions to 300mg / l to meet the process requirements. At present, the zinc smelting industry uses cuprous dechlorination. Cuprous and chloride ions form cuprous chloride precipitation. The main reaction formula is Cu + +CL - =CuCl↓, then use sodium hydroxide to chlorine the cuprous chloride, the produced cuprous hydroxide is returned for chlorine removal, and the chloride ions enter the evaporated crystallized salt in the form of sodium chloride. The sodium chloride and sodium sulfate solution produced by the alkali leaching of cuprous chloride is used for evaporation and crystallization. The salt produced by evaporation and crystallization does not meet the industrial product standards and cannot be sold, which increases the production cost. Summary of the invention
[0003] The purpose of the present invention is to provide a method for roasting regenerated copper in cuprous zinc removal by hydrometallurgy. By controlling roasting, cuprous oxide is oxidized to generate cupric oxide during roasting. While generating cupric oxide, chlorine gas is volatilized during roasting, thereby achieving the purpose of dechlorination. By adopting the method of roasting for dechlorination, energy consumption is greatly reduced, and pollution to the environment is reduced. At the same time, the regenerated copper obtained by electrolytic treatment is of purer quality and has better market competitiveness. The problem that the current zinc smelting industry uses cuprous oxide for dechlorination, cuprous oxide and chloride ions form cuprous chloride precipitation, and the main reaction formula is Cu + +CL - =CuCl↓, then use sodium hydroxide to chlorine the cuprous chloride, the produced cuprous hydroxide is returned for chlorine removal, and the chloride ions enter the evaporated crystallized salt in the form of sodium chloride. The sodium chloride and sodium sulfate solution produced by the alkali leaching of cuprous chloride is used for evaporation and crystallization. The salt produced by evaporation and crystallization does not meet the industrial product standards and cannot be sold, which brings the problem of rising production costs.
[0004] In order to solve the above technical problems, the present invention is achieved through the following technical solutions:
[0005] The invention discloses a method for roasting regenerated copper in the process of zinc hydrometallurgy and cuprous dechlorination, which comprises the following steps: in the process of zinc hydrometallurgy, zinc concentrate is leached with dilute sulfuric acid to generate a solution containing impurities such as copper and arsenic, which is called copper-rich solution; a certain amount of cuprous salt solution is added to the copper-rich solution; after reaction in a replacement device, copper ions in the copper-rich solution are precipitated as cuprous and copper salt is generated at the same time; the precipitated cuprous is filtered preliminarily to remove the copper-rich solution on the surface; then washing is performed to flush the copper-rich solution ions remaining on the surface; the flushed cuprous is dried; the dried cuprous is ground into cuprous powder by ball milling; the drying and roasting are performed separately; a ball mill is added at the same time to solve the problem that the zinc-chlorinated copper slag is sticky during roasting and affects the dechlorination rate.
[0006] As a preferred technical solution, cuprous powder is placed in a roasting furnace for roasting. During the roasting process, cuprous oxide is oxidized to generate cupric oxide. While generating cupric oxide, chlorine gas is volatilized during the roasting process, thereby achieving the purpose of dechlorination. The reaction equation is as follows: CuSO4+CuCl->Cu2Cl2+SO4^2-. By adopting the roasting treatment to remove chlorine, energy consumption is greatly reduced, and pollution to the environment is reduced. At the same time, the regenerated copper obtained by electrolytic treatment is of purer quality and has better market competitiveness. The roasting temperature of cuprous dechlorination is usually 600-800°C, and the time is usually 2-3 hours. No auxiliary materials are added during the high-temperature roasting process. After roasting, the chlorine content in the output is detected to be less than 0.5%, and the dechlorination rate is 96.7%. It can be returned to the dechlorination process to continue dechlorination, thereby realizing a process technology with low energy consumption, short process and high dechlorination rate. The cuprous roasting reaction equation is as follows: 2Cu2Cl2+O2->2Cu2O+2Cl2.
[0007] As a preferred technical solution, the gases (main components of which are hydrogen chloride, chlorine, sulfur dioxide, etc.) generated during the drying and roasting dechlorination process are passed through a chlorine spray tower for dust collection and two-stage distilled water countercurrent absorption, and finally 30% industrial hydrochloric acid is produced for sale.
[0008] As a preferred technical solution, the roasted copper oxide powder is mixed with a reducing agent (such as carbon powder, coal powder, etc.) and reduced in a reduction furnace. During the reduction process, the temperature is usually 1000-1100° C. The copper oxide reduction reaction equation is as follows: Cu2O+C->2Cu+CO. The copper oxide powder mixed with the reducing agent generates metallic copper after reduction. The metallic copper is smelted in a smelting furnace to become liquid copper water. The copper water is cast to obtain recycled copper. The recycled copper is electrolytically refined to become cathode copper.
[0009] The present invention has the following beneficial effects:
[0010] The present invention controls roasting, during which cuprous oxide generates cupric oxide. While generating cupric oxide, chlorine gas is volatilized during the roasting process, thereby achieving the purpose of removing chlorine. By adopting the roasting treatment method for removing chlorine, energy consumption is greatly reduced, and pollution to the environment is reduced. At the same time, the regenerated copper obtained by electrolytic treatment is of purer quality and has better market competitiveness.
[0011] In the roasting and dechlorination process, the present invention does not add additives, does not introduce oxygen, and does not use microwave heating. Chlorine in the dechlorination slag can be removed without adding any additives during the roasting process. Dechlorination is achieved through high-temperature roasting and a short process, thereby increasing the dechlorination efficiency and reducing the dechlorination cost.
[0012] The present invention uses a chlorine spray tower to collect dust from the gases (main components of which are hydrogen chloride, chlorine, sulfur dioxide, etc.) generated during the drying and roasting dechlorination process, and performs two-stage distilled water countercurrent absorption, and finally produces 30% industrial hydrochloric acid for sale. Chlorine, hydrogen chloride, and smoke solids can produce qualified industrial hydrochloric acid for sale after dust collection and distilled water absorption, thereby realizing resource utilization.
[0013] In the whole roasting and dechlorination process of the present invention, the whole technology generates no waste gas, waste residue, waste water, and no source of environmental pollution. Due to the above three advantages, low-cost resource processing of chloride ions is finally realized.
[0014] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.
[0016] Figure 1 The invention relates to a method for roasting and regenerating copper in a process of removing chlorine from cuprous zinc in a wet process of zinc smelting. DETAILED DESCRIPTION
[0017] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0018] See also Figure 1As shown, the present invention is a method for roasting regenerated copper in cuprous zinc dechlorination during wet zinc smelting, comprising the following steps: in the process of wet zinc smelting, zinc concentrate is leached with dilute sulfuric acid to generate a solution containing impurities such as copper and arsenic, called a copper-rich solution, a certain amount of cuprous salt solution is added to the copper-rich solution, after reaction in a displacement device, the copper ions in the copper-rich solution are precipitated as cuprous, and copper salt is generated at the same time, the precipitated cuprous is filtered to remove the copper-rich solution on the surface, and then washed to flush the residual copper-rich liquid ions on the surface, the flushed cuprous is dried, the dried cuprous is ground into cuprous powder by ball milling, the drying and roasting are carried out separately, and a ball mill is added at the same time to solve the problem of zinc-chlorine-containing copper slag being sticky during roasting and affecting the dechlorination rate.
[0019] The cuprous powder is placed in a roasting furnace for roasting. During the roasting process, cuprous oxide is generated to form cupric oxide. While generating cupric oxide, chlorine gas is volatilized during the roasting process, thereby achieving the purpose of dechlorination. The reaction equation is as follows: CuSO4+CuCl->Cu2Cl2+SO4^2-. The method of dechlorination by roasting greatly reduces energy consumption and reduces pollution to the environment. At the same time, the recycled copper obtained by electrolytic treatment is of purer quality and has better market competitiveness. The roasting temperature for cuprous dechlorination is usually 600-800℃, and the time is usually 2-3 hours. No auxiliary materials are added during the high-temperature roasting process. After roasting, the chlorine content in the output is detected to be below 0.5%, and the dechlorination rate is 96.7%. It can be returned to the dechlorination process to continue dechlorination, realizing a process technology with low energy consumption, short process and high dechlorination rate. The cuprous roasting reaction equation is as follows: 2Cu2Cl2+O2->2Cu2O+2Cl2.
[0020] The gases (main components: hydrogen chloride, chlorine, sulfur dioxide, etc.) generated during the drying and roasting dechlorination process are passed through a chlorine spray tower for dust collection and two-stage distilled water countercurrent absorption, and finally 30% industrial hydrochloric acid is produced for sale.
[0021] The calcined copper oxide powder is mixed with a reducing agent (such as carbon powder, coal powder, etc.) and reduced in a reduction furnace. The temperature during the reduction process is usually 1000-1100°C. The copper oxide reduction reaction equation is as follows: Cu2O+C->2Cu+CO. The copper oxide powder mixed with the reducing agent generates metallic copper after reduction. The metallic copper is smelted in a smelting furnace to become liquid copper water. The copper water is cast to obtain recycled copper. The recycled copper is electrolytically refined to become cathode copper.
[0022] A specific application of this embodiment is: during the process of wet zinc smelting, zinc concentrate is leached with dilute sulfuric acid to generate a solution containing impurities such as copper and arsenic, called a copper-rich solution; a certain amount of cuprous salt solution is added to the copper-rich solution; after a reaction in a displacement device, the copper ions in the copper-rich solution are precipitated as cuprous, and copper salt is generated at the same time; the precipitated cuprous is filtered to remove the copper-rich solution on the surface, and then washed to flush the residual copper-rich liquid ions on the surface; the washed cuprous is dried; the dried cuprous is ground into cuprous powder by ball milling; the cuprous powder is placed in a roasting furnace for roasting; the roasting process Cuprous oxide generates cupric oxide. While generating cupric oxide, chlorine will volatilize during the roasting process, so as to achieve the purpose of dechlorination. Cuprous oxide generates cupric oxide during the roasting process. While generating cupric oxide, chlorine will volatilize during the roasting process, so as to achieve the purpose of dechlorination. By adopting the method of dechlorination by roasting, energy consumption is greatly reduced and pollution to the environment is reduced. At the same time, the recycled copper obtained by electrolytic treatment is of purer quality and has better market competitiveness. The roasting temperature for cuprous dechlorination is usually 600-800℃ and the time is usually 2-3 hours. During the process, no additives are added, no oxygen is introduced, and microwave heating is not used. During the roasting process, chlorine in the dechlorination slag can be removed without adding any additives. Dechlorination is achieved through high-temperature roasting and a short process, which increases the efficiency of dechlorination and reduces the cost of dechlorination. The gases (main components of hydrogen chloride, chlorine, sulfur dioxide, etc.) generated during the drying and roasting dechlorination process are dusted in a chlorine spray tower and absorbed in two-stage distilled water countercurrents. Finally, 30% industrial hydrochloric acid is produced for sale. Chlorine, hydrogen chloride, and smoke solids can produce qualified industrial hydrochloric acid for sale after dust collection and absorption with distilled water, thus realizing resource utilization. The calcined copper oxide powder is mixed with a reducing agent (such as carbon powder, coal powder, etc.) and reduced in a reduction furnace. During the reduction process, the temperature is usually 1000-1100°C. The copper oxide powder mixed with the reducing agent generates metallic copper after reduction. The metallic copper is smelted in a smelting furnace to become liquid copper water. Regenerated copper is obtained by casting the copper water. The recycled copper is electrolytically refined to become cathode copper. During the entire roasting and dechlorination process, the entire technology does not produce waste gas, waste slag, or waste water, and there is no source of environmental pollution. Due to the above three advantages, low-cost resource processing of chloride ions is ultimately achieved.
[0023] It is worth noting that in the above system embodiment, the various units included are only divided according to functional logic, but are not limited to the above division, as long as the corresponding functions can be achieved; in addition, the specific names of the functional units are only for the convenience of distinguishing each other, and are not used to limit the scope of protection of the present invention.
[0024] In addition, those skilled in the art can understand that all or part of the steps in the above-mentioned embodiments can be completed by instructing related hardware through a program, and the corresponding program can be stored in a computer-readable storage medium.
[0025] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.
Claims
1. A method for roasting regenerated copper in the process of removing chlorine from cuprous zinc by hydrometallurgy, characterized in that: The steps include: In the process of hydrometallurgy, zinc concentrate is leached with dilute sulfuric acid to produce a solution containing impurities such as copper and arsenic, which is called copper-rich solution. A certain amount of cuprous salt solution is added to the copper-rich solution. After the reaction in the replacement device, the copper ions in the copper-rich solution are precipitated as cuprous and copper salt is generated at the same time. The precipitated cuprous acid is initially filtered to remove the copper-rich liquid on the surface, and then washed to flush the residual copper-rich liquid ions on the surface. The washed cuprous acid is dried and ball-milled to form cuprous acid powder. The particle size of the cuprous acid powder is 10-100 microns.
2. The method of claim 1 for removing chlorine from cuprous zinc by hydrometallurgy and roasting regenerated copper, characterized in that: The cuprous powder is placed in a roasting furnace for roasting. During the roasting process, cuprous oxide is oxidized to generate cupric oxide. While generating cupric oxide, chlorine gas is volatilized during the roasting process, thereby achieving the purpose of dechlorination. The cuprous dechlorination roasting temperature is usually 600-800℃, and the time is usually 2-3 hours. No auxiliary materials are added during the high-temperature roasting process. After roasting, the chlorine content in the output is detected to be below 0.5%, and the dechlorination rate is 96.7%, which can be returned to the dechlorination process to continue dechlorination. A process technology with low energy consumption, short process and high dechlorination rate has been achieved.
3. The method of claim 2 for roasting regenerated copper in cuprous zinc hydrometallurgy for removing chlorine, characterized in that: The gases (main components: hydrogen chloride, chlorine, sulfur dioxide, etc.) generated during the drying and roasting dechlorination process are passed through a chlorine spray tower for dust collection and two-stage distilled water countercurrent absorption, and finally 30% industrial hydrochloric acid is produced for sale.
4. The method of claim 3 for roasting regenerated copper in cuprous zinc hydrometallurgy for dechlorination, characterized in that: The roasted copper oxide powder is mixed with a reducing agent (such as carbon powder, coal powder, etc.) and reduced in a reduction furnace. During the reduction process, the temperature is usually 1000-1100°C. The copper oxide powder mixed with the reducing agent generates metallic copper after reduction. The metallic copper is smelted in a smelting furnace to become liquid copper water. The copper water is cast to obtain recycled copper, which is then electrolytically refined to become cathode copper.