Method for flotation of copper-cobalt oxide ore using magnesium-containing tailings water

Abstract

The present invention belongs to the field of flotation, specifically relating to a method for flotating copper-cobalt oxide ore using magnesium-containing tailings water. The magnesium-containing tailings water is used as flotation water to subject the cobalt-copper oxide ore to five-stage roughing. The first roughing stage is conducted in the presence of a sulfiding agent and a xanthate-thiocarbamate collector, the second roughing stage is conducted in the presence of a composite auxiliary agent, a sulfiding agent, and xanthate-hydroxamic acid. The third roughing stage is conducted in the presence of a sulfiding agent and xanthate-hydroxamic acid; and the fourth and fifth roughing stages are conducted in the presence of a hydroxamic acid collector. The composite auxiliary agent comprises component A and component B of formula (1); component A comprises at least one of ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium sulfate, and ammonium chloride. The composite collector comprises a xanthate collector and a hydroxamic acid collector. This method can address the problem of flotation degradation caused by the reuse of magnesium-containing tailings water, achieving excellent flotation results.

Description

Technical Field

[0001] The present invention relates to the field of nonferrous metal extraction technology and mineral processing, and in particular to a process for enhancing the flotation of copper-cobalt oxide ores by utilizing magnesium-containing tailings water. Technical Background

[0002] With the global demand for metals like copper and cobalt, higher-grade, more easily mined and utilized copper-cobalt ores are gradually being depleted. Consequently, a growing number of mining and smelting companies are conducting technological research and development focused on mining and utilizing low-grade, high-oxidation-rate copper-cobalt ores. Firstly, copper-cobalt oxide ores have complex compositions, with high oxidation rates for both copper and cobalt. The copper and cobalt that need to be recovered exist in a variety of forms and are finely distributed. Copper exists in various forms, including malachite, chrysocolla, and covellite, while cobalt exists in oxides, sulfides, carbonates, and hydrated oxides. These copper-cobalt minerals exhibit significant variations in selectivity, making it difficult to achieve optimal results with a single approach. Secondly, current beneficiation processes for copper-cobalt oxide ores are complex, with generally low recovery rates. Furthermore, as beneficiation time increases, wastewater containing high concentrations of calcium and magnesium ions accumulates, negating environmental protection measures. Therefore, developing a process that effectively utilizes tailings return water to enhance the flotation of copper-cobalt oxide ores would significantly improve water utilization, reduce the burden on tailings storage and treatment, and minimize or even eliminate environmental impacts.

[0003] Publication number CN 116532234 A Chinese patent document discloses a flotation process for high-oxidation copper ore, which first floats the sulfide ore, then deslimes, and finally floats the oxide ore, and the process adds a sulfiding agent during the grinding process, activates copper oxide before flotation, and improves the floatability of copper oxide. In the re-flotation process of the patent, copper oxide with different flotation difficulties is activated and sorted in stages, avoiding the oversulfurization caused by excessive sodium hydrosulfide, and improving the recovery rate of copper oxide ore. However, the shortcoming of this process is that, for high-oxidation copper ore, desliming can cause some copper-containing minerals to be removed with mud, reducing the copper recovery rate, and the process is not suitable for flotation containing high magnesium tail water, because the magnesium ion concentration in the tail water suppresses the flotation index. Therefore, it is necessary to find a suitable flotation process to enhance the flotation index under the conditions of copper oxide ore flotation using tail water. Summary of the Invention

[0004] Aiming at the problem of unsatisfactory flotation performance of copper-cobalt oxide ore caused by the reuse of magnesium-containing tailings water, the present invention provides a method for flotation of copper-cobalt oxide ore using magnesium-containing tailings water, aiming to solve the flotation degradation problem caused by magnesium-containing tailings water.

[0005] A method for flotation of copper-cobalt oxide ore using magnesium-containing tailings water, wherein magnesium-containing tailings water is used as flotation water to flot the copper-cobalt oxide ore, and the steps include:

[0006] Step (1):

[0007] Crushing and grinding the raw cobalt copper oxide ore and then slurrying to obtain raw ore slurry;

[0008] Step (2):

[0009] The raw ore pulp in step (1) is subjected to a first stage roughing in a flotation reagent a containing a sulfiding agent a, a composite collector a, and a frother to obtain a first roughing concentrate and a first roughing tailing; wherein the first roughing concentrate is subjected to a beneficiation treatment to obtain an oxidized concentrate I;

[0010] The flotation collector a includes xanthate collectors and thiocarbamate collectors;

[0011] Step (3):

[0012] The first rougher tailings are subjected to a second roughing process in a flotation reagent B containing a composite auxiliary agent, a sulfiding agent B, and a composite collector B to obtain a second rougher concentrate and a second rougher tailings; the second rougher tailings are subjected to a third roughing process in a flotation reagent C containing a composite collector B and a sulfiding agent B to obtain a third rougher concentrate and a third rougher tailings; the second rougher concentrate and the third flotation concentrate are combined to obtain an oxidized concentrate II;

[0013] The flotation aid comprises component A and component B of formula 1;

[0014] Component A includes at least one of ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium sulfate, and ammonium chloride;

[0015] Formula 1

[0016] In formula 1, A is carbonate ion, chloride ion, nitrate ion, acetate ion, carbonate ion, or phosphate ion; n is the absolute value of the valence of A; R a ~R c In the formula (a), at least one substituent is a C1-C3 alkyl group or an aminoalkyl group, and the remaining substituents are H, a C1-C3 alkyl group or an aminoalkyl group;

[0017] The composite collector b includes a xanthate collector and a hydroxamic acid collector;

[0018] Step (4):

[0019] The third rougher tailings are subjected to roughing in a flotation agent d containing a hydroxamic acid collector to obtain a rougher concentrate a and a rougher tailing b; the rougher concentrate a is subjected to beneficiation treatment to obtain an oxidized concentrate III;

[0020] Wherein, the water used in slurry preparation and roughing in steps (1) to (4) is the magnesium-containing tailings water.

[0021] To address the flotation degradation problem of copper-cobalt oxide ores caused by the reuse of magnesium-containing tailings water, the present invention innovatively adopts the multi-stage roughing method described above, combined with the second-stage roughing (step 2 roughing) components such as composite additives and composite collectors, as well as parameters, to solve the flotation degradation problem caused by the reuse of magnesium-containing tailings water and achieve excellent flotation results.

[0022] In the present invention, the copper grade in the copper-cobalt oxide ore is 1.0% to 3.0%, the cobalt grade is not less than 0.07%, and the cobalt-copper oxidation rate is greater than 90%.

[0023] In the present invention, in step (1), the raw ore is crushed to a fineness of 2-4 mm.

[0024] Products with a grinding fineness of less than 0.074mm account for 55% to 90% of the total mass.

[0025] In the raw ore slurry, the concentration of the cobalt oxide copper ore raw ore slurry is 30% to 35%.

[0026] In this solution, the sulfiding agents used (such as sulfiding agent a, sulfiding agent b, and sulfiding agent c) can be selected from at least one of NaHS and Na2S. However, the type and amount of each step can be adjusted as needed.

[0027] In the present invention, the xanthate collector may be any xanthate collector known in the industry, for example, a compound having the structure of Formula 2;

[0028] Formula 2

[0029] The R1 is solely a C2~C8 alkyl group.

[0030] In addition, the components and combinations of xanthate used in each flotation process can be routinely adjusted as needed.

[0031] In the present invention, the thiocarbamate collector can be a thiocarbamate collector known in the industry, for example, a compound having the structure of formula 3

[0032] Formula 3

[0033] The R2 is C2~C 10 Said R3, R4 are independently H or C2~C 10 of alkyl.

[0034] In the present invention, the hydroxamic acid collector may be a hydroxamic acid collector known in the industry, for example, a compound having a structure of Formula 4;

[0035] Formula 4

[0036] Preferably, the R5 is C2~C 10 alkyl, substituted alkyl, phenyl or substituted phenyl;

[0037] In the present invention, the foaming agent may be a foaming component known in the industry, for example, may include at least one of 2# oil and methyl isobutyl carbinol.

[0038] In the present invention, in step (2), the amount of the vulcanizing agent a added is 800-1000 g / ton of ore, the amount of the xanthate collector added is 200-500 g / ton of ore, the amount of the thiocarbamate collector added is 20-30 g / ton of ore, and the amount of the foaming agent added is 20-30 g / ton of ore.

[0039] In the present invention, in step (2), the selection process includes a first selection process and a second selection process, wherein an inhibitor is added in the first selection process.

[0040] In the present invention, the inhibitor includes at least one of CMC and water glass.

[0041] In the present invention, during the concentrating process of step 2, the amount of inhibitor added can be 100-300 g / t;

[0042] In the present invention, the selected tailings are returned to the previous flotation process.

[0043] In the present invention, the first-stage roughing tailings are subjected to the second-stage roughing treatment of step 3, wherein the second-stage roughing includes the second-stage roughing and the third-stage roughing processes.

[0044] In the present invention, the composite auxiliary agent is innovatively added in the second roughing process, and combined with the composite collector b, the targeting ability of the agent to the target mineral can be enhanced, the flotation inhibition problem caused by the reuse of magnesium-containing tailings water can be reduced, and excellent flotation capacity can be obtained.

[0045] In the present invention, in the composite auxiliary agent, the component A is ammonium bicarbonate. Research in the present invention shows that the use of the ammonium bicarbonate as component A has better synergy with component B, can further solve the flotation degradation problem caused by magnesium-containing tailings water, and can obtain better flotation performance.

[0046] In the present invention, in the component B, the R may further be an aminoalkyl group. Furthermore, the component B is ethylenediamine phosphate.

[0047] In the present invention, the component B can be and H nA is obtained by reaction, and n is the absolute value of the valence of A.

[0048] Preferably, in the composite auxiliary agent, the weight ratio of component A to component B is 1:0.1~1; preferably 1:0.3~0.8.

[0049] Preferably, in the second roughing stage, the dosage of the composite auxiliary agent is 300-450 g / t ore, the addition amount of the sulfiding agent b is 600-1200 g / ton ore; the dosage of the xanthate collector is 200-400 g / t ore, and the dosage of the hydroxamic acid collector is 20-80 g / t ore.

[0050] Preferably, in the third roughing stage, the amount of the components in the flotation reagent c is 30-110% of that in the flotation reagent b.

[0051] In the present invention, in step (4), the roughing process includes a two-stage roughing process, which comprises the following steps: subjecting the third-stage roughing tailings to a fourth-stage roughing process in advance to obtain a fourth roughing concentrate and a fourth roughing tailings; and then subjecting the fourth-stage roughing tailings to a fifth-stage roughing process to obtain a fifth-stage roughing concentrate and a fifth-stage roughing tailings; and compounding the fourth-stage roughing concentrate and the fifth-stage roughing concentrate to obtain the roughing concentrate a, and the fifth-stage roughing tailings to obtain the roughing tailings b.

[0052] In the present invention, in step (4), a sulfiding agent c, a regulator and a foaming agent are further added to the flotation reagent d in the fourth roughing process; the regulator includes ammonium bicarbonate;

[0053] Preferably, in the fourth roughing stage, the amount of sulfiding agent C added is 200-500 g / t ore, the amount of regulator added is 200-400 g / t ore; the amount of hydroxamic acid collector added is 30-100 g / t ore; and the amount of foaming agent added is 10-20 g / t ore.

[0054] Preferably, the amount of hydroxamic acid collector added in the fifth roughing stage is 20-50 g / t ore. In addition, the addition of sulfiding agent in the fifth roughing stage is also allowed, and the amount can be 100-300 g / t ore.

[0055] In the present invention, in step (4), the rougher concentrate a is subjected to two-stage cleaning treatment to obtain the oxidized concentrate III;

[0056] Preferably, an inhibitor is added during the first cleaning process of the cleaning treatment stage;

[0057] Preferably, the inhibitor comprises at least one of CMC and water glass;

[0058] Preferably, the dosage of the inhibitor is 100-300 g / t;

[0059] Preferably, the cleaned tailings are returned to the previous flotation process.

[0060] In the present invention, step (4) further includes the step of scavenging the roughing tailings b using a hydroxamic acid collector to obtain scavenged concentrate and scavenged tailings, and returning the scavenged concentrate to the roughing process of step 3; the scavenged tailings are the final tailings;

[0061] In the present invention, the water used in the slurrying, roughing, cleaning and scavenging processes of step (1) to step (4) is the magnesium-containing tailings water;

[0062] In the present invention, the magnesium-containing tailings water is high-magnesium tailings water with a magnesium ion content of 0.3 to 2.5 g / L;

[0063] In the present invention, calcium ions also exist in the magnesium-containing tailings water;

[0064] In the present invention, the concentration of calcium ions in the magnesium-containing tailings water is 0.3-2.0 g / L.

[0065] In the present invention, the scraping time of the roughing operation is 3 to 5 minutes, and the scraping time of the sweeping operation and the cleaning operation is 2 to 3 minutes.

[0066] Beneficial effects

[0067] The present invention innovatively combines the multi-stage roughing process with the second-stage roughing (step 2 roughing) components such as a composite auxiliary agent and a collector, as well as parameters, to solve the flotation degradation problem caused by the reuse of magnesium-containing tailings water, thereby achieving excellent flotation effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 This is a process flow chart for enhanced flotation of copper-cobalt oxide ore according to Examples 1 to 3 of the present invention. DETAILED DESCRIPTION

[0069] In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, a detailed description will be given below with reference to specific embodiments.

[0070] Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art; unless otherwise specified, the reagents used in the examples are commercially available.

[0071] The present invention provides a process for selectively utilizing high calcium and magnesium tailings water to enhance the flotation of copper-cobalt oxide ore, comprising the following steps:

[0072] (1) Grinding and pulping: The raw cobalt copper oxide ore is crushed, ground and then pulped to obtain raw ore pulp.

[0073] (2) Oxide ore roughing 1: NaHS, butyl xanthate + amyl xanthate + ethiocarbamate, 2 # After oiling, aeration flotation is carried out to obtain the first rougher concentrate and the first rougher tailings. The first rougher concentrate is subjected to two rounds of concentration to obtain oxidized concentrate I.

[0074] (3) Oxide ore roughing II and III: ammonium bicarbonate + ethylenediamine phosphate, NaHS + Na2S, a combination of butyl xanthate + amyl xanthate and hydroxamic acid are added to the first roughing tailings slurry in step (2) in sequence, followed by aeration flotation to obtain the oxide ore second roughing concentrate and the second roughing tailings; then NaHS + Na2S, butyl xanthate + amyl xanthate and hydroxamic acid are added to the second roughing tailings in sequence, followed by aeration flotation to obtain the oxide ore third roughing concentrate and the third roughing tailings; the second roughing concentrate and the third roughing concentrate are combined to obtain oxide concentrate II.

[0075] (4) Oxide ore roughing four and five: Na2S + ammonium bicarbonate, hydroxamic acid, 2 # After oil extraction, aeration flotation is carried out to obtain the fourth rougher concentrate and the fourth rougher tailings of the oxide ore; then Na2S and hydroxamic acid are added to the fourth rougher tailings in sequence, and then aeration flotation is carried out to obtain the fourth rougher concentrate and the fourth rougher tailings of the oxide ore; the fourth rougher concentrate and the fifth rougher concentrate are combined and then subjected to two rounds of concentration to obtain oxide concentrate III.

[0076] (5) Oxide ore scavenging: Add hydroxamic acid to the fifth roughing tailings slurry in step (4) and perform aeration flotation. Perform scavenging operation once. The scavenged concentrate enters the fifth roughing operation. The scavenged tailings are the final tailings.

[0077] Furthermore, in step (1), the crushing fineness of the raw ore is 2-4 mm. The product with a grinding fineness of less than 0.074 mm accounts for 55%-90% of the total mass.

[0078] Furthermore, the cobalt oxide copper ore pulp concentration in step (1) is 30% to 35%.

[0079] Furthermore, in step (2), the amount of NaHS added is 800-1000 g / ton of ore, the amount of butyl xanthate added is 100-250 g / ton of ore, and the amount of amyl xanthate added is 100-250 g / ton of ore, and the ratio of butyl xanthate to amyl xanthate added is 1:0.5-2 (which can be further 1:1), 2 # The amount of oil added is 20~30g / ton of ore.

[0080] Furthermore, in step (2), an inhibitor, carboxymethyl cellulose or water glass, is added in an amount of 100-300 g / t ore.

[0081] Furthermore, in step (3), the addition amounts of ammonium bicarbonate and ethylenediamine phosphate are 200-300 g / t ore and 100-150 g / t ore, respectively, and the addition ratio of ammonium bicarbonate to ethylenediamine phosphate is 1:0.3-0.8.

[0082] Furthermore, in step (3), the amount of NaHS added is 300-600 g / ton of ore, the amount of Na2S added is 300-600 g / ton of ore, and the ratio of NaHS to Na2S added is 1:0.5-2 (which can be further 1:1).

[0083] Furthermore, in step (3), the butyl xanthate + amyl xanthate combination has a ratio of 1:0.5~2 (furthermore, it can be 1:1), and the addition amounts of butyl xanthate and amyl xanthate are 100~200 g / t ore and 100~200 g / t ore, respectively.

[0084] Furthermore, the amount of hydroxamic acid added in step (3) is 20-80 g / t ore.

[0085] Furthermore, in step (4), the amount of Na2S added is 200-500 g / t ore, and the amount of ammonium bicarbonate added is 200-400 g / t ore.

[0086] Furthermore, in step (4), the amount of hydroxamic acid added is 30-100 g / t ore.

[0087] Furthermore, in step (4) 2 # The amount of oil added is 10~20g / t ore.

[0088] Furthermore, in step (4), an inhibitor carboxymethyl cellulose or water glass is added in an amount of 100-300 g / t.

[0089] Furthermore, in step (5), the amount of hydroxamic acid added is 20-50 g / ton of ore.

[0090] Furthermore, the scraping time for the roughing operation is 3 to 5 minutes, and the scraping time for the sweeping operation and the fine selection operation is 2 to 3 minutes.

[0091] Furthermore, it is used to process copper-cobalt oxide ore, in which the copper grade is 1.0% to 3.0%, the cobalt grade is not less than 0.07%, and the cobalt-copper oxidation rate is greater than 90%.

[0092] Furthermore, the water used in the mineral processing process comes from tailings water, which is characterized by high calcium and magnesium ion concentrations, with calcium ion concentrations of 0.3~2.0 g / L and magnesium ion concentrations of 0.3~2.5 g / L.

[0093] The flotation process of the present invention utilizes magnesium-containing tailings water and removes the inhibition of magnesium ions on oxide ore flotation through a reasonable reagent system, thereby obtaining a higher-grade copper-cobalt concentrate product.

[0094] The dosage of the following reagents refers to the weight of reagents required per ton of minerals.

[0095] The following are further specific implementation plans that can be cited:

[0096] Example 1

[0097] The test sample in this embodiment is a raw ore of a copper-cobalt oxide ore, wherein the cobalt grade is 0.11%, the copper grade is 1.85%, and the ore oxidation rate is 93.0%. The water used for flotation (referring to the water used in the pulping, roughing, cleaning, and scavenging stages) is the tailings pond smelting drainage, with a calcium ion concentration of 1.28 g / L and a magnesium ion concentration of 1.80 g / L. The flotation process is as follows:

[0098] (1) Grinding and slurrying: The test sample ore was ground to a fineness of less than 0.074 mm, and the product accounted for 70% of the total weight. Then, tail water was added to adjust the slurry to a concentration of 35% to obtain the ore slurry.

[0099] (2) To each ton of raw ore pulp, 800 g of sodium hydrosulfide, 250 g of sodium sulfide butyl xanthate, 250 g of amyl xanthate, and 30 g of No. 2 oil were added in sequence and stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain the first rougher concentrate and the first rougher tailings. 200 g of carboxymethyl cellulose was added to the first rougher concentrate and the oxidized concentrate I was obtained by two rounds of flotation.

[0100] (3) Composite additives (ammonium bicarbonate (component A) 300 g, ethylenediamine phosphate (component B) 150 g), NaHS 400 g, Na2S 400 g, butyl xanthate 200 g, amyl xanthate 200 g, and hydroxamic acid 40 g were sequentially added to the first rougher tailings slurry, and the hard-floating copper-cobalt ore was aerated and floated to obtain a second rougher concentrate and a second rougher tailings. NaHS 400 g, Na2S 400 g, butyl xanthate 200 g, amyl xanthate 200 g, and hydroxamic acid 40 g were sequentially added to the second rougher tailings, and the hard-floating copper-cobalt ore was aerated and floated to obtain a third rougher concentrate and a third rougher tailings. The second rougher concentrate and the third rougher concentrate were combined to obtain an oxidized concentrate II.

[0101] (4) To the third rougher tailings slurry, 400 g of sodium sulfide, 300 g of ammonium bicarbonate, 50 g of benzohydroxamic acid, and 10 g of No. 2 oil were added in sequence, stirred, and aerated flotation was performed to obtain a fourth rougher concentrate and a fourth rougher tailings. To the fourth rougher tailings slurry, 200 g of sodium sulfide and 50 g of benzohydroxamic acid were added in sequence, stirred, and aerated flotation was performed to obtain a fifth rougher concentrate and a fifth rougher tailings. The fourth and fifth rougher concentrate slurries were combined, 200 g of carboxymethyl cellulose was added, and then a second round of cleaning was performed to obtain oxidized concentrate III.

[0102] (5) Add 40 g of benzohydroxamic acid to the fifth rougher tailings and perform aeration flotation to obtain scavenger concentrate and final tailings. The scavenger concentrate is returned to the fifth rougher.

[0103] Example 2

[0104] The test sample of this embodiment is a raw ore of a copper-cobalt oxide ore, wherein the cobalt grade is 0.17%, the copper grade is 1.95%, the ore oxidation rate is 94.5%, the flotation water is the tailings pond smelting drainage, the calcium ion concentration is 1.28 g / L, and the magnesium ion concentration is 1.80 g / L. The flotation process is as follows:

[0105] (1) Grinding and slurrying: The test sample ore was ground to a fineness of less than 0.074 mm, and the product accounted for 75% of the total weight. Then, tail water was added to adjust the slurry to a concentration of 35% to obtain the ore slurry.

[0106] (2) To each ton of raw ore pulp, 1000 g of sodium hydrosulfide, 250 g of sodium sulfide butyl xanthate, 250 g of amyl xanthate, and 30 g of No. 2 oil were added in sequence and stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain the first rougher concentrate and the first rougher tailings. 250 g of carboxymethyl cellulose was added to the first rougher concentrate and the oxidized concentrate I was obtained by two rounds of flotation.

[0107] (3) 300 g of ammonium bicarbonate, 150 g of ethylenediamine phosphate, 500 g of NaHS, 500 g of Na2S, 200 g of butyl xanthate, 200 g of amyl xanthate, and 50 g of hydroxamic acid were added to the first rougher tailings slurry in sequence, and the hard-floating copper-cobalt ore was aerated and floated to obtain a second rougher concentrate and a second rougher tailings. 500 g of NaHS, 500 g of Na2S, 200 g of butyl xanthate, 200 g of amyl xanthate, and 50 g of hydroxamic acid were added to the second rougher tailings in sequence, and the hard-floating copper-cobalt ore was aerated and floated to obtain a third rougher concentrate and a third rougher tailings. The second rougher concentrate and the third rougher concentrate were combined to obtain an oxidized concentrate II.

[0108] (4) To the third rougher tailings slurry, 500 g of sodium sulfide, 400 g of ammonium bicarbonate, 40 g of benzohydroxamic acid, and 10 g of No. 2 oil were added in sequence, stirred, and aerated flotation was performed to obtain a fourth rougher concentrate and a fourth rougher tailings. To the fourth rougher tailings slurry, 300 g of sodium sulfide and 40 g of benzohydroxamic acid were added in sequence, stirred, and aerated flotation was performed to obtain a fifth rougher concentrate and a fifth rougher tailings. The fourth and fifth rougher concentrate slurries were combined, 200 g of carboxymethyl cellulose was added, and then the slurries were cleaned twice to obtain oxidized concentrate III.

[0109] (5) Add 30 g of benzohydroxamic acid to the fifth rougher tailings and perform aeration flotation to obtain scavenger concentrate and final tailings. The scavenger concentrate is returned to the fifth rougher.

[0110] Example 3

[0111] Compared with Example 1, the only difference is that the type of component A in the composite auxiliary agent in step 3 is changed, and the amount of component A and other operations and conditions are the same as in Example 1; the experimental groups are:

[0112] Group A: Component A is ammonium carbonate;

[0113] Group B: Component A is ammonium sulfate.

[0114] Comparative Example 1

[0115] Compared with Example 1, the only difference is that in step 3, no composite auxiliary agent is added, and other operations and parameters are the same as in Example 1.

[0116] Comparative Example 2

[0117] Compared with Example 1, the only difference is that in step 3, component A is missing from the composite auxiliary agent, and the amount of the remaining auxiliary agent is the same as that of the composite auxiliary agent in Example 1. Other operations and parameters are also the same as in Example 1.

[0118] Comparative Example 3

[0119] Compared with Example 1, the only difference is that in step 3, component B is missing from the composite auxiliary agent, and the amount of the remaining auxiliary agent is the same as that of the composite auxiliary agent in Example 1. Other operations and parameters are also the same as in Example 1.

[0120] Comparative Example 4

[0121] Compared with Example 1, the only difference is that in step 3, the benzohydroxamic acid is replaced with an equal amount of a xanthate collector (including butyl xanthate and amyl xanthate in a weight ratio of 1:1). Other operations and parameters are the same as those in Example 1.

[0122] Analysis and testing: The concentrate yields and concentrate copper and cobalt recoveries of Examples 1 to 3 and Comparative Examples 1 to 4 were measured respectively, and the results are recorded in Table 1.

[0123]

[0124] As shown in Examples 1-2 and Comparative Examples 1-3, the combination of Component A and Component B as a composite adjuvant can address the flotation degradation problem caused by the reuse of magnesium-containing tailings water. Furthermore, as shown in Examples 1 and 3, when Component A in the composite adjuvant is ammonium bicarbonate, a better synergistic advantage of the composite adjuvant can be achieved. Furthermore, as shown in Example 2 and Comparative Example 4, the use of xanthate and hydroxamic acid collectors in the roughing process can be further combined with the composite adjuvant to further address the deterioration effect of magnesium-containing tailings water on flotation.

Claims

1. A method for flotation of copper-cobalt oxide ore using magnesium-containing tailings water, characterized in that: The flotation of copper-cobalt oxide ore is carried out using magnesium-containing tailings water as flotation water, and the steps include: Step (1): Crushing and grinding the raw cobalt copper oxide ore and then slurrying to obtain raw ore slurry; Step (2): The raw ore pulp in step (1) is subjected to a first stage roughing in a flotation reagent a containing a sulfiding agent a, a composite collector a, and a frother to obtain a first roughing concentrate and a first roughing tailing; wherein the first roughing concentrate is subjected to a beneficiation treatment to obtain an oxidized concentrate I; The composite collector a includes xanthate collectors and thiocarbamate collectors; Step (3): The first rougher tailings are subjected to a second roughing process in a flotation reagent B containing a composite auxiliary agent, a sulfiding agent B, and a composite collector B to obtain a second rougher concentrate and a second rougher tailings; the second rougher tailings are subjected to a third roughing process in a flotation reagent C containing a composite collector B and a sulfiding agent B to obtain a third rougher concentrate and a third rougher tailings; the second rougher concentrate and the third rougher concentrate are combined to obtain an oxidized concentrate II; The composite auxiliary agent includes component A and component B of formula 1; Component A includes at least one of ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium sulfate, and ammonium chloride; Formula 1 In formula 1, A is carbonate ion, chloride ion, nitrate ion, acetate ion, carbonate ion, or phosphate ion; n is the absolute value of the valence of A; R a ~R c In the formula (a), at least one substituent is a C1-C3 alkyl group or an aminoalkyl group, and the remaining substituents are H, a C1-C3 alkyl group or an aminoalkyl group; The composite collector b includes a xanthate collector and a hydroxamic acid collector; Step (4): The third rougher tailings are subjected to roughing in a flotation agent d containing a hydroxamic acid collector to obtain a rougher concentrate a and a rougher tailing b; the rougher concentrate a is subjected to beneficiation treatment to obtain an oxidized concentrate III; Wherein, the water used in slurry preparation and roughing in steps (1) to (4) is the magnesium-containing tailings water.

2. The method according to claim 1, wherein The copper grade in the copper-cobalt oxide ore is 1.0%~3.0%, the cobalt grade is not less than 0.07%, and the cobalt-copper oxidation rate is greater than 90%.

3. The method according to claim 1, wherein In the step (1), the raw ore is crushed to a fineness of 2-4 mm.

4. The method according to claim 1, wherein In step (1), the product with a grinding fineness of less than 0.074 mm accounts for 55% to 90% of the total mass; In the raw ore slurry, the concentration of the cobalt oxide copper ore raw ore slurry is 30% to 35%.

5. The method according to claim 1, wherein The sulfiding agent a and the sulfiding agent b are each at least one of NaHS and Na2S.

6. The method according to claim 1, wherein The xanthate collector is a compound having the structure of formula 2; Formula 2 The R1 is solely a C2~C8 alkyl group.

7. The method according to claim 1, wherein The thiol carbamate collector is a compound having a structure of formula 3 Formula 3 The R2 is C2~C 10 Said R3, R4 are independently H or C2~C 10 of alkyl.

8. The method according to claim 1, wherein The hydroxamic acid collector is a compound having a structure of formula 4; Formula 4 The R5 is C2~C 10 alkyl, substituted alkyl, phenyl or substituted phenyl.

9. The method according to claim 1, wherein The foaming agent includes at least one of 2# oil and methyl isobutyl carbinol.

10. The method according to claim 1, wherein In step (2), the amount of the vulcanizing agent a added is 800-1000 g / ton of ore, the amount of the xanthate collector added is 200-500 g / ton of ore, the amount of the thiocarbamate collector added is 20-30 g / ton of ore, and the amount of the foaming agent added is 20-30 g / ton of ore.

11. The method according to claim 10, wherein In step (2), the selection process includes a first selection process and a second selection process, wherein an inhibitor is added in the first selection process; The inhibitor includes at least one of CMC and water glass; The amount of inhibitor added is 100~300 g / t; The selected tailings are returned to the previous flotation process.

12. The method according to claim 1, wherein In the composite auxiliary agent, the component A is ammonium bicarbonate; The component B is ethylenediamine phosphate; In the composite auxiliary agent, the weight ratio of component A to component B is 1:0.1~1.

13. The method according to claim 1, wherein In the second roughing stage, the dosage of composite auxiliary agent is 300~450g / t ore, the dosage of sulfiding agent B is 600~1200g / ton ore; the dosage of xanthate collector is 200~400 g / t ore, and the dosage of hydroxamic acid collector is 20~80 g / t ore.

14. The method according to claim 1, wherein In the third roughing stage, the dosage of the component in flotation reagent c is 30~110% of that in flotation reagent b.

15. The method according to claim 1, wherein In step (4), the roughing process includes a two-stage roughing process, which comprises the following steps: subjecting the third-stage roughing tailings to a fourth-stage roughing process in advance to obtain a fourth roughing concentrate and a fourth roughing tailings; and then subjecting the fourth roughing tailings to a fifth-stage roughing process to obtain a fifth-stage roughing concentrate and a fifth-stage roughing tailings; and compounding the fourth roughing concentrate and the fifth-stage roughing concentrate to obtain the roughing concentrate a, and the fifth-stage roughing tailings to obtain the roughing tailings b.

16. The method according to claim 15, wherein In step (4), a sulfiding agent c, a regulator and a foaming agent are further added to the flotation reagent d in the fourth roughing process; the regulator includes ammonium bicarbonate.

17. The method according to claim 16, wherein In the fourth roughing stage, the addition amount of sulfiding agent C is 200~500g / t ore, the addition amount of regulator is 200~400g / t ore; the addition amount of hydroxamic acid collector is 30~100g / t ore; and the addition amount of foaming agent is 10~20g / t ore.

18. The method according to claim 15, wherein In the fifth roughing stage, the addition amount of hydroxamic acid collector is 20~50g / t ore.

19. The method according to claim 1, wherein In step (4), the rougher concentrate a is subjected to two-stage cleaning treatment to obtain the oxidized concentrate III.

20. The method according to claim 19, wherein In step (4), an inhibitor is added during the first stage of the cleaning process in the cleaning treatment stage; The inhibitor includes at least one of CMC and water glass; The dosage of the inhibitor is 100-300 g / t.

21. The method according to claim 1, wherein In step (4), the selected tailings are returned to the previous flotation process.

22. The method of claim 1, wherein Step (4) further includes scavenging the roughing tailings b using a hydroxamic acid collector to obtain scavenged concentrate and scavenged tailings, and returning the scavenged concentrate to the roughing process of step 3; the scavenged tailings are the final tailings; The dosage of hydroxamic acid collector in the scavenging stage is 20~50g / ton of ore.

23. The method according to any one of claims 1 to 22, wherein: The magnesium-containing tailings water is high-magnesium tailings water with a magnesium ion content of 0.3 to 2.5 g / L.

24. The method according to claim 23, wherein Calcium ions also exist in the magnesium-containing tailings water.

25. The method of claim 24, wherein: The concentration of calcium ions in the magnesium-containing tailings water is 0.3-2.0 g / L.

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