Method for synchronously improving recovery rates of copper and cobalt in high-oxidation-rate copper-cobalt ore and low-grade copper-cobalt oxide concentrate

Abstract

The invention discloses a method for synchronously improving the recovery rate of copper and cobalt in high-oxidation-rate copper-cobalt ore and low-grade copper oxide-cobalt concentrate, which comprises the following steps: (1) carrying out copper sulfide flotation on the high-oxidation-rate copper-cobalt ore to obtain high-copper tailings; (2) the low-grade copper-cobalt concentrate and the high-copper tailings are mixed according to the mass ratio of 1: (1-2), and mixed ore is obtained; (3) the obtained mixed ore and a sulfuric acid solution system leaching agent are stirred and mixed, and slurry is obtained; (4) leaching the obtained slurry at normal temperature, and carrying out solid-liquid separation to obtain leached residues and leached liquid; (5) carrying out washing, extraction, reverse extraction and electrodeposition on the obtained leaching residues to obtain metal copper; and removing iron from the raffinate, and adding magnesium oxide into the iron-removed liquid for precipitation to obtain crude cobalt hydroxide. According to the method, the high-copper tailings and the low-grade copper oxide cobalt concentrate are subjected to the processes of ore blending, size mixing, normal-temperature sulfuric acid leaching and the like, the final copper leaching rate is 95% or above, and the cobalt leaching rate is 70% or above.

Description

Technical Field

[0001] The invention relates to the technical field of hydrometallurgy, and in particular to a method for synchronously improving the recovery rates of copper and cobalt in high-oxidation-rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate. Background Art

[0002] The copper resources of the Democratic Republic of the Congo occupy an important position in the world's copper resources, and it is one of the most important copper and cobalt producers. According to the "Country (Region) Guide for Overseas Investment Cooperation" issued by the Ministry of Commerce of China in 2023, the copper resources of the Democratic Republic of the Congo are 75 million tons, accounting for 15% of the world; the cobalt reserves are 4.5 million tons, accounting for 50% of the world. The known deposits in the Democratic Republic of the Congo contain up to 58 million tons of copper, and are concentrated in Katanga Province in the southeast of the Democratic Republic of the Congo, located in the famous Central African copper-cobalt mineralization belt.

[0003] With the advancement of the national "Belt and Road" initiative, in response to the country's "going out" strategy to encourage domestic enterprises to make more overseas investments, a large number of Chinese mining companies have participated in the "wave" of solid mineral resource development in Africa. The copper-cobalt mines currently being developed in the Democratic Republic of the Congo are basically mixed ores of near-surface sulfide and oxide ores that are shallowly buried and easy to explore and develop. The copper in these copper-cobalt mines is mainly malachite, cuprite, malachite, azurite, phosphorite, copper oxide, chalcocite, and sulfide copper-cobalt mines; cobalt is mainly found in minerals such as hydrocobaltite, copper-sulfur cobalt mines, and copper-cobalt-containing limonite; the gangue minerals are mainly quartz, iron minerals, etc. Among them, the cobalt in copper-sulfur cobalt mines, hydrocobalt mines, and copper-cobalt-containing limonite mostly exists in the form of trivalent cobalt, which cannot be directly leached by sulfuric acid and requires the addition of a reducing agent for leaching.

[0004] At present, most of the mixed ore processing processes in the Democratic Republic of the Congo are sulfur-first and oxygen-later flotation to produce copper-cobalt sulfide concentrate and copper-cobalt oxide concentrate. The copper-cobalt sulfide concentrate is sold separately or processed in other ways, while the copper-cobalt oxide concentrate is recovered through a hydrometallurgical system to recover valuable metals such as copper and cobalt. When the hydrometallurgical process treats a single copper-cobalt oxide crude concentrate, it is usually necessary to add reducing agents such as sodium sulfite, sodium pyrosulfite, sulfur dioxide, and ferrous salts to reduce and leach cobalt. These methods are not only complex and costly, but also use iron salts as reducing agents, which will introduce a large amount of iron ions into the slurry, making it difficult to remove iron in the subsequent cobalt precipitation process, and the cobalt loss rate is high in the iron removal process. Although the use of sulfite and SO2 as reducing agents will not introduce harmful impurities into the system, in an acidic system, sulfite is easy to decompose and release SO2, and SO2 has a low solubility. The SO2 released during the leaching process will deteriorate the working environment during the industrial production process, increasing the consumption of reducing agents and production costs while causing environmental pollution.

[0005] Invention patent CN107858506A discloses a leaching process from hydrocobaltite + cobalt salt intermediate, which uses Fe2+ As a reducing agent, the pH is adjusted to leach cobalt with a cobalt salt intermediate, wherein the oxidation method is to introduce high-pressure air, and the cobalt salt intermediate is cobalt hydroxide / cobalt carbonate. This method reduces the amount of oxidant added and increases the leaching rate of cobalt, but there are problems of high pressure and high cost of reducing agent. The invention patent with publication number CN108315553A discloses a method for leaching cobalt sulfide ore at normal pressure using a sodium chlorate-sulfuric acid system, wherein sulfuric acid is used to dissolve the ore, sodium chlorate is used as an oxidant, sulfur is oxidized into sulfate ions and enters the solution, and Fe 2+ Oxidized to Fe 3+ , Fe 3+ The redox reaction with the cobalt sulfide ore is beneficial to the leaching of cobalt. This method has low equipment requirements, short production cycle, low energy consumption, and the leaching rate of cobalt reaches more than 99%, but the intermediate product of the oxidant is ClO2, which is not conducive to impurity removal. Therefore, improving and perfecting the existing copper-cobalt ore reduction leaching process to achieve efficient and environmentally friendly leaching of copper and cobalt metals from copper-cobalt ore without increasing production costs and process difficulties is a difficult problem to be solved in the copper-cobalt ore leaching process. Summary of the invention

[0006] The invention provides a method for synchronously improving the recovery rates of copper and cobalt in high-oxidation-rate copper-cobalt ore and low-grade copper-cobalt oxide concentrate, so as to solve the technical problems of high impurity removal difficulty, high cobalt loss rate and easy environmental pollution caused by adding a reducing agent when treating a single copper-cobalt oxide crude concentrate in the existing hydrometallurgical process.

[0007] According to one aspect of the present invention, a method for synchronously improving the recovery rates of copper and cobalt in high-oxidation copper-cobalt ore and low-grade oxidized copper-cobalt concentrate is provided, wherein the high-oxidation copper-cobalt ore has a Cu grade of 3-5%, a cobalt grade of 0.2-0.5%, and a sulfur content of 0.1-0.5%; the low-grade oxidized copper-cobalt concentrate has a Cu grade of 8-10% and a cobalt grade of 0.5-0.8%, and the method comprises the following steps:

[0008] (1) performing copper sulfide flotation on the high oxidation rate copper-cobalt ore to obtain high-copper tailings;

[0009] (2) mixing the low-grade copper-cobalt concentrate and the high-grade copper tailings in a mass ratio of 1:(1-2) to obtain a mixed ore;

[0010] (3) stirring and mixing the obtained mixed ore with a sulfuric acid solution system leaching agent to obtain a slurry; the mass concentration of the slurry is 15-20%;

[0011] (4) leaching the slurry obtained in step (3) at room temperature, and obtaining leaching residue and leaching liquid after solid-liquid separation;

[0012] (5) washing the obtained leaching residue to obtain washing residue and washing liquid; extracting the obtained leaching liquid to obtain a loaded organic phase and a raffinate; wherein the obtained washing liquid is used in the extraction step, and the obtained washing residue is discharged for tail treatment;

[0013] (6) stripping and electrowinning the obtained loaded organic phase to obtain metallic copper;

[0014] (7) removing iron from the raffinate obtained from the stripping in step (6) to obtain a deironed liquid and deironed precipitate residue, wherein the deironed precipitate residue is discharged, and magnesium oxide is added to the deironed liquid for precipitation to obtain crude cobalt hydroxide.

[0015] Furthermore, the method for flotation of copper sulfide from the high oxidation rate copper-cobalt ore in step (1) comprises the following steps:

[0016] (a) mixing a high oxidation rate copper-cobalt ore having a particle size of -200 mesh and accounting for 70-73% with water to obtain a slurry, wherein the mass percentage concentration of the slurry is 30-35%;

[0017] (b) adding a collector and a frother to the obtained ore pulp to carry out sulfide ore flotation to obtain a coarse copper-cobalt sulfide concentrate and a rougher tailings;

[0018] (c) performing a scavenging operation on the obtained rougher tailings to obtain copper sulfide scavenged ore and scavenged tailings, wherein the copper sulfide scavenged ore enters step (b) for sulfide ore roughing, and the tailings are high-copper tailings.

[0019] Furthermore, the collector is sodium dithiocarbonate-O-butyl ester, and the addition amount is 100-150 g / ton of high oxidation rate copper-cobalt ore.

[0020] Furthermore, the foaming agent is pine oil, and the addition amount is 10-20 g / ton of high oxidation rate copper-cobalt ore.

[0021] Furthermore, the high-copper tailings have a Cu grade of 3-5%, a cobalt grade of 0.3-0.5%, and a sulfur content of 0.01-0.15%.

[0022] Furthermore, the low-grade copper-cobalt oxide concentrate is an intermediate product obtained by first flotating sulfide ore, then flotating copper oxide, and then flotating cobalt from a medium-grade copper-cobalt oxide mixed ore.

[0023] Furthermore, the leaching time of the slurry obtained by leaching at room temperature in step (4) is more than 5 hours.

[0024] Furthermore, the step (4) further includes concentrating the leached slurry before the solid-liquid separation.

[0025] Furthermore, in step (5), washing the obtained leaching residue comprises stirring and washing the obtained leaching residue with clean water having a pH value of 6.5-7.5 under natural conditions.

[0026] Furthermore, in the step (4), the slurry liquid-to-solid ratio in the leaching process is 5:1.

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

[0028] (1) The present invention pre-floats the sulfide ore of the copper sulfide minerals that are easy to float in the high-oxidation rate copper-cobalt ore, and adopts the processes of ore blending, slurry adjustment, and normal temperature sulfuric acid leaching for the high-copper tailings and low-grade copper-cobalt oxide concentrate obtained after the flotation of the sulfide ore. The copper and cobalt in the high-copper tailings and low-grade copper-cobalt oxide concentrate with poor single leaching effect are effectively synergistically leached. In the synergistic leaching products of the high-copper tailings and low-grade copper-cobalt oxide concentrate finally obtained, the copper leaching rate is above 95%, and the cobalt leaching rate is above 70%.

[0029] (2) The present invention directly leaches the solid raw materials of high-copper tailings and low-grade copper-cobalt oxide concentrate. The leaching system consists of high-copper tailings, low-grade copper-cobalt oxide concentrate, sulfuric acid, and an aqueous phase. Valuable metals such as Cu and Co that are difficult to leach in the material at room temperature are continuously converted into soluble sulfates, which enter the solution in the form of ions for recycling. The synergistic treatment process has strong practicality for high-copper tailings and low-grade copper-cobalt oxide concentrates with complex structures and variable properties, and effectively realizes the synergistic treatment of the two. The leaching agent is only a sulfuric acid solution system, the leaching cost is low, and the subsequent treatment process is simple and mature. By performing the above treatment on complex high-oxidation rate copper-cobalt ores and low-grade copper-cobalt oxide concentrates, the copper and cobalt contents in the final leaching slag are greatly reduced, thereby avoiding a large amount of copper and cobalt products being wasted in the leaching tailings during the mining and processing process.

[0030] In addition to the above-described purposes, features and advantages, the present invention has other purposes, features and advantages. The present invention will be further described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The drawings constituting a part of this application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0032] Figure 1 It is a schematic diagram of a treatment process for preparing high-copper tailings from high-oxidation rate copper-cobalt mixed ore according to a preferred embodiment of the present invention;

[0033] Figure 2 It is a schematic diagram of a treatment process flow of a medium oxidation rate copper-cobalt ore according to a preferred embodiment of the present invention;

[0034] Figure 3 It is a schematic diagram of a process flow of co-processing high-copper tailings and low-grade copper-cobalt oxide concentrate according to a preferred embodiment of the present invention;

[0035] Figure 4 It is a schematic diagram of a coordinated processing device for high-copper tailings and low-grade copper-cobalt oxide concentrate according to a preferred embodiment of the present invention.

[0036] In the figure: 1. High-copper tailings feed pipe; 2. High-copper tailings slurry flowmeter; 3. Low-grade copper-cobalt oxide concentrate feed pipe; 4. Low-grade copper-cobalt oxide concentrate slurry flowmeter; 5. Thickener; 6. Feed valve; 7. Feed pump; 8. Leaching tank; 9. Agitator; 10. First discharge valve; 11. Second discharge valve; 12. Discharge pump; 13. Sulfuric acid pipe; 14. Sulfuric acid flowmeter; 15. Sulfuric acid valve; 16. Flowmeter; 17. Control valve; 18. Clean water pipeline. DETAILED DESCRIPTION

[0037] The embodiments of the present invention are described in detail below with reference to the accompanying drawings. However, the present invention can be implemented in many different ways as defined and covered below.

[0038] The embodiment of the first aspect of the present invention provides a method for synchronously improving the recovery rates of copper and cobalt in a high-oxidation copper-cobalt ore and a low-grade oxidized copper-cobalt concentrate, wherein the high-oxidation copper-cobalt ore has a Cu grade of 3-5%, a cobalt grade of 0.2-0.5%, and a sulfur content of 0.1-0.5%; and the low-grade oxidized copper-cobalt concentrate has a Cu grade of 8-10% and a cobalt grade of 0.5-0.8%, and the method comprises the following steps:

[0039] (1) performing copper sulfide flotation on the high oxidation rate copper-cobalt ore to obtain high-copper tailings; the high-copper tailings have a Cu grade of 3-5%, a cobalt grade of 0.3-0.5%, and a sulfur content of 0.01-0.15%;

[0040] (2) mixing the low-grade copper-cobalt concentrate and the high-grade copper tailings in a mass ratio of 1:(1-2) to obtain a mixed ore;

[0041] (3) stirring and mixing the obtained mixed ore with a sulfuric acid solution system leaching agent to obtain a slurry; the mass concentration of the slurry is 15-20%;

[0042] (4) leaching the slurry obtained in step (3) at room temperature, concentrating the leached slurry, and then performing solid-liquid separation to obtain leached residue and leaching liquid;

[0043] (5) washing the obtained leaching residue to obtain washing residue and washing liquid; extracting the obtained leaching liquid to obtain a loaded organic phase and a raffinate; wherein the obtained washing liquid is used in the extraction step, and the obtained washing residue is discharged for tail treatment;

[0044] (6) stripping and electrowinning the obtained loaded organic phase to obtain metallic copper;

[0045] (7) removing iron from the raffinate obtained from the stripping in step (6) to obtain a deironed liquid and deironed precipitate residue, wherein the deironed precipitate residue is discharged, and magnesium oxide is added to the deironed liquid for precipitation to obtain crude cobalt hydroxide.

[0046] According to a typical embodiment of the present invention, the method for producing the high oxidation rate copper-cobalt ore and the low-grade oxidized copper-cobalt concentrate is as follows: Figure 1 shown. Figure 1 A simple production process of high-copper tailings and low-grade copper-cobalt oxide concentrate is shown.

[0047] See also Figure 4 , Figure 4 Schematic diagram of the coordinated processing unit for high-copper tailings and low-grade copper-cobalt oxide concentrate.

[0048] The coordinated processing device of high-copper tailings and low-grade copper-cobalt oxide concentrate comprises a thickener 5 and a leaching tank 8. The thickener 5 is used for mixing low-grade copper-cobalt concentrate and high-copper tailings. The leaching tank 8 is used for mixed leaching of low-grade copper-cobalt concentrate and high-copper tailings sulfuric acid solution system leaching agent. The thickener 5 is connected with a high-copper tailings feed pipe 1 and a low-grade copper-cobalt oxide concentrate feed pipe 3, and a high-copper tailings slurry flowmeter 2 and a low-grade copper-cobalt oxide concentrate slurry flowmeter 4 are respectively provided on the high-copper tailings feed pipe 1 and the low-grade copper-cobalt oxide concentrate feed pipe 3; the mixed ore in the thickener 5 enters the leaching tank 8 through a feed valve 6 and a feed pump 7. One or more leaching tanks 8 can be provided. An agitator 9 is provided in the leaching tank 8 for stirring the slurry during the leaching process; a sulfuric acid pipe 13 and a clean water pipe are connected to the leaching tank 8, and a sulfuric acid flowmeter 14 and a sulfuric acid valve 15 are provided on the sulfuric acid pipe 13; a clean water flowmeter 16 and a control valve 17 are provided on the clean water pipe 18; a first discharge valve 10 and a second discharge valve 11 connected to a discharge pump 12 are provided at the bottom of the leaching tank 8 for discharging after the leaching is completed.

[0049] In an embodiment of the present invention, low-grade copper-cobalt concentrate and high-copper tailings are mixed in a thickener at a mass ratio of 1: (1-2), and the mixed ore obtained after mixing is transported to a leaching tank 8 through a feed valve 6 and a feed pump 7, and leached after adding sulfuric acid and stirring evenly. The first discharge valve 10 and the second discharge valve 11 are connected to the discharge pump 12 and used in conjunction with each other for discharge after leaching. The leaching agent in the leaching process is a sulfuric acid solution system, and the sulfuric acid solution is fed through a sulfuric acid pipe 13. The sulfuric acid dosage is controlled by a sulfuric acid flowmeter 14 and a sulfuric acid valve 15, and the pH of the slurry during the leaching process is 1-1.5. The slurry liquid-to-solid ratio in the leaching process is 5:1, and the stirring leaching is performed by an agitator 9.

[0050] like Figure 3-4 As shown in the figure, under the above conditions, the copper in the mixed ore is mainly present in malachite (2CuCO3·Cu(OH)2), cuprite (Cu2O), chrysocolla (CuSiO3·2H2O), azurite (Cu3(CO3)2(OH)2), pyrocopperite (Cu2(PO4)(OH)), copper oxide (CuO), chalcocite (CuS) and pyrocobaltite (CuCo2S4); the cobalt is mainly present in hydrocobaltite (CoO(OH) x ), copper-cobalt sulfide ore (CuCo2S4) and copper-cobalt limonite; the gangue minerals are mainly quartz, iron minerals, etc. During the acid leaching process, the copper, cobalt and gangue minerals in the material will react with the acid and enter the solution in the form of ions and convert into soluble sulfates. The main reactions occurring in the collaborative leaching process are as follows:

[0051] The main reactions of malachite (basic copper carbonate Cu(OH)2·CuCO3), cuprite (Cu2O), chrysocolla (CuSiO3·2H2O), azurite (Cu3(CO3)2(OH)2), phosphate copper (Cu2(PO4)(OH)) and copper oxide (CuO) in the ore in aqueous solution of sulfuric acid are shown in (1) to (6):

[0052] Cu(OH)2·CuCO3 + 2H2SO4 → 2CuSO4 + 3H2O + CO3↑ (1)

[0053] Cu2O + H2SO4 → Cu↓ + CuSO4 + H2O (2)

[0054] CuSiO3·2H2O +H2SO4+2H2O→CuSO4·5H2O + SiO2↓(slag) (3)

[0055] 2CuCO3·Cu(OH)2 +3H2SO4 =3CuSO4 +4H2O+2CO2↑ (4)

[0056] Cu2(PO4)(OH) + 2H2SO4 = 2CuSO4 + H2O+ H3PO4 (5)

[0057] CuO + H2SO4 →CuSO4 + H2O (6)

[0058] The valuable metal cobalt in the ore mainly exists in the form of oxides and sulfides, such as hydrocobaltite (CoO(OH) x ), copper cobalt sulfide (CuC O2 S4). Co2O3 and CuC O2S4 cannot be completely dissolved in H2SO4, but will ionize a small amount of Co in acidic solution. 3+ .

[0059] Therefore, in the conventional cobalt leaching process, a certain amount of reducing agent (such as Na2SO3, iron powder, ferrous ion compounds, etc.) must be added to reduce it to divalent cobalt that is easily soluble in acid to increase the leaching rate of cobalt. The main chemical reactions involved are shown in formulas (7) to (8):

[0060] CoO + H2SO4 → CoSO4 + H2O (7)

[0061] Co2O3 + Na2SO3 + 2H2SO4 → 2CoSO4 + Na2SO4 + 2H2O (8)

[0062] The gangue minerals in the ore are mainly iron minerals (iron oxides, goethite), dolomite, etc. The reaction of some impurity components with sulfuric acid is shown in equations (9) to (11):

[0063] 2FeO(OH) + 3H2SO4 → Fe2(SO4)3 + 4H2O (9)

[0064] Fe2O3 + 3H2SO4 → Fe(SO4)3 + 3H2O (10)

[0065] MgCO3 + H2SO4 → MgSO4+ H2O + CO2↑ (11)

[0066] The products of the reaction with sulfuric acid in formula (9) and (10) are mainly Fe 2+ , Fe 3+ Existing in ionic form, Fe 2+ It has reducing properties and can directly convert Co 3+ Reduction to Co 2+ Goethite is generated, as shown in formula (12); the generated FeOOH continues to react with H2SO4, as shown in formula (13):

[0067] Co(OH)3 + Fe 2+ = Co 2+ + FeOOH + H2O (12)

[0068] 2FeOOH + 6H + → 2Fe 3+ + 4H2O (13)

[0069] During the leaching and stirring process, as the copper oxide reacts with the acid, the sulfide ores that exist in conjunction with the oxide ores in the form of intergrowths and combinations are exposed in the solution. These sulfide ores are mainly chalcocite (CuS) and copper-cobalt sulfide (CuCo2S4). The sulfides of these sulfide ores exposed in the solution are oxidized by the Fe in the solution. 3+ 、Co 3+ Oxidation to generate S and Cu 2+ , Fe 3+ 、Co 3 + It is reduced to Fe 2+ 、Co 2+ The overall reaction during the leaching process is shown in equations (14) and (15):

[0070] 2CuS + 4H + + Fe 3+ = 2Cu 2+ + 2S + Fe 2+ (14)

[0071] 2CuS + 4H + + Co 3+ = 2Cu 2+ + 2S + Co 2+ (15)

[0072] The ionization equilibrium of CuS and CuCo2S4 in solution is shown in equations (16) and (17):

[0073] CuS = Cu 2+ + S 2－ (16)

[0074] CuCo2S4 = Cu 2+ +2Co 3+ + 4S 2－ (17)

[0075] In an acidic environment, the ionized S 2－ The ions are converted into hydrosulfuric acid by the sulfuric acid in the system, as shown in formula (18):

[0076] S 2－ + 2H + = H2S (18)

[0077] Because hydrosulfuric acid is a weak acid, S 2－ Almost all of it exists in the form of hydrosulfuric acid. At the same time, hydrosulfuric acid is replaced by Co in the solution. 3+ , Fe 3+ Oxidation of elemental sulfur, see formula (19) to (20):

[0078] H2S + 2Co 3+ → 2H + + S↓+ 2 Co 2+ (19)

[0079] H2S + 2Fe 3+ → 2H + + S↓+ 2 Fe 2+ (20)

[0080] The generated elemental sulfur is very likely to appear in the form of colloids, because sulfur colloids can absorb hydrogen sulfide ions HS in the solution － The negative charge, coupled with the adsorption of the micelle itself, causes a considerable amount of Fe to be adsorbed on the surface of the sulfur micelle. 2+ Ion, Fe 2+ It reacts with the O2 dissolved into the solution during stirring to generate Fe 3+ , see formula (21):

[0081] 4Fe 2+ + 4H + + O2 → 4Fe 3+ + 2H2O (21)

[0082] Fe 3+ Continue to oxidize elemental S to HSO 3－ , H2SO3 and a small amount of SO3 2－ , see formula (22):

[0083] S + 4Fe 3+ + 3H2O → H2SO3 + 4Fe 2+ + 4H + (twenty two)

[0084] H2SO3 reacts with O2 dissolved in the solution to generate SO4 2－ , see formula (23):

[0085] 2H2SO3 + O2 → 2SO4 2－ + 4H + (twenty three)

[0086] The above reaction continues until CuS, CuCo2S4, CoO(OH) x Stop after all substances have reacted completely.

[0087] The reaction speed of high-copper tailings (high-oxidation rate copper-cobalt ore sulfur tailings) and low-grade copper-cobalt oxide concentrate with sulfuric acid is very slow in a single case. When the two are mixed in the thickener 5 and fed into the leaching tank 8, the leaching agent is mainly an aqueous solution of sulfuric acid. The products generated by the reaction of the two with sulfuric acid and the redox ions ionized by themselves play a good promoting role. Through further redox reactions, high-copper tailings and low-grade copper-cobalt oxide concentrates are synergistically leached, and sulfur is produced as a very small amount of elemental sulfur and sulfate. The leaching process completely eliminates the emission of SO2, H2S, and NOX vapors, and also improves the synergistic leaching rate of Cu and Co metals in the two.

[0088] The invention adopts high-copper tailings and low-grade oxidized copper-cobalt concentrate as synergistic leaching raw materials, which fundamentally solves the problem of high cost and high investment of single treatment of high-oxidation copper-cobalt ore sulfur tailings and low-grade oxidized copper-cobalt concentrate. Leaching is carried out under normal temperature conditions. Compared with high-temperature roasting, oxygen pressure leaching, ammonia leaching and other operating processes, while saving energy and environmental protection investment, the process operation safety is almost the same as conventional sulfuric acid leaching.

[0089] The leaching time of the slurry obtained by leaching at room temperature is more than 5 hours, and the preferred leaching time is generally 5-6 hours. When the leaching time reaches 5-6 hours, the operation is stopped, and the mixed ore slurry after leaching is fed to the thickener for concentration and liquid-solid separation by using a slurry pump.

[0090] The leached residue contains iron, manganese, calcium, silicon, etc. It is washed with clean water with a pH of 6.5-7.5 under natural conditions. After washing, the slurry is fed into the filter press again. The washing liquid is mixed with the leaching liquid and fed into the next process. The leached residue is sent to the slag yard for stacking.

[0091] High-copper tailings (sulfur tailings from high-oxidation copper-cobalt ore) and low-grade copper-cobalt oxide concentrates contain a large amount of silicate minerals and iron minerals such as malachite, cuprite, chalcocite, azurite, phosphorite, copper oxide, chalcocite, pyrocobaltite, hydrocobaltite and quartz. The method of the present invention is used to collaboratively process and recover the valuable metals copper and cobalt in high-copper tailings and low-grade copper-cobalt oxide concentrates. Even if the contents of impurity elements such as calcium, iron, cadmium, manganese and phosphorus in the gangue silicate minerals are high, the leaching of Cu and Co metals in the collaborative leaching process of the two is not affected. The Cu leaching rate can reach more than 90%, and the Co leaching rate can reach more than 70%, thereby realizing the comprehensive recovery of copper and cobalt resources in high-copper tailings and low-grade copper-cobalt oxide concentrates.

[0092] The collaborative processing method proposed in the present invention has very broad application prospects in the field of hydrometallurgy and has the following characteristics:

[0093] (1) There is no need for pre-treatment of high-oxidation copper-cobalt ore sulfur tailings and low-grade oxidized copper-cobalt concentrates. The flotation process required for the enrichment process is simple, the process is simple, and the equipment investment is small. The Cu grade of the high-oxidation copper-cobalt ore after flotation is 3-5%, the cobalt grade is 0.2-0.5%, and the sulfur content is 0.1-0.5%; the Cu grade of the low-grade oxidized copper-cobalt concentrate is 8-10%, and the cobalt grade is 0.5-0.8%. The actual processing process does not require a large investment.

[0094] (2) The synergistic leaching material is composed of high-copper tailings obtained after flotation of sulfide ore with high oxidation rate and low-grade oxidized copper-cobalt concentrate obtained by flotation of copper-cobalt mixed ore with medium oxidation rate. The material is easy to obtain and consists of two single materials. Cu and Co can be leached simultaneously in an aqueous solution of sulfuric acid.

[0095] (3) The material composition of the leaching process is simple, and no other additives or redox agents are required. The slurry is evenly mixed in the leaching tank 8, and the redox ions generated during the reaction between the mineral itself and H2SO4 are used to accelerate the decomposition of the difficult-to-react substances under acidic conditions. While reducing the consumption of reducing agents, the main metals copper and Co in the two are leached simultaneously.

[0096] (4) The synergistic leaching process is carried out in a closed container at room temperature with moderate stirring, and the actual production control is simple.

[0097] (5) The collaborative leaching process does not have the problems of environmental pollution and high cost caused by the addition of reducing agents such as Na2SO3 and SO2, and the process flow is simple and clean.

[0098] In an embodiment of the present invention, the method for flotation of copper sulfide on the high oxidation rate copper-cobalt ore in step (1) comprises the following steps:

[0099] (a) mixing a high oxidation rate copper-cobalt ore having a particle size of -200 mesh and accounting for 70-73% with water to obtain a slurry, wherein the mass percentage concentration of the slurry is 30-35%;

[0100] (b) adding a collector and a frother to the obtained ore pulp to carry out sulfide ore flotation to obtain a coarse copper-cobalt sulfide concentrate and a rougher tailings;

[0101] (c) performing a scavenging operation on the obtained rougher tailings to obtain copper sulfide scavenged ore and scavenged tailings, wherein the copper sulfide scavenged ore enters step (b) for sulfide ore roughing, and the tailings are high-copper tailings.

[0102] According to a typical embodiment of the present invention, the method for producing the high-copper tailings is as follows: Figure 2 shown. Figure 2The process flow diagram of preparing high-copper tailings from high-oxidation copper-cobalt ore is shown. The treatment method includes the steps of preparing slurry and flotation treatment. The slurry preparation refers to preparing a slurry from a mixture of high-oxidation copper-cobalt ore and water, wherein the particle size of -200 mesh in the slurry accounts for 70-73% of the total particle weight; the flotation treatment includes roughing and scavenging in sequence.

[0103] The concentration of the ore pulp is 30-35%, and the pH is natural pH7-8. After grinding, the high oxidation copper-cobalt ore obtains a slurry of a certain concentration, and the slurry is mixed with water for slurry adjustment and flotation. The present invention preferably controls the mass percentage concentration of the ore pulp to 30-35% and sends it to the flotation tank for flotation because it is necessary to consider the separation effect of sulfide ores required in the subsequent treatment process. When flotation is performed at a slurry concentration within this range, it can ensure that the sulfide ores in the high oxidation copper-cobalt ore are separated to the greatest extent; when the slurry concentration is lower than 30% or higher than 35%, it is not conducive to the clean separation of the sulfide ores in the high oxidation copper-cobalt ore. The pH of the slurry system is 7-8, which is the natural pH of the high oxidation copper-cobalt mixed ore after grinding and slurry adjustment. Flotation within this pH range has no effect on the separation of sulfide ores in the high oxidation copper-cobalt mixed ore.

[0104] The flotation process includes a roughing step and a scavenging step, wherein the roughing step includes adding a collector and a frother to the slurry and stirring and sorting to obtain a rough concentrate and a roughing tailing, and the stirring and sorting time is 3-4 minutes; the scavenging step includes stirring and sorting the roughing tailing once, and the stirring and sorting time is 3-4 minutes.

[0105] The main purpose of roughing is to recover the sulfide ore in the high oxidation rate copper-cobalt ore. One roughing is enough to float out 50-80% of the sulfide ore. The specific operation is to send the pulp with a certain concentration into the flotation tank, and add the collector and frother to the pulp system in the flotation tank while stirring; the collector is added to float out the sulfide ore in the pulp. The working principle of the collector is that the collector reacts with the surface of the sulfide ore to form chemical adsorption, increase the hydrophobicity of the sulfide ore and then adhere to the foam and float together with the foam; the frother is added to increase the amount of foam and its viscosity during the foaming process, which is conducive to the adhesion of the sulfide ore to the surface of the foam. Stirring is to make the flotation reagents such as collectors and frothers more fully mixed with the pulp. Generally, the stirring time can be 3-4 minutes. Controlling the time within this range is enough to make the sulfide ore and the flotation reagent fully mixed.

[0106] In the embodiment of the present application, the collector is sodium dithiocarbonate-O-butyl ester, and the addition amount is 100-150 g / ton of high oxidation rate copper-cobalt ore. The foaming agent is pine oil, and the addition amount is 10-20 g / ton of high oxidation rate copper-cobalt ore.

[0107] The tailings after roughing are fed into the next foam tank for scavenging, and the foam product obtained by scavenging is returned to the roughing section. Among them, the flotation reagents in the scavenging stage can include a collector, sodium salt of thiocarbonate-O-butyl ester, and a foaming agent, pine oil; in the sulfide ore scavenging step, the addition amount of sodium salt of dithiocarbonate-O-butyl ester is 20-50 grams / ton of high oxidation rate copper-cobalt ore; the addition amount of pine oil is 2-5 grams / ton of high oxidation rate copper-cobalt ore; the scavenging time can be 3-4 minutes. In step (c), the obtained roughing tailings are scavenged once, and the scavenging once produces sulfide ore middlings and tailings, and the sulfide ore middlings are returned to the roughing step; the tailings are high copper tailings, wherein the Cu grade is 3-5%, the cobalt grade is 0.3-0.5%, and the sulfur content is 0.01-0.15%.

[0108] In the embodiments of the present application, the low-grade oxidized copper-cobalt concentrate is an intermediate product obtained by first flotation of sulfide ore, then flotation of oxidized copper, and then flotation of cobalt from a medium-grade oxidized copper-cobalt mixed ore, wherein the Cu grade is about 8-10% and the cobalt grade is about 0.5-0.8%.

[0109] The following examples describe the present disclosure in more detail, and these examples are intended for illustrative purposes only.

[0110] Example 1

[0111] A medium-oxidation copper-cobalt mixed ore (containing 2.62% copper, 0.278% cobalt and 0.25% sulfur) of a mining company in the Democratic Republic of the Congo was first floated into sulfide ore, then floated into oxidized copper, and then floated into oxidized copper and cobalt to obtain a low-grade oxidized copper-cobalt concentrate (containing 8.67% copper and 0.734% cobalt); a high-oxidation copper-cobalt mixed ore (containing 4.05% copper, 0.364% cobalt and 0.19% sulfur) was floated into sulfide ore to obtain a high-copper tailings (containing 3.91% copper, 0.344% cobalt and 0.09% sulfur).

[0112] Take the copper-cobalt oxide concentrate containing 8.67% copper and 0.74% cobalt, and the high-copper tailings containing 3.91% copper, 0.344% cobalt and 0.09% sulfur, and mix them into a mixed ore in a ratio of 1:2 and add them into a leaching stirring tank with a model specification of 13.5*14.5m. The effective volume of the stirring tank is 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.59%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0113] After leaching, the mixed liquid is passed through the discharge pump 4 to the next process for subsequent treatment such as concentration and filtration. The subsequent treatment includes: using a thickener to concentrate and separate the mixed liquid after leaching to obtain a leachate and a leach residue, the leach residue is stirred and washed to obtain a washing liquid and a washing residue, the washing residue is discharged, and the washing liquid and the leachate are mixed and then enter the extraction-stripping process to prepare cathode copper by electrolysis; the raffinate obtained in the stripping process is subjected to an iron removal filtering process to obtain an iron removal filtrate and an iron removal precipitate, wherein the iron removal precipitate is discharged, the iron removal filtrate is subjected to a copper removal filtering process to obtain a copper removal filtrate, and the copper removal filtrate is subjected to a cobalt precipitation process to prepare crude cobalt hydroxide. The total copper content in the washing residue after leaching is determined by an atomic absorption spectrometer, and the synergistic leaching copper leaching rate of the low-grade copper-cobalt oxide concentrate and the high-copper tailings is calculated to be 96.04% and the cobalt leaching rate is 73.76%.

[0114] Example 2

[0115] A medium-oxidation copper-cobalt mixed ore (containing 2.467% copper, 0.192% cobalt and 0.14% sulfur) of a mining company in the Democratic Republic of the Congo was first floated into sulfide ore, then floated into oxidized copper, and then floated into oxidized copper and cobalt to obtain a low-grade oxidized copper-cobalt concentrate (containing 8.07% copper and 0.714% cobalt); a high-oxidation copper-cobalt mixed ore (containing 4.67% copper, 0.304% cobalt and 0.45% sulfur) was floated into sulfide ore to obtain a high-copper tailings (containing 4.32% copper, 0.30% cobalt and 0.13% sulfur).

[0116] Take the copper-cobalt oxide concentrate containing 8.07% copper and 0.714% cobalt, and the high-copper tailings containing 4.32% copper, 0.30% cobalt, and 0.13% sulfur, and mix them into a mixed ore in a ratio of 1:2 and add them into a leaching stirring tank with a model specification of 13.5*14.5m. The effective volume of the stirring tank is 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.39%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0117] After leaching, the mixed liquid is passed through the discharge pump 4 to the next process for subsequent treatment such as concentration and filtration. The subsequent treatment includes: using a thickener to concentrate and separate the mixed liquid after leaching to obtain a leachate and a leach residue, stirring and washing the leach residue to obtain a washing liquid and a washing residue, discharging the washing residue, mixing the washing liquid and the leachate and entering the extraction-stripping process for electrolytic production of cathode copper; the raffinate obtained in the extraction process is subjected to an iron removal filtration process to obtain an iron removal filtrate, the iron removal filtrate is subjected to a copper removal filtration process to obtain a copper removal filtrate, and the copper removal filtrate is subjected to a cobalt precipitation process to prepare crude cobalt hydroxide. The total copper content in the washing residue after leaching is determined by an atomic absorption spectrometer, and the synergistic leaching copper leaching rate of the low-grade copper-cobalt oxide concentrate and the high-copper tailings is calculated to be 95.42% and 73.25% respectively.

[0118] Example 3

[0119] A mining company in the Democratic Republic of the Congo obtained a low-grade oxidized copper-cobalt concentrate (containing 9.88% copper and 0.688% cobalt) from a medium-oxidation copper-cobalt mixed ore (containing 2.71% copper, 0.149% cobalt and 0.21% sulfur) by first flotation of sulfide ore, then flotation of oxidized copper and then flotation of oxidized copper and cobalt; a high-oxidation copper-cobalt mixed ore (containing 4.18% copper, 0.428% cobalt and 0.13% sulfur) was obtained by flotation of sulfide ore to obtain high-copper tailings (containing 3.36% copper, 0.355% cobalt and 0.05% sulfur).

[0120] Take low-grade copper-cobalt oxide concentrate containing 9.88% copper and 0.688% cobalt, and high-copper tailings containing 3.36% copper, 0.355% cobalt and 0.05% sulfur, and mix them into a mixed ore in a ratio of 1:1 and add them into a leaching stirring tank with a model specification of 13.5*14.5m. The effective volume of the stirring tank is 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.27%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0121] After leaching, the mixed liquid is passed through the discharge pump 4 to the next process for subsequent treatment such as concentration and filtration. The subsequent treatment includes: using a thickener to concentrate and separate the mixed liquid after leaching to obtain a leachate and a leach residue, stirring and washing the leach residue to obtain a washing liquid and a washing residue, discharging the washing residue, mixing the washing liquid and the leachate and entering the extraction-stripping process for electrolytic production of cathode copper; the raffinate obtained in the extraction process is subjected to an iron removal filtration process to obtain an iron removal filtrate, the iron removal filtrate is subjected to a copper removal filtration process to obtain a copper removal filtrate, and the copper removal filtrate is subjected to a cobalt precipitation process to prepare crude cobalt hydroxide. The total copper content in the washing residue after leaching is determined by an atomic absorption spectrometer, and the synergistic leaching copper leaching rate of the low-grade copper-cobalt oxide concentrate and the high-copper tailings is calculated to be 94.08% and 70.42% respectively.

[0122] Example 4

[0123] A mining company in the Democratic Republic of the Congo obtained a low-grade oxidized copper-cobalt concentrate (containing 8.2% copper and 0.676% cobalt) from a medium-oxidation copper-cobalt mixed ore (containing 2.29% copper, 0.175% cobalt and 0.14% sulfur) by first flotation of sulfide ore, then flotation of oxidized copper and then flotation of oxidized copper and cobalt; a high-oxidation copper-cobalt mixed ore (containing 4.67% copper, 0.304% cobalt and 0.45% sulfur) was used to obtain a high-copper tailings (containing 3.16% copper, 0.356% cobalt and 0.06% sulfur) by flotation of sulfide ore.

[0124] Take low-grade copper-cobalt oxide concentrate containing 8.2% copper and 0.676% cobalt, and high-copper tailings containing 3.16% copper, 0.356% cobalt and 0.06% sulfur, and mix them into a mixed ore at a ratio of 1:1.5 and add them into a leaching stirring tank with a model specification of 13.5*14.5m. The effective volume of the stirring tank is 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.27%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0125] After leaching, the mixed liquid is passed through the discharge pump 4 to the next process for subsequent treatment such as concentration and filtration. The subsequent treatment includes: using a thickener to concentrate and separate the mixed liquid after leaching to obtain a leachate and a leach residue, stirring and washing the leach residue to obtain a washing liquid and a washing residue, discharging the washing residue, mixing the washing liquid and the leachate and entering the extraction-stripping process for electrolytic production of cathode copper; the raffinate obtained in the extraction process is subjected to an iron removal filtration process to obtain an iron removal filtrate, the iron removal filtrate is subjected to a copper removal filtration process to obtain a copper removal filtrate, and the copper removal filtrate is subjected to a cobalt precipitation process to prepare crude cobalt hydroxide. The total copper content in the washing residue after leaching is determined by an atomic absorption spectrometer, and the synergistic leaching copper leaching rate of the low-grade copper-cobalt oxide concentrate and the high-copper tailings is calculated to be 94.98% and 72.26% respectively.

[0126] Comparative Example 1

[0127] In Example 1, a low-grade copper-cobalt oxide concentrate (containing 8.67% copper and 0.734% cobalt) was obtained by first flotation of sulfide ore, then flotation of copper oxide, and then flotation of copper-cobalt oxide from a copper-cobalt mixed ore (containing 2.62% copper, 0.278% cobalt, and 0.25% sulfur) in a mining company in the Democratic Republic of the Congo.

[0128] Take low-grade copper-cobalt oxide concentrate containing 8.67% copper and 0.245% cobalt, without adding high-copper tailings, and directly add it into the leaching stirring tank with a model specification of 13.5*14.5m. The effective volume of the stirring tank is 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.27%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0129] After leaching, the mixed liquid is passed through the discharge pump 4 to the next process for subsequent treatment such as concentration and filtration, and the subsequent treatment is the same as that in Example 1. The total copper content in the washed residue after leaching is measured by atomic absorption spectrometer, and the copper leaching rate of the single leaching of the low-grade copper-cobalt oxide concentrate is calculated to be 93.30%, and the cobalt leaching rate is 51.35%.

[0130] Comparative Example 2

[0131] In Example 1, a high-copper tailing (containing 3.91% copper, 0.344% cobalt, and 0.09% sulfur) was obtained by flotation of sulfide ore from a high-oxidation rate copper-cobalt mixed ore (containing 4.05% copper, 0.364% cobalt, and 0.19% sulfur) of a mining company in the Democratic Republic of the Congo.

[0132] Take high-copper tailings containing 3.91% copper, 0.344% cobalt and 0.09% sulfur, without adding low-grade copper-cobalt oxide concentrate, and directly add them into the leaching stirring tank with a model specification of 13.5*14.5m. The effective volume of the stirring tank is 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.27%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0133] After leaching, the mixed liquid is fed into the next process through the discharge pump 8 for subsequent treatment such as concentration and filtration, and the subsequent treatment is the same as in Example 1. The total copper content in the washed residue after leaching is measured by atomic absorption spectrometer, and the copper leaching rate of the single leaching of high-copper tailings is calculated to be 95.03% and the cobalt leaching rate is 22.17%.

[0134] Comparative Example 3

[0135] qu Low-grade copper-cobalt oxide concentrate (containing 9.11% copper and 0.705% cobalt) from a mining company in the Democratic Republic of the Congo; Take the low-grade copper-cobalt oxide concentrate containing 9.11% copper and 0.705% cobalt, without adding high-copper tailings, and directly add it into the leaching stirring tank with a model specification of 13.5*14.5m, and the effective volume of the stirring tank is 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.27%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0136] After leaching, the mixed liquid is passed through the discharge pump 8 to the next process for subsequent treatment such as concentration and filtration, and the subsequent treatment is the same as that in Example 1. The total copper content in the washed residue after leaching is measured by an atomic absorption spectrometer, and the total copper content in the washed residue after leaching is measured by an atomic absorption spectrometer. The copper leaching rate of the single leaching of the low-grade copper-cobalt oxide concentrate is calculated to be 91.18%, and the cobalt leaching rate is 52.34%.

[0137] Comparative Example 4

[0138] In Example 4, a low-grade copper-cobalt oxide concentrate (containing 8.2% copper and 0.676% cobalt) was obtained by first flotation of sulfide ore, then flotation of copper oxide, and then flotation of copper oxide and cobalt oxide from a copper-cobalt mixed ore (containing 2.29% copper, 0.175% cobalt, and 0.14% sulfur) in a mining enterprise in the Democratic Republic of the Congo. The copper-cobalt oxide concentrate containing 8.2% copper and 0.676% cobalt was directly fed into a leaching stirring tank with a model specification of 13.5*14.5m without adding high copper tailings, and the effective volume of the stirring tank was 2000m 3 , add 1 mol / L sulfuric acid aqueous solution to adjust the mass percentage concentration of the slurry to 15.27%, and the slurry is leached while stirring in the leaching tank 1, keeping the temperature of the leaching tank at room temperature, and the leaching time is 6 hours.

[0139] After leaching, the mixed liquid is passed through the discharge pump 8 to the next process for subsequent treatment such as concentration and filtration, and the subsequent treatment is the same as that in Example 1. The total copper content in the washed residue after leaching is measured by an atomic absorption spectrometer, and the total copper content in the washed residue after leaching is measured by an atomic absorption spectrometer. The copper leaching rate of the single leaching of the low-grade copper-cobalt oxide concentrate is calculated to be 92.17%, and the cobalt leaching rate is 52.09%.

[0140] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for simultaneously improving the recovery rates of copper and cobalt in high-oxidation copper-cobalt ore and low-grade oxidized copper-cobalt concentrate, characterized in that: The high-oxidation copper-cobalt ore has a Cu grade of 3-5%, a cobalt grade of 0.2-0.5%, and a sulfur content of 0.1-0.5%; the low-grade oxidized copper-cobalt concentrate has a Cu grade of 8-10% and a cobalt grade of 0.5-0.8%. The method comprises the following steps: (1) performing copper sulfide flotation on the high oxidation rate copper-cobalt ore to obtain high-copper tailings; (2) mixing the low-grade copper-cobalt concentrate and the high-grade copper tailings in a mass ratio of 1:(1-2) to obtain a mixed ore; (3) stirring and mixing the obtained mixed ore with a sulfuric acid solution system leaching agent to obtain a slurry; the mass concentration of the slurry is 15-20%; (4) subjecting the slurry obtained in step (3) to solid-liquid separation to obtain leaching residue and leaching liquid; (5) washing the obtained leaching residue to obtain washing residue and washing liquid; extracting the obtained leaching liquid to obtain a loaded organic phase and a raffinate; wherein the obtained washing liquid is used in the extraction step, and the obtained washing residue is discharged for tail treatment; (6) stripping and electrowinning the obtained loaded organic phase to obtain metallic copper; (7) The obtained raffinate is treated to remove iron and copper to prepare crude cobalt hydroxide.

2. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate according to claim 1, characterized in that: The method for flotation of copper sulfide from the high oxidation rate copper-cobalt ore in step (1) comprises the following steps: (a) mixing a high oxidation rate copper-cobalt ore having a particle size of -200 mesh and accounting for 70-73% with water to obtain a slurry, wherein the mass percentage concentration of the slurry is 30-35%; (b) adding a collector and a frother to the obtained ore pulp to carry out sulfide ore flotation to obtain a coarse copper-cobalt sulfide concentrate and a rougher tailings; (c) performing a scavenging operation on the obtained rougher tailings to obtain copper sulfide scavenged ore and scavenged tailings, wherein the copper sulfide scavenged ore enters step (b) for sulfide ore roughing, and the tailings are high-copper tailings.

3. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate according to claim 2, characterized in that: The collector is sodium dithiocarbonate-O-butyl ester, and the addition amount is 100-150 g / ton of high oxidation rate copper-cobalt ore.

4. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate according to claim 2, characterized in that: The foaming agent is pine oil, and the added amount is 10-20 g / ton of high oxidation rate copper-cobalt ore.

5. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate according to claim 1 or 2, characterized in that: The high-copper tailings have a Cu grade of 3-5%, a cobalt grade of 0.3-0.5%, and a sulfur content of 0.01-0.15%.

6. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate according to claim 1, characterized in that: The low-grade copper-cobalt oxide concentrate is an intermediate product obtained from a medium-grade copper-cobalt oxide mixed ore by first flotation of sulfide ore, then flotation of copper oxide, and finally flotation of cobalt.

7. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate according to claim 1, characterized in that: The leaching time of the slurry obtained by leaching at room temperature in the step (4) is more than 5 hours.

8. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low-grade oxidized copper-cobalt concentrate according to claim 1, characterized in that: The step (4) also includes concentrating the leached slurry before the solid-liquid separation.

9. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low grade oxidized copper-cobalt concentrate according to claim 1, characterized in that: The step (5) of washing the obtained leaching residue comprises stirring and washing the obtained leaching residue with clean water having a pH value of 6.5-7.5 under natural conditions.

10. The method for synchronously improving the recovery rates of copper and cobalt in high oxidation rate copper-cobalt ore and low grade oxidized copper-cobalt concentrate according to claim 1, characterized in that: The slurry liquid-to-solid ratio in the leaching process in step (4) is 5:1.

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