Method for producing cathode copper through collaborative smelting of copper sulfide concentrate and copper oxide concentrate

Abstract

The invention discloses a method for producing cathode copper through collaborative smelting of copper sulfide concentrate and copper oxide concentrate, which comprises the following steps: (1) preparing a copper sulfide concentrate system: roasting the copper sulfide concentrate to form roasted sand, leaching by utilizing an electrodeposition mixed solution, and then carrying out dense clarification to obtain dense underflow 1 and dense overflow 1; the dense overflow (1) is divided into two paths, the first path enters an electrodeposition rich solution pool to produce cathode copper through electrodeposition and is converted into an electrodeposition barren solution, the electrodeposition barren solution and the electrodeposition rich solution are mixed into an electrodeposition mixed solution, and the electrodeposition mixed solution is returned to calcine leaching; the second path serves as a system open circuit and is sent to copper oxide concentrate leaching; and (2) a copper oxide concentrate system: leaching the copper oxide concentrate by utilizing the raffinate and the second path of dense overflow 1, and performing dense clarification to obtain dense underflow 2 and dense overflow 2 for extraction-electrodeposition to produce cathode copper. By flexibly adjusting the open circuit quantity of the dense overflow (1), the two production systems are matched with each other, efficient operation is achieved, impurity enrichment is prevented, and meanwhile the production cost is saved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrometallurgy of copper-cobalt ore, and in particular to a method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper. Background Art

[0002] The copper-cobalt ore belt in the Democratic Republic of the Congo belongs to the richest area of the world's largest sedimentary rock-hosted copper-cobalt deposits, with rich copper-cobalt mineral resources. The minerals mainly exist in the form of copper-cobalt associated ores. The hydrometallurgy technology can efficiently recover valuable metals such as copper and cobalt at the same time, and has a weak dependence on continuous power supply, especially suitable for the local production conditions of frequent power outages (restrictions). It is widely used in local mining enterprises.

[0003] In recent years, with the gradual increase in the mining depth, most of the copper ores with high oxidation rate and easy to process have been mined, and the Democratic Republic of the Congo has entered the stage of mixed sulfur-oxygen mining. For sulfur-oxygen mixed ores, the main beneficiation process usually adopts the "sulfur first and oxygen second" flotation process to produce copper sulfide concentrate, copper oxide concentrate, etc. Copper oxide concentrate can be directly used as a smelting raw material and better integrated into the classic hydrometallurgical process of leaching-extraction-electrowinning to produce cathode copper products. In contrast, how to efficiently incorporate copper sulfide concentrate into the hydrometallurgy process to produce high-quality cathode copper products needs further research and improvement.

[0004] The mainstream hydrometallurgical treatment processes for copper sulfide concentrate include oxygen pressure leaching process and roasting leaching process. The oxygen pressure leaching process oxidizes copper sulfide into soluble sulfate or metal oxide through the reaction under high-pressure oxygen-rich conditions to achieve efficient leaching of copper and cobalt. Chinese patents such as a method for oxygen pressure leaching of copper sulfide concentrate and a copper smelting method (publication number: CN111225988B), a process for efficiently recovering copper from lead matte by oxygen pressure acid leaching-cyclone electrolysis technology (publication number: CN104831064A) etc. all adopt this technology. However, this process has high requirements for the design, production and operation level of the reaction vessel, requires a large amount of auxiliary materials, and has a high management difficulty. In addition, the sulfur in the sulfide ore finally exists in the oxygen pressure leaching solution in the form of sulfate radical, and the system faces the problem of acid expansion, and additional acid neutralization is required, resulting in poor operating costs and economic benefits. The process of roasting-leaching-electrowinning of copper sulfide concentrate to produce cathode copper was adopted in the last century, but it still faces the problem of acid expansion and requires the use of a neutralizing agent to remove acid. In addition, this process also has the enrichment of iron, resulting in low electrowinning efficiency, high power consumption per ton of copper, and poor quality of cathode copper, etc. Currently, mining enterprises in the Democratic Republic of the Congo mostly adopt the process of roasting-leaching-extraction-electrowinning of copper sulfide concentrate. For example, Chinese patent CN112251598 A solves the problem of acid expansion by means of oxidizing the ore to consume acid during the leaching process. However, compared with the leaching-electrowinning process, this process also has disadvantages such as a long process and poor economic benefits. Summary of the Invention

[0005] The present invention provides a method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper, which not only makes full use of the advantages of the short process flow and good benefits of the roasting-leaching-electrowinning process for copper sulfide concentrate, but also solves a series of problems generated in the actual application process of the traditional process. At the same time, by using the characteristic that copper oxide concentrate consumes acid during the leaching process, it not only reduces the consumption of neutralizing agent in the traditional roasting-leaching-electrowinning process, but also reduces the sulfuric acid consumption, significantly improving the economic benefits.

[0006] According to one aspect of the present invention, there is provided a method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper, including the following:

[0007] Copper sulfide concentrate system: After the copper sulfide concentrate is roasted, roasted ore is obtained. The roasted ore is leached with an electrowinning mixed solution, and after leaching, thickening and clarification are carried out to obtain thickened underflow ① and thickened overflow ①;

[0008] The thickened overflow ① is divided into two paths. The first path enters the electrowinning workshop through the electrowinning rich liquid pool to produce cathode copper products and is converted into electrowinning lean liquid. The electrowinning lean liquid and the electrowinning rich liquid are mixed to obtain an electrowinning mixed solution, which is then returned to the roasted ore leaching process; The second path is an open circuit of the system and is transported to the copper oxide concentrate leaching process;

[0009] The thickened underflow ① is filtered and washed under pressure to obtain roasted ore leaching residue and filtrate ① under pressure, and the filtrate ① under pressure is transported to the copper oxide concentrate leaching process;

[0010] Copper oxide concentrate system: The copper oxide concentrate is leached with raffinate, the second path of thickened overflow ①, filtrate ① under pressure and filtrate ② under pressure, and after leaching, thickening and clarification are carried out to obtain thickened underflow ② and thickened overflow ②;

[0011] The thickened underflow ② is filtered and washed under pressure to obtain filter cake and filtrate ② under pressure, and the filtrate ② under pressure is returned to the copper oxide concentrate leaching process;

[0012] The thickened overflow ② enters the extraction process to supply the extraction-electrowinning process to produce cathode copper; The thickened overflow ② is converted into raffinate after extraction, and a part of the obtained raffinate is returned to the copper oxide concentrate leaching process.

[0013] Further, the electrowinning rich liquid and the electrowinning lean liquid in the electrowinning mixed solution in the copper sulfide concentrate system are mixed in a volume ratio of 0 to 1:1.

[0014] Further, the solution copper acid concentration of the electrowinning mixed solution and is 160 - 210 g / L;

[0015] Among them:

[0016] ——copper ion concentration;

[0017] —— relative molecular mass of sulfuric acid;

[0018] Mr (Cu) —— relative atomic mass of Cu;

[0019] —— concentration of sulfuric acid.

[0020] Further, sulfuric acid and neutral water are also added in the roasting and leaching process of the copper sulfide concentrate to keep the copper acid concentration in the solution and maintained within the range of 160 - 210 g / L.

[0021] Further, in the leaching process of the roasted ore in the copper sulfide concentrate, the pulp concentration is 4% - 8%, the reaction temperature is 40°C - 80°C, the reaction time is 5 - 9 h, and the copper concentration at the end of the reaction is 60 g / L - 110 g / L.

[0022] Further, the roasting process of the copper sulfide concentrate can be carried out by one or more of oxidation roasting, semi - oxidation roasting or sulfation roasting.

[0023] Further, in the leaching process of the copper oxide concentrate, the pH value at the end of leaching is controlled within the range of 1.2 - 1.8.

[0024] Further, the intermediate pressure filtrate ② in the copper oxide concentrate is returned to the leaching process of the copper oxide concentrate.

[0025] Further, it includes a copper sulfide concentrate leaching - electrowinning system and a copper oxide concentrate extraction - electrowinning system to produce cathode copper. By flexibly adjusting the treatment amounts of the copper sulfide concentrate and the copper oxide concentrate and the open - circuit amount of the thickening overflow ①, the two production systems cooperate with each other and both systems operate efficiently.

[0026] Further, in the copper oxide concentrate system, another part of the raffinate is used as an open - circuit in the system and enters the cobalt recovery system to ensure the recovery of cobalt in the solution of the entire smelting system and avoid the enrichment of impurities in the solution system.

[0027] The present invention has the following beneficial effects:

[0028] (1) The present invention not only has the advantages of the traditional roasting - leaching - electrowinning process for copper sulfide concentrate. The first - stage thickening overflow ① of the roasted ore leaching directly enters the electrowinning workshop to produce cathode copper, without the need for an extraction process, with a short process flow and good economic benefits. At the same time, it also solves a series of problems in the practical application of the traditional roasting - leaching - electrowinning process for copper sulfide concentrate. By using the second - stage thickening overflow ① as the solution discharge for the leaching process of copper oxide concentrate, some impurity ions (from the leaching of impurity ions in the ore) and excessive sulfuric acid (from the conversion of metal sulfides in the ore to sulfates during roasting and back to sulfuric acid during electrowinning) in the copper sulfide concentrate leaching - electrowinning system are discharged from the system. Then, by adding neutral water, it effectively prevents the enrichment of impurity ions inside the leaching - electrowinning system and also alleviates the problem of acid swelling, providing a prerequisite for high - efficiency electrowinning production of high - quality cathode copper in the leaching - electrowinning process.

[0029] (2) In the copper sulfide concentrate leaching - electrowinning system of the present invention, the excessive sulfuric acid enters the leaching process of copper oxide concentrate through the second - stage thickening overflow ①. By utilizing the acid - consuming characteristics during the leaching of copper oxide concentrate, it not only solves the problem of acid swelling in the leaching - electrowinning process, reducing the consumption of additional neutralizing agents, but also solves the problem of acid consumption during the leaching of copper oxide concentrate, reducing the amount of externally added sulfuric acid and significantly reducing the production cost.

[0030] (3) The present invention can flexibly adjust the solution discharge amount of the second - stage thickening overflow ① to the leaching process of copper oxide concentrate, adapting to the complex and variable production situations of ore grades and throughput of copper sulfide concentrate, copper oxide concentrate, etc. The coordinated cooperation of the two types of ores matches the dual - system production balance of the copper sulfide concentrate leaching - electrowinning system and the copper oxide concentrate extraction - electrowinning system, with strong system stability. When the grade of copper sulfide concentrate decreases or the throughput decreases, the discharge amount of the second - stage thickening overflow ① can be reduced, and the throughput of copper oxide concentrate can be increased to achieve stable copper supply in the leaching - electrowinning system and the extraction - electrowinning system, ensuring stable and efficient production of the two electrowinning systems. Similarly, when the grade of copper oxide concentrate decreases or the throughput decreases, the throughput of copper sulfide concentrate and the discharge amount of the second - stage thickening overflow ① can be increased to make up for the insufficient copper supply capacity of copper oxide concentrate, and stable copper supply in the leaching - electrowinning system and the extraction - electrowinning system can also be achieved, ensuring stable and efficient production of the two electrowinning systems.

[0031] (4) In the present invention, the solution in the electrowinning rich liquid pool can bypass the electrowinning process and directly enter the electrowinning mixed liquid pool, and the solution in the electrowinning mixed liquid pool can also bypass the calcine leaching process and directly return to the electrowinning rich liquid pool. The function is to flexibly control the liquid levels of the two solution pools of electrowinning rich liquid and electrowinning mixed liquid to reach a balanced state. For example, when the copper sulfide roasting and leaching system is shut down for maintenance, the calcine leaching process does not require the electrowinning mixed liquid, but the downstream electrowinning workshop still maintains normal production. Then, the liquid in the electrowinning rich liquid pool needs to enter the electrowinning workshop, be converted into electrowinning lean liquid, and then enter the electrowinning mixed liquid pool. If the solution in the electrowinning mixed liquid pool does not move, it will cause the liquid level of the electrowinning rich liquid pool to keep dropping, while the liquid level of the electrowinning mixed liquid pool to keep rising, and electrowinning will be forced to stop production. The copper storage and copper supply functions of the solution under the leaching - electrowinning production system are that when the copper leached from the copper sulfide concentrate is greater than the copper produced by electrowinning and the copper amount in the first - stage thickening overflow ① discharged to the open circuit, the copper concentration in the solution of the electrowinning rich liquid pool rises, and the amount of solution entering the electrowinning workshop decreases (the copper demand of the electrowinning workshop is certain). A part directly enters the electrowinning mixed liquid pool, and its copper concentration also rises accordingly, and the copper storage amount of the solution system increases. On the contrary, it decreases. The copper storage and copper supply functions of the solution can reduce the dependence of electrowinning on the copper supply amount from the upstream ore treatment. When the copper supply amount from ore leaching increases or decreases in the short term, the downstream electrowinning workshop can maintain stable and efficient production. In this way, the copper storage function and copper supply function of the solution in the leaching - electrowinning system can be realized, which can ensure that when the calcine leaching or electrowinning process is shut down / reduced in production, other processes can still produce stably and normally, and the system processing capacity can be stabilized.

[0032] (5) In the present invention, further, in a step - by - step open - circuit manner, the second part of the raffinate is used as the system open - circuit and enters the cobalt recovery system, which not only ensures the recovery of cobalt in the solution of the entire smelting system but also avoids the enrichment of impurities in the copper oxide concentrate extraction - electrowinning solution system.

[0033] In addition to the purposes, features, and advantages described above, the present invention has other purposes, features, and advantages. The present invention will be further described in detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings forming a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0035] Figure 1 It is a process flow diagram for the co - smelting of copper sulfide concentrate and copper oxide concentrate to produce cathode copper. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] The embodiments of the present invention will be described in detail below with reference to the drawings, but the present invention can be implemented in many different ways defined and covered by the following.

[0037] An embodiment of the first aspect of the present invention provides a method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper, including the following steps:

[0038] (1) Copper sulfide concentrate system: After the copper sulfide concentrate is roasted, roasted ore is obtained. The roasted ore is leached with an electrowinning mixed solution, and after leaching, thickening and clarification are carried out to obtain thickened underflow ① and thickened overflow ①;

[0039] The thickened overflow ① is divided into two paths. The first path enters the electrowinning workshop through the electrowinning rich liquid pool to produce cathode copper products and is converted into electrowinning lean liquid. The electrowinning lean liquid and the electrowinning rich liquid are mixed to obtain an electrowinning mixed solution, which is then returned to the roasted ore leaching process; The second path is an open circuit of the system and is transported to the copper oxide concentrate leaching process;

[0040] The thickened underflow ① is filtered and washed under pressure to obtain roasted ore leaching residue and filtrate ① under pressure. The filtrate ① under pressure is transported to the copper oxide concentrate leaching process;

[0041] (2) Copper oxide concentrate system: The copper oxide concentrate is leached with raffinate, the second path of thickened overflow ①, filtrate ① under pressure and filtrate ② under pressure, and after leaching, thickening and clarification are carried out to obtain thickened underflow ② and thickened overflow ②;

[0042] The thickened underflow ② is filtered and washed under pressure to obtain filter cake under pressure and filtrate ② under pressure. The filter cake under pressure is discharged and stockpiled outside, and the filtrate ② under pressure is returned to the copper oxide concentrate leaching process;

[0043] The thickened overflow ② enters the extraction workshop for the extraction-electrowinning process to produce cathode copper; The thickened overflow ② is converted into raffinate after extraction. The raffinate is at least divided into two parts. The first part is returned to the copper oxide concentrate leaching process, and the second part enters the cobalt recovery system. See Figure 1 .

[0044] In the embodiment of the present application, the thickened underflow ① and thickened overflow ① obtained from the leaching of roasted ore in the copper sulfide concentrate system are fully utilized. Among them, the thickened overflow ① directly enters the electrowinning workshop to produce cathode copper, without the need for an extraction process, with a short process flow and good economic benefits. At the same time, by using the second path of thickened overflow ① as the solution open circuit of the copper oxide concentrate leaching process, some impurity ions (derived from the leaching of impurity ions in the ore) and excessive sulfuric acid (derived from the conversion of metal sulfides in the ore into sulfates during roasting and into sulfuric acid during electrowinning) in the leaching-electrowinning system of the copper sulfide concentrate system are discharged from the system, and then neutral water is added, effectively solving the problems of impurity ion enrichment and acid swelling inside the traditional leaching-electrowinning system, providing a prerequisite for the high-efficiency production of high-quality cathode copper in the leaching-electrowinning system.

[0045] In the embodiments of the present application, the excess sulfuric acid in the copper sulfide concentrate leaching - electrowinning system enters the copper oxide concentrate leaching process through the open circuit of the second thickening overflow ①. By utilizing the acid - consuming characteristics during the leaching of copper oxide concentrate, it not only solves the problem of acid expansion in the leaching - electrowinning process, reduces the consumption of additional neutralizing agents, but also solves the problem of acid consumption during the leaching of copper oxide concentrate, reduces the amount of externally added sulfuric acid, and significantly reduces the production cost.

[0046] In the embodiments of the present application, by flexibly adjusting the open - circuit amount of the solution of the second thickening overflow ① to the copper oxide concentrate leaching process, it can adapt to the complex and variable production situations such as the ore grades and throughput of copper sulfide concentrate and copper oxide concentrate. The coordinated cooperation of the two ores can match the double - system production balance of the copper sulfide concentrate leaching - electrowinning system and the copper oxide concentrate extraction - electrowinning system, and the system has strong stability. When the grade of copper sulfide concentrate drops or the throughput decreases, the open - circuit amount of the second thickening overflow ① can be reduced, and the throughput of copper oxide concentrate can be increased to achieve stable copper supply in the leaching - electrowinning system and the extraction - electrowinning system, ensuring the stable and efficient production of the two electrowinning systems; similarly, when the grade of copper oxide concentrate drops or the throughput decreases, the throughput of copper sulfide concentrate and the open - circuit amount of the second thickening overflow ① can be increased to make up for the insufficient copper supply capacity of copper oxide concentrate, and also achieve stable copper supply in the leaching - electrowinning system and the extraction - electrowinning system, ensuring the stable and efficient production of the two electrowinning systems.

[0047] In the embodiments of the present application, the solution in the electrowinning rich - liquid pool can bypass the electrowinning process and directly enter the electrowinning mixed - liquid pool, and the solution in the electrowinning mixed - liquid pool can also bypass the roasted ore leaching process and directly return to the electrowinning rich - liquid pool, thereby realizing the copper storage function and copper supply function of the leaching - electrowinning system solution. It can ensure that when the roasted ore leaching or electrowinning process stops / has a production reduction, other processes can still produce stably and normally, and the stable processing capacity of the system is maintained.

[0048] In the embodiments of the present application, further, in a step - by - step open - circuit manner, the second part of the raffinate is used as the system open - circuit and enters the cobalt recovery system, which not only ensures the recovery of cobalt in the solution of the entire smelting system but also avoids the enrichment of impurities in the copper oxide concentrate extraction - electrowinning solution system.

[0049] In the embodiments of the present application, the electrowinning rich liquid and the electrowinning lean liquid in the electrowinning mixed liquid of the copper sulfide concentrate are mixed in a volume ratio of 0 - 1:1; the solution copper acid concentration of the electrowinning mixed liquid is 160 - 210 g / L;

[0050] wherein:

[0051] —— copper ion concentration;

[0052] —— relative molecular mass of sulfuric acid;

[0053] Mr (Cu) ——Relative atomic mass of Cu;

[0054] ——Concentration of sulfuric acid.

[0055] In the embodiment of the present application, after the leaching process of the calcine in the copper sulfide concentrate, sulfuric acid and neutral water are added to the thickening overflow ① to make the solution copper acid concentration and maintained within the range of 160 - 210 g / L.

[0056] If the solution copper acid concentration of the electrowinning mixed solution is higher than 210 g / L or lower than 160 g / L, the quality of the cathode copper will be affected.

[0057] In the calcine leaching process, the main calcine product is mixed with the electrowinning mixed solution, and sulfuric acid and neutral water are added for acid leaching. Metal oxides and sulfates in the calcine enter the solution. The main reaction processes are as follows:

[0058] CuO + 2H + → C u 2+ + H2O

[0059]

[0060] In addition to the main elements, other substances will also react in the calcine leaching reaction process and enter the solution. The reaction processes are as follows:

[0061] Fe2O3 + 6H + → 2Fe 3+ + 3H2O

[0062]

[0063] MgO + 2H + → Mg 2+ + H2O

[0064] CaO + 2H + → Ca 2+ + H20

[0065] Al2O3 + 6H + → 2Al 3+ + 3H2O

[0066] Fe 3+ Or O2 further oxidizes to SO4 2- :

[0067]

[0068] In the embodiment of the present application, in the leaching process of roasted ore in copper sulfide concentrate, the pulp concentration is 4% - 8%, the reaction temperature is 40°C - 80°C, the reaction time is 5 - 9 h, and the copper concentration at the reaction end point is 60 g / L - 110 g / L. Setting the pulp concentration, reaction temperature, and reaction time within the above ranges can enable the roasted ore to have a better leaching effect. If it is lower than the protection range, the leaching effect may be unsatisfactory. If it is higher than the range, it is also possible, but the input cost will increase.

[0069] The pulp concentration is the concentration of roasted ore in the leaching solution, and the pulp concentration can be any one of 4% - 8%; the reaction temperature is any one of 40°C - 80°C; the reaction time is any one of 5 h - 9 h.

[0070] In the embodiment of the present application, the roasting process of copper sulfide concentrate is carried out by one or more of oxidation roasting, semi-oxidation roasting, or sulfation roasting. The main purpose is to convert the copper in the ore into metal oxides or sulfates that are easy to acid leach.

[0071] In the embodiment of the present application, in the leaching process of copper oxide concentrate, the pH value at the leaching end point is controlled within the range of 1.2 - 1.8. Generally, copper oxide cobalt ore can achieve a better leaching effect within the range of pH 1.2 - 1.8. At the same time, the acid concentration in the leaching end point solution is basically within 10 g / L, and a more ideal extraction effect can be achieved after entering the extraction (the higher the acid concentration in the solution, the lower the extraction rate). In the embodiment of the present application, the medium-pressure filtrate ② of the copper oxide concentrate is returned to the copper oxide concentrate leaching process. The main purpose here is to merge into the thickening overflow ②. The functions of thickening and pressure filtration are both solid-liquid separation. Generally, after thickening, the bottom slurry concentration is increased, and then it enters the pressure filtration to make the solid-liquid separation more thorough, and the solutions are gathered together and enter the next process.

[0072] In the embodiment of the present application, the raffinate of the copper oxide concentrate also includes a second part, and the second part is opened to the cobalt recovery system to produce cobalt products. While realizing the recovery of cobalt in the ore, it also effectively avoids the enrichment of impurity concentration in a certain system and has an adverse impact on the stable operation of the overall process through the step-by-step opening of multiple production systems (the leaching - electrowinning system of copper sulfide concentrate is opened to the extraction - electrowinning system of copper oxide concentrate, and the extraction - electrowinning system of copper oxide concentrate is opened to the cobalt recovery system).

[0073] The object of the present invention is the copper-cobalt ore in Central Africa. If all the raffinate is returned to the leaching process, two problems will occur. One is that the cobalt element in the solution is not recovered in time to produce cobalt products, resulting in waste of mineral resources. The other is that the system will have a water swelling problem (the reason is that there are several places in this production system that need to add neutral water to the system, and there is also rainwater flowing into the system, but there is no place to open the system).

[0074] The following examples describe more specifically the content disclosed in this application, and these examples are only for illustrative purposes.

[0075] Example 1

[0076] This example is a production practice of co-smelting copper oxide concentrate and copper sulfide concentrate products of a copper-cobalt hydrometallurgical enterprise in the Democratic Republic of the Congo to produce cathode copper. The main element analysis results are shown in Table 1:

[0077] Table 1 Main element detection results of copper oxide concentrate and copper sulfide concentrate products (%)

[0078]

[0079] The above copper sulfide concentrate roasting adopts an oxidation roasting process with a roasting temperature of 750 °C;

[0080] The roasted ore after roasting and treatment of copper sulfide concentrate is leached with an electrowinning mixed solution. At the beginning stage, the copper concentration in the mixed solution is 45 g / L, and the copper acid concentration in the solution and

[0081] The pulp concentration in the roasted ore leaching process is 8%, the reaction temperature is 80 °C, and the reaction time is 9 h. During the reaction process, the copper concentration increases to 91 g / L, and the copper acid concentration in the solution and increases to 172 g / L, and neutral water and sulfuric acid are added for adjustment.

[0082] In the copper sulfide concentrate roasting - leaching - electrowinning system, the second thickening overflow ① is open, resulting in a reduction in the system solution volume. By supplementing neutral water, the total system solution volume is maintained basically unchanged, so that the copper concentration in the leaching solution is reduced to 60 g / L. At the same time, concentrated sulfuric acid is supplemented to maintain the copper acid concentration in the solution entering the electrowinning rich liquid pool and Through actual production practice, it is shown that when the copper acid concentration in the leaching - electrowinning process is controlled within the range of 160 - 210 g / L, the electrowinning workshop can maintain normal and stable production.

[0083] In the copper oxide concentrate system, the copper oxide concentrate is leached using the raffinate, the second thickening overflow ①, the pressure filtrate ①, and the pressure filtrate ②, keeping the pH at the end of leaching at 1.8. The copper oxide concentrate leaching residue contains 3.29% Cu, and the leaching rate is 83.55%;

[0084] In this example, the treatment volume of copper sulfide concentrate is 660 t / d - 760 t / d, the treatment volume of copper oxide concentrate is 600 t / d - 1200 t / d, and the thickening overflow ① is open to the copper oxide concentrate leaching process for 30 m 3 / h, at the beginning of the open-circuit stage, the copper content in the electrowinning mixed solution is 45 g / L, and the copper content in the electrowinning rich solution is 60 g / L. With the production operation, the copper stored in the solution of the copper sulfide concentrate leaching - electrowinning system increases, and the copper content in the electrowinning mixed solution gradually increases to 75 g / L, and the copper content in the electrowinning rich solution is 110 g / L. Subsequently, the thickening overflow ① is diverted to the open circuit of the copper oxide concentrate leaching process, increasing to 80 m 3 / h, the copper content in the electrowinning mixed solution and the electrowinning rich solution gradually decreases, and the copper stored in the solution of the copper sulfide concentrate leaching - electrowinning system decreases.

[0085] According to the ore grades, throughput, and production capacity of multiple downstream electrowinning processes of copper sulfide concentrate and copper oxide concentrate, by flexibly adjusting the throughput of copper sulfide concentrate and copper oxide concentrate and the open-circuit volume of the second thickening overflow ①, stable copper supply to the copper sulfide concentrate leaching - electrowinning system and the copper oxide concentrate extraction - electrowinning system can be achieved, maintaining a high-load stable production state in downstream processes and efficiently producing cathode copper products.

[0086] Example 2

[0087] This example is a production practice of co-smelting sulfur-oxygen copper concentrates to produce cathode copper from copper oxide concentrate and copper sulfide concentrate products of a copper-cobalt hydrometallurgical enterprise in the Democratic Republic of the Congo. The main element analysis results are shown in Table 2:

[0088] Table 2 Main element detection results of copper oxide concentrate and copper sulfide concentrate products (%)

[0089]

[0090] The above-mentioned roasting of copper sulfide concentrate adopts an oxidation roasting process with a roasting temperature of 750 °C;

[0091] The roasted ore after roasting the copper sulfide concentrate is leached with the electrowinning mixed solution, the copper concentration of the mixed solution is 75 g / L, and the copper acid concentration of the solution and

[0092] The pulp concentration in the roasted ore leaching process is 4%, the reaction temperature is 60 °C, the reaction time is 5 h, the copper concentration at the reaction end point is 101 g / L, and the copper acid concentration of the solution and

[0093] In the copper sulfide concentrate roasting - leaching - electrowinning system, the second thickening overflow ① is in an open circuit, the system solution volume decreases, and by supplementing a small amount of neutral water, the total system solution volume is maintained basically unchanged. After leaching, the copper concentration decreases to 80 g / L, and at the same time, concentrated sulfuric acid is supplemented to maintain the copper acid concentration of the solution entering the electrowinning rich liquid pool and Actual production practice shows that when the copper acid concentration in the leaching - electrowinning process is controlled within the range of 160 - 210 g / L, the electrowinning workshop can maintain normal and stable production.

[0094] The copper oxide concentrate is leached using raffinate, the second-stage thickener overflow ①, filtrate ① and filtrate ②, maintaining the pH at the end of leaching at 1.2. The copper oxide concentrate leaching residue contains 2.99% Cu, and the leaching rate is 84.05%.

[0095] In this embodiment, the treatment capacity of copper sulfide concentrate is 660 t / d to 760 t / d, the treatment capacity of copper oxide concentrate is 600 t / d to 1200 t / d, and 30 to 80 m of the thickener overflow liquid is diverted to the copper oxide concentrate leaching process 3 / h. When diverted, the electrowinning mixed solution contains 75 g / L of Cu, and the electrowinning rich solution contains 100 g / L of copper. The copper storage in the solution of the copper sulfide concentrate roasting - leaching - electrowinning process is at a peak. Under the condition of not affecting the downstream electrowinning process, the maintenance work of some upstream processes such as copper sulfide concentrate roasting and copper oxide concentrate leaching can be gradually carried out. The system has high flexibility and strong stability.

[0096] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, various changes and modifications can be made to the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper, characterized in that, It includes the following: Copper sulfide concentrate system: The copper sulfide concentrate is roasted to form calcine, which is then leached with an electrowinning mixed solution. After thickening and clarification, thickened underflow ① and thickened overflow ① are obtained; The thickened overflow ① is divided into two paths. The first path enters the electrowinning workshop through the electrowinning rich solution tank to produce cathode copper and is converted into electrowinning lean solution, which is output to the electrowinning mixed solution tank and mixed with the electrowinning rich solution to form an electrowinning mixed solution; The second path is an open circuit of the system and is transported to the copper oxide concentrate leaching process; The thickened underflow ① is filtered and washed under pressure to obtain roasted ore leaching residue and filtrate ① under pressure, and the filtrate ① under pressure is transported to the copper oxide concentrate leaching process; Copper oxide concentrate system: The copper oxide concentrate is leached with raffinate, the second path of thickened overflow ①, filtrate ① under pressure, and filtrate ② under pressure. After leaching, thickening and clarification are carried out to obtain thickened underflow ② and thickened overflow ②; The thickened underflow ② is filtered and washed under pressure to obtain filter cake under pressure and filtrate ② under pressure; The thickened overflow ② enters the extraction process and produces cathode copper through the extraction - electrowinning process; The thickened overflow ② is converted into raffinate after extraction, and a part of the obtained raffinate is returned to the copper oxide concentrate leaching process.

2. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1, wherein The electrowinning rich solution and electrowinning lean solution in the electrowinning mixed solution of the copper sulfide concentrate are mixed in a volume ratio of 0 - 1:

1.

3. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 2, wherein The solution copper acid concentration of the electrowinning mixed solution and is 160 - 210 g / L; Among them: ——Copper ion concentration; —— relative molecular mass of sulfuric acid; Mr (Cu) —— relative atomic mass of Cu; —— Sulfuric acid concentration.

4. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1, wherein In the leaching process of the roasted ore in the copper sulfide concentrate, sulfuric acid and neutral water are also added to keep the copper acid concentration in the solution and maintained within the range of 160 - 210 g / L.

5. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1 or 4, characterized in that, In the leaching process of the calcine in the copper sulfide concentrate, the pulp concentration is 4% - 8%, the reaction temperature is 40°C - 80°C, the reaction time is 5 - 9h, and the copper concentration at the reaction end point is 60g / L - 110g / L.

6. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1, characterized in that, The roasting process of the copper sulfide concentrate is carried out by one or more of oxidation roasting, semi - oxidation roasting, or sulfation roasting.

7. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1, wherein, In the leaching process of the copper oxide concentrate, the pH value at the leaching end point is controlled within the range of 1.2 - 1.

8.

8. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1, characterized in that, The filtrate ② under pressure in the copper oxide concentrate is returned to the copper oxide concentrate leaching process.

9. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1, wherein, It includes a copper sulfide concentrate leaching - electrowinning system and a copper oxide concentrate extraction - electrowinning system to produce cathode copper. By flexibly adjusting the treatment amounts of the copper sulfide concentrate and the copper oxide concentrate and the open - circuit amount of the thickened overflow ①, the two production systems cooperate with each other, and both systems operate efficiently.

10. The method for co-smelting copper sulfide concentrate and copper oxide concentrate to produce cathode copper according to claim 1, characterized in that, In the copper oxide concentrate system, another part of the raffinate is also used as an open circuit of the system and enters the cobalt recovery system to ensure the recovery of cobalt in the solution of the entire smelting system and avoid the enrichment of impurities in the solution system.

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