Flotation method for high-calcium-magnesium copper cobalt oxide ore and combined collecting agent

Abstract

The invention relates to the technical field of beneficiation of copper cobalt oxide ores, and discloses a flotation method for high-calcium-magnesium copper cobalt oxide ores and a combined collecting agent. The positive and negative mixed flotation technology is adopted, a combined collecting agent composed of oxidized paraffin soap, sodium oleate and divalent metal cations is adopted in the reverse flotation process, the total recovery rate of copper and cobalt reaches 90% or above, and the leaching acid consumption is 20-60 kg / t.feeding ore. The combined collecting agent adopted by the method is small in dosage, good in collecting performance and small in toxicity, compared with an existing copper oxide cobalt ore flotation technology, the method can improve the copper and cobalt recovery rate by 10% or above, leaching acid consumption is remarkably reduced, the production cost is remarkably reduced, the technological process is simple, and industrial application and popularization are easy.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing and nonferrous metal extraction, and in particular to a flotation method for high-calcium and magnesium-oxide copper-cobalt ore and a combined collector. Background Art

[0002] Copper and cobalt are widely used in many fields such as batteries, electronics, and metallurgy. Copper-cobalt oxide ore is an important mineral type in copper-cobalt ore resources and is widely distributed in major mining areas around the world. With the exploitation and utilization of resources, copper sulfide ore and easily selected copper-cobalt oxide ore are decreasing, and high-calcium-magnesium copper-cobalt oxide ore is gradually being mined and utilized. However, it is difficult to achieve efficient recovery of copper-cobalt resources by using conventional positive flotation process to treat copper-cobalt oxide ore, and the subsequent wet leaching acid consumption is large and the production cost is high. Therefore, it is of great significance to strengthen the flotation recovery research of high-calcium-magnesium copper-cobalt oxide ore, improve its comprehensive utilization rate, and reduce leaching acid consumption and production costs.

[0003] In terms of high calcium and magnesium oxidized copper-cobalt ores, Chinese patent CN118186209A reported "a combined leaching method for high acid consumption and easy bubbling oxidized copper-cobalt ores", which is to add concentrated sulfuric acid and high copper raffinate for pre-leaching, and then add concentrated sulfuric acid for leaching, but the cost of this method is relatively high. Chinese patent CN109201312A announced "a beneficiation and smelting method for oxidized copper-cobalt ores containing easily floating gangue", which introduces easily floating gangue collectors and inhibitors to achieve the separation of gangue minerals from useful minerals, but the process flow of this method is complicated. Chinese patent CN118807990A reported "a flotation method for high calcium and magnesium oxidized copper-cobalt ores", which introduced a combination of xanthate and salicylic hydroxamic acid collectors. Although better indicators were obtained, the cost of the reagents was relatively high, and the separation of useful minerals from gangue minerals was limited. Summary of the invention

[0004] In order to solve the problems of low copper and cobalt recovery rate, high production cost and high leaching acid consumption in the flotation method of high calcium and magnesium oxide copper and cobalt ore in the existing methods and technologies, the first object of the present invention is to provide a combined collector for flotation of high calcium and magnesium oxide copper and cobalt ore, which increases the hydrophobicity of the mineral through the synergistic adsorption of oxidized paraffin soap and sodium oleate, and utilizes the strengthening effect of metal ions to achieve a significant improvement in flotation efficiency at a lower dosage.

[0005] The second object of the present invention is to provide a flotation method for high calcium and magnesium copper-cobalt oxide ore, which achieves a copper and cobalt recovery rate greater than 90% in the high calcium and magnesium copper-cobalt oxide ore by adopting a "positive and negative mixed flotation" process to treat the high calcium and magnesium copper-cobalt oxide ore, and a leaching acid consumption of 20 to 60 kg / t·feed ore.

[0006] In order to achieve the above technical purpose, the present invention provides a combined collector for flotation of high calcium and magnesium copper-cobalt oxide ore, including oxidized paraffin soap, sodium oleate and divalent metal cations.

[0007] The action mechanism of the composite collector of the present invention can be analyzed from the perspective of surface chemistry, intermolecular interaction and coordination chemistry. In the technical solution of the present invention, the carboxyl group, ester group and aldehyde group in the composite collector are synergistically adsorbed on the dolomite surface, thereby enhancing the hydrophobicity of the surface. Specifically, the oxidized paraffin soap is a surfactant of long-chain hydrocarbons, contains carboxyl group, aldehyde group, ester group and other solid-philic groups, and can be adsorbed to the calcium and magnesium sites exposed on the surface of the gangue mineral dolomite. Sodium oleate is a long-chain fatty acid salt, and the carboxylic acid functional group contained in it can be adsorbed on the dolomite surface. The combination of the two produces a synergistic adsorption effect, and the sodium oleate provides additional hydrophobic force, while the oxidized paraffin soap increases the intermolecular adsorption force, thereby improving the hydrophobicity of the dolomite surface. In addition, the metal ions further strengthen the adsorption of the collector on the dolomite surface by forming a colloidal complex, and can coordinate with oxidized paraffin soap and sodium oleate to generate a stable colloidal complex, which has the characteristics of strong hydrophobicity and polarity, strengthens the adsorption of the collector molecules on the calcium and magnesium sites on the dolomite surface, and enhances the hydrophobicity of the dolomite surface to improve the flotation performance. Therefore, the composite collector of the present invention can significantly improve the flotation efficiency of the calcium and magnesium gangue mineral dolomite with a small amount of use, and reduces the influence of calcium and magnesium elements in the subsequent copper oxide wet leaching process.

[0008] As a preferred solution, the combined collector is composed of oxidized paraffin soap, sodium oleate and divalent metal cations in a mass percentage of (50-60)%: (20-40)%: (10-20)%. Oxidized paraffin soap as the main collector ensures sufficient adsorption and hydrophobicity of the collector molecules on the dolomite surface, an appropriate amount of sodium oleate can further enhance the hydrophobicity of the dolomite surface, and an appropriate amount of metal ions can form a stable colloidal complex through coordination to improve the adsorption capacity. Too low dosage of the three will lead to a decrease in adsorption and collection capacity and a decrease in dolomite flotation performance; while too high dosage will lead to a strong hydrophilicity of the mineral surface, reduced selectivity, and increased cost. Further preferably, the combined collector is composed of oxidized paraffin soap, sodium oleate and divalent metal cations in a mass percentage of (50-55)%: 30%: (15-20)%.

[0009] As a preferred embodiment, the divalent metal cation is Ca 2+ Mg 2+ 、Zn 2+ and Pb 2+ At least one of the following. The divalent metal ions selected in the present invention have the properties of high solubility, relatively low cost, and safe use. If the divalent metal cations are replaced with monovalent metal cations, the colloidal complex cannot be effectively formed, thereby reducing the removal effect of calcium and magnesium.

[0010] The present invention also provides a flotation method for high-calcium-magnesium-oxide copper-cobalt ore. The high-calcium-magnesium-oxide copper-cobalt ore is subjected to grinding and pulping treatment to obtain ore pulp; a sulfiding agent and a xanthate collector are added to the ore pulp to carry out positive flotation of copper and cobalt to obtain a foam concentrate I and a middling; the middling ore is subjected to reverse flotation of calcium-magnesium gangue minerals using the combined collector according to any one of claims 1 to 3 to obtain an underflow concentrate II and tailings; and the foam concentrate I and the underflow concentrate II are combined to obtain an oxide copper-cobalt concentrate.

[0011] The high calcium and magnesium oxide copper-cobalt ore targeted by the present invention has a high calcium and magnesium grade, the gangue is embedded and wrapped on cobalt and copper, and has an inhibitory effect on copper and cobalt during the flotation process. In addition, the oxidation rate of copper and cobalt is high and the floatability is poor, resulting in the need for complex positive flotation process and high leaching acid consumption in the prior art to achieve the recovery of copper and cobalt resources. The present invention proposes a "positive and reverse mixed flotation" process, that is, first positive flotation of copper and cobalt minerals, and then reverse flotation combined with a special combined collector to remove calcium and magnesium gangue minerals. In the positive flotation process, a sulfiding agent is added to convert copper oxide and cobalt oxide into copper sulfide and cobalt sulfide that are easily captured by xanthate collectors, thereby improving their floatability. In the positive flotation process, all concentrates are utilized, and the tailings can enter the reverse flotation, which effectively solves the problem of copper and cobalt resources running tail in the positive flotation in the prior art, and realizes the efficient separation of copper and cobalt minerals and calcium and magnesium gangue minerals.

[0012] At the same time, the flotation process of the present invention can be characterized by adsorption on the surface sites of calcium-magnesium gangue minerals by using a reverse flotation operation combined with a collector, thereby increasing the hydrophobicity of the mineral surface and deeply removing most of the acid-consuming calcium-magnesium minerals, thereby significantly reducing the acid consumption in the leaching process.

[0013] As a preferred solution, the calcium and magnesium grades of the high calcium and magnesium oxide copper-cobalt ore are both greater than 8%, and the oxidation rate is greater than 90%. The oxide copper-cobalt ore used in the present invention has high calcium and magnesium grades, high oxidation rates of copper and cobalt, and poor floatability.

[0014] As a preferred solution, the fineness of the grinding treatment is -0.074 mm, accounting for 55% to 85%; the concentration of the slurry is 20 to 50wt%.

[0015] As a preferred solution, the sulfiding agent includes at least one of sodium sulfide and sodium hydrosulfide; the xanthate includes at least one of propyl xanthate, butyl xanthate and amyl xanthate. More preferably, the sulfiding agent is sodium hydrosulfide, and the xanthate collector is amyl xanthate.

[0016] As a preferred solution, the positive flotation includes three roughing steps, including: subjecting the pulp to the first roughing stage to obtain the first roughing concentrate and the first roughing tailings, and subjecting the first roughing tailings to the second roughing stage to obtain the second roughing concentrate and the second roughing tailings, and subjecting the second roughing tailings to the third roughing stage to obtain the third roughing concentrate and the third roughing tailings; combining the first roughing concentrate, the second roughing concentrate, and the third roughing concentrate to obtain the foam concentrate I; the third roughing tailings is the middling ore. At present, the industrial treatment method of copper-cobalt oxide ore is often a combined beneficiation and smelting process, that is, first beneficiation and then wet leaching. Because the flotation concentrate has to enter the wet leaching operation, the grade requirement of the flotation concentrate is not very high, mainly acid consumption and production cost, so the flotation process does not need to add beneficiation operations.

[0017] As a preferred solution, the reagent system of the first rough selection is: 500-700 g / t of vulcanizing agent, 600-800 g / t of xanthate collector, and 20-50 g / t of foaming agent; the reagent system of the second rough selection is: 100-200 g / t of vulcanizing agent, 300-400 g / t of xanthate collector; the reagent system of the third rough selection is: 50-100 g / t of vulcanizing agent, and 100-200 g / t of xanthate collector.

[0018] As a preferred solution, the foaming agent is a common foaming agent type, such as 2# oil.

[0019] As a preferred solution, the reverse flotation includes a roughing step, and the reagent system is as follows: the dosage of the combined collector is 500-1000 g / t.

[0020] As a preferred solution, the copper-cobalt oxide concentrate is subjected to wet leaching to obtain copper-cobalt.

[0021] The present invention provides a flotation method for high calcium and magnesium copper-cobalt oxide ore, comprising the following steps:

[0022] S1. The raw material of high calcium and magnesium oxide copper-cobalt ore is crushed, ground and pulped;

[0023] S2. Use the "sulfide-xanthate" method to flotation useful copper-cobalt minerals to obtain foam concentrate I and middlings;

[0024] S3. The middlings are then reverse floated using a combined collector to obtain underflow concentrate II and tailings;

[0025] S4. Mixing the foam concentrate I and the underflow concentrate II to form an oxide copper-cobalt concentrate, wherein the recovery rates of copper and cobalt are both greater than 90%; and sending the tailings to the tailings pond;

[0026] S5. The copper-cobalt oxide concentrate is subjected to wet leaching, wherein the copper-cobalt leaching rate is above 90%, and the leaching acid consumption is 20-60 kg / t·feed ore.

[0027] As a preferred solution, the grade of the middling copper is greater than 0.2%.

[0028] As a preferred solution, the wet leaching conditions are: the leaching temperature is room temperature, the leaching time is 1 to 4 hours, the liquid-solid ratio (L / Kg) is (3 to 5):1, the leaching endpoint pH is 1.5 to 2.0, and the leaching reagent is sulfuric acid.

[0029] Compared with the prior art, the present invention has the following beneficial technical effects:

[0030] (1) The "positive and negative mixed flotation" process of high calcium and magnesium oxide copper-cobalt ore provided by the present invention firstly performs positive flotation to separate useful copper-cobalt minerals, and then uses negative flotation to remove calcium and magnesium gangue minerals. Compared with the existing positive flotation process of oxide copper-cobalt ore, this process can solve the problem of copper and cobalt resources running off in positive flotation, increase the copper and cobalt recovery rate by 10% or more, and efficiently separate useful minerals from calcium and magnesium gangue minerals, with a simple process.

[0031] (2) The combined collector provided by the present invention for the calcium-magnesium gangue mineral dolomite can be synergistically adsorbed on the surface of dolomite through the carboxyl group, ester group and aldehyde group in oxidized paraffin soap and sodium oleate, thereby enhancing the hydrophobicity of the surface; and the divalent metal cations further strengthen the adsorption of the collector on the surface of dolomite by forming a colloidal complex, so that the flotation efficiency of the calcium-magnesium gangue mineral dolomite is significantly improved; and the dosage is small, the cost is low, and the use is safe.

[0032] (3) The flotation process provided by the present invention can significantly reduce the acid consumption and production cost of the wet leaching process, solving the problems of high acid consumption, low leaching rate, and high production cost in the existing process. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a flotation process flow chart of Examples 1 to 3 of the present invention.

[0034] Figure 2 It is a comparison chart of flotation test results of Examples 1 to 3 of the present invention and Comparative Examples 1 to 3.

[0035] Figure 3 It is a comparison chart of the leaching test results of Examples 1 to 3 of the present invention and Comparative Examples 1 to 3. DETAILED DESCRIPTION

[0036] The following specific examples are intended to further illustrate the content of the present invention, but are not intended to limit the scope of protection of the claims of the present invention. The pharmaceutical agents used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0037] Example 1

[0038] The ore of a high calcium and magnesium oxidized copper-cobalt ore has a copper grade of 1.56%, a cobalt grade of 0.19%, a calcium grade of 9.46%, a magnesium grade of 8.13%, an oxidation rate of more than 90%, and a calcium and magnesium gangue mineral of dolomite. It is a typical high calcium and magnesium oxidized copper-cobalt ore. The specific flotation experimental steps are as follows:

[0039] (1) Grinding and slurry adjustment: The crushed copper-cobalt oxide ore is ground, with a grinding fineness of -0.074 mm accounting for 70%, and then water is added to adjust the slurry concentration to 33wt%.

[0040] (2) Positive flotation operation: The order and process of adding flotation reagents are as follows: Figure 1 As shown, in the first roughing operation, 600 g / t of sulfiding agent NaHS, 700 g / t of collector amyl xanthate, and 20 g / t of 2# oil were added in sequence, and flotation was performed for 5 min; in the second roughing operation, 200 g / t of sulfiding agent NaHS and 400 g / t of collector amyl xanthate were added in sequence, and flotation was performed for 5 min; in the third roughing operation, 100 g / t of sulfiding agent NaHS and 200 g / t of collector amyl xanthate were added in sequence, and flotation was performed for 5 min; the concentrates from the three roughing operations were mixed together to form concentrate I, and the tailings were subjected to reverse flotation.

[0041] (3) Reverse flotation operation: The flotation reagent addition and process are as follows: Figure 1 As shown in the figure, the three-stage flotation tailings were subjected to reverse flotation to remove calcium and magnesium. The collector A was composed of 50% oxidized paraffin soap, 40% sodium oleate, and 10% Ca 2+ It is prepared by compounding, with a dosage of 500g / t and flotation for 5min; the underflow product in the reverse flotation tank is mixed with concentrate I to form copper-cobalt concentrate, and the foam product is tailings.

[0042] (4) Wet leaching operation: The copper-cobalt concentrate was subjected to wet leaching operation, the leaching temperature was room temperature, the leaching time was 4 hours, the liquid-to-solid ratio (L / Kg) was 3:1, the leaching endpoint pH was 1.8, and the leaching reagent was sulfuric acid.

[0043] In this embodiment, the total concentrate yield is 51.27%, the copper grade is 2.95%, and the total recovery rate of copper is 93.51%; the cobalt grade is 0.32%, the total recovery rate of cobalt is 92.09%, the calcium removal rate is 80.84%, the magnesium removal rate is 78.97%, and the leaching acid consumption is 50kg / t·feed ore.

[0044] Example 2

[0045] The ore of a high calcium and magnesium oxidized copper-cobalt ore has a copper grade of 1.81%, a cobalt grade of 0.20%, a calcium grade of 9.15%, a magnesium grade of 8.02%, an oxidation rate of more than 90%, and a calcium and magnesium gangue mineral of dolomite. It is a typical high calcium and magnesium oxidized copper-cobalt ore. The specific flotation experimental steps are as follows:

[0046] (1) Grinding and slurry adjustment: The crushed copper-cobalt oxide ore is ground, with a grinding fineness of -0.074 mm accounting for 65%, and then water is added to adjust the slurry concentration to 30wt%.

[0047] (2) Positive flotation operation: The order and process of adding flotation reagents are as follows: Figure 1 As shown, in the first roughing operation, sulfiding agent Na2S 500g / t, collector butyl xanthate 800g / t, and 2# oil 20g / t were added in sequence, and flotation was performed for 5min; in the second roughing operation, sulfiding agent Na2S 200g / t and collector butyl xanthate 400g / t were added in sequence, and flotation was performed for 5min; in the third roughing operation, sulfiding agent Na2S 100g / t and collector butyl xanthate 200g / t were added in sequence, and flotation was performed for 5min; the concentrates from the three roughing operations were mixed together to form concentrate I, and the tailings were subjected to reverse flotation.

[0048] (3) Reverse flotation operation: The flotation reagent addition and process are as follows: Figure 1 As shown in the figure, the three-stage forward flotation tailings were subjected to reverse flotation to remove calcium and magnesium. The collector A was composed of 60% oxidized paraffin soap, 30% sodium oleate, and 10% Zn 2+ It is prepared by compounding, with a dosage of 600g / t and flotation for 5min; the underflow product in the reverse flotation tank is mixed with concentrate I to form copper-cobalt concentrate, and the foam product is tailings.

[0049] (4) Wet leaching operation: The copper-cobalt concentrate was subjected to wet leaching operation, the leaching temperature was room temperature, the leaching time was 4 hours, the leaching reagent was sulfuric acid, the liquid-to-solid ratio (L / Kg) was 3:1, and the leaching endpoint pH was 2.0.

[0050] In this embodiment, the total concentrate yield is 49.53%, the copper grade is 3.17%, and the total recovery rate of copper is 92.84%; the cobalt grade is 0.40%, the total recovery rate of cobalt is 92.33%, the calcium removal rate is 82.33%, the magnesium removal rate is 79.64%, and the leaching acid consumption is 45kg / t·feed ore.

[0051] Example 3

[0052] The ore of a high calcium and magnesium oxidized copper-cobalt ore has a copper grade of 1.63%, a cobalt grade of 0.15%, a calcium grade of 10.37%, a magnesium grade of 9.59%, an oxidation rate of more than 90%, and a calcium and magnesium gangue mineral of dolomite. It is a typical high calcium and magnesium oxidized copper-cobalt ore. The specific flotation experimental steps are as follows:

[0053] (1) Grinding and slurry adjustment: The crushed copper-cobalt oxide ore is ground, with a grinding fineness of -0.074 mm accounting for 75%, and then water is added to adjust the slurry concentration to 35wt%.

[0054] (2) Positive flotation operation: The order and process of adding flotation reagents are as follows: Figure 1 As shown, in the first roughing operation, sulfiding agent NaHS 700 g / t, collector amyl xanthate 600 g / t, and 2# oil 20 g / t were added in sequence, and flotation was performed for 5 min; in the second roughing operation, sulfiding agent NaHS 100 g / t and collector amyl xanthate 300 g / t were added in sequence, and flotation was performed for 5 min; in the third roughing operation, sulfiding agent NaHS 50 g / t and collector amyl xanthate 100 g / t were added in sequence, and flotation was performed for 5 min; the concentrates from the three roughing operations were mixed together to form concentrate I, and the tailings were subjected to reverse flotation.

[0055] (3) Reverse flotation operation: The flotation reagent addition and process are as follows: Figure 1 As shown in the figure, the three-stage flotation tailings were subjected to reverse flotation to remove calcium and magnesium. The collector A was composed of 50% oxidized paraffin soap, 30% sodium oleate, and 20% Mg 2+ It is prepared by compounding, with a dosage of 500g / t and flotation for 5min; the underflow product in the reverse flotation tank is mixed with concentrate I to form copper-cobalt concentrate, and the foam product is tailings.

[0056] (4) Wet leaching operation: The copper-cobalt concentrate was subjected to wet leaching operation, the leaching temperature was room temperature, the leaching time was 3 hours, the leaching reagent was sulfuric acid, the liquid-to-solid ratio (L / Kg) was 3:1, and the leaching endpoint pH was 1.8.

[0057] In this embodiment, the total concentrate yield is 52.04%, the copper grade is 3.08%, and the total recovery rate of copper is 93.72%; the cobalt grade is 0.39%, the total recovery rate of cobalt is 93.05%, the calcium removal rate is 81.52%, the magnesium removal rate is 78.29%, and the leaching acid consumption is 60kg / t·feed ore.

[0058] Comparative Example 1

[0059] Compared with Example 1, the only difference is that the reverse flotation is changed to positive flotation, that is, four positive flotation roughing operations, the fourth roughing operation NaHS50g / t, collector amyl xanthate 200g / t; the other conditions and parameters are the same as in Example 1.

[0060] Comparative Example 2

[0061] Compared with Example 2, the only difference is that the reverse flotation is changed to positive flotation, that is, four positive flotation roughing operations, the fourth roughing operation Na2S 50g / t, collector butyl xanthate 100g / t; the other conditions and parameters are the same as Example 2.

[0062] Comparative Example 3

[0063] Compared with Example 3, the only difference is that the reverse flotation is changed to positive flotation, that is, four positive flotation roughing operations, the fourth roughing operation NaHS 50g / t, collector amyl xanthate 100g / t; the other conditions and parameters are the same as those in Example 3.

[0064] according to Figure 2 It shows that the recovery rates of copper and cobalt in Comparative Examples 1 to 3, which only adopt the process of forward flotation, will decrease by about 10% compared with the process of forward and reverse mixed flotation in Examples 1 to 3. Figure 3 It shows that the acid consumption of subsequent wet leaching is significantly increased in Comparative Examples 1 to 3 which only adopt the process of direct flotation compared with Examples 1 to 3 which adopt the process of direct and reverse mixed flotation.

[0065] Comparative Example 4

[0066] Compared with Example 1, the only difference is that the reverse flotation collector A is prepared by compounding 50% oxidized paraffin soap and 50% sodium oleate by mass fraction; the other conditions and parameters are the same as those in Example 1.

[0067] In this comparative example, the total concentrate yield is 52.71%, the copper grade is 2.82%, and the total recovery rate of copper is 91.13%; the cobalt grade is 0.27%, the total recovery rate of cobalt is 91.48%, the calcium removal rate is 71.72%, the magnesium removal rate is 69.36%, and the leaching acid consumption is 90kg / t·feed ore.

[0068] Comparative Example 5

[0069] Compared with Example 2, the only difference is that the amount of reverse flotation collector A is 400 g / t; the other conditions and parameters are the same as those in Example 2.

[0070] In this comparative example, the total concentrate yield is 48.57%, the copper grade is 2.94%, and the total recovery rate of copper is 88.26%; the cobalt grade is 0.38%, the total recovery rate of cobalt is 88.94%, the calcium removal rate is 73.11%, the magnesium removal rate is 70.62%, and the leaching acid consumption is 85kg / t·feed ore.

[0071] Comparative Examples 4 to 5 show that reducing the amount of reverse flotation collector or not adding divalent metal cations will affect the copper and cobalt recovery rate, and the calcium and magnesium removal rates will decrease, and the leaching acid consumption will increase.

Claims

1. A combined collector for flotation of high calcium and magnesium copper-cobalt oxide ore, characterized in that: Includes oxidized paraffin soap, sodium oleate and divalent metal cations.

2. A combined collector for flotation of a high calcium and magnesium copper-cobalt oxide ore according to claim 1, characterized in that: The invention is composed of oxidized paraffin soap, sodium oleate and divalent metal cations according to the mass percentage of (50-60) %: (20-40) %: (10-20) %.

3. A combined collector for flotation of a high calcium and magnesium copper-cobalt oxide ore according to claim 2, characterized in that: The divalent metal cation is Ca 2+ Mg 2+ 、Zn 2+ and Pb 2+ At least one of .

4. A flotation method for high calcium and magnesium oxide copper-cobalt ore, characterized in that: The high calcium and magnesium oxide copper-cobalt ore is subjected to grinding and pulping treatment to obtain ore pulp; a sulfiding agent and a xanthate collector are added to the ore pulp for forward flotation of copper and cobalt to obtain a foam concentrate I and a middling; the middling ore is subjected to reverse flotation of calcium and magnesium gangue minerals using the combined collector according to any one of claims 1 to 3 to obtain an underflow concentrate II and tailings; and the foam concentrate I and the underflow concentrate II are combined to obtain an oxide copper-cobalt concentrate.

5. A flotation method for high calcium and magnesium oxide copper-cobalt ore according to claim 4, characterized in that: The calcium and magnesium grades in the high-calcium-magnesium oxide copper-cobalt ore are both greater than 8%, and the oxidation rate is greater than 90%.

6. A flotation method for high calcium and magnesium oxide copper-cobalt ore according to claim 5, characterized in that: The fineness of the grinding treatment is -0.074 mm, accounting for 55% to 85%; the concentration of the ore pulp is 20 to 50wt%.

7. A flotation method for high calcium and magnesium oxide copper-cobalt ore according to claim 4, characterized in that: The sulfiding agent includes at least one of sodium sulfide and sodium hydrosulfide; the xanthate includes at least one of propyl xanthate, butyl xanthate and amyl xanthate.

8. A flotation method for high calcium and magnesium oxide copper-cobalt ore according to claim 7, characterized in that: The positive flotation includes three roughing steps, including: subjecting the pulp to a first roughing stage to obtain a first roughing concentrate and a first roughing tailing, subjecting the first roughing tailing to a second roughing stage to obtain a second roughing concentrate and a second roughing tailing, subjecting the second roughing tailing to a third roughing stage to obtain a third roughing concentrate and a third roughing tailing; combining the first roughing concentrate, the second roughing concentrate and the third roughing concentrate to obtain a froth concentrate I; the third roughing tailing is the middling ore; The reagent system for the first roughing is: 500-700g / t of vulcanizing agent, 600-800g / t of xanthate collector, and 20-50g / t of foaming agent; The reagent system for the second roughing is: 100-200g / t of vulcanizing agent, 300-400g / t of xanthate collector; The reagent system for the third rough selection is: 50-100g / t of vulcanizing agent and 100-200g / t of xanthate collector.

9. A flotation method for high calcium and magnesium oxide copper-cobalt ore according to claim 4, characterized in that: The reverse flotation includes a roughing step, and the reagent system is as follows: the dosage of the combined collector is 500-1000 g / t.

10. A flotation method for high calcium and magnesium oxide copper-cobalt ore according to any one of claims 4 to 9, characterized in that: The copper-cobalt oxide concentrate is subjected to wet leaching to obtain copper-cobalt.

Images