Method for synchronously treating high-copper-cobalt dolomite and raffinate to recover copper and cobalt

Abstract

A method for synchronously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate comprises the steps that raw ore pulp of the high-copper-cobalt dolomite is subjected to a neutralization reaction with raffinate A to obtain flotation tailings obtained through sulphide ore flotation, and neutralized ore pulp is obtained; carrying out solid-liquid separation on the neutralized ore pulp to obtain neutralized feed liquid and neutralized slag; the neutralization slag and the raffinate B are mixed and leached to obtain leached ore pulp; and carrying out solid-liquid separation on the leached ore pulp to obtain leached material liquid and leached residues. According to the method, the high-copper-cobalt dolomite is adopted as a neutralizer of the raffinate, so that the technical problem that cobalt in the high-copper-cobalt dolomite is difficult to recover is solved, and meanwhile, the problem that the production cost is high due to the fact that a large amount of lime is consumed during raffinate neutralization is fundamentally solved.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrometallurgy, and particularly to a method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt. Background Art

[0002] The Democratic Republic of the Congo is an important producer of copper and cobalt resources in the world. Among them, the copper metal reserves are 75 million tons, making it one of the countries with relatively large reserves in the world. The cobalt metal reserves are 3.6 million tons, accounting for about 50.70% of the world's total reserves, making it the largest cobalt producer in the world. Currently, more than twenty kinds of copper-cobalt minerals have been discovered in production. The main copper minerals are malachite, followed by chalcocite, chrysocolla, tenorite, and a small amount of djurleite, phosphocopper, clinoclase, covellite, chalcopyrite, bornite, cuprite, native copper, etc.; the main cobalt minerals are cobaltite and cobaltite copper, followed by cobaltite, cobalt dolomite, manganese-cobalt-copper hydrated oxide, etc. Other metal minerals include pyrite, limonite, hematite, and a small amount of rutile, etc. Among them, cobalt dolomite ore is a refractory copper-cobalt-containing metal ore, and the effect of recovering valuable copper and cobalt metals from it using various common beneficiation technologies for other copper-cobalt ores is not ideal. Currently, there is no good treatment plan for cobalt dolomite in the industry. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to overcome the above-mentioned defects existing in the prior art and provide a method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt with good copper-cobalt recovery effect.

[0004] The technical solution adopted by the present invention to solve its technical problems is as follows: A method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt, including: the flotation tailings obtained by the flotation of the raw ore pulp of the high copper-cobalt dolomite are subjected to a neutralization reaction with raffinate A to obtain a neutralized pulp; the neutralized pulp is subjected to solid-liquid separation to obtain a neutralized feed liquid and a neutralized residue;

[0005] The neutralized residue is mixed and leached with raffinate B to obtain a leached pulp; the leached pulp is subjected to solid-liquid separation to obtain a leached feed liquid and a leached residue;

[0006] The copper grade of the high copper-cobalt dolomite is 1.2 wt% or more; the oxidation rate of the high copper-cobalt dolomite is 65 wt% or less;

[0007] The sulfuric acid content in raffinate A is 8 g / L or more; the sulfuric acid content in raffinate B is 8 g / L or more;

[0008] The iron content in raffinate B is 1 g / L or more;

[0009] The leaching temperature for the mixed leaching of the neutralized residue and raffinate B is 55 °C or more.

[0010] Preferably, the copper grade of the high copper-cobalt dolomite is 1.5 wt% to 4.0 wt%.

[0011] Preferably, the cobalt grade of the high copper-cobalt dolomite is 0.5 wt% to 1.5 wt%.

[0012] Preferably, the oxidation rate of the high copper-cobalt dolomite is 20 wt% to 60 wt%.

[0013] Preferably, the raffinate A is from a hydrometallurgical process for copper recovery.

[0014] Preferably, the copper content in the raffinate A is 1.5 - 2.5 g / L.

[0015] Preferably, the cobalt content in the raffinate A is 2.5 - 3.5 g / L.

[0016] Preferably, the iron content in the raffinate A is 2.5 - 3.5 g / L.

[0017] Preferably, the manganese content in the raffinate A is 0.5 - 1.0 g / L.

[0018] Preferably, the calcium content in the raffinate A is 0.5 - 0.8 g / L.

[0019] Preferably, the magnesium content in the raffinate A is 10 - 13 g / L.

[0020] Preferably, the aluminum content in the raffinate A is 1.5 - 2.0 g / L.

[0021] Preferably, the sulfuric acid content in the raffinate A is 15 - 25 g / L.

[0022] Preferably, the raffinate B is from a hydrometallurgical process for copper recovery.

[0023] Preferably, the copper content in the raffinate B is 1.5 - 2.5 g / L.

[0024] Preferably, the cobalt content in the raffinate B is 2.5 - 3.5 g / L.

[0025] Preferably, the iron content in the raffinate B is 2.5 - 3.5 g / L.

[0026] Preferably, the manganese content in the raffinate B is 0.5 - 1.0 g / L.

[0027] Preferably, the calcium content in the raffinate B is 0.5 - 0.8 g / L.

[0028] Preferably, the magnesium content in the raffinate B is 10 - 13 g / L.

[0029] Preferably, the aluminum content in the raffinate B is 1.5 - 2.0 g / L.

[0030] Preferably, the sulfuric acid content in the raffinate B is 15 - 25 g / L.

[0031] Preferably, the raw ore pulp is obtained by grinding high - copper - cobalt dolomite.

[0032] Preferably, the particle fineness of the raw ore pulp is such that the particle size fraction of - 0.074 mm accounts for 70 wt% - 75 wt%.

[0033] Preferably, the concentration of the raw ore pulp is 30 wt% - 35 wt%.

[0034] Preferably, before the flotation tailings are mixed with raffinate A, the pulp concentration of the flotation tailings is concentrated to 50 wt% - 55 wt%.

[0035] Preferably, the weight ratio of the used flotation tailings to raffinate A is 1:4 - 10.

[0036] Preferably, the neutralization reaction time between the flotation tailings and raffinate A is 3 - 5 h.

[0037] Preferably, the weight ratio of the used neutralization residue to raffinate B is 10 - 15:90 - 85.

[0038] Preferably, the leaching time for the mixed leaching of the neutralization residue and raffinate B is 3 - 5 h.

[0039] Preferably, the leaching temperature for the mixed leaching of the neutralization residue and raffinate B is 70 - 80 °C.

[0040] Preferably, the sulfide ore flotation includes a roughing process and a scavenging process.

[0041] Preferably, the roughing process includes one - stage or two - stage or more roughing.

[0042] Preferably, the scavenging process includes one - stage or two - stage or more scavenging.

[0043] Preferably, the roughing tailings obtained from the roughing process enter the scavenging process.

[0044] Preferably, the scavenging tailings obtained from the scavenging process are the flotation tailings obtained from the sulfide ore flotation.

[0045] Preferably, the collector used in the sulfide ore flotation is sodium butyl xanthate.

[0046] Preferably, the frother used in the sulfide ore flotation is pine oil.

[0047] Preferably, the total dosage of the collector in the roughing process is 200 - 300 g / t.

[0048] Preferably, the total dosage of the foaming agent in the rough selection process is 20 - 50 g / t.

[0049] Preferably, the total dosage of the collector in the scavenging process is 40 - 100 g / t.

[0050] Preferably, the total dosage of the foaming agent in the scavenging process is 5 - 20 g / t.

[0051] Preferably, the sulfide ore flotation further includes a cleaning process.

[0052] Preferably, the cleaning process includes one stage or two or more stages of cleaning.

[0053] Preferably, the rough concentrate obtained from the rough selection process enters the cleaning process.

[0054] Preferably, the scavenger concentrate obtained from the scavenging process enters the rough selection process.

[0055] Preferably, the cleaning tailings obtained from the cleaning process enter the rough selection process.

[0056] Preferably, the cleaning concentrate obtained from the cleaning process is the flotation concentrate obtained from the sulfide ore flotation.

[0057] Preferably, the blank cleaning is adopted in the cleaning process.

[0058] More preferably, the rough selection process includes two or more stages of rough selection: the rough concentrate obtained from each stage of rough selection enters the cleaning process; the rough tailings obtained from the last stage of rough selection enter the scavenging process, and the tailings obtained from other stages of rough selection enter the next stage of rough selection.

[0059] More preferably, the scavenging process includes two or more stages of scavenging: the scavenger concentrate obtained from the first stage of scavenging returns to the rough selection process, and the concentrates obtained from other stages of scavenging return to the previous stage of scavenging; the scavenger tailings obtained from the last stage of scavenging are the flotation tailings, and the tailings obtained from other stages of scavenging enter the next stage of scavenging.

[0060] More preferably, the cleaning process includes two or more stages of cleaning: the cleaning tailings obtained from the first stage of cleaning return to the rough selection process, and the tailings obtained from other stages of cleaning return to the previous stage of cleaning; the cleaning concentrate obtained from the last stage of cleaning is the flotation concentrate, and the concentrates obtained from other stages of cleaning enter the next stage of cleaning.

[0061] Further preferably, the rough selection process includes two stages of rough selection:

[0062] For the first stage of rough selection in the rough selection process, the obtained tailings enter the second stage of rough selection, and the obtained concentrate enters the first stage of cleaning;

[0063] In the second rough selection stage of the rough selection process, the resulting tailings enter the first scavenging stage, and the resulting concentrate enters the first cleaning stage.

[0064] More preferably, the scavenging process includes two stages of scavenging:

[0065] In the first scavenging stage of the scavenging process, the resulting tailings enter the second scavenging stage, and the resulting concentrate enters the last rough selection stage;

[0066] In the second scavenging stage of the scavenging process, the resulting tailings are the flotation tailings, and the resulting concentrate enters the first scavenging stage.

[0067] More preferably, the cleaning process includes four stages of cleaning:

[0068] In the first cleaning stage of the cleaning process, the resulting tailings enter the last rough selection stage, and the resulting concentrate enters the second cleaning stage;

[0069] In the second cleaning stage of the cleaning process, the resulting tailings enter the first rough selection stage, and the resulting concentrate enters the third cleaning stage;

[0070] In the third cleaning stage of the cleaning process, the resulting tailings enter the second rough selection stage, and the resulting concentrate enters the fourth cleaning stage;

[0071] In the fourth cleaning stage of the cleaning process, the resulting tailings enter the third rough selection stage, and the resulting concentrate is the flotation concentrate.

[0072] Even more preferably, in the first rough selection stage of the rough selection process, the dosage of the collector is 150 - 180 g / t.

[0073] Even more preferably, in the first rough selection stage of the rough selection process, the dosage of the frother is 20 - 30 g / t.

[0074] Even more preferably, in the second rough selection stage of the rough selection process, the dosage of the collector is 70 - 90 g / t.

[0075] Even more preferably, in the second rough selection stage of the rough selection process, the dosage of the frother is 10 - 15 g / t.

[0076] Even more preferably, in the first scavenging stage of the scavenging process, the dosage of the collector is 30 - 40 g / t.

[0077] Even more preferably, in the first scavenging stage of the scavenging process, the dosage of the frother is 5 - 10 g / t.

[0078] Even more preferably, in the second scavenging stage of the scavenging process, the dosage of the collector is 20 - 30 g / t.

[0079] Further preferably, for the second stage of scavenging in the scavenging process, the dosage of the foaming agent is 1 to 5 g / t.

[0080] Preferably, the method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt further includes: subjecting the neutralized slurry and / or the leached slurry to iron and aluminum removal neutralization to obtain an iron and aluminum removal slurry; separating the solid and liquid of the iron and aluminum removal slurry to obtain an iron and aluminum removal post-liquid and iron and aluminum slag.

[0081] More preferably, the neutralization end point of the iron and aluminum removal neutralization is that the pH value of the slurry is 3.8 to 4.2.

[0082] More preferably, the neutralizing agent used for the iron and aluminum removal neutralization is lime.

[0083] Further preferably, the neutralizing agent used for the iron and aluminum removal neutralization is lime milk with a concentration of 9 wt% to 10 wt%.

[0084] Preferably, the method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt further includes: subjecting the iron and aluminum removal post-liquid to copper and cobalt precipitation neutralization to obtain a copper and cobalt precipitation slurry; separating the solid and liquid of the copper and cobalt precipitation slurry to obtain a copper and cobalt precipitation post-liquid and copper and cobalt slag;

[0085] More preferably, the neutralization end point of the copper and cobalt precipitation neutralization is that the pH value of the slurry is 6.8 to 7.2.

[0086] More preferably, the neutralizing agent used for the copper and cobalt precipitation neutralization is lime.

[0087] Further preferably, the neutralizing agent used for the copper and cobalt precipitation neutralization is lime milk with a concentration of 9 wt% to 10 wt%.

[0088] The present invention has the following beneficial effects:

[0089] (1) The present invention uses the sulfide ore flotation tailings of high copper-cobalt dolomite to replace lime to neutralize the residual acid in the raffinate, and simultaneously recovers the valuable copper and cobalt metals in the flotation tailings of high copper-cobalt dolomite. The process of direct grinding-flotation-flotation tailings leaching is adopted. A large amount of sulfide copper-cobalt ore in the raw ore is pre-recovered by flotation, and then the carbonate gangue minerals in the sulfide ore flotation tailings are used to neutralize the residual acid in the raffinate that needs to be discharged from the system. While greatly reducing the dosage of the neutralizing agent lime, the comprehensive recovery and utilization of the valuable copper and cobalt metals in two different resources, namely high copper-cobalt dolomite flotation tailings and raffinate, are also realized;

[0090] (2) The present invention not only effectively utilizes the characteristic of high acid consumption of carbonate minerals in cobalt dolomite to neutralize the residual acid in the raffinate, but also utilizes the residual acid and the redox ions carried in the raffinate to recover valuable copper and cobalt metals in the flotation tailings of cobalt dolomite. It not only realizes the effective treatment of the raffinate, but also realizes the efficient leaching of valuable copper and cobalt metals in cobalt dolomite. In the leaching stage of the neutralization residue, the leaching rates of copper and cobalt are as high as over 97% and 98% respectively. In the beneficiation and leaching processes, the comprehensive recovery rates of copper and cobalt can reach over 98% and 96% respectively;

[0091] (3) The present invention adopts the process of neutralizing the raffinate and heating and leaching the neutralization residue to treat the flotation tailings of high copper-cobalt dolomite. No additives are added during the whole process. By utilizing the reducibility of low-valent copper in the still-existing small amount of copper sulfide (chalcocite) in the flotation tailings and the oxidizability of high-valent cobalt, the self-oxidation-reduction reaction of the two under medium-temperature conditions enables copper and cobalt to be fully converted into ions and enter the solution, realizing their effective recovery;

[0092] (4) The treatment method of the raffinate provided by the present invention is an important link in the copper-cobalt hydrometallurgy system. By adopting the treatment method provided by the present invention, the raffinate that needs to be discharged from the system can be neutralized by using the refractory carbonate gangue in the flotation tailings of high copper-cobalt dolomite, and then the valuable metals in the neutralized liquid and the neutralization residue are recovered respectively. The impurities in the raffinate and the introduced flotation tailings of cobalt dolomite are discharged from the system in stages, greatly reducing the production pressure of the system;

[0093] (5) The present invention uses the sulfide ore flotation tailings of refractory high copper-cobalt dolomite to replace lime, reducing the amount of water generated during the neutralization process. While reducing the water expansion in the copper-cobalt metallurgy system, it also reduces the production cost. At the same time, it realizes the efficient recovery of valuable minerals in refractory cobalt dolomite, truly achieving "cost reduction and efficiency increase" in the production and operation process of mining enterprises.

[0094] In addition to the purposes, features and advantages described above, the present invention has other purposes, features and advantages. The following will refer to the accompanying drawings for a further detailed description of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] The drawings forming a part of this application are used to provide a further understanding of the present invention. The schematic embodiments and descriptions thereof of the present invention are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0096] Figure 1 is a process flow schematic diagram of the method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt in the preferred embodiment of the present invention;

[0097] Figure 2 is a photo of the ore of high copper-cobalt dolomite in Example 1 of the present invention;

[0098] Figure 3 It is a process flow schematic diagram of the method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt in Embodiment 1 of the present invention;

[0099] Figure 4 It is a process flow schematic diagram of flotation in the method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt in Embodiment 1 of the present invention. Detailed implementation manners

[0100] In order to make the objectives, solutions and beneficial technical effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments and the accompanying drawings. It should be noted that the embodiments described in this specification are only for explaining the present invention and not for limiting the present invention.

[0101] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, although not explicitly recited, each point or single value between the range endpoints is included in this range. Thus, each point or single value can be used as its own lower or upper limit and combined with any other point or single value or combined with other lower or upper limits to form a range not explicitly recited.

[0102] In the description herein, it should be noted that unless otherwise specified, "above" and "below" include this number, the meaning of "multiple" in "one or more" is two or more, and the meaning of "multiple" in "one or more" is two or more.

[0103] As Figure 1 shown in the process flow chart of, the embodiment of the present invention provides a method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt, including: the flotation tailings obtained by sulfide ore flotation of the raw ore pulp of the high copper-cobalt dolomite are subjected to a neutralization reaction with raffinate A to obtain a neutralized pulp; the neutralized pulp is subjected to solid-liquid separation to obtain a neutralized feed liquid and a neutralized residue;

[0104] the neutralized residue is mixed and leached with raffinate B to obtain a leached pulp; the leached pulp is subjected to solid-liquid separation to obtain a leached feed liquid and a leached residue;

[0105] the copper grade of the high copper-cobalt dolomite is 1.2 wt% or more; the oxidation rate of the high copper-cobalt dolomite is 65 wt% or less;

[0106] the sulfuric acid content in the raffinate A is 8 g / L or more; the sulfuric acid content in the raffinate B is 8 g / L or more;

[0107] The raffinate B contains 1 g / L or more of iron;

[0108] The leaching temperature for the mixed leaching of the neutralization residue and the raffinate B is 55 °C or higher.

[0109] The main copper and cobalt elements in the high copper-cobalt dolomite, raffinate A, and raffinate B are extracted into the neutralization feed liquid and the leaching feed liquid. After further impurity removal and / or purification treatment of the neutralization feed liquid and the leaching feed liquid, the enrichment of copper and cobalt elements can be achieved. The obtained leaching residue is subjected to tailing discharge treatment. The high copper-cobalt dolomite contains relatively more valuable metals with difficult leaching properties. A part of them can be recovered first by sulfide ore flotation, reducing the leaching difficulty and the interference of difficult-to-leach components on the subsequent process, and improving the recovery effect.

[0110] The method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt provided by the embodiments of the present invention has the following advantages:

[0111] (1) Using the sulfide ore flotation tailings of high copper-cobalt dolomite to replace lime to neutralize the residual acid in the raffinate, and simultaneously recovering the copper and cobalt valuable metals in the flotation tailings of high copper-cobalt dolomite. Adopting the process of direct grinding-flotation-flotation tailings leaching, a large amount of copper-cobalt sulfide ore in the raw ore is pre-recovered by flotation, and then the carbonate gangue minerals in the sulfide ore flotation tailings are used to neutralize the residual acid in the raffinate that needs to be discharged from the system. While greatly reducing the dosage of the neutralizing agent lime, the comprehensive recovery and utilization of copper and cobalt valuable metals in two different resources, namely the flotation tailings of high copper-cobalt dolomite and the raffinate, are also realized;

[0112] (2) Both effectively utilize the characteristic of high acid consumption of carbonate minerals in cobalt dolomite to neutralize the residual acid in the raffinate, and use the residual acid in the raffinate and the carried oxidation-reduction ions to recover the copper and cobalt valuable metals in the flotation tailings of cobalt dolomite. Both the effective treatment of the raffinate and the efficient leaching of copper and cobalt valuable metals in cobalt dolomite are realized; in the leaching stage of the neutralization residue, the copper and cobalt leaching rates are as high as over 97% and 98% respectively. In the beneficiation and leaching processes, the comprehensive recovery rates of copper and cobalt can reach over 98% and 96% respectively;

[0113] (3) Adopting the process of raffinate neutralization and warm leaching of the neutralization residue to treat the flotation tailings of high copper-cobalt dolomite, no additives are added during the whole process. Utilizing the reducibility of low-valent copper in the still-existing small amount of copper sulfide (chalcocite) and the oxidizability of high-valent cobalt in the flotation tailings, the self-oxidation-reduction reaction of the two under medium-temperature conditions enables copper and cobalt to be fully converted into ions and enter the solution, realizing their effective recovery;

[0114] (4) The treatment method for raffinate provided in the embodiments of the present invention is an important part of the copper-cobalt hydrometallurgy system. By using the treatment method provided in the present invention, the raffinate that needs to be discharged from the system can be neutralized by using the refractory carbonate gangue in the high copper-cobalt dolomite flotation tailings, and then the valuable metals in the neutralized liquid and neutralized slag are recovered respectively. The impurities in the raffinate and the cobalt dolomite flotation tailings introduced into the system are discharged from the system in stages, greatly reducing the production pressure of the system;

[0115] (5) Using the sulfide ore flotation tailings of high copper-cobalt dolomite that is difficult to recycle and treat to replace lime reduces the amount of water generated during the neutralization process. While reducing the water expansion in the copper-cobalt metallurgy system, it also reduces the production cost. At the same time, it realizes the efficient recovery of valuable minerals in the refractory cobalt dolomite, truly achieving "cost reduction and efficiency increase" in the production and operation process of mining enterprises.

[0116] In the embodiments of the present invention, the copper grade of the high copper-cobalt dolomite is 1.5 wt% - 4.0 wt%.

[0117] In the embodiments of the present invention, the cobalt grade of the high copper-cobalt dolomite is 0.5 wt% - 1.5 wt%.

[0118] In the embodiments of the present invention, the oxidation rate of the high copper-cobalt dolomite is 20 wt% - 60 wt%. The oxidation rate refers to the proportion of copper and cobalt oxides in the ore.

[0119] In the embodiments of the present invention, the raffinate A comes from the hydrometallurgy process for recovering copper.

[0120] In the embodiments of the present invention, the raffinate A is the raffinate obtained after the extraction process of the hydrometallurgy system treats the copper sulfate-cobalt feed liquid.

[0121] In some embodiments of the present invention, the copper content in the raffinate A is 1.5 - 2.5 g / L. For the raffinate obtained after the extraction process of a general hydrometallurgy system treats the copper sulfate-cobalt feed liquid, the element content conforms to this range.

[0122] In some embodiments of the present invention, the cobalt content in the raffinate A is 2.5 - 3.5 g / L. For the raffinate obtained after the extraction process of a general hydrometallurgy system treats the copper sulfate-cobalt feed liquid, the element content conforms to this range.

[0123] In some embodiments of the present invention, the iron content in the raffinate A is 2.5 - 3.5 g / L. For the raffinate obtained after the extraction process of a general hydrometallurgy system treats the copper sulfate-cobalt feed liquid, the element content conforms to this range.

[0124] In some embodiments of the present invention, the raffinate A contains 0.5 - 1.0 g / L of manganese. The elemental content of the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a general hydrometallurgical system conforms to this range.

[0125] In some embodiments of the present invention, the raffinate A contains 0.5 - 0.8 g / L of calcium. The elemental content of the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a general hydrometallurgical system conforms to this range.

[0126] In some embodiments of the present invention, the raffinate A contains 10 - 13 g / L of magnesium. The elemental content of the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a general hydrometallurgical system conforms to this range.

[0127] In some embodiments of the present invention, the raffinate A contains 1.5 - 2.0 g / L of aluminum. The elemental content of the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a general hydrometallurgical system conforms to this range.

[0128] In some embodiments of the present invention, the sulfuric acid content in the raffinate A is 15 - 25 g / L. The sulfuric acid in the raffinate A reacts with copper minerals and gangue minerals in the ore that are easily soluble in acid.

[0129] In an embodiment of the present invention, the raffinate B comes from a hydrometallurgical process for copper recovery.

[0130] In an embodiment of the present invention, the raffinate B is the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a hydrometallurgical system.

[0131] In some embodiments of the present invention, the raffinate B contains 1.5 - 2.5 g / L of copper. The elemental content of the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a general hydrometallurgical system conforms to this range.

[0132] In some embodiments of the present invention, the raffinate B contains 2.5 - 3.5 g / L of cobalt. The elemental content of the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a general hydrometallurgical system conforms to this range.

[0133] In some embodiments of the present invention, the raffinate B contains 2.5 - 3.5 g / L of iron. The iron element in the raffinate B not only has its own oxidizing / reducing property, but also promotes the progress of oxidation-reduction as a reaction medium. The elemental content of the raffinate obtained by treating copper sulfate-cobalt feed liquid through the extraction process of a general hydrometallurgical system conforms to this range; when the iron content is higher, the leaching effect is better, but generally the iron content of the obtained raffinate is not so high; experimental studies show that when the iron content of the raffinate is lower, the leaching effect will decrease slightly, but when it reaches above 1 g / L, the overall impact is not significant.

[0134] In some embodiments of the present invention, the raffinate B contains 0.5 to 1.0 g / L of manganese. The elemental content of the raffinate obtained by treating a copper sulfate-cobalt feed solution through a general hydrometallurgical system extraction process conforms to this range.

[0135] In some embodiments of the present invention, the raffinate B contains 0.5 to 0.8 g / L of calcium. The elemental content of the raffinate obtained by treating a copper sulfate-cobalt feed solution through a general hydrometallurgical system extraction process conforms to this range.

[0136] In some embodiments of the present invention, the raffinate B contains 10 to 13 g / L of magnesium. The elemental content of the raffinate obtained by treating a copper sulfate-cobalt feed solution through a general hydrometallurgical system extraction process conforms to this range.

[0137] In some embodiments of the present invention, the raffinate B contains 1.5 to 2.0 g / L of aluminum. The elemental content of the raffinate obtained by treating a copper sulfate-cobalt feed solution through a general hydrometallurgical system extraction process conforms to this range.

[0138] In some embodiments of the present invention, the sulfuric acid content in the raffinate B is 15 to 25 g / L. The raffinate B provides an acidic environment to promote leaching.

[0139] In an embodiment of the present invention, the raw ore pulp is obtained by grinding high copper-cobalt dolomite.

[0140] In an embodiment of the present invention, the particle fineness of the raw ore pulp is such that the particle size fraction of -0.074 mm accounts for 70 wt% to 75 wt%.

[0141] In an embodiment of the present invention, the concentration of the raw ore pulp is 30 wt% to 35 wt%. The concentration of the raw ore pulp can be controlled during the grinding process, and the pulp with the corresponding concentration can be directly obtained after grinding; or it can be concentrated or diluted according to the pulp concentration after grinding to make the concentration meet the requirements.

[0142] In an embodiment of the present invention, before the flotation tailings are mixed with the raffinate A, the pulp concentration of the flotation tailings is concentrated to 50 wt% to 55 wt%.

[0143] In an embodiment of the present invention, the weight ratio of the flotation tailings to the raffinate A used is 1:4 to 10.

[0144] In some embodiments of the present invention, after the flotation tailings are mixed with the raffinate A, the concentration of the resulting pulp is 5 wt% to 10 wt%.

[0145] In an embodiment of the present invention, the neutralization reaction time between the flotation tailings and the raffinate A is 3 to 5 h.

[0146] There is no strict restriction on the reaction temperature for the neutralization reaction between flotation tailings and raffinate A, and it can be carried out at general ambient temperatures.

[0147] In the embodiments of the present invention, the weight ratio of the neutralization residue to raffinate B used is 10 - 15:90 - 85. That is, after the neutralization residue and raffinate B are mixed, the pulp concentration is 10wt% - 15wt%.

[0148] In the embodiments of the present invention, the leaching time for the mixed leaching of the neutralization residue and raffinate B is 3 - 5h.

[0149] In the embodiments of the present invention, the leaching temperature for the mixed leaching of the neutralization residue and raffinate B is 70 - 80°C.

[0150] Leaching can be carried out under medium-temperature conditions. Compared with operation processes such as high-temperature roasting, oxygen pressure leaching, and reduction leaching, while saving energy and environmental protection investment, the process operation safety is almost no different from that of conventional sulfuric acid leaching.

[0151] In some embodiments of the present invention, the sulfide ore flotation includes a roughing process and a scavenging process.

[0152] In some embodiments of the present invention, the roughing process includes one or more than two stages of roughing.

[0153] In some embodiments of the present invention, the scavenging process includes one or more than two stages of scavenging.

[0154] In some embodiments of the present invention, the roughing tailings obtained from the roughing process enter the scavenging process.

[0155] In some embodiments of the present invention, the scavenging tailings obtained from the scavenging process are the flotation tailings obtained from the sulfide ore flotation.

[0156] In some embodiments of the present invention, the collector used for the sulfide ore flotation is sodium butyl xanthate (i.e., xanthate).

[0157] In some embodiments of the present invention, the frother used for the sulfide ore flotation is pine oil (i.e., 2 # oil).

[0158] In some embodiments of the present invention, the total dosage of the collector in the roughing process is 200 - 300g / t.

[0159] In some embodiments of the present invention, the total dosage of the frother in the roughing process is 20 - 50g / t.

[0160] In some embodiments of the present invention, the total dosage of the collector in the scavenging process is 40 - 100g / t.

[0161] In some embodiments of the present invention, the total dosage of the frother in the scavenging process is 5 to 20 g / t.

[0162] In some embodiments of the present invention, the sulfide ore flotation further includes a cleaning process. The cleaning can recover a part of valuable copper and cobalt metals in the form of copper-cobalt sulfide concentrate.

[0163] In some embodiments of the present invention, the cleaning process includes one stage or two or more stages of cleaning.

[0164] In some embodiments of the present invention, the rougher concentrate obtained in the roughening process enters the cleaning process.

[0165] In some embodiments of the present invention, the scavenger concentrate obtained in the scavenging process enters the roughening process.

[0166] In some embodiments of the present invention, the cleaning tailings obtained in the cleaning process enter the roughening process.

[0167] In some embodiments of the present invention, the cleaning concentrate obtained in the cleaning process is the flotation concentrate obtained from the sulfide ore flotation.

[0168] In some embodiments of the present invention, the cleaning process adopts blank cleaning.

[0169] In some embodiments of the present invention, the roughening process includes two or more stages of roughening: the rougher concentrate obtained in each stage of roughening enters the cleaning process; the rougher tailings obtained in the last stage of roughening enter the scavenging process, and the tailings obtained in other stages of roughening enter the next stage of roughening.

[0170] In some embodiments of the present invention, the scavenging process includes two or more stages of scavenging: the scavenger concentrate obtained in the first stage of scavenging returns to the roughening process, and the concentrates obtained in other stages of scavenging return to the previous stage of scavenging; the scavenger tailings obtained in the last stage of scavenging are the flotation tailings, and the tailings obtained in other stages of scavenging enter the next stage of scavenging.

[0171] In some embodiments of the present invention, the cleaning process includes two or more stages of cleaning: the cleaning tailings obtained in the first stage of cleaning return to the roughening process, and the tailings obtained in other stages of cleaning return to the previous stage of cleaning; the cleaning concentrate obtained in the last stage of cleaning is the flotation concentrate, and the concentrates obtained in other stages of cleaning enter the next stage of cleaning.

[0172] In some embodiments of the present invention, the roughening process includes two stages of roughening:

[0173] For the first stage of roughening in the roughening process, the obtained tailings enter the second stage of roughening, and the obtained concentrate enters the first stage of cleaning;

[0174] In the second rough selection of the rough selection process, the tailings obtained enter the first scavenging, and the concentrate obtained enters the first cleaning.

[0175] In some embodiments of the present invention, the scavenging process includes two-stage scavenging:

[0176] In the first scavenging of the scavenging process, the tailings obtained enter the second scavenging, and the concentrate obtained enters the last rough selection;

[0177] In the second scavenging of the scavenging process, the tailings obtained are flotation tailings, and the concentrate obtained enters the first scavenging.

[0178] In some embodiments of the present invention, the cleaning process includes four-stage cleaning:

[0179] In the first cleaning of the cleaning process, the tailings obtained enter the last rough selection, and the concentrate obtained enters the second cleaning;

[0180] In the second cleaning of the cleaning process, the tailings obtained enter the first rough selection, and the concentrate obtained enters the third cleaning;

[0181] In the third cleaning of the cleaning process, the tailings obtained enter the second rough selection, and the concentrate obtained enters the fourth cleaning;

[0182] In the fourth cleaning of the cleaning process, the tailings obtained enter the third rough selection, and the concentrate obtained is flotation concentrate.

[0183] In some embodiments of the present invention, in the first rough selection of the rough selection process, the dosage of the collector is 150 - 180 g / t.

[0184] In some embodiments of the present invention, in the first rough selection of the rough selection process, the dosage of the frother is 20 - 30 g / t.

[0185] In some embodiments of the present invention, in the second rough selection of the rough selection process, the dosage of the collector is 70 - 90 g / t.

[0186] In some embodiments of the present invention, in the second rough selection of the rough selection process, the dosage of the frother is 10 - 15 g / t.

[0187] In some embodiments of the present invention, in the first scavenging of the scavenging process, the dosage of the collector is 30 - 40 g / t.

[0188] In some embodiments of the present invention, in the first scavenging of the scavenging process, the dosage of the frother is 5 - 10 g / t.

[0189] In some embodiments of the present invention, in the second scavenging of the scavenging process, the dosage of the collector is 20 - 30 g / t.

[0190] In some embodiments of the present invention, for the second stage of scavenging in the scavenging process, the dosage of the foaming agent is 1 - 5 g / t.

[0191] In some embodiments of the present invention, the method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt further includes: performing iron and aluminum removal neutralization on the neutralized feed liquid and / or the leached feed liquid to obtain an iron and aluminum removal slurry; separating the solid and liquid of the iron and aluminum removal slurry to obtain an iron and aluminum removal post-liquid and an iron and aluminum slag. The obtained iron and aluminum slag is subjected to tailings disposal, and impurities in the raffinate and cobalt dolomite entering the system are discharged from the system in segments, greatly reducing the production pressure of the system.

[0192] In some embodiments of the present invention, the neutralization end point of the iron and aluminum removal neutralization is that the pH value of the slurry is 3.8 - 4.2.

[0193] In some embodiments of the present invention, the neutralizing agent used for the iron and aluminum removal neutralization is lime. Only a small amount of lime neutralization is required to discharge impurities from the system, reducing the impurity content of the entire system and improving the product quality.

[0194] In some embodiments of the present invention, the neutralizing agent used for the iron and aluminum removal neutralization is lime milk with a concentration of 9 wt% - 10 wt%. Adding lime in the form of lime milk has a higher dispersion efficiency and the neutralization reaction occurs more evenly.

[0195] In some embodiments of the present invention, the method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt further includes: performing copper and cobalt precipitation neutralization on the iron and aluminum removal post-liquid to obtain a copper and cobalt precipitation slurry; separating the solid and liquid of the copper and cobalt precipitation slurry to obtain a copper and cobalt precipitation post-liquid and a copper and cobalt slag. The obtained copper and cobalt precipitation post-liquid is subjected to tailings disposal, and impurities in the raffinate and cobalt dolomite entering the system are discharged from the system in segments, greatly reducing the production pressure of the system. The copper grade in the obtained copper and cobalt slag is about 5 wt% - 6 wt%, and the cobalt grade is about 5 wt% - 8 wt%, and it can enter the leaching system for back dissolution to recover valuable copper and cobalt metals.

[0196] In some embodiments of the present invention, the neutralization end point of the copper and cobalt precipitation neutralization is that the pH value of the slurry is 6.8 - 7.2.

[0197] In some embodiments of the present invention, the neutralizing agent used for the copper and cobalt precipitation neutralization is lime. Only a small amount of lime neutralization is required to discharge impurities from the system, reducing the impurity content of the entire system and improving the product quality.

[0198] In some embodiments of the present invention, the neutralizing agent used for the copper and cobalt precipitation neutralization is lime milk with a concentration of 9 wt% - 10 wt%. Adding lime in the form of lime milk has a higher dispersion efficiency and the neutralization reaction occurs more evenly.

[0199] The cobalt dolomite ore involved in the present invention is a refractory copper-cobalt metal ore. The effects of recovering valuable copper and cobalt metals from it using various conventional beneficiation techniques are not ideal, and there is currently no good treatment plan for cobalt dolomite in the industry. In addition to cobalt dolomite ore, various low-grade cobalt ores are often involved in the field of ore recovery, such as copper-cobalt ore flotation tailings, other low-grade copper-cobalt oxide ore raw ores, mineralized waste rocks, etc. Copper-cobalt ore flotation tailings refer to the products in the sorting operation of ore dressing with relatively low copper and cobalt component contents and cannot be used for production and are stored in the tailings pond. Under the existing technical conditions in the industry, they do not have great recycling value; Mineralized waste rocks refer to the solid materials generated during the mining process, with copper and cobalt grades lower than the industrial grade and not entering subsequent operations such as ore dressing. They have certain recycling value, but are temporarily stored unused due to high production and treatment costs. The main problems encountered in the recovery of these low-grade cobalt ores are: due to the low content of valuable metals, the average processing cost per ton of product is high, while the beneficiation difficulty itself is not very large. The grades of cobalt dolomite ore are high and low, and generally, due to the difficulty of obtaining good recovery effects with existing production processes, they are temporarily stored. For the copper-cobalt ore in the northwest part of the Central African ore belt, due to the control of the ore deposit by strata and structures, the influence of external hydrothermal and weathering effects, on the one hand, the oxidation degree is relatively high and the composition of valuable minerals is complex; on the other hand, a large amount of wall rock alteration is induced, mainly silicification, carbonatization, and talcification, belonging to high-carbonate gangue-type oxidized ore, and the smelting and recovery are difficult.

[0200] At present, in the copper-cobalt metal production enterprises in the Democratic Republic of the Congo using hydrometallurgical processes, to ensure the quality of copper-cobalt products, a part of the liquid must be periodically opened out of the system during the production process to reduce the content of impurity ions in the system and relieve the water swelling pressure of the system, generally in the form of raffinate. The raffinate opened out of the system, in addition to containing a large amount of impurity metal ions in the liquid, also contains a certain amount of sulfuric acid. If directly discharged, it will inevitably cause serious environmental pollution problems. The traditional method for treating raffinate is to neutralize it by adding lime until it meets the discharge standard and then discharge it. A large amount of lime is often required during the production process. The resulting waste of resources and increase in production costs are urgent problems to be solved by the hydrometallurgical production enterprises in the Democratic Republic of the Congo.

[0201] The embodiment of the present invention uses high-copper cobalt dolomite to replace lime as the neutralizing agent for raffinate, solves the technical problem of difficult recovery of cobalt in high-copper cobalt dolomite, and fundamentally solves the problem of high production costs caused by the large consumption of lime in raffinate neutralization. After the iron-aluminum removal neutralization and copper-cobalt precipitation neutralization processes, the comprehensive recovery rates of copper and cobalt can both reach over 95%.

[0202] During the neutralization reaction of the flotation tailings and raffinate A in the embodiments of the present invention, the main reactions that occur between the carbonate gangue minerals and other gangue minerals present in the flotation tailings and sulfuric acid in the raffinate are shown in formulas (1) to (5):

[0203] CaCO 3 + H 2 SO 4 = CaSO 4 + H 2 O + CO 2 ↑ (1)

[0204] MgCO 3 + H 2 SO 4 = MgSO 4 + H 2 O + CO 2 ↑ (2)

[0205] CoCO 3 + H 2 SO 4 = CoSO 4 + H 2 O + CO 2 ↑ (3)

[0206] MnCO 3 + H 2 SO 4 = MnSO 4 + H 2 O + CO 2 ↑ (4)

[0207] A1 2 O 3 +3H 2 SO 4 → A1 2 (SO) 4 + 3H 2 O (5)

[0208] Meanwhile, copper minerals such as malachite, chrysocolla, and libethenite that are easily soluble in sulfuric acid at room temperature and present in the flotation tailings also react with sulfuric acid in the raffinate, as shown in formulas (6) to (8):

[0209] CuCO 3 ·Cu(OH) 2 +2H 2 SO 4 → 2CuSO 4 + 3H 2 O + 2CO2 ↑ (6)

[0210] CuSiO 3· 2H 2 O + H 2 SO 4 → CuSO 4 + SiO 2 +3H 2 O (7)

[0211] Cu 2 (PO 4 )OH + 2H 2 SO 4 → 2CuSO 4 + H 2 O + H 3 PO 4 (8)

[0212] After the above neutralization process, the copper minerals and gangue minerals in the ore that are easily soluble in acid have basically reacted completely with the sulfuric acid in the raffinate. However, a small amount of copper-cobalt sulfide ore and high-valent cobalt oxides that are insoluble in sulfuric acid at room temperature still exist in the form of solids in the neutralization slag. These copper compounds are mainly chalcocite (4Cu 2 S·CuS), covellite (CuS), bornite (Cu 5 FeS 4 ) and carrollite (CuCo 2 S 4 ), and the cobalt compounds are mainly cobalt compounds of Co 3+ .

[0213] Copper in the sulfide state and trivalent cobalt compounds are insoluble in acid at room temperature. However, during the heating process of leaching the neutralization slag with raffinate B, as the raffinate is added again and the temperature of the reaction system increases, these compounds will still undergo weak ionization in the presence of H + and transfer into the solution in ionic form. There is a certain amount of Fe 2+ and Fe 3+ in the raffinate. Fe 2+ has reducibility, and under heating conditions, H + will accelerate the redox reaction and can directly reduce Co 3+ to Co 2+ while generating goethite. The generated FeOOH then continues to react with H 2 SO 4 . The reaction equations are shown in Equations (9) and (10):

[0214] Co(OH) 3 + Fe2+ = Co 2+ + FeOOH + H 2 O (9)

[0215] 2FeOOH + 6H + → 2Fe 3+ + 4H 2 O (10)

[0216] During the heating leaching process, as the redox reaction proceeds, the oxidized ores and sulfide ores that exist in combination with the oxidized ores in the form of inclusions and aggregates are gradually dissociated and exposed in the solution; these sulfide ores are mainly chalcocite (CuS) and carrollite (CuCo 2 S 4 )), and these sulfide minerals exposed in the solution are oxidized by Fe 3+ , Co 3+ in the solution to generate S, Cu 2+ , Fe 3+ , Co 3+ itself is reduced to Fe 2+ , Co 2+ . The overall reactions are shown in equations (11) and (12):

[0217] 2CuS + 4H + + Fe 3+ = 2Cu 2+ + 2S + Fe 2+ (11)

[0218] 2CuS + 4H + + Co 3+ = 2Cu 2+ + 2S + Co 2+ (12)

[0219] The ionization equilibria of CuS and CuCo 2 S 4 in the solution are shown in equations (13) and (14):

[0220] CuS = Cu 2+ + S 2－ (13)

[0221] CuCo 2 S 4 = Cu 2+ + 2Co 3+ + 4S 2－ (14)

[0222] In an acidic environment, the ionized S 2－The ions are converted into hydrosulfuric acid by the sulfuric acid in the system, as shown in formula (15):

[0223] S 2－ + 2H + = H 2 S (15)

[0224] Hydrogen sulfide is a weak acid. In acidic solution, 2－ Almost all of it exists in the form of hydrosulfuric acid. At the same time, hydrosulfuric acid is absorbed by the Co in the solution. 3+ , Fe 3+ Oxidation of elemental sulfur, see formula (16), (17):

[0225] H 2 S + 2Co 3+ → 2H + + S↓+ 2 Co 2+ (16)

[0226] H 2 S + 2Fe 3+ → 2H + + S↓+ 2 Fe 2+ (17)

[0227] The generated elemental sulfur is very likely to appear in the form of colloids, because sulfur colloids can absorb hydrogen sulfide ions HS in the solution － The negative charge, coupled with the adsorption of the micelle itself, causes a considerable amount of Fe to be adsorbed on the surface of the sulfur micelle. 2+ Ion, Fe 2+ The O dissolved in the solution during stirring 2 The reaction generates Fe 3+ , see formula (18):

[0228] 4Fe 2+ + 4H + + O 2 → 4Fe 3+ + 2H 2 O (18)

[0229] Fe 3+ Continue to oxidize elemental S to HSO 3 － , H 2 SO 3 and a small amount of SO 3 2－ , see formula (19):

[0230] S + 4Fe 3+ + 3H 2 O → H 2 SO 3+ 4Fe 2+ + 4H + (19)

[0231] H 2 SO 3 reacts with the dissolved O 2 to generate SO 4 2－ , as shown in Equation (20):

[0232] 2H 2 SO 3 + O 2 → 2SO 4 2－ + 4H + (20)

[0233] The above reactions stop until all the substances such as CuS, CuCo 2 S 4 , CoO(OH) x in the solution have completely reacted.

[0234] In the iron and aluminum neutralization of some embodiments of the present invention, when lime is used as the neutralizing agent, OH - has obvious selectivity for iron and aluminum (Ksp(Fe(OH) 3 ) = 1.1*10 -36 , Ksp(Al(OH) 2 ) = 3.0*10 -34 , Ksp(Al(OH) 3 ) = 3.0*10 -34 ), and can preferentially react with iron and aluminum to precipitate as iron hydroxide and aluminum hydroxide. In the range of pH 3.8 - 4.2, the main reactions occurring to the ions in the solution are as follows, as shown in Equations (21) - (24):

[0235] Fe 2+ + 2OH - = Fe(OH) 2 ↓ (21)

[0236] Fe 3+ + 3OH - = Fe(OH) 3 ↓ (22)

[0237] Al 3+ + 2OH - = Al 2 (OH) 4 ↓ (23)

[0238] 2H + + OH- = H 2 O (24)

[0239] In some embodiments of the present invention, when copper and cobalt are precipitated and neutralized from the liquid after solid-liquid separation and iron and aluminum removal, as the pH of the solution increases, when the pH of the solution increases to 6.8 - 7.2, a large amount of Cu 2+ , Co 2+ in the solution reacts with OH - to form copper hydroxide and cobalt hydroxide precipitates, which enter the precipitate residue and become the finally recoverable copper-cobalt slag. The main reactions are shown in equations (25) and (26).

[0240] Cu 2+ + 2OH - = Cu (OH) 2 ↓ (25)

[0241] Co 2+ + 3OH - = Co(OH) 2 ↓ (26)

[0242] Examples

[0243] The following examples more specifically describe the content disclosed in the present invention. These examples are for illustrative purposes only, as various modifications and variations within the scope of the present invention are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight. Unless otherwise stated, all reagents used in the examples can be obtained through conventional commercial channels or synthesized according to conventional methods and can be used directly without further treatment. Unless otherwise stated, the instruments used in the examples can be obtained through conventional commercial channels.

[0244] Example 1

[0245] A copper-cobalt hydrometallurgy production enterprise in the Democratic Republic of the Congo needs to open a circuit for the raffinate of the system, which contains 1.61 g / L of copper, 2.57 g / L of cobalt, 2.65 g / L of iron, 0.52 g / L of manganese, 0.61 g / L of calcium, 10.73 g / L of magnesium, 1.55 g / L of aluminum, and a residual sulfuric acid content of 16.03 g / L. In this example, this raffinate is co-treated with high-copper-cobalt dolomite to recover copper and cobalt; the copper grade of the high-copper-cobalt dolomite is 2.19%, the cobalt grade is 0.684%, and the oxidation rate is 24.78%. The typical appearance of the high-copper-cobalt dolomite in this example is as Figure 2 shown.

[0246] As Figure 3 , Figure 4As shown in the process flow chart, the method for synchronously processing high copper-cobalt dolomite and raffinate to recover copper and cobalt in this embodiment is carried out according to the following steps:

[0247] (1) Grinding: Grind the high copper-cobalt dolomite. The grinding water is fresh water and the concentrated return water of the pulp after grinding; the fineness of the ground product is such that the proportion of the -0.074mm particle size fraction is 74.42%, and the pulp concentration is 33.35% of the raw ore pulp.

[0248] (2) Flotation: Conduct sulfide ore flotation with two-stage roughing, two-stage scavenging, and four-stage blank cleaning;

[0249] Roughing 1: Add 160 g / t of collector (sodium butyl xanthate) to the raw ore pulp obtained in step (1), stir for 2 min, then add 20 g / t of frother (pine oil), stir for 1 min, and then conduct air flotation to obtain copper-cobalt sulfide roughing concentrate 1 and sulfide ore roughing tailings 1; the obtained sulfide ore roughing tailings 1 enter roughing 2, and the obtained copper-cobalt sulfide roughing concentrate 1 enters cleaning 1;

[0250] Roughing 2: Add 70 g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 min, then add 10 g / t of frother (pine oil), stir for 1 min, and then conduct air flotation to obtain copper-cobalt sulfide roughing concentrate 2 and sulfide ore roughing tailings 2; the obtained sulfide ore roughing tailings 2 enter scavenging 1, and the obtained copper-cobalt sulfide roughing concentrate 2 enters cleaning 1;

[0251] Scavenging 1: Add 30 g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 min, then add 5 g / t of frother (pine oil), stir for 1 min, and then conduct air flotation to obtain copper-cobalt sulfide scavenging concentrate 1 and sulfide ore scavenging tailings 1; the obtained copper-cobalt sulfide scavenging concentrate 1 is returned to roughing 2, and the obtained sulfide ore scavenging tailings 1 enter scavenging 2;

[0252] Scavenging 2: Add 20 g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 min, then add 2.5 g / t of frother (pine oil), stir for 1 min, and then conduct air flotation to obtain copper-cobalt sulfide scavenging concentrate 2 and sulfide ore scavenging tailings 2; the obtained copper-cobalt sulfide scavenging concentrate 2 is returned to scavenging 1, and the obtained sulfide ore scavenging tailings 2 are the flotation tailings;

[0253] Cleaning 1: The pulp undergoes the first-stage cleaning to obtain copper-cobalt sulfide concentrate 1 and copper-cobalt sulfide cleaning tailings 1; the obtained copper-cobalt sulfide cleaning tailings 1 are returned to roughing 2, and the obtained copper-cobalt sulfide concentrate 1 enters cleaning 2;

[0254] Cleaning 2: The pulp undergoes the second-stage cleaning to obtain copper-cobalt sulfide concentrate 2 and copper-cobalt sulfide cleaning tailings 2; the obtained copper-cobalt sulfide cleaning tailings 2 are returned to cleaning 1, and the obtained copper-cobalt sulfide concentrate 2 enters cleaning 3;

[0255] Scavenging 3: The pulp undergoes scavenging in the third stage to obtain copper-cobalt sulfide concentrate 3 and copper-cobalt sulfide scavenging tailings 3; the obtained copper-cobalt sulfide scavenging tailings 3 are returned to scavenging 2, and the obtained copper-cobalt sulfide concentrate 3 enters scavenging 4;

[0256] Scavenging 4: The pulp undergoes scavenging in the fourth stage to obtain copper-cobalt sulfide concentrate 4 and copper-cobalt sulfide scavenging tailings 4; the obtained copper-cobalt sulfide scavenging tailings 4 are returned to scavenging 3, and the obtained copper-cobalt sulfide concentrate 4 is the flotation concentrate.

[0257] (3) Raffinate neutralization: The pulp of the flotation tailings obtained in step (2) is concentrated to a concentration of 50.77%, and diluted with raffinate to a pulp concentration of 7.5% for neutralization reaction. After the neutralization reaction lasts for 4 h at room temperature, neutralized pulp is obtained, and solid-liquid separation is performed to obtain neutralized feed liquid and neutralized slag.

[0258] (4) Warm leaching of neutralized slag: Raffinate is added to the neutralized slag obtained in step (3), and adjusted to a pulp concentration of 14.47% for warm leaching. The leaching temperature is controlled at 78 °C and the leaching time is 4 h. The obtained leaching pulp is subjected to solid-liquid separation to obtain leached feed liquid and leached slag; the leached slag is washed and then discharged for tailing treatment.

[0259] (5) Iron and aluminum removal neutralization: The leached feed liquid and the neutralized feed liquid obtained in steps (3) and (4) are combined as the pre-iron and aluminum removal liquid. A 10% lime milk is slowly added to the pre-iron and aluminum removal liquid for iron and aluminum removal neutralization. When the pH value of the pulp is 3.86, the addition of lime milk is stopped to obtain iron and aluminum removal pulp. Solid-liquid separation is performed to obtain post-iron and aluminum removal liquid and iron and aluminum slag, and the iron and aluminum slag is discharged for tailing treatment.

[0260] (6) Copper and cobalt precipitation neutralization: A 10% lime milk is slowly added to the post-iron and aluminum removal liquid for copper and cobalt precipitation neutralization. When the pH value of the pulp is 6.85, the addition of lime milk is stopped to obtain copper and cobalt precipitation pulp. Solid-liquid separation is performed to obtain post-copper and cobalt precipitation liquid and copper and cobalt slag; the post-copper and cobalt precipitation liquid is discharged for tailing treatment; the copper and cobalt slag is the final product obtained in this example, and valuable copper and cobalt metals can be recovered by redissolving through the leaching system.

[0261] Using the method of this example, high copper-cobalt dolomite can obtain a copper-cobalt sulfide flotation concentrate with a yield of 2.69%, Cu grade of 61.88%, recovery rate of 75.84%, Co grade of 5.707%, and recovery rate of 22.45% through sulfide ore flotation; sulfide ore flotation tailings with a yield of 97.31%, Cu grade of 0.55%, recovery rate of 24.16%, Co grade of 0.545%, and recovery rate of 77.55%. Using this sulfide ore flotation tailings for one-stage raffinate room temperature neutralization leaching and one-stage neutralization tailings warm leaching, for every 1 m 3The raffinate can simultaneously consume 267.04 kg of sulfide ore flotation tailings. The comprehensive recovery rates of copper and cobalt in the final whole process are 98.46% and 95.84% respectively, and the lime consumption is 53.78 kg (lime) / m 3 (raffinate). Compared with directly neutralizing the raffinate with lime, the lime consumption is reduced by 196.22 kg (lime) / m 3 (raffinate).

[0262] Example 2

[0263] A copper-cobalt hydrometallurgy production enterprise in the Democratic Republic of the Congo needs to open-circuit the system. The raffinate contains 1.93 g / L of copper, 3.00 g / L of cobalt, 2.89 g / L of iron, 0.74 g / L of manganese, 0.67 g / L of calcium, 11.99 g / L of magnesium, 1.71 g / L of aluminum, and the residual sulfuric acid content is 21.24 g / L; in this example, this raffinate is co-treated with high copper-cobalt dolomite to recover copper and cobalt; the copper grade of the high copper-cobalt dolomite is 2.82%, the cobalt grade is 1.065%, and the oxidation rate is 28.57%.

[0264] The method for simultaneously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt in this example is carried out according to the following steps:

[0265] (1) Grinding: Grind the high copper-cobalt dolomite, and the grinding water is clear water and the concentrated return water of the pulp after grinding; the obtained grinding product fineness is that the particle size fraction of -0.074 mm accounts for 73.79%, and the pulp concentration is 33.35% of the raw ore pulp.

[0266] (2) Flotation: Conduct sulfide ore flotation with two-stage roughing, two-stage scavenging, and four-stage blank cleaning;

[0267] Roughing 1: Add 170 g / t of collector (sodium butyl xanthate) to the raw ore pulp obtained in step (1), stir for 2 min, then add 25 g / t of foaming agent (pine oil), stir for 1 min, and then conduct air flotation to obtain rough concentrate 1 of copper-cobalt sulfide and rough tailings 1 of sulfide ore; the obtained rough tailings 1 of sulfide ore enter roughing 2, and the obtained rough concentrate 1 of copper-cobalt sulfide enters cleaning 1;

[0268] Roughing 2: Add 80 g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 min, then add 15 g / t of foaming agent (pine oil), stir for 1 min, and then conduct air flotation to obtain rough concentrate 2 of copper-cobalt sulfide and rough tailings 2 of sulfide ore; the obtained rough tailings 2 of sulfide ore enter scavenging 1, and the obtained rough concentrate 2 of copper-cobalt sulfide enters cleaning 1;

[0269] Scavenging 1: Add 35 g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 min, then add 7.5 g / t of frother (pine oil), stir for 1 min, and then conduct air flotation to obtain scavenged concentrate 1 of copper-cobalt sulfide and scavenged tailings 1 of sulfide ore; the obtained scavenged concentrate 1 of copper-cobalt sulfide is returned to roughing 2, and the obtained scavenged tailings 1 of sulfide ore enter scavenging 2;

[0270] Scavenging 2: Add 25 g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 min, then add 2.5 g / t of frother (pine oil), stir for 1 min, and then conduct air flotation to obtain scavenged concentrate 2 of copper-cobalt sulfide and scavenged tailings 2 of sulfide ore; the obtained scavenged concentrate 2 of copper-cobalt sulfide is returned to scavenging 1, and the obtained scavenged tailings 2 of sulfide ore are the flotation tailings;

[0271] Cleaning 1: The pulp undergoes the first-stage cleaning to obtain cleaned concentrate 1 of copper-cobalt sulfide and cleaned tailings 1 of copper-cobalt sulfide; the obtained cleaned tailings 1 of copper-cobalt sulfide are returned to roughing 2, and the obtained cleaned concentrate 1 of copper-cobalt sulfide enters cleaning 2;

[0272] Cleaning 2: The pulp undergoes the second-stage cleaning to obtain cleaned concentrate 2 of copper-cobalt sulfide and cleaned tailings 2 of copper-cobalt sulfide; the obtained cleaned tailings 2 of copper-cobalt sulfide are returned to cleaning 1, and the obtained cleaned concentrate 2 of copper-cobalt sulfide enters cleaning 3;

[0273] Cleaning 3: The pulp undergoes the third-stage cleaning to obtain cleaned concentrate 3 of copper-cobalt sulfide and cleaned tailings 3 of copper-cobalt sulfide; the obtained cleaned tailings 3 of copper-cobalt sulfide are returned to cleaning 2, and the obtained cleaned concentrate 3 of copper-cobalt sulfide enters cleaning 4;

[0274] Cleaning 4: The pulp undergoes the fourth-stage cleaning to obtain cleaned concentrate 4 of copper-cobalt sulfide and cleaned tailings 4 of copper-cobalt sulfide; the obtained cleaned tailings 4 of copper-cobalt sulfide are returned to cleaning 3, and the obtained cleaned concentrate 4 of copper-cobalt sulfide is the flotation concentrate.

[0275] (3) Neutralization of raffinate: Concentrate the pulp of the flotation tailings obtained in step (2) to a concentration of 51.32%, add raffinate to dilute the pulp concentration to 7.5% for neutralization reaction. After the neutralization reaction lasts for 4 h at room temperature, neutralized pulp is obtained, and solid-liquid separation is carried out to obtain neutralized feed liquid and neutralized slag.

[0276] (4) Warm leaching of neutralized slag: Add raffinate to the neutralized slag obtained in step (3), adjust to a pulp concentration of 14.63% for warm leaching, control the leaching temperature at 75 °C and the leaching time at 4 h. The obtained leaching pulp is subjected to solid-liquid separation to obtain leaching feed liquid and leaching slag; the leaching slag is washed and then discharged for tailing treatment.

[0277] (5) Iron and aluminum removal and neutralization: The leaching slurry obtained in steps (3) and (4) is combined with the neutralization slurry as the pre-liquid for iron and aluminum removal. Slowly add lime milk with a concentration of 10% to the pre-liquid for iron and aluminum removal for iron and aluminum removal and neutralization. Stop adding lime milk when the pH value of the pulp is 3.91 to obtain the iron and aluminum removal pulp. After solid-liquid separation, the post-liquid for iron and aluminum removal and the iron and aluminum slag are obtained. The iron and aluminum slag is discharged for tailing treatment.

[0278] (6) Copper and cobalt precipitation and neutralization: Slowly add lime milk with a concentration of 10% to the post-liquid for iron and aluminum removal for copper and cobalt precipitation and neutralization. Stop adding lime milk when the pH value of the pulp is 6.90 to obtain the copper and cobalt precipitation pulp. After solid-liquid separation, the post-liquid for copper and cobalt precipitation and the copper and cobalt slag are obtained; the post-liquid for copper and cobalt precipitation is discharged for tailing treatment; the copper and cobalt slag is the final product obtained in this embodiment, and valuable metals such as copper and cobalt can be recovered by redissolution through the leaching system.

[0279] Using the method of this embodiment, high copper-cobalt dolomite can obtain a copper-cobalt sulfide flotation concentrate with a yield of 3.43%, a Cu grade of 60.79%, a recovery rate of 73.95%, a Co grade of 6.881%, and a recovery rate of 22.13% through sulfide ore flotation; a sulfide ore flotation tailing with a yield of 96.57%, a Cu grade of 0.76%, a recovery rate of 26.05%, a Co grade of 0.859%, and a recovery rate of 77.87%. Using this sulfide ore flotation tailing for one-stage raffinate normal-temperature neutralization leaching and one-stage neutralization tailing heating leaching, 272.87 kg of sulfide ore flotation tailing can be consumed simultaneously per 1 m 3 of raffinate. The overall copper and cobalt comprehensive recovery rates of the final whole process are 98.10% and 95.21% respectively, and the lime consumption is 52.62 kg (lime) / m 3 (raffinate). Compared with directly using lime to neutralize the raffinate, the lime consumption is reduced by 197.38 kg (lime) / m 3 (raffinate).

[0280] Example 3

[0281] A copper-cobalt hydrometallurgy production enterprise in the Democratic Republic of the Congo needs to open-circuit the raffinate of the system, which contains 2.42 g / L of copper, 3.31 g / L of cobalt, 3.09 g / L of iron, 0.84 g / L of manganese, 0.72 g / L of calcium, 12.01 g / L of magnesium, 1.83 g / L of aluminum, and the residual sulfuric acid content is 24.01 g / L; this embodiment uses this raffinate and high copper-cobalt dolomite to jointly treat and recover copper and cobalt; the copper grade of the high copper-cobalt dolomite is 3.61%, the cobalt grade is 1.231%, and the oxidation rate is 27.98%.

[0282] The method for synchronously treating high copper-cobalt dolomite and raffinate to recover copper and cobalt in this embodiment is carried out according to the following steps:

[0283] (1) Grinding: Grind the high copper-cobalt dolomite. The grinding water is fresh water and the concentrated return water of the pulp after grinding; The fineness of the ground product is 74.87% of the -0.074mm particle size fraction, and the pulp concentration is 33.35% of the raw ore pulp.

[0284] (2) Flotation: Conduct sulfide ore flotation with two-stage roughing, two-stage scavenging, and four-stage blank cleaning;

[0285] Roughing 1: Add 180g / t of collector (sodium butyl xanthate) to the raw ore pulp obtained in step (1), stir for 2 minutes, then add 30g / t of foaming agent (pine oil), stir for 1 minute, and then conduct air flotation to obtain rough concentrate 1 of copper-cobalt sulfide and rough tailings 1 of sulfide ore; The obtained rough tailings 1 of sulfide ore enter roughing 2, and the obtained rough concentrate 1 of copper-cobalt sulfide enters cleaning 1;

[0286] Roughing 2: Add 90g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 minutes, then add 15g / t of foaming agent (pine oil), stir for 1 minute, and then conduct air flotation to obtain rough concentrate 2 of copper-cobalt sulfide and rough tailings 2 of sulfide ore; The obtained rough tailings 2 of sulfide ore enter scavenging 1, and the obtained rough concentrate 2 of copper-cobalt sulfide enters cleaning 1;

[0287] Scavenging 1: Add 40g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 minutes, then add 10g / t of foaming agent (pine oil), stir for 1 minute, and then conduct air flotation to obtain scavenging concentrate 1 of copper-cobalt sulfide and scavenging tailings 1 of sulfide ore; The obtained scavenging concentrate 1 of copper-cobalt sulfide is returned to roughing 2, and the obtained scavenging tailings 1 of sulfide ore enter scavenging 2;

[0288] Scavenging 2: Add 30g / t of collector (sodium butyl xanthate) to the pulp, stir for 2 minutes, then add 5g / t of foaming agent (pine oil), stir for 1 minute, and then conduct air flotation to obtain scavenging concentrate 2 of copper-cobalt sulfide and scavenging tailings 2 of sulfide ore; The obtained scavenging concentrate 2 of copper-cobalt sulfide is returned to scavenging 1, and the obtained scavenging tailings 2 of sulfide ore are the flotation tailings;

[0289] Cleaning 1: The pulp undergoes the first-stage cleaning to obtain cleaning concentrate 1 of copper-cobalt sulfide and cleaning tailings 1 of copper-cobalt sulfide; The obtained cleaning tailings 1 of copper-cobalt sulfide are returned to roughing 2, and the obtained cleaning concentrate 1 of copper-cobalt sulfide enters cleaning 2;

[0290] Cleaning 2: The pulp undergoes the second-stage cleaning to obtain cleaning concentrate 2 of copper-cobalt sulfide and cleaning tailings 2 of copper-cobalt sulfide; The obtained cleaning tailings 2 of copper-cobalt sulfide are returned to cleaning 1, and the obtained cleaning concentrate 2 of copper-cobalt sulfide enters cleaning 3;

[0291] Cleaning 3: The pulp undergoes the third-stage cleaning to obtain cleaning concentrate 3 of copper-cobalt sulfide and cleaning tailings 3 of copper-cobalt sulfide; The obtained cleaning tailings 3 of copper-cobalt sulfide are returned to cleaning 2, and the obtained cleaning concentrate 3 of copper-cobalt sulfide enters cleaning 4;

[0292] Concentrate 4: The pulp undergoes the fourth-stage concentration to obtain copper-cobalt sulfide concentrate 4 and copper-cobalt sulfide concentrated tailings 4; the obtained copper-cobalt sulfide concentrated tailings 4 are returned to the third-stage concentration, and the obtained copper-cobalt sulfide concentrate 4 is the flotation concentrate.

[0293] (3) Neutralization of raffinate: The pulp of the flotation tailings obtained in step (2) is concentrated to a concentration of 52.21%, and diluted with raffinate to a pulp concentration of 7.5% for neutralization reaction. After the neutralization reaction lasts for 4 h at room temperature, neutralized pulp is obtained, and solid-liquid separation is performed to obtain neutralized feed liquid and neutralized slag.

[0294] (4) Warm leaching of neutralized slag: Raffinate is added to the neutralized slag obtained in step (3), and the pulp concentration is adjusted to 14.09% for warm leaching. The leaching temperature is controlled at 75 °C and the leaching time is 4 h. The obtained leaching pulp is subjected to solid-liquid separation to obtain leaching feed liquid and leaching slag; the leaching slag is washed and then discharged for tailing treatment.

[0295] (5) Iron and aluminum removal by neutralization: The leaching feed liquid and the neutralized feed liquid obtained in step (3) and step (4) are combined as the liquid before iron and aluminum removal. A 10% lime milk is slowly added to the liquid before iron and aluminum removal for iron and aluminum removal by neutralization. When the pH value of the pulp is 4.01, the addition of lime milk is stopped to obtain iron and aluminum removal pulp, and solid-liquid separation is performed to obtain the liquid after iron and aluminum removal and iron and aluminum slag. The iron and aluminum slag is discharged for tailing treatment.

[0296] (6) Copper and cobalt precipitation by neutralization: A 10% lime milk is slowly added to the liquid after iron and aluminum removal for copper and cobalt precipitation by neutralization. When the pH value of the pulp is 6.99, the addition of lime milk is stopped to obtain copper and cobalt precipitation pulp, and solid-liquid separation is performed to obtain the liquid after copper and cobalt precipitation and copper-cobalt slag; the liquid after copper and cobalt precipitation is discharged for tailing treatment; the copper-cobalt slag is the final product obtained in this embodiment, and valuable copper and cobalt metals can be recovered by redissolution through the leaching system.

[0297] Using the method of this embodiment, high-copper-cobalt dolomite can obtain copper-cobalt sulfide flotation concentrate with a yield of 4.18%, Cu grade of 63.82%, recovery rate of 73.97%, Co grade of 6.98%, and recovery rate of 23.17% through sulfide ore flotation; sulfide ore flotation tailings with a yield of 95.82%, Cu grade of 0.98%, recovery rate of 26.03%, Co grade of 0.980%, and recovery rate of 76.29%. Using the sulfide ore flotation tailings for one-stage raffinate room-temperature neutralization leaching and one-stage neutralized tailings warm leaching, 289.54 kg of sulfide ore flotation tailings can be consumed per cubic meter of raffinate. The overall copper and cobalt comprehensive recovery rates of the whole process are 98.27% and 95.28% respectively, and the lime consumption is 50.03 kg (lime) / m 3 (raffinate). Compared with directly using lime to neutralize the raffinate, the lime consumption is reduced by 199.97 kg (lime) / m 3 (raffinate). 3raffinate

[0298] Comparative Example 1

[0299] For other low-grade mixed copper-cobalt ores, the existing main treatment method in the industry is to first flotation the sulfide copper-cobalt ore, and then carry out sulfide flotation on the obtained flotation tailings for copper-cobalt oxide. The specific process is as follows: First, the most common xanthate collectors (butyl xanthate or amyl xanthate) are used for sulfide ore flotation, and the dosage is usually controlled between 100-300 g / t for the total dosage in roughing and scavenging according to the ore grade; after sulfide ore flotation, the obtained flotation tailings are sulfided with a sulfiding agent for the copper-cobalt oxide ore in the tailings, and then copper-cobalt oxide is flotated. The commonly used sulfiding agents are sodium sulfide and sodium hydrosulfide; the process of sulfide flotation of copper-cobalt oxide ore is usually controlled at 1-7 stages of oxide ore flotation according to the grade and oxidation rate of copper-cobalt oxide in the ore. The total dosage of the sulfiding agent for 1-7 stages of oxide ore flotation is usually controlled between 5-8 kg / t according to the different oxidation rates of the ore. The collector used for sulfide flotation of oxide ore is the common xanthate collector (butyl xanthate or amyl xanthate), and the total dosage is between 300-400 g / t; the frother used in the process of sulfide copper-cobalt ore flotation and copper-cobalt oxide ore flotation is No. 2 oil, and the total dosage is between 80-120 g / t. Using this method to treat the cobalt dolomite samples in Example 1, Example 2 and Example 3, the beneficiation indexes are shown in Table 1:

[0300] Table 1 Beneficiation indexes of direct flotation of sulfide ore - sulfide flotation of oxide ore for cobalt dolomite

[0301]

[0302] As can be seen from Table 1, for the raw ore samples in Example 1, Example 2 and Example 3 treated by the conventional beneficiation process of direct flotation of sulfide ore - sulfide flotation of oxide ore, the total copper recoveries are 85.17%, 87.60% and 85.50% respectively, which are 13.29%, 10.50% and 12.77% lower than the comprehensive copper recoveries of the whole process in Example 1, Example 2 and Example 3 respectively; in Comparative Example 1, the total cobalt recoveries are 43.26%, 38.14% and 41.80% respectively, which are 52.58%, 57.07% and 53.48% lower than the comprehensive cobalt recoveries of the whole process in Example 1, Example 2 and Example 3 respectively. It can be seen that if the cobalt dolomite is treated by the conventional process of first directly flotation of sulfide copper-cobalt ore - sulfide ore flotation tailings and then sulfide flotation of copper-cobalt oxide, the recovery effect of copper and cobalt is poor.

[0303] Comparative Example 2

[0304] In this comparative example, acid leaching tests were carried out on the sulfide ore flotation tailings in Example 1, Example 2 and Example 3, and samples with similar tailings grades after flotation of other copper-cobalt ore raw ores. The test conditions were a pulp mass liquid-solid ratio of 6:1, a leaching time of 4 h, and the pH of the pulp was controlled within the range of 1.5±0.01 by directly adding 98% concentrated sulfuric acid during the leaching process. After the leaching was completed, the pulp was filtered, and the residual acid concentration in the filtrate was measured by acid-base neutralization titration. After the filter residue was washed and dried, the elemental contents of copper and cobalt were determined by ICP method. According to the analysis and detection results, the acid consumption and the corresponding leaching rate were calculated, from which the treatment difficulty of the ore could be reflected. The results are shown in Table 2. The 1#, 2# and 3# copper-cobalt ores involved are all copper-cobalt ores without cobalt dolomite from an open-pit mining pit in a certain mining area in Lualaba Province, Democratic Republic of the Congo. The 1#, 2# and 3# copper-cobalt ores are respectively close to the copper and cobalt grades of the cobalt dolomite in Example 1, Example 2 and Example 3, with similar oxidation rates, and the main component of the sulfide ore is chalcocite.

[0305] The process method for obtaining the 1# copper-cobalt ore flotation sulfide ore tailings from the 1# copper-cobalt ore is the same as the process method for obtaining the flotation tailings from the cobalt dolomite raw ore in Example 1; the process method for obtaining the 2# copper-cobalt ore flotation sulfide ore tailings from the 2# copper-cobalt ore is the same as the process method for obtaining the flotation tailings from the cobalt dolomite raw ore in Example 2; the process method for obtaining the 3# copper-cobalt ore flotation sulfide ore tailings from the 3# copper-cobalt ore is the same as the process method for obtaining the flotation tailings from the cobalt dolomite raw ore in Example 3.

[0306] Table 2 Comparative analysis of acid consumption differences between cobalt dolomite copper-cobalt ore flotation tailings and other copper-cobalt ore flotation tailings

[0307]

[0308] As can be seen from Table 2, compared with the flotation sulfide ore tailings of other general copper and cobalt grades, the copper and cobalt leaching rates of the cobalt dolomite flotation tailings in each example of the present invention are significantly lower than those of the flotation sulfide ore tailings of other copper-cobalt ores (especially cobalt element), while the net acid consumption is much higher than that of the flotation sulfide ore tailings of other copper-cobalt ores with similar grades. That is, under the same treatment process conditions, the recovery effects of copper and cobalt in the flotation copper sulfide tailings of cobalt dolomite copper-cobalt ore are poor and the acid consumption is higher. This also reflects the poor recovery effect and high cost of treating cobalt dolomite by conventional processes.

Claims

1. A method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate, characterized in that: include: The flotation tailings obtained by flotation of the raw ore pulp of the high-copper-cobalt dolomite through sulfide ore flotation are subjected to a neutralization reaction with the raffinate A to obtain a neutralized ore pulp; the neutralized ore pulp is separated into a solid and a liquid to obtain a neutralized liquid and a neutralized slag; The neutralized residue is mixed with the raffinate B for leaching to obtain a leached slurry; the leached slurry is solid-liquid separated to obtain a leached liquid and leached residue; The copper grade of the high-copper-cobalt dolomite is above 1.2wt%; the oxidation rate of the high-copper-cobalt dolomite is below 65wt%; The sulfuric acid content in the raffinate A is greater than 8 g / L; the sulfuric acid content in the raffinate B is greater than 8 g / L; The raffinate B contains more than 1 g / L of iron; The leaching temperature of the mixed leaching of the neutralized residue and the raffinate B is above 55°C.

2. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to claim 1, characterized in that: The copper grade of the high-copper-cobalt dolomite is 1.5wt% to 4.0wt%; the cobalt grade of the high-copper-cobalt dolomite is 0.5wt% to 1.5wt%; the oxidation rate of the high-copper-cobalt dolomite is 20wt% to 60wt%; The raffinate A comes from a hydrometallurgical process for recovering copper; the raffinate A contains 1.5-2.5 g / L copper; the raffinate A contains 2.5-3.5 g / L cobalt; the raffinate A contains 2.5-3.5 g / L iron; the raffinate A contains 0.5-1.0 g / L manganese; the raffinate A contains 0.5-0.8 g / L calcium; the raffinate A contains 10-13 g / L magnesium; the raffinate A contains 1.5-2.0 g / L aluminum; the raffinate A contains 15-25 g / L sulfuric acid; The raffinate B comes from a hydrometallurgical process for recovering copper; the raffinate B contains 1.5 to 2.5 g / L copper; the raffinate B contains 2.5 to 3.5 g / L cobalt; the raffinate B contains 2.5 to 3.5 g / L iron; the raffinate B contains 0.5 to 1.0 g / L manganese; the raffinate B contains 0.5 to 0.8 g / L calcium; the raffinate B contains 10 to 13 g / L magnesium; the raffinate B contains 1.5 to 2.0 g / L aluminum; the raffinate B contains 15 to 25 g / L sulfuric acid; The raw ore pulp is obtained by grinding the high-copper-cobalt dolomite; The raw ore pulp has a particle size of -0.074 mm, which accounts for 70 wt% to 75 wt%; The concentration of the raw ore slurry is 30wt% to 35wt%; Before the flotation tailings are mixed with the raffinate A, the slurry concentration of the flotation tailings is concentrated to 50wt% to 55wt%; The weight ratio of the flotation tailings to the raffinate A used is 1:4-10; The neutralization reaction time of flotation tailings and raffinate A is 3 to 5 hours; The weight ratio of the neutralized residue to the raffinate B used is 10-15:90-85; The leaching time of the mixed leaching of the neutralized residue and the raffinate B is 3 to 5 hours; The leaching temperature of the mixed leaching of the neutralized residue and the raffinate B is 70-80°C.

3. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to claim 1 or 2, characterized in that: The sulfide ore flotation includes a roughing process and a scavenging process; the roughing process includes one or more stages of roughing; the scavenging process includes one or more stages of scavenging; the roughing tailings obtained in the roughing process enter the scavenging process; the scavenging tailings obtained in the scavenging process are flotation tailings obtained from the sulfide ore flotation; The collector used in the flotation of the sulfide ore is sodium butyl xanthate; the frother used in the flotation of the sulfide ore is pine oil; The total amount of collector used in the roughing process is 200-300 g / t; The total amount of foaming agent used in the roughing process is 20-50 g / t; The total amount of collector used in the scavenging process is 40-100 g / t; The total amount of the foaming agent used in the scavenging process is 5 to 20 g / t.

4. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to claim 3, characterized in that: The sulfide ore flotation also includes a beneficiation process; the beneficiation process includes one or more stages of beneficiation; the roughing concentrate obtained in the roughing process enters the beneficiation process; the scavenging concentrate obtained in the scavenging process enters the roughing process; the beneficiated tailings obtained in the beneficiation process enter the roughing process; the beneficiated concentrate obtained in the beneficiation process is the flotation concentrate obtained by the sulfide ore flotation; the beneficiation process adopts blank beneficiation.

5. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to claim 3 or 4, characterized in that: The roughing process includes two or more stages of roughing: The rougher concentrate obtained in each roughing stage enters the concentrating process; The tailings from the last roughing stage enter the scavenging process, and the tailings from the other roughing stages enter the next roughing stage; The sweeping process includes two or more sweeping stages: The scavenged concentrate obtained in the first stage of scavenging is returned to the roughing process, and the concentrate obtained in other stages of scavenging is returned to the previous stage of scavenging; The tailings obtained from the last stage of scavenging are flotation tailings, and the tailings obtained from other stages of scavenging enter the next stage of scavenging; The concentrating process includes more than two stages of concentrating: The tailings obtained from the first stage of concentration are returned to the roughing process, and the tailings obtained from other stages of concentration are returned to the previous stage of concentration; The concentrated ore obtained in the last stage of concentration is the flotation concentrate, and the concentrates obtained in other stages of concentration enter the next stage of concentration.

6. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to claim 5, characterized in that: The roughing process includes two stages of roughing: The first stage of the roughing process is roughing, the tailings obtained enter the second stage of roughing, and the concentrate obtained enters the first stage of concentrating; The second stage of roughing in the roughing process, the tailings obtained enter the first stage of scavenging, and the concentrate obtained enters the first stage of concentrating; The scanning process includes two stages of scanning: The first stage of the scavenging process is scavenging, the tailings obtained enter the second stage of scavenging, and the concentrates obtained enter the final stage of roughing; The tailings obtained in the second stage of the scavenging process are flotation tailings, and the concentrates obtained enter the first stage of scavenging; The selection process includes four stages of selection: In the first stage of the concentrating process, the tailings obtained enter the final stage of roughing, and the concentrate obtained enters the second stage of concentrating; The tailings obtained in the second stage of the concentrating process enter the first stage of roughing, and the concentrates obtained enter the third stage of concentrating; The tailings obtained in the third stage of the concentrating process enter the second stage of roughing, and the concentrate enters the fourth stage of concentrating; The tailings obtained in the fourth stage of the concentrating process enter the third stage of roughing, and the concentrate obtained is the flotation concentrate; In the first stage of the roughing process, the amount of collector used is 150-180 g / t; In the first stage of the roughing process, the amount of the foaming agent is 20-30 g / t; In the second roughing stage of the roughing process, the amount of collector used is 70-90 g / t; In the second roughing step of the roughing process, the amount of the foaming agent is 10-15 g / t; In the first stage of the scavenging process, the amount of collector used is 30-40 g / t; In the first stage of the scavenging process, the amount of the foaming agent is 5-10 g / t; In the second stage of the scavenging process, the amount of collector used is 20-30 g / t; In the second stage of the scavenging process, the amount of the foaming agent used is 1 to 5 g / t.

7. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to any one of claims 1 to 6, characterized in that: The method also includes: neutralizing the neutralization liquid and / or the leaching liquid to remove iron and aluminum to obtain an iron-removed aluminum slurry; performing solid-liquid separation on the iron-removed aluminum slurry to obtain an iron-removed aluminum liquid and iron-aluminum slag; and the neutralization endpoint of the iron-removed aluminum neutralization is a slurry pH value of 3.8 to 4.

2.

8. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to claim 7, characterized in that: The neutralizing agent used for the iron and aluminum removal neutralization is lime, and the preferred concentration is 9wt% to 10wt% lime milk.

9. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to any one of claims 1 to 8, characterized in that: The method also includes: neutralizing the iron and aluminum removal liquid with copper and cobalt to obtain a copper and cobalt ore slurry; separating the copper and cobalt ore slurry into solid and liquid to obtain a copper and cobalt ore liquid and copper-cobalt slag; and the neutralization end point of the copper and cobalt neutralization is a slurry pH value of 6.8 to 7.

2.

10. The method for simultaneously treating high-copper-cobalt dolomite and recovering copper and cobalt from raffinate according to claim 9, characterized in that: The neutralizing agent used for neutralizing the copper-cobalt precipitation is lime, and the preferred concentration is 9wt% to 10wt% lime milk.

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