A flotation method for high calcium magnesium oxide copper cobalt ore and combined collector

Abstract

The present invention relates to the technical field of copper-cobalt oxide ore beneficiation, and discloses a flotation method for high-calcium-magnesium copper-cobalt oxide ore and a combined collector. The present invention adopts a "forward and reverse mixed flotation" process, and uses a combined collector comprising oxidized paraffin soap, sodium oleate, and divalent metal cations in the reverse flotation process, resulting in a total copper and cobalt recovery rate exceeding 90%, and a leaching acid consumption of 20 to 60 kg / t·feed ore. The combined collector used in the present invention has a low dosage, good collection performance, and low toxicity. Compared with existing copper-cobalt oxide ore flotation processes, this method can achieve a copper and cobalt recovery rate increased by more than 10%, and significantly reduces leaching acid consumption, significantly reduces production costs, and has a simple process flow, making it easy to promote and apply in industry.

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-magnesium copper-cobalt oxide ore and a combined collector. Background Art

[0002] Copper and cobalt are widely used in a variety of fields, including batteries, electronics, and metallurgy. Copper-cobalt oxide ore is an important type of mineral in copper-cobalt ore resources and is widely distributed in major mining areas around the world. With the mining and utilization of resources, copper sulfide ores and easily selected copper-cobalt oxide ores are becoming increasingly scarce, and high-calcium-magnesium copper-cobalt oxide ores are gradually being mined and utilized. However, the conventional direct flotation process for treating copper-cobalt oxide ore makes it difficult to achieve efficient recovery of copper and cobalt resources, and the subsequent wet leaching process consumes a lot of acid, resulting in high production costs. Therefore, it is of great significance to strengthen research on the flotation recovery 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-magnesium copper-cobalt oxide ores, Chinese patent CN118186209A reported a "combined leaching method for copper-cobalt oxide ores with high acid consumption and easy bubbling". This method is to add concentrated sulfuric acid and high-copper extract solution for pre-leaching, and then add concentrated sulfuric acid for leaching, but this method is relatively expensive. Chinese patent CN109201312A announced a "metallurgical treatment method for copper-cobalt oxide ores containing easily floatable gangue". This method introduces easily floatable 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-magnesium copper-cobalt oxide ores". This method introduces a combination of xanthate and salicylic hydroxamic acid collectors. Although good indicators are achieved, the cost of the reagents is high, and the separation of useful minerals from gangue minerals is 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 copper-cobalt oxide ore in existing methods and technologies, the first object of the present invention is to provide a combined collector for the flotation of high calcium and magnesium copper-cobalt oxide ore, which increases the hydrophobicity of the mineral through the synergistic adsorption of oxidized paraffin soap and sodium oleate, and simultaneously utilizes the strengthening effect of metal ions to achieve a significant improvement in flotation efficiency at a lower dosage.

[0005] A second object of the present invention is to provide a flotation method for high-calcium-magnesium copper-cobalt oxide ore. By adopting a "forward and reverse mixed flotation" process to treat the high-calcium-magnesium copper-cobalt oxide ore, the copper and cobalt recovery rates in the high-calcium-magnesium copper-cobalt oxide ore are both greater than 90%, and the leaching acid consumption is 20 to 60 kg / t of feed ore.

[0006] In order to achieve the above technical objectives, the present invention provides a combined collector for flotation of high calcium magnesium copper oxide cobalt ore, comprising 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 perspectives of surface chemistry, intermolecular interaction and coordination chemistry. In the technical solution of the present invention, the carboxyl groups, ester groups and aldehyde groups in the composite collector are synergistically adsorbed on the dolomite surface, thereby enhancing the surface hydrophobicity. Specifically, the oxidized paraffin soap is a long-chain hydrocarbon surfactant containing carboxyl groups, aldehyde groups, ester groups and other solid-philic groups, which 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 containing carboxylic acid functional groups that can be adsorbed on the dolomite surface. The combination of the two produces a synergistic adsorption effect, with the sodium oleate providing additional hydrophobic interaction and the oxidized paraffin soap increasing the intermolecular adsorption force, thereby improving the hydrophobicity of the dolomite surface. In addition, the metal ions further enhance the adsorption of the collector on the dolomite surface by forming a colloidal complex. The metal ions can coordinate with oxidized paraffin soap and sodium oleate to form a stable colloidal complex. This complex has a strong combination of hydrophobicity and polarity, which strengthens the adsorption of the collector molecules on the calcium and magnesium sites on the dolomite surface, enhancing the hydrophobicity of the dolomite surface to improve flotation performance. Therefore, the composite collector of the present invention can significantly improve the flotation efficiency of the calcium and magnesium gangue mineral dolomite at a low dosage, reducing the impact 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. An appropriate amount of metal ions can form a stable colloidal complex through coordination to improve the adsorption capacity. Too low a dosage of the three will lead to a decrease in adsorption and collection capacity and a decrease in dolomite flotation performance; while too high a 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 solution, 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 properties such as 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 copper-cobalt oxide ore. The method comprises the following steps: subjecting the raw ore of the high-calcium-magnesium copper-cobalt oxide ore to grinding and pulping to obtain ore pulp; adding a sulfiding agent and a xanthate collector to the ore pulp for forward flotation of copper and cobalt to obtain a foam concentrate I and a middling; using the middling ore for 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 combining the foam concentrate I and the underflow concentrate II to obtain a copper-cobalt oxide concentrate.

[0011] The high-calcium-magnesium oxide copper-cobalt ore targeted by the present invention has a high calcium and magnesium grade, and gangue intercalates and encapsulates cobalt and copper, inhibiting copper and cobalt during flotation. Furthermore, the oxidation rate of copper and cobalt is high and the floatability is poor. Consequently, the prior art requires a complex forward flotation process and high leaching acid consumption to recover copper and cobalt resources. The present invention proposes a "forward and reverse mixed flotation" process, which involves first performing forward flotation on copper and cobalt minerals, and then using reverse flotation combined with a special combined collector to remove the calcium-magnesium gangue minerals. During the forward 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, improving their floatability. Furthermore, all concentrates are utilized during the forward flotation process, while the tailings can enter reverse flotation. This effectively solves the problem of copper and cobalt resources running away from the tailings during forward flotation in the prior art, achieving efficient separation of copper-cobalt minerals and calcium-magnesium gangue minerals.

[0012] At the same time, the flotation process of the present invention can characteristically adsorb on the surface sites of calcium magnesium gangue minerals by using reverse flotation operations in combination with collectors, 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 ore pulp is 20 to 50 wt%.

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

[0016] As a preferred solution, the forward flotation process includes three roughing steps, including: subjecting the ore pulp to a first roughing stage to obtain a first rougher concentrate and a first rougher tailing; subjecting the first rougher tailing to a second roughing stage to obtain a second rougher concentrate and a second rougher tailing; subjecting the second rougher tailing to a third roughing stage to obtain a third rougher concentrate and a third rougher tailing; combining the first rougher concentrate, the second rougher concentrate, and the third rougher concentrate to obtain a froth concentrate I; and the third rougher tailing is the middlings. Currently, the industrial treatment method for copper-cobalt oxide ores is often a combined dressing and smelting process, i.e., beneficiation followed by wet leaching. Because the flotation concentrate must undergo wet leaching, the requirements for the flotation concentrate grade are not very high, primarily due to acid consumption and production costs, so no additional dressing process is required in the flotation process.

[0017] As a preferred solution, the reagent system for the first roughing 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 for the second roughing is: 100-200 g / t of vulcanizing agent, 300-400 g / t of xanthate collector; and the reagent system for the third roughing 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 combined collector dosage 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-magnesium copper-cobalt oxide ore, comprising the following steps:

[0022] S1. Crushing and grinding the high calcium magnesium oxide copper cobalt ore into pulp;

[0023] S2. Using the "sulfide - xanthate" method for positive flotation of useful copper and 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. The foam concentrate I and the underflow concentrate II are mixed to form a copper-cobalt oxide concentrate, with copper and cobalt recoveries greater than 90%; the tailings are sent to the tailings pond;

[0026] S5. Wet leaching the copper-cobalt oxide concentrate, wherein the copper-cobalt leaching rate reaches over 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: leaching temperature is room temperature, leaching time is 1 to 4 hours, liquid-solid ratio (L / Kg) is (3 to 5):1, 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 "direct and reverse mixed flotation" process of high calcium and magnesium copper-cobalt oxide ore provided by the present invention first performs forward flotation to separate useful copper and cobalt minerals, and then uses reverse flotation to remove calcium and magnesium gangue minerals. Compared with the existing forward flotation process of copper and cobalt oxide ore, this process can solve the problem of copper and cobalt resources running off during forward 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 dolomite surface through the carboxyl, ester and aldehyde groups in the 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 dolomite surface by forming a colloidal complex, thereby significantly improving the flotation efficiency of the calcium-magnesium gangue mineral dolomite; 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 The figures are a comparison of the flotation test results of Examples 1 to 3 of the present invention and Comparative Examples 1 to 3.

[0035] Figure 3 The figures are comparative diagrams 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 present invention, but are not intended to limit the scope of protection 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 magnesium oxide copper-cobalt ore has a copper grade of 1.56%, a cobalt grade of 0.19%, a calcium grade of 9.46%, and a magnesium grade of 8.13%. The oxidation rate is greater than 90%, and the calcium magnesium gangue mineral is dolomite. It is a typical high calcium magnesium oxide 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 to 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 collecting agent amyl xanthate, and 20 g / t of 2# oil were added in sequence, and flotation was carried out for 5 minutes. In the second roughing operation, 200 g / t of sulfiding agent NaHS and 400 g / t of collecting agent amyl xanthate were added in sequence, and flotation was carried out for 5 minutes. In the third roughing operation, 100 g / t of sulfiding agent NaHS and 200 g / t of collecting agent amyl xanthate were added in sequence, and flotation was carried out for 5 minutes. 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 reverse flotation decalcification and magnesium removal operation is carried out on the tailings of the three-stage flotation. The collector A is composed of 50% oxidized paraffin soap: 40% sodium oleate: 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-solid ratio (L / Kg) was 3:1, the leaching end point 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 copper recovery rate is 93.51%; the cobalt grade is 0.32%, the total cobalt recovery rate is 92.09%, the calcium removal rate is 80.84%, the magnesium removal rate is 78.97%, and the leaching acid consumption is 50 kg / t·feed ore.

[0044] Example 2

[0045] The ore of a high calcium magnesium oxide 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 magnesium gangue mineral of dolomite. It is a typical high calcium magnesium oxide 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 to 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, 500 g / t of sulfiding agent Na2S, 800 g / t of butyl xanthate collector, and 20 g / t of 2# oil were added in sequence, and flotation was carried out for 5 minutes. In the second roughing operation, 200 g / t of sulfiding agent Na2S and 400 g / t of butyl xanthate collector were added in sequence, and flotation was carried out for 5 minutes. In the third roughing operation, 100 g / t of sulfiding agent Na2S and 200 g / t of butyl xanthate collector were added in sequence, and flotation was carried out for 5 minutes. The concentrates from the three roughing operations were mixed together to form concentrate I, and the tailings were then 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 reverse flotation decalcification and magnesium removal operation is carried out on the tailings of the three-stage direct flotation. The collector A is 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 end point pH was 2.0.

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

[0051] Example 3

[0052] The ore of a high calcium magnesium oxide 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 magnesium gangue mineral of dolomite. It is a typical high calcium magnesium oxide 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 to 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 carried out for 5 minutes; 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 carried out for 5 minutes; 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 carried out for 5 minutes; 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 reverse flotation decalcification and magnesium removal operation is carried out on the tailings of the three-stage flotation. The collector A is composed of 50% oxidized paraffin soap: 30% sodium oleate: 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 end point pH was 1.8.

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

[0058] Comparative Example 1

[0059] Compared with Example 1, the only difference is that reverse flotation is changed to direct flotation, that is, four direct flotation roughing operations are performed. In the fourth roughing operation, NaHS 50 g / t and the collector amyl xanthate 200 g / t are used. The other conditions and parameters are the same as those in Example 1.

[0060] Comparative Example 2

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

[0062] Comparative Example 3

[0063] Compared with Example 3, the only difference is that reverse flotation is replaced by direct flotation, that is, four direct flotation roughing operations are performed. In the fourth roughing operation, 50 g / t of NaHS and 100 g / t of amyl xanthate as the collector are used. 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 using only forward flotation are reduced by about 10% compared with the forward and reverse mixed flotation process 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; the other conditions and parameters are the same as those in Example 1.

[0067] In this comparative example, the total concentrate yield was 52.71%, the copper grade was 2.82%, and the total copper recovery was 91.13%; the cobalt grade was 0.27%, the total cobalt recovery was 91.48%, the calcium removal rate was 71.72%, the magnesium removal rate was 69.36%, and the leaching acid consumption was 90 kg / 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 was 48.57%, the copper grade was 2.94%, and the total copper recovery was 88.26%; the cobalt grade was 0.38%, the total cobalt recovery was 88.94%, the calcium removal rate was 73.11%, the magnesium removal rate was 70.62%, and the leaching acid consumption was 85 kg / t·feed ore.

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

Claims

1. A combined collector for flotation of high calcium magnesium copper oxide cobalt ore, characterized by: It is composed of oxidized paraffin soap, sodium oleate and divalent metal cations in the mass percentage of (50~60)%: (20~40)%: (10~20)%; the divalent metal cation is Ca 2+ Mg 2+ 、Zn 2+ and Pb 2+ At least one of .

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

3. A flotation method for high calcium magnesium copper oxide cobalt ore according to claim 2, characterized in that: The calcium and magnesium grades in the high-calcium-magnesium copper-cobalt oxide ore are both greater than 8%, and the oxidation rate is greater than 90%.

4. A flotation method for high calcium magnesium copper oxide cobalt ore according to claim 3, characterized in that: The fineness of the grinding treatment is -0.074mm, accounting for 55% to 85%; the concentration of the ore pulp is 20 to 50wt%.

5. A flotation method for high calcium magnesium copper oxide cobalt ore according to claim 3, 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.

6. A flotation method for high calcium magnesium copper oxide cobalt ore according to claim 5, characterized in that: The direct 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 sulfiding agent, 300~400g / t of xanthate collector; The reagent system for the third roughing is: 50~100g / t of sulfiding agent and 100~200g / t of xanthate collector.

7. The flotation method of a high calcium magnesium copper oxide cobalt ore according to claim 2, 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.

8. A flotation method for high calcium magnesium copper oxide cobalt ore according to any one of claims 2 to 7, characterized in that: The copper-cobalt oxide concentrate is subjected to wet leaching to obtain copper-cobalt.

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