Method for asynchronously recovering copper and cobalt in sulfur-oxygen mixed copper-cobalt ore tailings through combination of dressing and smelting

Abstract

The invention discloses a method for asynchronously recovering copper and cobalt in sulfur-oxygen mixed copper-cobalt ore tailings through dressing and smelting combination. The sulfur-oxygen mixed copper-cobalt ore tailings are divided into a coarse fraction, a medium fraction and a fine fraction according to particle sizes; the coarse fraction is subjected to ore grinding and copper sulfide flotation, part of copper and cobalt are recycled, and coarse fraction tailings are obtained; the medium fraction is subjected to copper sulfide flotation, copper oxide flotation and magnetic separation, part of copper and cobalt are recycled, and medium fraction tailings are obtained; the fine fraction is subjected to magnetic separation, part of copper and cobalt are recycled, and fine fraction tailings are obtained; and neutralizing one or more than two of the coarse-fraction tailings, the medium-fraction tailings and the fine-fraction tailings to recover part of copper and cobalt. According to the characteristics of the sulfur-oxygen mixed copper-cobalt ore tailings, the sulfur-oxygen mixed copper-cobalt ore tailings are divided into different size fractions, and different grading processes are adopted for treatment. And efficient enrichment and recovery of copper minerals and cobalt minerals with different properties in the sulfur-oxygen mixed copper-cobalt ore tailings are realized through a multi-process combined grading process.

Description

Technical Field

[0001] The invention relates to a method for recovering resources of tailings, and in particular to a method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings. Background Art

[0002] Copper has been an indispensable metal in human society since ancient times. In the process of industrialization, it has been widely used in many fields, such as light industry and electrical industry, due to its good thermal conductivity, electrical conductivity, corrosion resistance, ductility and tensile strength. Copper ranks second in China's consumption of non-ferrous metal materials. As an important additive in the magnetic materials industry, cobalt has properties such as ferromagnetism, high temperature resistance and corrosion resistance. It is widely used in aerospace, machinery manufacturing and other industries, and is a key raw material for the manufacture of cemented carbide. The industrial demand for copper and cobalt is growing, but the resources that are easy to mine are decreasing, and people are beginning to turn to low-grade copper-cobalt ores. These ore tailings have high economic value, but are difficult to be comprehensively recycled due to technical and conditional limitations. How to use these resources efficiently and at low cost has become a major economic research topic.

[0003] The Democratic Republic of the Congo is an important producer of copper and cobalt resources in the world, with 75 million tons of copper reserves and 3.6 million tons of cobalt reserves, accounting for about 50.70% of the world's total reserves. It is the world's largest cobalt producer. Copper mainly exists in the form of copper oxide and copper sulfide minerals, while cobalt is mainly a companion mineral of copper. The copper resources of the Democratic Republic of the Congo occupy an important position in the world, with its copper reserves accounting for 15% of the world's total and its cobalt reserves accounting for 50% of the world's total. The known copper deposits contain up to 58 million tons, mainly concentrated in the southeastern Katanga Province, located in the Central African Copper-Cobalt Mineralization Belt.

[0004] For the sulfur-oxygen mixed copper-cobalt ore in the Democratic Republic of the Congo, the conventional separation method is "sulfur first, then oxygen", that is, to add adjusters, collectors and frothers to the pulp that has reached a certain particle size after the grinding process to float out the copper sulfide minerals, and to flotate the copper sulfide tailings by first sulfiding and then adding collectors and frothers to float out the copper oxide minerals. However, for the stockpiled sulfur-oxygen mixed copper-cobalt tailings, after years of accumulation, the tailings are large in volume, and the easy-to-select components have been selected. The further efficient recovery of the remaining difficult-to-select components has become an urgent problem to be solved. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined beneficiation and smelting, which has a good recovery effect on the copper and cobalt elements in the tailings.

[0006] The technical solution adopted by the present invention to solve the technical problem is as follows: a method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined asynchronous smelting and smelting, wherein the sulfur-oxygen mixed copper-cobalt ore tailings are divided into coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings, medium-grained sulfur-oxygen mixed copper-cobalt ore tailings and fine-grained sulfur-oxygen mixed copper-cobalt ore tailings according to the particle size; the particle size of the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings is above 0.074 mm; the particle size of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is below 0.038 mm; the particle size of the medium-grained sulfur-oxygen mixed copper-cobalt ore tailings is 0.038 mm to 0.074 mm;

[0007] The coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are subjected to ore grinding and copper sulfide flotation to recover part of copper and cobalt and obtain coarse-grained tailings;

[0008] The medium-sized sulfur-oxygen mixed copper-cobalt ore tailings are subjected to copper sulfide flotation, copper oxide flotation and magnetic separation to recover part of copper and cobalt and obtain medium-sized tailings;

[0009] The fine-grained sulfur-oxygen mixed copper-cobalt ore tailings are subjected to magnetic separation to recover part of the copper and cobalt and obtain fine-grained tailings;

[0010] One or more of the coarse-grained tailings, the medium-grained tailings and the fine-grained tailings are neutralized to recover part of the copper and cobalt.

[0011] Preferably, in the sulfur-oxygen mixed copper-cobalt ore tailings, the copper grade is 0.60% to 1.30%, the cobalt grade is 0.10% to 0.40%, and the copper oxidation rate is above 80%.

[0012] Preferably, in the sulfur-oxygen mixed copper-cobalt ore tailings, the content of malachite is 0.44wt% to 0.81wt%, the content of copper-cobalt pyrolusite is 0.35wt% to 0.98wt%, the content of copper-containing limonite is 1.51wt% to 2.38wt%, and the content of cobalt dolomite is 1.72wt% to 2.85wt%.

[0013] Preferably, after one or more of the coarse-grained tailings, the medium-grained tailings, and the fine-grained tailings are concentrated, they are neutralized with the raffinate from the smelting system to a pH value of 1.2 to 2.0, and the solid and liquid are separated to obtain an underflow and a neutralization overflow liquid; the raffinate contains 0.2 to 2.5 g / L copper, 0.5 to 4.0 g / L cobalt, 1.0 to 4.0 g / L iron, and a sulfuric acid content of 10 to 30 g / L;

[0014] The first-stage neutralization overflow liquid is subjected to second-stage neutralization with lime milk until the pH value is 3.2 to 4.2, and solid-liquid separation is performed to obtain second-stage neutralization slag and second-stage neutralization overflow liquid;

[0015] The two-stage neutralization overflow liquid is neutralized with lime milk in three stages until the pH value is 6.2-7.2, and the solid-liquid is separated to obtain three-stage neutralization slag and three-stage neutralization overflow liquid.

[0016] More preferably, the concentration before neutralization is: adjusting the pulp concentration to 40-45%.

[0017] More preferably, the raffinate contains 0.5 to 1.0 g / L copper.

[0018] More preferably, the raffinate contains 1.5 to 2.5 g / L of cobalt.

[0019] More preferably, the raffinate contains 2.0 to 2.5 g / L of iron.

[0020] More preferably, the raffinate contains 0.5 to 1.5 g / L manganese.

[0021] More preferably, the raffinate contains 0.5 to 0.9 g / L calcium.

[0022] More preferably, the raffinate contains 10 to 15 g / L of magnesium.

[0023] More preferably, the raffinate contains 1.0 to 1.5 g / L aluminum.

[0024] More preferably, the sulfuric acid content of the raffinate is 14-20 g / L.

[0025] More preferably, the endpoint of the first stage neutralization is a pH value of 1.5 to 1.8, the slurry concentration after the first stage neutralization is 22 to 25%, and the neutralization reaction time is 3 to 4 hours.

[0026] More preferably, the endpoint of the second-stage neutralization is a pH value of 3.5 to 4.0, the slurry concentration after the second-stage neutralization is 22 to 25%, and the neutralization reaction time is 8 to 10 hours.

[0027] More preferably, the endpoint of the three-stage neutralization is a pH value of 6.5 to 7.0, the pulp concentration after the three-stage neutralization is 22 to 25%, and the neutralization reaction time is 2 to 4 hours.

[0028] Preferably, the copper sulfide flotation includes roughing, concentrating and scavenging; the slurry is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage; copper and cobalt are recovered into the copper sulfide concentrate, and the copper sulfide tailings are used for the next step of processing.

[0029] Preferably, the copper oxide flotation includes roughing, concentrating and scavenging; the slurry is subjected to roughing to obtain copper oxide roughing concentrate and copper oxide roughing tailings; the copper oxide roughing concentrate is subjected to concentrating to obtain copper oxide concentrate and copper oxide concentrating tailings; the copper oxide roughing tailings are subjected to scavenging to obtain copper oxide scavenging concentrate and copper oxide tailings; the copper oxide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper oxide concentrating tailings are returned to the flotation process to enter the roughing stage; copper and cobalt are recovered to the copper oxide concentrate, and the copper oxide tailings are used for the next step of processing.

[0030] Preferably, the magnetic separation of the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings includes magnetic roughing and magnetic concentration, and the magnetic separation intensity is above 0.7 T; the ore pulp is subjected to magnetic roughing to obtain magnetic roughing concentrate and magnetic roughing tailings; the magnetic roughing concentrate is subjected to magnetic concentration to obtain magnetic concentration concentrate and magnetic concentration tailings; the magnetic roughing tailings are magnetic separation tailings; the magnetic concentration tailings are magnetic separation tailings; copper and cobalt are recovered into the magnetic concentration concentrate, and the magnetic separation tailings are used for the next step of processing.

[0031] Preferably, the magnetic separation of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings includes magnetic roughing, magnetic scavenging and magnetic concentration, and the magnetic separation intensity is above 0.7 T; the ore pulp is subjected to magnetic roughing to obtain magnetic roughing concentrate and magnetic roughing tailings; the magnetic roughing tailings are subjected to magnetic scavenging to obtain magnetic scavenging concentrate and magnetic scavenging tailings; the magnetic roughing concentrate and / or magnetic scavenging concentrate are subjected to magnetic concentration to obtain magnetic concentration concentrate and magnetic concentration tailings; the magnetic scavenging tailings are magnetic separation tailings; the magnetic concentration tailings are magnetic separation tailings; copper and cobalt are recovered to the magnetic separation concentrate, and the magnetic separation tailings are used for the next step of processing.

[0032] Preferably, the collector for copper sulfide flotation comprises butyl xanthate or a combination of amyl xanthate and butyl xanthate.

[0033] Preferably, the frother for copper sulfide flotation comprises pine oil.

[0034] Preferably, the sulfiding agent for copper oxide flotation comprises a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:0-1.

[0035] Preferably, the collector for copper oxide flotation comprises butyl xanthate or a combination of amyl xanthate and butyl xanthate.

[0036] Preferably, the frother for copper oxide flotation comprises pine oil.

[0037] Preferably, the magnetic separation uses a high gradient magnetic separator.

[0038] Preferably, the collector for copper sulfide flotation comprises butyl xanthate or a combination of amyl xanthate and butyl xanthate in a mass ratio of 2 to 1:1.

[0039] Preferably, the collector for copper oxide flotation comprises butyl xanthate or a combination of amyl xanthate and butyl xanthate in a mass ratio of 2 to 1:1.

[0040] More preferably, in the roughing stage of copper sulfide flotation, the amount of collector used is 60-100 g / t, and the amount of frother used is 10-20 g / t.

[0041] More preferably, in the scavenging stage of copper sulfide flotation, the amount of collector used is 10-20 g / t, and the amount of frother used is 5-10 g / t.

[0042] More preferably, in the roughing stage of copper oxide flotation, the dosage of sulfiding agent is 2000-3000 g / t, the dosage of collector is 100-250 g / t, and the dosage of frother is 10-20 g / t.

[0043] More preferably, in the scavenging stage of the copper oxide flotation, the dosage of the sulfiding agent is 200-800 g / t, the dosage of the collector is 10-200 g / t, and the dosage of the frother is 0-10 g / t.

[0044] More preferably, the magnetic separation intensity of the rough magnetic separation is 0.9-1.3T.

[0045] More preferably, the magnetic separation intensity of the magnetic sweep separation is 0.9-1.3T.

[0046] More preferably, the magnetic separation intensity of the magnetic concentration is 0.8T to 1.2T.

[0047] Preferably, the grinding is as follows: grinding the ore pulp to a particle size of less than 0.074 mm, where the particles account for 70-80% and the ore pulp concentration is 30%-35%.

[0048] Preferably, the slurry concentration of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is 25% to 40%.

[0049] Preferably, the slurry concentration of the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings is 25% to 40%.

[0050] Preferably, the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings are stirred and scrubbed with dilute acid before copper sulfide flotation.

[0051] Preferably, after the flotation of copper oxide, the tailings slurry obtained is concentrated to a slurry concentration of 55% to 60%, and then mixed with clean water to be diluted to a slurry concentration of 34% to 40%.

[0052] More preferably, the amount of the dilute acid is 0.2-1 kg / t.

[0053] More preferably, activated carbon is also used for drug removal during dilution, and the amount of activated carbon added is 150-200 g / t.

[0054] The present invention has the following beneficial effects: the present invention divides the sulfur-oxygen mixed copper-cobalt ore tailings into coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings, medium-grained sulfur-oxygen mixed copper-cobalt ore tailings, and fine-grained sulfur-oxygen mixed copper-cobalt ore tailings according to their characteristics, and adopts different separation processes for treatment. Through the separation process of copper sulfide flotation, copper oxide flotation, strong magnetic separation, and flotation magnetic separation combined, the efficient enrichment and recovery of copper minerals and cobalt minerals of different properties in the sulfur-oxygen mixed copper-cobalt ore tailings is achieved.

[0055] 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 below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] 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:

[0057] Figure 1 This is a process flow chart for the combined asynchronous recovery of copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by smelting in Example 1 of the present invention. DETAILED DESCRIPTION

[0058] In order to make the purpose, scheme and beneficial technology of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments and drawings. It should be pointed out that the embodiments described in this specification are only for explaining the present invention, not for limiting the present invention.

[0059] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unambiguous range; and any lower limit can be combined with other lower limits to form an unambiguous range, and any upper limit can be combined with any other upper limit to form an unambiguous range. In addition, although not explicitly stated, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unambiguous range.

[0060] In the description of this article, it should be noted that, unless otherwise specified, “above” and “below” are inclusive of the number, and the “multiple” in “one or more” means two or more, and the “multiple” in “one or more” means two or more.

[0061] The embodiment of the present invention provides a method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined asynchronous smelting. The sulfur-oxygen mixed copper-cobalt ore tailings are divided into coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings, medium-grained sulfur-oxygen mixed copper-cobalt ore tailings and fine-grained sulfur-oxygen mixed copper-cobalt ore tailings according to the particle size; the particle size of the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings is greater than 0.074 mm; the particle size of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is less than 0.038 mm; the particle size of the medium-grained sulfur-oxygen mixed copper-cobalt ore tailings is 0.038 mm to 0.074 mm;

[0062] The coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are subjected to ore grinding and copper sulfide flotation to recover part of copper and cobalt and obtain coarse-grained tailings;

[0063] The medium-sized sulfur-oxygen mixed copper-cobalt ore tailings are subjected to copper sulfide flotation, copper oxide flotation and magnetic separation to recover part of copper and cobalt and obtain medium-sized tailings; wherein the tailings obtained from the copper sulfide flotation are used for copper oxide flotation, and the tailings obtained from the copper oxide flotation are used for magnetic separation;

[0064] The fine-grained sulfur-oxygen mixed copper-cobalt ore tailings are subjected to magnetic separation to recover part of the copper and cobalt and obtain fine-grained tailings;

[0065] One or more of the coarse-grained tailings, the medium-grained tailings and the fine-grained tailings are neutralized to recover part of the copper and cobalt.

[0066] The tailings of sulfur-oxygen mixed copper-cobalt ore are complex in composition and difficult to recycle. The inventors of the present invention have found through research that the composition of the tailings particles is related to their particle size. If the tailings of sulfur-oxygen mixed copper-cobalt ore are first sorted by the particle size of the tailings particles, and then recycled in a targeted manner, the recovery effect can be significantly improved. The oxide ore components in the tailings of sulfur-oxygen mixed copper-cobalt ore mainly enter the medium-grained sulfur-oxygen mixed copper-cobalt ore tailings and the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings. Therefore, the sorted coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are not necessary and not suitable for oxide ore flotation; the medium-grained sulfur-oxygen mixed copper-cobalt ore tailings obtained after sorting have relatively good flotation indicators, and the reagent consumption is greatly reduced compared to the unsorted situation, and flotation has a good recovery effect; the content of magnetic oxide ore in the sorted fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is high, and the recovery effect is better by magnetic separation.

[0067] The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined asynchronous smelting and smelting provided in the embodiment of the present invention has the following advantages: the present invention divides the sulfur-oxygen mixed copper-cobalt ore tailings into coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings, medium-grained sulfur-oxygen mixed copper-cobalt ore tailings, and fine-grained sulfur-oxygen mixed copper-cobalt ore tailings according to their characteristics, and adopts different separation processes for treatment. Through the separation process of copper sulfide flotation, copper oxide flotation, high-intensity magnetic separation, and flotation magnetic separation, efficient enrichment and recovery of copper minerals and cobalt minerals of different properties in the sulfur-oxygen mixed copper-cobalt ore tailings are achieved.

[0068] The multi-size sulfur-oxygen mixed copper-cobalt ore tailings can be obtained by hydraulic mining with a sand dredging vessel.

[0069] In some embodiments of the present invention, vibrating screens and / or cyclones are used for classification. Classification is to classify tailings according to the size of tailings particles, and other technologies with similar sorting principles and that can play an effective role can also be used.

[0070] In an embodiment of the present invention, in the sulfur-oxygen mixed copper-cobalt ore tailings, the copper grade is 0.60% to 1.30%, the cobalt grade is 0.10% to 0.40%, and the copper oxidation rate is above 80%.

[0071] In an embodiment of the present invention, in the sulfur-oxygen mixed copper-cobalt ore tailings, the content of malachite is 0.44wt% to 0.81wt%, the content of copper-cobalt pyrolusite is 0.35wt% to 0.98wt%, the content of copper-containing limonite is 1.51wt% to 2.38wt%, and the content of cobalt dolomite is 1.72wt% to 2.85wt%. The copper-cobalt minerals in the sulfur-oxygen mixed copper-cobalt ore in the Central African copper-cobalt mineralization belt are complex in nature, containing a large amount of malachite with poor floatability, copper-cobalt pyrolusite with weak magnetism, copper-containing limonite, and cobalt dolomite with high acid consumption. Simple separation methods cannot achieve a good recovery effect. The recovery rate of cobalt in the Central African copper-cobalt mineralization belt is usually low due to the presence of cobalt dolomite. If it is leached by direct wet method, the acid consumption is high.

[0072] In an embodiment of the present invention, after one or more of the coarse-grained tailings, the medium-grained tailings, and the fine-grained tailings are concentrated, they are neutralized with the raffinate from the smelting system to a pH value of 1.2 to 2.0, and the solid-liquid is separated to obtain a section of underflow and a section of neutralization overflow liquid; the raffinate contains 0.2 to 2.5 g / L of copper, 0.5 to 4.0 g / L of cobalt, 1.0 to 4.0 g / L of iron, and a sulfuric acid content of 10 to 30 g / L; the section of underflow can be used in other processes for leaching cobalt; the Fe carried in the raffinate 2+The low-price copper of a small amount of sulfide ores (mainly chalcocite) in fine-grained tailings and the copper-bearing limonite in the sulfur-oxygen mixed copper-cobalt ore tailings are all reducible. The self-oxidation-reduction reaction is realized by utilizing the reducibility and the oxidizability of high-price cobalt, and the leaching rate of cobalt is effectively improved without adding a reducing agent.

[0073] The first stage neutralization overflow liquid is subjected to second stage neutralization with lime milk to a pH value of 3.2 to 4.2, and solid-liquid separation is performed to obtain second stage neutralization slag and second stage neutralization overflow liquid; the second stage neutralization slag is an iron-aluminum neutralization slag;

[0074] The two-stage neutralization overflow liquid is subjected to three-stage neutralization with lime milk to a pH value of 6.2 to 7.2, and solid-liquid separation is performed to obtain three-stage neutralization slag and three-stage neutralization overflow liquid. Copper and cobalt are recovered into the three-stage neutralization slag, and the three-stage neutralization slag is collected, dissolved, and then crude cobalt hydroxide is obtained through a conventional cobalt precipitation process. Coarse-grained tailings, medium-grained tailings, and fine-grained tailings contain high cobalt and are mainly composed of cobalt dolomite. The tailings containing cobalt dolomite and carbonate gangue minerals have high acid consumption in leaching. After "three-stage neutralization", not only the cobalt that is difficult to be separated in the ore dressing process is recovered without additional consumption of sulfuric acid, but also it replaces lime to neutralize part of the acid in the raffinate, greatly reducing lime consumption.

[0075] In some embodiments of the present invention, the concentration before neutralization is: adjusting the pulp concentration to 40-45%.

[0076] In some embodiments of the present invention, the raffinate contains 0.5-1.0 g / L copper.

[0077] In some embodiments of the present invention, the raffinate contains 1.5 to 2.5 g / L of cobalt.

[0078] In some embodiments of the present invention, the raffinate contains 2.0-2.5 g / L of iron.

[0079] In some embodiments of the present invention, the raffinate contains 0.5-1.5 g / L manganese.

[0080] In some embodiments of the present invention, the raffinate contains 0.5-0.9 g / L calcium.

[0081] In some embodiments of the present invention, the raffinate contains 10-15 g / L magnesium.

[0082] In some embodiments of the present invention, the raffinate contains 1.0-1.5 g / L aluminum.

[0083] In some embodiments of the present invention, the sulfuric acid content of the raffinate is 14-20 g / L.

[0084] In some embodiments of the present invention, the endpoint of the first stage of neutralization is a pH value of 1.5 to 1.8, the slurry concentration after the first stage of neutralization is 22 to 25%, and the neutralization reaction time is 3 to 4 hours.

[0085] In some embodiments of the present invention, the endpoint of the second-stage neutralization is a pH value of 3.5 to 4.0, the pulp concentration after the second-stage neutralization is 22 to 25%, and the neutralization reaction time is 8 to 10 hours.

[0086] In some embodiments of the present invention, the endpoint of the three-stage neutralization is a pH value of 6.5 to 7.0, the pulp concentration after the three-stage neutralization is 22 to 25%, and the neutralization reaction time is 2 to 4 hours.

[0087] In some embodiments of the present invention, the copper sulfide flotation includes roughing, concentrating and scavenging; the slurry is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage; copper and cobalt are recovered to the copper sulfide concentrate, and the copper sulfide tailings are used for the next step of processing.

[0088] In some embodiments of the present invention, the copper oxide flotation includes roughing, concentrating and scavenging; the slurry is subjected to roughing to obtain copper oxide roughing concentrate and copper oxide roughing tailings; the copper oxide roughing concentrate is subjected to concentrating to obtain copper oxide concentrate and copper oxide concentrating tailings; the copper oxide roughing tailings are subjected to scavenging to obtain copper oxide scavenging concentrate and copper oxide tailings; the copper oxide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper oxide concentrating tailings are returned to the flotation process to enter the roughing stage; copper and cobalt are recovered to the copper oxide concentrate, and the copper oxide tailings are used for the next step of processing.

[0089] In some embodiments of the present invention, the magnetic separation of the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings includes magnetic roughing and magnetic concentration, and the magnetic separation intensity is above 0.7 T; the ore pulp is subjected to magnetic roughing to obtain magnetic roughing concentrate and magnetic roughing tailings; the magnetic roughing concentrate is subjected to magnetic concentration to obtain magnetic concentration concentrate and magnetic concentration tailings; the magnetic roughing tailings are magnetic separation tailings; the magnetic concentration tailings are magnetic separation tailings; copper and cobalt are recovered into the magnetic concentration concentrate, and the magnetic separation tailings are used for the next step of processing.

[0090] In some embodiments of the present invention, the magnetic separation of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings includes magnetic roughing, magnetic scavenging and magnetic concentration, and the magnetic separation intensity is above 0.7 T; the ore pulp is subjected to magnetic roughing to obtain magnetic roughing concentrate and magnetic roughing tailings; the magnetic roughing tailings are subjected to magnetic scavenging to obtain magnetic scavenging concentrate and magnetic scavenging tailings; the magnetic roughing concentrate and / or magnetic scavenging concentrate are subjected to magnetic concentration to obtain magnetic concentration concentrate and magnetic concentration tailings; the magnetic scavenging tailings are magnetic separation tailings; the magnetic concentration tailings are magnetic separation tailings; copper and cobalt are recovered to the magnetic concentration concentrate, and the magnetic separation tailings are used for the next step of processing.

[0091] In an embodiment of the present invention, the collector for flotation of copper sulfide includes butyl xanthate or a combination of amyl xanthate and butyl xanthate. Butyl xanthate has good selectivity; amyl xanthate has a longer hydrocarbon chain and stronger collecting ability. The ore involved in the present invention has poor floatability, and it is suitable to use a xanthate with stronger collecting ability to improve the recovery effect.

[0092] In an embodiment of the present invention, the frother for copper sulfide flotation includes pine oil.

[0093] In an embodiment of the present invention, the sulfiding agent for copper oxide flotation comprises a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:0-1.

[0094] In an embodiment of the present invention, the collector for flotation of copper oxide includes butyl xanthate or a combination of amyl xanthate and butyl xanthate. Butyl xanthate has good selectivity; amyl xanthate has a longer hydrocarbon chain and stronger collecting ability. The ore involved in the present invention has poor floatability and is suitable for using a xanthate with stronger collecting ability to improve the recovery effect.

[0095] In an embodiment of the present invention, the frother for copper oxide flotation comprises pine oil.

[0096] In an embodiment of the present invention, the magnetic separation adopts a high gradient magnetic separator.

[0097] In some embodiments of the present invention, the flotation of copper sulfide includes more than two stages.

[0098] In some embodiments of the present invention, the flotation of copper oxide includes two or more stages.

[0099] In some embodiments of the present invention, the collector for copper sulfide flotation includes butyl xanthate or a combination of amyl xanthate and butyl xanthate in a mass ratio of 2 to 1: 1. Butyl xanthate has good selectivity; amyl xanthate has a longer hydrocarbon chain and stronger collecting ability. The ore involved in the present invention has poor floatability and is suitable for using a xanthate with stronger collecting ability to improve the recovery effect.

[0100] In some embodiments of the present invention, the collector for flotation of copper oxide includes butyl xanthate or a combination of amyl xanthate and butyl xanthate in a mass ratio of 2 to 1: 1. Butyl xanthate has good selectivity; amyl xanthate has a longer hydrocarbon chain and stronger collecting ability. The ore involved in the present invention has poor floatability and is suitable for using a xanthate with stronger collecting ability to improve the recovery effect.

[0101] In some embodiments of the present invention, in the roughing stage of copper sulfide flotation, the amount of collector used is 60-100 g / t, and the amount of frother used is 10-20 g / t.

[0102] In some embodiments of the present invention, in the scavenging stage of copper sulfide flotation, the amount of collector used is 10-20 g / t, and the amount of frother used is 5-10 g / t.

[0103] In some embodiments of the present invention, in the roughing stage of copper oxide flotation, the dosage of sulfiding agent is 2000-3000 g / t, the dosage of collector is 100-250 g / t, and the dosage of frother is 10-20 g / t.

[0104] In some embodiments of the present invention, in the scavenging stage of copper oxide flotation, the dosage of sulfiding agent is 200-800 g / t, the dosage of collector is 10-200 g / t, and the dosage of frother is 0-10 g / t.

[0105] In some embodiments of the present invention, the magnetic separation intensity of the rough magnetic separation is 0.9-1.3T.

[0106] In some embodiments of the present invention, the magnetic separation intensity of the magnetic sweep separation is 0.9-1.3T.

[0107] In some embodiments of the present invention, the magnetic separation intensity of the magnetic concentration is 0.8T to 1.2T.

[0108] In an embodiment of the present invention, the grinding is: grinding the pulp until the particles with a particle size of less than 0.074 mm account for 70-80%, and the pulp concentration is 25%-40%. The grinding can be performed by ball milling. Grinding the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings fully separates the useful minerals from the gangue, which is beneficial to flotation separation and leaching in subsequent stages.

[0109] In an embodiment of the present invention, the slurry concentration of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is 25% to 40%.

[0110] In an embodiment of the present invention, the slurry concentration of the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings is 25% to 40%.

[0111] In some embodiments of the present invention, the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings are stirred and scrubbed with dilute acid before copper sulfide flotation. The surface of the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings is prone to form a hydrophilic layer, which is not easy to react with the flotation agent. Scrubbing with dilute acid helps the mineral to expose the fresh surface, which is beneficial to flotation.

[0112] In some embodiments of the present invention, after copper oxide flotation, the tailings slurry is concentrated to a slurry concentration of 55% to 60%, and then mixed with clean water to dilute to a slurry concentration of 34% to 40%. Concentration can achieve the effect of drug removal, and the overflow water obtained can be used in copper sulfide flotation and / or copper oxide flotation.

[0113] In some embodiments of the present invention, the amount of the dilute acid is 0.2-1 kg / t.

[0114] In some embodiments of the present invention, activated carbon is also used for drug removal during dilution, and the amount of activated carbon added is 150-200 g / t. Activated carbon can adsorb residual agents, and can be removed from tailings by screening after drug removal. Activated carbon has a developed pore structure, a large specific surface area and abundant surface chemical groups, and has a strong specific adsorption capacity, especially for residual organic agents in the slurry.

[0115] The weakly magnetic copper-cobalt pyrolusite and copper-containing limonite in the flotation scavenging tailings have weak magnetism and fineness, and need to be magnetically agglomerated under the action of a magnetic field to be better separated from non-magnetic minerals. However, the residual reagent on the surface of the target mineral makes the target mineral have good hydrophobicity and is not easy to agglomerate. Therefore, the removal of the reagent eliminates the influence of the reagent on the magnetic agglomeration of the target mineral to a certain extent, so that it can be better captured by the magnetic medium. The present invention uses concentration and activated carbon to remove the reagent from the flotation scavenging tailings entering the magnetic separation, thereby improving the magnetic separation recovery effect.

[0116] Example

[0117] The following examples describe the disclosure of the present invention in more detail, and these examples are intended for illustrative purposes only, as it will be apparent to those skilled in the art that various modifications and variations will be made within the scope of the disclosure of the present invention. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight. Unless otherwise stated, all reagents used in the examples are available through conventional commercial sources or are synthesized according to conventional methods and can be used directly without further processing. Unless otherwise stated, the instruments used in the examples are available through conventional commercial sources.

[0118] Embodiment 1:

[0119] The process flow chart of Example 1 is as follows Figure 1 shown.

[0120] The present embodiment relates to a multi-grade sulfur-oxygen mixed copper-cobalt ore tailings, containing 0.95% copper, 0.20% cobalt, and 81% copper oxidation rate; wherein the copper-cobalt minerals are complex in nature, with a content of 0.60wt% malachite, a content of 0.77wt% copper-cobalt pyrolusite, a content of 1.99wt% copper-containing limonite, and a content of 2.39wt% cobalt dolomite. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by smelting and asynchronous separation in the present embodiment is carried out in the following steps:

[0121] (1) Classification: A sand mining ship conducts hydraulic sand mining in the old tailings pond, and uses a vibrating screen to classify the multi-grained sulfur-oxygen mixed copper-cobalt ore tailings to obtain coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings with a particle size of 0.074 mm or more and raw ore slurry; the raw ore slurry is concentrated to 38wt% by a thickener and then classified again to obtain fine-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry of -0.038mm and medium-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry of -0.074mm+0.038mm; the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are conveyed to a ball mill by a belt for grinding to obtain coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry, of which the fineness is -0.074mm, accounting for 75%, and the slurry concentration is 35wt%.

[0122] (2) Multi-grade mineral processing:

[0123] The beneficiation of coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0124] The copper sulfide flotation is carried out, including one stage of roughing, three stages of concentrating and one stage of scavenging; the pulp is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate 1 and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0125] The collector in the roughing stage is amyl xanthate: butyl xanthate in a mass ratio of 1:1, with a dosage of 75g / t; the foaming agent is 2# oil, with a dosage of 15g / t; stir for 4 minutes after adding the agents;

[0126] The collector in the scavenging stage is amyl xanthate: butyl xanthate in a mass ratio of 1:1, with a dosage of 10g / t; the foaming agent is 2# oil, with a dosage of 8g / t; stir for 4 minutes after adding the agents;

[0127] The obtained copper sulfide tailings are coarse-grained tailings; proceed to step (3).

[0128] The beneficiation of medium-sized sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0129] The ore pulp is stirred and scrubbed with dilute sulfuric acid, and the amount of dilute sulfuric acid used is 0.8kg / t; after scrubbing, copper sulfide flotation is carried out, including a roughing stage, three concentrating stages and a scavenging stage; the ore pulp is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate 2 and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0130] The collector in the roughing stage of copper sulfide flotation is a combination of amyl xanthate and butyl xanthate in a mass ratio of 1:1, with a dosage of 100g / t; the frother is 2# oil, with a dosage of 20g / t; after adding the reagents, stir for 4 minutes;

[0131] The collector in the flotation scavenging stage of copper sulfide is a combination of amyl xanthate and butyl xanthate in a mass ratio of 1:1, with a dosage of 10g / t; the frother is 2# oil, with a dosage of 8g / t; after adding the reagents, stir for 4 minutes;

[0132] The obtained copper sulfide tailings are subjected to copper oxide flotation, including one stage of roughing, three stages of concentrating and one stage of scavenging; the pulp is subjected to roughing to obtain copper oxide roughing concentrate and copper oxide roughing tailings; the copper oxide roughing concentrate is subjected to concentrating to obtain copper oxide concentrate and copper oxide concentrating tailings; the copper oxide roughing tailings are subjected to scavenging to obtain copper oxide scavenging concentrate and copper oxide tailings; the copper oxide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper oxide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0133] The sulfiding agent in the roughing stage of copper oxide flotation is a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:1, with a dosage of 2000g / t; the collector is amyl xanthate and butyl xanthate in a mass ratio of 2:1, with a dosage of 200g / t; the frother is 2# oil in a dosage of 10g / t; after adding the reagents, stir for 5 minutes;

[0134] The sulfiding agent in the flotation scavenging stage of copper oxide is a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:1, with a dosage of 400g / t; the collector is amyl xanthate and butyl xanthate in a mass ratio of 2:1, with a dosage of 40g / t; the frother is 2# oil, with a dosage of 5g / t; stir for 5 minutes after adding the reagents;

[0135] The obtained copper oxide tailings are concentrated to a pulp concentration of 58%, then diluted with water, and 150 g / t of activated carbon is used for dedoping; the pulp concentration after dilution is 35%, and it is fed into a high gradient magnetic separator for a first magnetic roughing separation, with a background field strength of 1.2 T, to obtain a magnetic roughing concentrate and a magnetic roughing tailing; the magnetic roughing concentrate is subjected to a first magnetic concentration, with a background field strength of 1.0 T, to obtain a magnetic concentrate 1 and a magnetic concentration tailing; the magnetic roughing tailings and the magnetic concentration tailings are medium-sized tailings; and the process proceeds to step (3).

[0136] The beneficiation of fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0137] The magnetic separation of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings includes a magnetic roughing separation, a magnetic scavenging separation and a magnetic concentrating separation; the ore pulp is subjected to magnetic roughing separation to obtain a magnetic roughing concentrate and a magnetic roughing tailings; the magnetic roughing tailings are subjected to magnetic scavenging separation to obtain a magnetic scavenging concentrate and a magnetic scavenging tailings; the magnetic roughing concentrate and the magnetic scavenging concentrate are subjected to magnetic concentrating to obtain a magnetic concentrate 2 and a magnetic concentrating tailings;

[0138] The magnetic separation intensity of the rough magnetic separation is 1.3T; the magnetic separation intensity of the scavenging magnetic separation is 1.2T; the magnetic separation intensity of the concentrating magnetic separation is 0.8T; the magnetic scavenging tailings and the magnetic concentrating tailings are fine-grained tailings; proceed to step (3).

[0139] (3) Three-stage neutralization: The coarse-grained tailings, medium-grained tailings and fine-grained tailings are concentrated to 42 wt% and pumped to a neutralization stirring tank of the "three-stage neutralization" system; a raffinate containing 0.5 g / l copper, 1.5 g / l cobalt, 2.0 g / l iron and 15 g / l sulfuric acid is added to the neutralization stirring tank, and neutralized for 4 hours at room temperature, with an end point pH value of 1.6 and a slurry concentration of 25 wt% after neutralization; solid-liquid separation is performed to obtain an underflow and a phase. Neutralize the overflow liquid; send the overflow liquid from the first stage neutralization into the second stage neutralization tank, add lime milk, neutralize for 10 hours at room temperature, the end point pH value is 3.8, and the pulp concentration after neutralization is 25wt%; separate the solid and liquid to obtain the second stage neutralization slag and the second stage neutralization overflow liquid; send the overflow liquid from the second stage neutralization into the third stage neutralization tank, add lime milk, neutralize for 4 hours at room temperature, the end point pH value is 6.5, and the pulp concentration after neutralization is 25wt%; separate the solid and liquid to obtain the third stage neutralization slag and the third stage neutralization overflow liquid.

[0140] After the treatment of the sulfur-oxygen mixed copper-cobalt ore tailings in this embodiment, copper and cobalt are recovered into the copper sulfide concentrate 1, copper sulfide concentrate 2, copper oxide concentrate, magnetic separation concentrate 1, magnetic separation concentrate 2 obtained in step (2) and the three-stage neutralization slag (high cobalt and low copper neutralization slag) obtained in step (3). The test results are shown in Table 1. Finally, the total copper recovery rate is 93.56% and the total cobalt recovery rate is 71.23%. Among them, the copper grade of copper sulfide concentrate 1 is 32.32% and the cobalt grade is 0.34%, the copper grade of copper sulfide concentrate 2 is 42.26% and the cobalt grade is 0.32%, the copper grade of copper oxide concentrate is 15.46% and the cobalt grade is 0.73%, the copper grade of magnetic concentrate is 3.58% and the cobalt grade is 0.85%, the copper recovery rate of ore dressing is 76.70%, and the cobalt recovery rate is 25.94%; the copper grade of high-cobalt and low-copper neutralized slag is 3.85%, the cobalt grade is 2.18%, the copper recovery rate is 72.36%, the cobalt recovery rate is 61.15%, the copper recovery rate relative to the original ore is 16.86%, and the cobalt recovery rate is 45.29%.

[0141] Table 1 Experimental results of Example 1: Combined asynchronous recovery of sulfur-oxygen mixed copper-cobalt ore tailings copper and cobalt

[0142]

[0143] Compared with directly using lime to neutralize the raffinate, the consumption of lime in this embodiment is reduced by 180.22 kg / m 3 (Raffinate).

[0144] Embodiment 2:

[0145] The present embodiment relates to a multi-grade sulfur-oxygen mixed copper-cobalt ore tailings, containing 1.10% copper, 0.27% cobalt, and 85% copper oxidation rate; wherein the copper-cobalt minerals are complex in nature, with a content of 0.78wt% malachite, 0.89wt% copper-cobalt pyrolusite, 2.01wt% copper-containing limonite, and 2.70wt% cobalt dolomite. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by smelting and asynchronous separation in the present embodiment is carried out in the following steps:

[0146] (1) Classification: A sand mining ship hydraulically mines sand in the old tailings pond, and uses a linear screen to classify the multi-grained sulfur-oxygen mixed copper-cobalt ore tailings to obtain coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings with a particle size of 0.074 mm or more and raw ore slurry; the raw ore slurry is concentrated to 29wt% by a thickener and then classified again to obtain fine-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry of -0.038mm and medium-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry of -0.074mm+0.038mm; the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are conveyed to a ball mill by a belt for grinding to obtain coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry, the fineness of which is -0.074mm, accounting for 76%, and the slurry concentration is 32wt%.

[0147] (2) Multi-grade mineral processing:

[0148] The beneficiation of coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0149] The copper sulfide flotation is carried out, including one stage of roughing, three stages of concentrating and one stage of scavenging; the pulp is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate 1 and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0150] The collector in the roughing stage is amyl xanthate: butyl xanthate in a mass ratio of 1:1, with a dosage of 88g / t; the foaming agent is 2# oil, with a dosage of 18g / t; stir for 4 minutes after adding the agents;

[0151] The collector in the scavenging stage is amyl xanthate: butyl xanthate in a mass ratio of 1:1, with a dosage of 15g / t; the foaming agent is 2# oil, with a dosage of 8g / t; stir for 4 minutes after adding the agents;

[0152] The obtained copper sulfide tailings are coarse-grained tailings; proceed to step (3).

[0153] The beneficiation of medium-sized sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0154] The ore pulp is stirred and scrubbed with dilute sulfuric acid, and the amount of dilute sulfuric acid used is 0.9 kg / t; after scrubbing, copper sulfide flotation is carried out, including one stage of roughing, three stages of concentrating and one stage of scavenging; the ore pulp is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate 2 and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0155] The collector in the roughing stage of copper sulfide flotation is a combination of amyl xanthate and butyl xanthate in a mass ratio of 1:1, with a dosage of 100g / t; the frother is 2# oil, with a dosage of 20g / t; after adding the reagents, stir for 4 minutes;

[0156] The collector in the flotation scavenging stage of copper sulfide is a combination of amyl xanthate and butyl xanthate in a mass ratio of 1:1, with a dosage of 15g / t; the frother is 2# oil, with a dosage of 10g / t; after adding the reagents, stir for 4 minutes;

[0157] The obtained copper sulfide tailings are subjected to copper oxide flotation, including one stage of roughing, three stages of concentrating and one stage of scavenging; the pulp is subjected to roughing to obtain copper oxide roughing concentrate and copper oxide roughing tailings; the copper oxide roughing concentrate is subjected to concentrating to obtain copper oxide concentrate and copper oxide concentrating tailings; the copper oxide roughing tailings are subjected to scavenging to obtain copper oxide scavenging concentrate and copper oxide tailings; the copper oxide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper oxide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0158] The sulfiding agent in the roughing stage of copper oxide flotation is a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:1, with a dosage of 2500g / t; the collector is amyl xanthate and butyl xanthate in a mass ratio of 2:1, with a dosage of 250g / t; the frother is 2# oil, with a dosage of 20g / t; stir for 5 minutes after adding the reagents;

[0159] The sulfiding agent in the flotation scavenging stage of copper oxide is a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:1, with a dosage of 600g / t; the collector is amyl xanthate and butyl xanthate in a mass ratio of 2:1, with a dosage of 100g / t; the frother is 2# oil in a dosage of 5g / t; after adding the reagents, stir for 5 minutes;

[0160] The obtained copper oxide tailings are concentrated to a pulp concentration of 55%, then diluted with water, and 160 g / t of activated carbon is used for dedoping; the pulp concentration after dilution is 40%, and it is fed into a high gradient magnetic separator for a first magnetic roughing separation, with a background field strength of 1.2 T, to obtain a magnetic roughing concentrate and a magnetic roughing tailing; the magnetic roughing concentrate is subjected to a first magnetic concentration, with a background field strength of 1.0 T, to obtain a magnetic concentrate 1 and a magnetic concentration tailing; the magnetic roughing tailings and the magnetic concentration tailings are medium-sized tailings; and step (3) is entered.

[0161] The beneficiation of fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0162] The magnetic separation of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings includes a magnetic roughing separation, a magnetic scavenging separation and a magnetic concentrating separation; the ore pulp is subjected to magnetic roughing separation to obtain a magnetic roughing concentrate and a magnetic roughing tailings; the magnetic roughing tailings are subjected to magnetic scavenging separation to obtain a magnetic scavenging concentrate and a magnetic scavenging tailings; the magnetic roughing concentrate and the magnetic scavenging concentrate are subjected to magnetic concentrating to obtain a magnetic concentrate 2 and a magnetic concentrating tailings;

[0163] The magnetic separation intensity of the rough magnetic separation is 1.3T; the magnetic separation intensity of the scavenging magnetic separation is 1.2T; the magnetic separation intensity of the concentrating magnetic separation is 1.1T; the magnetic scavenging tailings and the magnetic concentrating tailings are fine-grained tailings; proceed to step (3).

[0164] (3) Three-stage neutralization: The coarse-grained tailings, medium-grained tailings and fine-grained tailings are concentrated to 42 wt% and pumped to a neutralization stirring tank of the "three-stage neutralization" system; a raffinate containing 0.6 g / l copper, 1.7 g / l cobalt, 2.5 g / l iron and 20 g / l sulfuric acid is added to the neutralization stirring tank, and neutralized for 4 hours at room temperature, with an end point pH of 1.8 and a slurry concentration of 23 wt% after neutralization; solid-liquid separation is performed to obtain an underflow and a phase. Neutralize the overflow liquid; send the overflow liquid from the first stage neutralization into the second stage neutralization tank, add lime milk, neutralize for 10 hours at room temperature, the end point pH value is 3.5, and the pulp concentration after neutralization is 22wt%; separate the solid and liquid to obtain the second stage neutralization slag and the second stage neutralization overflow liquid; send the second stage neutralization overflow liquid into the third stage neutralization tank, add lime milk, neutralize for 4 hours at room temperature, the end point pH value is 6.8, and the pulp concentration after neutralization is 22wt%; separate the solid and liquid to obtain the third stage neutralization slag and the third stage neutralization overflow liquid.

[0165] After the treatment of the sulfur-oxygen mixed copper-cobalt ore tailings in this embodiment, copper and cobalt are recovered into the copper sulfide concentrate 1, copper sulfide concentrate 2, copper oxide concentrate, magnetic separation concentrate 1, magnetic separation concentrate 2 obtained in step (2) and the three-stage neutralization slag (high cobalt and low copper neutralization slag) obtained in step (3). The test results are shown in Table 2. Finally, the total copper recovery rate is 94.78% and the total cobalt recovery rate is 74.77%. Among them, the copper grade of copper sulfide concentrate 1 is 35.32%, and the cobalt grade is 0.35%, the copper grade of copper sulfide concentrate 2 is 45.26%, and the cobalt grade is 0.30%, the copper grade of copper oxide concentrate is 17.99%, and the cobalt grade is 1.03%, the copper grade of magnetic concentrate is 3.86%, and the cobalt grade is 1.12%, the copper recovery rate of ore dressing is 78.93%, and the cobalt recovery rate is 27.19%; the copper grade of high-cobalt and low-copper neutralized slag is 3.93%, and the cobalt grade is 2.90%, the copper recovery rate is 75.24%, and the cobalt recovery rate is 65.34%, the copper recovery rate relative to the original ore is 15.86%, and the cobalt recovery rate is 47.57%.

[0166] Table 2 Experimental results of Example 2: Combined asynchronous recovery of sulfur-oxygen mixed copper-cobalt ore tailings copper and cobalt

[0167]

[0168] Compared with directly using lime to neutralize the raffinate, under the same conditions, the consumption of lime is reduced by 175.01kg / m3 (raffinate).

[0169] Embodiment 3:

[0170] The present embodiment relates to a multi-grade sulfur-oxygen mixed copper-cobalt ore tailings, containing 0.76% copper, 0.15% cobalt, and 83% copper oxidation rate; wherein the copper-cobalt minerals are complex in nature, with a content of 0.49wt% malachite, 0.43wt% copper-cobalt pyrolusite, 1.62wt% copper-containing limonite, and 1.89wt% cobalt dolomite. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by smelting and asynchronous separation in the present embodiment is carried out in the following steps:

[0171] (1) Classification: A sand mining ship hydraulically mines sand in the old tailings pond, and uses a linear screen to classify the multi-grained sulfur-oxygen mixed copper-cobalt ore tailings to obtain coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings with a particle size of 0.074 mm or more and raw ore slurry; the raw ore slurry is concentrated to 35wt% by a thickener and then classified again to obtain fine-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry of -0.038mm and medium-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry of -0.074mm+0.038mm; the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are conveyed to a ball mill by a belt for grinding to obtain coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings slurry, the fineness of which is -0.074mm, accounting for 78%, and the slurry concentration is 30wt%.

[0172] (2) Multi-grade mineral processing:

[0173] The beneficiation of coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0174] The copper sulfide flotation is carried out, including one stage of roughing, three stages of concentrating and one stage of scavenging; the pulp is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate 1 and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0175] The collector in the roughing stage is amyl xanthate: butyl xanthate in a mass ratio of 1:1, and the dosage is 60g / t; the foaming agent is 2# oil, and the dosage is 10g / t; stir for 4 minutes after adding the reagents;

[0176] The collector in the scavenging stage is amyl xanthate: butyl xanthate in a mass ratio of 1:1, with a dosage of 10g / t; the foaming agent is 2# oil, with a dosage of 5g / t; stir for 4 minutes after adding the agents;

[0177] The obtained copper sulfide tailings are coarse-grained tailings; proceed to step (3).

[0178] The beneficiation of medium-sized sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0179] The ore pulp is stirred and scrubbed with dilute sulfuric acid, and the amount of dilute sulfuric acid used is 0.8kg / t; after scrubbing, copper sulfide flotation is carried out, including a roughing stage, three concentrating stages and a scavenging stage; the ore pulp is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate 2 and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0180] The collector in the roughing stage of copper sulfide flotation is a combination of amyl xanthate and butyl xanthate in a mass ratio of 1:1, with a dosage of 60g / t; the frother is 2# oil, with a dosage of 10g / t; after adding the reagents, stir for 4 minutes;

[0181] The collector in the flotation scavenging stage of copper sulfide is a combination of amyl xanthate and butyl xanthate in a mass ratio of 1:1, with a dosage of 10g / t; the frother is 2# oil, with a dosage of 5g / t; after adding the reagents, stir for 4 minutes;

[0182] The obtained copper sulfide tailings are subjected to copper oxide flotation, including one stage of roughing, three stages of concentrating and one stage of scavenging; the pulp is subjected to roughing to obtain copper oxide roughing concentrate and copper oxide roughing tailings; the copper oxide roughing concentrate is subjected to concentrating to obtain copper oxide concentrate and copper oxide concentrating tailings; the copper oxide roughing tailings are subjected to scavenging to obtain copper oxide scavenging concentrate and copper oxide tailings; the copper oxide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper oxide concentrating tailings are returned to the flotation process to enter the roughing stage;

[0183] The sulfiding agent in the roughing stage of copper oxide flotation is a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:1, with a dosage of 2100g / t; the collector is amyl xanthate and butyl xanthate in a mass ratio of 2:1, with a dosage of 220g / t; the frother is 2# oil, with a dosage of 15g / t; stir for 5 minutes after adding the reagents;

[0184] The sulfiding agent in the flotation scavenging stage of copper oxide is a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:1, with a dosage of 200g / t; the collector is amyl xanthate and butyl xanthate in a mass ratio of 2:1, with a dosage of 60g / t; the frother is 2# oil, with a dosage of 2g / t; stir for 5 minutes after adding the reagents;

[0185] The obtained copper oxide tailings are concentrated to a pulp concentration of 58%, then diluted with water, and 180 g / t of activated carbon is used for dedoping; the pulp concentration after dilution is 40%, and it is fed into a high gradient magnetic separator for a first magnetic roughing separation, with a background field strength of 1.2 T, to obtain a magnetic roughing concentrate and a magnetic roughing tailing; the magnetic roughing concentrate is subjected to a first magnetic concentration, with a background field strength of 1.0 T, to obtain a magnetic concentrate 1 and a magnetic concentration tailing; the magnetic roughing tailings and the magnetic concentration tailings are medium-sized tailings; and step (3) is entered.

[0186] The beneficiation of fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is as follows:

[0187] The magnetic separation of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings includes a magnetic roughing separation, a magnetic scavenging separation and a magnetic concentrating separation; the ore pulp is subjected to magnetic roughing separation to obtain a magnetic roughing concentrate and a magnetic roughing tailings; the magnetic roughing tailings are subjected to magnetic scavenging separation to obtain a magnetic scavenging concentrate and a magnetic scavenging tailings; the magnetic roughing concentrate and the magnetic scavenging concentrate are subjected to magnetic concentrating to obtain a magnetic concentrate 2 and a magnetic concentrating tailings;

[0188] The magnetic separation intensity of the rough magnetic separation is 1.3T; the magnetic separation intensity of the scavenging magnetic separation is 1.2T; the magnetic separation intensity of the concentrating magnetic separation is 1.2T; the magnetic scavenging tailings and the magnetic concentrating tailings are fine-grained tailings; proceed to step (3).

[0189] (3) Three-stage neutralization: The coarse-grained tailings, medium-grained tailings and fine-grained tailings are concentrated to 42 wt% and pumped to a neutralization stirring tank of the "three-stage neutralization" system; a raffinate containing 0.8 g / l copper, 1.8 g / l cobalt, 2.5 g / l iron and 18 g / l sulfuric acid is added to the neutralization stirring tank, and neutralized for 4 hours at room temperature, with an end point pH of 1.5 and a slurry concentration of 23 wt% after neutralization; solid-liquid separation is performed to obtain an underflow and a phase. Neutralize the overflow liquid; send the overflow liquid from the first stage neutralization into the second stage neutralization tank, add lime milk, neutralize for 10 hours at room temperature, the end point pH value is 3.6, and the pulp concentration after neutralization is 25wt%; separate the solid and liquid to obtain the second stage neutralization slag and the second stage neutralization overflow liquid; send the overflow liquid from the second stage neutralization into the third stage neutralization tank, add lime milk, neutralize for 4 hours at room temperature, the end point pH value is 6.6, and the pulp concentration after neutralization is 25wt%; separate the solid and liquid to obtain the third stage neutralization slag and the third stage neutralization overflow liquid.

[0190] After the treatment of the sulfur-oxygen mixed copper-cobalt ore tailings in this embodiment, copper and cobalt are recovered into the copper sulfide concentrate 1, copper sulfide concentrate 2, copper oxide concentrate, magnetic separation concentrate 1, magnetic separation concentrate 2 obtained in step (2) and the three-stage neutralization slag (high-cobalt and low-copper neutralization slag) obtained in step (3). The test results are shown in Table 3, and the indicators of total copper recovery rate of 93.58% and total cobalt recovery rate of 73.91% are finally obtained. Among them, the copper grade of copper sulfide concentrate 1 is 28.22%, and the cobalt grade is 0.29%, the copper grade of copper sulfide concentrate 2 is 36.44%, and the cobalt grade is 0.28%, the copper grade of copper oxide concentrate is 13.66%, and the cobalt grade is 0.63%, the copper grade of magnetic concentrate is 3.11%, and the cobalt grade is 0.70%, the copper recovery rate of ore dressing is 75.71%, and the cobalt recovery rate is 26.63%; the copper grade of high-cobalt and low-copper neutralized slag is 3.08%, and the cobalt grade is 1.61%, the copper recovery rate is 73.59%, and the cobalt recovery rate is 64.43%, the copper recovery rate relative to the original ore is 17.87%, and the cobalt recovery rate is 47.27%.

[0191] Table 3 Experimental results of Example 3: Combined asynchronous recovery of sulfur-oxygen mixed copper-cobalt ore tailings copper and cobalt

[0192]

[0193] Compared with directly using lime to neutralize the raffinate, under the same conditions, the consumption of lime is reduced by 189.76kg / m3 (raffinate).

[0194] 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.

[0195] Comparative Example 1

[0196] The method for recovering copper and cobalt from multi-size sulfur-oxygen mixed copper-cobalt ore tailings in this comparative example is basically the same as the method in Example 3, with the only difference being that the tailings do not enter the "three-stage neutralization" system for neutralization and leaching after the mineral processing process.

[0197] After the treatment of the sulfur-oxygen mixed copper-cobalt ore tailings in this comparative example, copper and cobalt are recovered to obtain the copper sulfide concentrate 2, copper oxide concentrate, magnetic separation concentrate 1, and magnetic separation concentrate 2 in step (2).

[0198] The final result of Comparative Example 1 is shown in Table 4. As can be seen from Table 4, the total copper recovery rate is 76.21% and the total cobalt recovery rate is 26.31%. Among them, the copper grade of copper sulfide concentrate 1 is 28.55% and the cobalt grade is 0.32%, the copper grade of copper sulfide concentrate 2 is 35.89% and the cobalt grade is 0.29%, the copper grade of copper oxide concentrate is 13.88% and the cobalt grade is 0.59%, and the copper grade of magnetic separation concentrate is 3.01% and the cobalt grade is 0.72%.

[0199] Table 4 Comparative Example 1 Recovery of copper and cobalt from multi-grade sulfur-oxygen mixed copper-cobalt ore tailings

[0200]

[0201] The conventional leaching process for recovering cobalt metal in tailings consumes 5 to 8 times the acid of leaching normal ore, resulting in poor overall economic benefits. If only the mineral processing process is used to recover copper and cobalt resources, most of the cobalt resources will be lost. The combined mineral processing and smelting process of the present application, and the process of asynchronously recovering cobalt resources using a "three-stage neutralization" system, can not only recover copper and cobalt resources, but also save the amount of sulfuric acid and lime.

[0202] Comparative Example 2

[0203] The method for recovering copper and cobalt from multi-size sulfur-oxygen mixed copper-cobalt ore tailings in this comparative example is basically the same as the method in Example 3, with the only difference being that the sulfur-oxygen mixed copper-cobalt ore tailings without being classified directly enters the grinding process, and after grinding, is divided into fine-size sulfur-oxygen mixed copper-cobalt ore tailings of -0.038 mm and medium-size sulfur-oxygen mixed copper-cobalt ore tailings according to the 0.038 mm standard, and copper and cobalt in the tailings are recovered through multi-size beneficiation and three-stage neutralization.

[0204] After the treatment of the sulfur-oxygen mixed copper-cobalt ore tailings in this comparative example, copper and cobalt are recovered into the copper sulfide concentrate 2 obtained in step (2), the copper oxide concentrate, the magnetic separation concentrate 1, the magnetic separation concentrate 2 and the three-stage neutralization slag (high-cobalt and low-copper neutralization slag) obtained in step (3). Since there is no coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings during the treatment process, there is no copper sulfide concentrate 1 in this comparative example.

[0205] The final recovery results of Comparative Example 2 are shown in Table 5: It can be seen that the total copper recovery rate is 87.56% and the total cobalt recovery rate is 71.37%. Among them, the copper grade of copper sulfide concentrate 2 is 29.11%, the cobalt grade is 0.25%, the copper grade of copper oxide concentrate is 9.45%, the cobalt grade is 0.43%, the copper grade of magnetic concentrate is 3.78%, the cobalt grade is 0.54%, the copper recovery rate of ore dressing is 69.11%, and the cobalt recovery rate is 24.50%; the copper grade of high cobalt and low copper neutralization slag is 3.34%, the cobalt grade is 1.68%, the copper recovery rate is 59.72%, the cobalt recovery rate is 62.09%, and the copper recovery rate relative to the original ore is 18.45%, and the cobalt recovery rate is 46.88%.

[0206] Table 5 Comparative Example 2 Recovery of copper and cobalt from multi-grade sulfur-oxygen mixed copper-cobalt ore tailings

[0207]

[0208] Comparative Example 3

[0209] The method for recovering copper and cobalt from multi-size sulfur-oxygen mixed copper-cobalt ore tailings in this comparative example is basically the same as the method in Example 3, with the only difference being that the coarse-size sulfur-oxygen mixed copper-cobalt ore tailings are not recovered, i.e., after classification by the vibrating screen, the +0.074 mm size tailings are directly discarded without grinding and flotation operations.

[0210] After the treatment of the sulfur-oxygen mixed copper-cobalt ore tailings in this comparative example, copper and cobalt are recovered into the copper sulfide concentrate 2 obtained in step (2), the copper oxide concentrate, the magnetic separation concentrate 1, the magnetic separation concentrate 2 and the three-stage neutralization slag (high-cobalt and low-copper neutralization slag) obtained in step (3). Since there is no coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings during the treatment process, there is no copper sulfide concentrate 1 in this comparative example.

[0211] The final recovery results of Comparative Example 3 are shown in Table 6: It can be seen that the total copper recovery rate is 90.66% and the total cobalt recovery rate is 72.78%. Among them, the copper grade of the copper sulfide concentrate is 35.99%, the cobalt grade is 0.29%, the copper grade of the copper oxide concentrate is 13.58%, the cobalt grade is 0.60%, the copper grade of the magnetic concentrate is 2.99%, the cobalt grade is 0.71%, the copper recovery rate of the ore dressing is 72.63%, and the cobalt recovery rate is 26.51%; the copper grade of the high cobalt and low copper neutralization slag is 3.18%, the cobalt grade is 1.61%, the copper recovery rate is 65.89%, the cobalt recovery rate is 62.96%, and the copper recovery rate relative to the original ore is 18.03%, and the cobalt recovery rate is 46.27%.

[0212] Table 6 Comparative Example 3 Recovery of copper and cobalt from multi-grade sulfur-oxygen mixed copper-cobalt ore tailings

[0213]

[0214] It can be seen from Comparative Examples 2 and 3 that Comparative Example 3 adopts the method of directly discarding the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings for treatment, but the recovery rate is lower than that of Comparative Example 2 which directly grinds the ore without classification. It can be seen that if the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are not handled properly, they will have a great negative impact on recovery.

Claims

1. A method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined beneficiation and asynchronous smelting, characterized in that: The sulfur-oxygen mixed copper-cobalt ore tailings are divided into coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings, medium-grained sulfur-oxygen mixed copper-cobalt ore tailings and fine-grained sulfur-oxygen mixed copper-cobalt ore tailings according to the particle size; the particle size of the coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings is above 0.074 mm; the particle size of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is below 0.038 mm; the particle size of the medium-grained sulfur-oxygen mixed copper-cobalt ore tailings is 0.038 mm to 0.074 mm; The coarse-grained sulfur-oxygen mixed copper-cobalt ore tailings are subjected to ore grinding and copper sulfide flotation to recover part of copper and cobalt and obtain coarse-grained tailings; The medium-sized sulfur-oxygen mixed copper-cobalt ore tailings are subjected to copper sulfide flotation, copper oxide flotation and magnetic separation to recover part of copper and cobalt and obtain medium-sized tailings; The fine-grained sulfur-oxygen mixed copper-cobalt ore tailings are subjected to magnetic separation to recover part of the copper and cobalt and obtain fine-grained tailings; One or more of the coarse-grained tailings, the medium-grained tailings and the fine-grained tailings are neutralized to recover part of the copper and cobalt.

2. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined beneficiation and asynchronous smelting according to claim 1, characterized in that: The sulfur-oxygen mixed copper-cobalt ore tailings have a copper grade of 0.60% to 1.30%, a cobalt grade of 0.10% to 0.40%, and a copper oxidation rate of more than 80%; In the sulfur-oxygen mixed copper-cobalt ore tailings, the content of malachite is 0.44wt%-0.81wt%, the content of copper-cobalt pyrolusite is 0.35wt%-0.98wt%, the content of copper-containing limonite is 1.51wt%-2.38wt%, and the content of cobalt dolomite is 1.72wt%-2.85wt%.

3. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined asynchronous smelting and selection according to claim 1 or 2, characterized in that: After one or more of the coarse-grained tailings, the medium-grained tailings, and the fine-grained tailings are concentrated, they are neutralized with the raffinate from the smelting system to a pH value of 1.2 to 2.0, and the solid and liquid are separated to obtain an underflow and a neutralization overflow liquid; the raffinate contains 0.2 to 2.5 g / L copper, 0.5 to 4.0 g / L cobalt, 1.0 to 4.0 g / L iron, and 10 to 30 g / L sulfuric acid; The first-stage neutralization overflow liquid is subjected to second-stage neutralization with lime milk until the pH value is 3.2 to 4.2, and solid-liquid separation is performed to obtain second-stage neutralization slag and second-stage neutralization overflow liquid; The two-stage neutralization overflow liquid is neutralized with lime milk in three stages until the pH value is 6.2-7.2, and the solid-liquid is separated to obtain three-stage neutralization slag and three-stage neutralization overflow liquid.

4. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined asynchronous smelting and selection according to claim 3 is characterized in that: The concentration before neutralization is as follows: adjusting the slurry concentration to 40-45%; The raffinate contains 0.5-1.0 g / L copper; the raffinate contains 1.5-2.5 g / L cobalt; the raffinate contains 2.0-2.5 g / L iron; the raffinate contains 0.5-1.5 g / L manganese; the raffinate contains 0.5-0.9 g / L calcium; the raffinate contains 10-15 g / L magnesium; the raffinate contains 1.0-1.5 g / L aluminum; the raffinate contains 14-20 g / L sulfuric acid; The end point of the first stage neutralization is pH 1.5-1.8, the pulp concentration after the first stage neutralization is 22-25%, and the neutralization reaction time is 3-4 hours; The end point of the second stage neutralization is pH 3.5-4.0, the pulp concentration after the second stage neutralization is 22-25%, and the neutralization reaction time is 8-10 hours; The end point of the three-stage neutralization is a pH value of 6.5 to 7.0, the pulp concentration after the three-stage neutralization is 22 to 25%, and the neutralization reaction time is 2 to 4 hours.

5. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined beneficiation and asynchronous smelting according to claim 1, characterized in that: The copper sulfide flotation includes roughing, concentrating and scavenging; the pulp is subjected to roughing to obtain copper sulfide roughing concentrate and copper sulfide roughing tailings; the copper sulfide roughing concentrate is subjected to concentrating to obtain copper sulfide concentrate and copper sulfide concentrating tailings; the copper sulfide roughing tailings are subjected to scavenging to obtain copper sulfide scavenging concentrate and copper sulfide tailings; the copper sulfide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper sulfide concentrating tailings are returned to the flotation process to enter the roughing stage; copper and cobalt are recovered into the copper sulfide concentrate, and the copper sulfide tailings are used for the next step of processing; The copper oxide flotation includes roughing, concentrating and scavenging; the pulp is subjected to roughing to obtain copper oxide roughing concentrate and copper oxide roughing tailings; the copper oxide roughing concentrate is subjected to concentrating to obtain copper oxide concentrate and copper oxide concentrating tailings; the copper oxide roughing tailings are subjected to scavenging to obtain copper oxide scavenging concentrate and copper oxide tailings; the copper oxide scavenging concentrate is returned to the flotation process to enter the roughing stage; the copper oxide concentrating tailings are returned to the flotation process to enter the roughing stage; copper and cobalt are recovered into the copper oxide concentrate, and the copper oxide tailings are used for the next step of processing; The magnetic separation of the medium-sized sulfur-oxygen mixed copper-cobalt ore tailings includes magnetic roughing and magnetic concentration, and the magnetic separation intensity is above 0.7T; the ore pulp is subjected to magnetic roughing to obtain magnetic roughing concentrate and magnetic roughing tailings; the magnetic roughing concentrate is subjected to magnetic concentration to obtain magnetic concentration concentrate and magnetic concentration tailings; the magnetic roughing tailings are magnetic separation tailings; the magnetic concentration tailings are magnetic separation tailings; copper and cobalt are recovered into the magnetic concentration concentrate, and the magnetic separation tailings are used for the next step of processing; The magnetic separation of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings includes magnetic roughing, magnetic scavenging and magnetic concentration, and the magnetic separation intensity is above 0.7 T; the ore pulp is subjected to magnetic roughing to obtain magnetic roughing concentrate and magnetic roughing tailings; the magnetic roughing tailings are subjected to magnetic scavenging to obtain magnetic scavenging concentrate and magnetic scavenging tailings; the magnetic roughing concentrate and / or magnetic scavenging concentrate are subjected to magnetic concentration to obtain magnetic concentration concentrate and magnetic concentration tailings; the magnetic scavenging tailings are magnetic separation tailings; the magnetic concentration tailings are magnetic separation tailings; copper and cobalt are recovered into the magnetic separation concentrate, and the magnetic separation tailings are used for the next step of processing.

6. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined asynchronous smelting and selection according to claim 1 or 5, characterized in that: The collector for copper sulfide flotation includes butyl xanthate or a combination of amyl xanthate and butyl xanthate; The frother for copper sulfide flotation includes pine oil; The sulfiding agent for copper oxide flotation comprises a combination of sodium hydrosulfide and sodium sulfide in a mass ratio of 1:0-1; The collector for flotation of copper oxide includes butyl xanthate or a combination of amyl xanthate and butyl xanthate; The frother for flotation of copper oxide includes pine oil; Magnetic separation uses a high gradient magnetic separator.

7. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined asynchronous smelting and selection according to claim 6, characterized in that: The collector for flotation of copper sulfide includes butyl xanthate or a combination of amyl xanthate and butyl xanthate in a mass ratio of 2 to 1:1; the collector for flotation of copper oxide includes butyl xanthate or a combination of amyl xanthate and butyl xanthate in a mass ratio of 2 to 1:

1.

8. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined selection and smelting asynchronously according to any one of claims 5 to 7, characterized in that: In the roughing stage of the copper sulfide flotation, the amount of the collector is 60-100 g / t, and the amount of the frother is 10-20 g / t; In the scavenging stage of copper sulfide flotation, the amount of collector is 10-20 g / t, and the amount of frother is 5-10 g / t; In the roughing stage of the copper oxide flotation, the dosage of the sulfiding agent is 2000-3000 g / t, the dosage of the collector is 100-250 g / t, and the dosage of the frother is 10-20 g / t; In the scavenging stage of the copper oxide flotation, the dosage of the sulfiding agent is 200-800 g / t, the dosage of the collector is 10-200 g / t, and the dosage of the frother is 0-10 g / t; The magnetic separation intensity of the rough magnetic separation is 0.9~1.3T; the magnetic separation intensity of the scanning magnetic separation is 0.9~1.3T; the magnetic separation intensity of the fine magnetic separation is 0.8T~1.2T.

9. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined selection and smelting asynchronously according to any one of claims 1, 2 and 5, characterized in that: The grinding process comprises: grinding the ore pulp to a particle size of less than 0.074 mm, accounting for 70% to 80%, and the ore pulp concentration is 30% to 35%; the ore pulp concentration of the fine-grained sulfur-oxygen mixed copper-cobalt ore tailings is 25% to 40%; the ore pulp concentration of the medium-grained sulfur-oxygen mixed copper-cobalt ore tailings is 25% to 40%; The medium-sized sulfur-oxygen mixed copper-cobalt ore tailings are stirred and scrubbed with dilute acid before copper sulfide flotation; After copper oxide flotation, the tailings slurry obtained is concentrated to a slurry concentration of 55% to 60%, and then mixed with clean water to be diluted to a slurry concentration of 34% to 40%.

10. The method for recovering copper and cobalt from sulfur-oxygen mixed copper-cobalt ore tailings by combined beneficiation and smelting asynchronously according to claim 9, characterized in that: The dosage of the dilute acid is 0.2-1 kg / t; activated carbon is also used for drug removal during dilution, and the added amount of activated carbon is 150-200 g / t.

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