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

Abstract

The invention belongs to the field of flotation, and particularly relates to a method for flotation of copper cobalt oxide ore by using magnesium-containing tailing water, the magnesium-containing tailing water is used as flotation water to carry out five-stage roughing on the copper cobalt oxide ore, the first-stage roughing is carried out under a vulcanizing agent and a xanthate-thionocarbamate collecting agent, and the second-stage roughing is carried out under the action of a flotation agent; and the second-stage roughing is carried out under the condition of containing a compound additive, a vulcanizing agent and xanthate-hydroximic acid. The third-stage roughing is carried out under the action of a vulcanizing agent and xanthate-hydroximic acid; and the fourth-section roughing process and the fifth-section roughing process are carried out under the action of a hydroximic acid collecting agent. The compound additive comprises a component A and a component B with a structure shown in a formula 1 (# imgabs0 #); the component A comprises at least one of ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium sulfate and ammonium chloride; and the composite collecting agent comprises a xanthate collecting agent and a hydroximic acid collecting agent. By means of the method, the problem of flotation degradation caused by magnesium-containing tailing water recycling can be solved, and the excellent flotation effect can be achieved.

Description

Technical Field

[0001] The invention relates to the field of nonferrous metal extraction technology and ore dressing, and in particular to a process for strengthening the flotation of oxidized copper-cobalt ore by using magnesium-containing tailings water. Technical Background

[0002] With the current world demand for metals such as copper and cobalt, higher-grade and easier-to-mine copper-cobalt ores are gradually being mined and exhausted. More and more mining and smelting companies are conducting technical research and development in the direction of mining and utilization of low-grade, high-oxidation-rate copper-cobalt ores. On the one hand, the composition of oxidized copper-cobalt ores is complex, and the oxidation rates of copper and cobalt are both very high. The copper and cobalt that need to be recovered exist in complex forms and have fine embedded particle sizes. Among them, the forms of copper include malachite, chrysocolla, covellite, etc., and the forms of cobalt include oxides, sulfides, carbonates, and water oxides. These copper-cobalt minerals have great differences in selectivity methods, and a single method is difficult to achieve the ideal goal. On the other hand, the current beneficiation process for oxidized copper-cobalt ores is complex, the recovery rate is generally not high, and as the beneficiation time increases, more and more beneficiation wastewater containing high concentrations of calcium and magnesium ions accumulates, without taking advantage of environmental protection. Therefore, the development of an effective method for strengthening the flotation of oxidized copper-cobalt ores by using beneficiation tailings backwater will greatly improve the efficiency of water utilization, reduce the pressure of tailings storage and treatment, and reduce or even eliminate the impact on environmental pollution.

[0003] The Chinese patent document with publication number CN 116532234 A discloses a flotation process for high oxidation copper ore, which first floats the sulfide ore, then desludging, 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 flotation process of the patent, copper oxide with different flotation difficulties is activated and sorted in stages, avoiding 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, desludging will cause some copper-containing minerals to be removed with mud to reduce 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 is suppressed and the flotation index decreases. Therefore, it is necessary to find a suitable flotation process to strengthen the flotation index under the conditions of flotation of copper oxide ore using tail water. Summary of the invention

[0004] In view of the problem that the flotation performance of copper-cobalt oxide ore is not ideal due to 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 the magnesium-containing tailings water is used as flotation water to flotation the copper-cobalt oxide ore, and the steps include:

[0006] Step (1):

[0007] The raw ore of the cobalt oxide copper ore is crushed, ground and then slurried 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 roughing tailings are subjected to a second stage of roughing in a flotation reagent b containing a composite auxiliary agent, a sulfiding agent b, and a composite collector b to obtain a second roughing concentrate and a second roughing tailings; the second roughing tailings are subjected to a third stage of roughing in a flotation reagent c containing a composite collector b and a sulfiding agent b to obtain a third roughing concentrate and a third roughing tailings; the second roughing 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 which at least one substituent is a C1-C3 alkyl or aminoalkyl group, and the remaining substituents are H, a C1-C3 alkyl or 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] The water used in slurry preparation and roughing in step (1) to step (4) is the magnesium-containing tailings water.

[0021] In view of the flotation degradation problem of copper-cobalt oxide ore caused by the reuse of magnesium-containing tailings water, the present invention innovatively adopts the multi-stage roughing, and cooperates with the second stage roughing (step 2 roughing) of the composite auxiliary agent, composite collector and other components and parameters, so as to solve the flotation degradation problem caused by the reuse of magnesium-containing tailings water and obtain excellent flotation effect.

[0022] In the present invention, the copper grade in the oxidized copper-cobalt 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 the 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 scheme, the sulfiding agent (such as sulfiding agent a, sulfiding agent b, sulfiding agent c, etc.) used 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 a structure of Formula 2;

[0028] Formula 2

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

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

[0031] In the present invention, the thiocarbamate collector may be a thiocarbamate collector known in the industry, for example, a compound having a 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 concentrating process includes a first concentrating process and a second concentrating process, wherein an inhibitor is added in the first concentrating process.

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

[0041] In the present invention, during the beneficiation process of step 2, the amount of inhibitor added may 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 ability can be obtained.

[0045] In the present invention, in the composite auxiliary agent, the component A is ammonium bicarbonate. The present invention shows that the use of the ammonium bicarbonate as component A has better combined 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, wherein 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 dosage of the sulfiding agent b is 600-1200 g / t 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 dosage 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 frother are further added to the flotation reagent d in the fourth roughing process; the regulator comprises ammonium bicarbonate;

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

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

[0055] In the present invention, in step (4), the rougher concentrate a is subjected to two-stage concentration 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 concentrated 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 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 fine operation is 2 to 3 minutes.

[0066] Beneficial Effects

[0067] The present invention innovatively adopts the multi-stage roughing, and combines the components and parameters of the composite auxiliary agent collector in the second stage roughing (step 2 roughing), so as to solve the flotation degradation problem caused by the reuse of magnesium-containing tailings water, and obtain excellent flotation effect. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0069] In order to make the technical problems to be solved, technical solutions and advantages of the present invention more clear, they are described in detail below in conjunction with 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 slurried to obtain raw ore pulp.

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

[0074] (3) Oxidized 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 an oxide ore second roughing concentrate and a 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 an oxide ore third roughing concentrate and a third roughing tailings; the second roughing concentrate and the third roughing concentrate are combined to obtain an oxide concentrate II.

[0075] (4) Oxide ore roughing 4 and 5: Na2S + ammonium bicarbonate, hydroxamic acid, 2 # After oil is removed, 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 concentrated twice to obtain the oxide concentrate III.

[0076] (5) Scavenging of oxide ore: Add hydroxamic acid to the fifth roughing tailings slurry in step (4) and then perform aeration flotation. Perform scavenging operation once, and 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 slurry 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 (furthermore, it can be 1:1), # 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 amounts of ammonium bicarbonate and ethylenediamine phosphate added are 200-300 g / t ore and 100-150 g / t ore, respectively, and the ratio of ammonium bicarbonate to ethylenediamine phosphate added 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 (furthermore, it can be 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 added amounts of butyl xanthate and amyl xanthate are 100-200 g / t ore and 100-200 g / t ore, respectively.

[0084] Furthermore, in step (3), the amount of hydroxamic acid added 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 oxidized copper-cobalt 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 of 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%, the ore oxidation rate is 93.0%, the flotation water (referring to the water used in each stage of slurry preparation, roughing, concentrating and scavenging) is the tailings pond smelting drainage, the calcium ion concentration is 1.28 g / L, the magnesium ion concentration is 1.80 g / L, and the flotation process is as follows:

[0098] (1) Grinding and slurrying: The test sample raw ore is ground to a fineness of less than 0.074 mm and the product accounts for 70% of the total weight. Then, tailing water is added to adjust the slurry to a concentration of 35% to obtain raw 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 2# oil were added in sequence, and the mixture was stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain a first roughing concentrate and a first roughing tailings. 200 g of carboxymethyl cellulose was added to the first roughing concentrate, and two rounds of flotation were performed to obtain an oxidized concentrate I.

[0100] (3) Add composite additives (ammonium bicarbonate (component A) 300g, ethylenediamine phosphate (component B) 150g), NaHS 400g, Na2S 400g, butyl xanthate 200g, amyl xanthate 200g, hydroxamic acid 40g) to the first rougher tailings slurry in sequence, and aerate the hard-floating copper-cobalt ore to obtain the second rougher concentrate and the second rougher tailings. Add NaHS 400g, Na2S 400g, butyl xanthate 200g, amyl xanthate 200g, hydroxamic acid 40g to the second rougher tailings in sequence, and aerate the hard-floating copper-cobalt ore to obtain the third rougher concentrate and the third rougher tailings. The second rougher concentrate and the third rougher concentrate are combined to obtain an oxidized concentrate II.

[0101] (4) 400 g of sodium sulfide, 300 g of ammonium bicarbonate, 50 g of benzohydroxamic acid, and 10 g of 2# oil were added to the third rougher tailings slurry in sequence, stirred, and aerated flotation was performed to obtain the fourth rougher concentrate and the fourth rougher tailings; 200 g of sodium sulfide and 50 g of benzohydroxamic acid were added to the fourth rougher tailings slurry in sequence, stirred, and aerated flotation was performed to obtain the fifth rougher concentrate and the fifth rougher tailings. After the fourth and fifth rougher concentrate slurries were combined, 200 g of carboxymethyl cellulose was added and then the oxidized concentrate III was obtained.

[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 water used for flotation is the tailings pond smelting drainage, the calcium ion concentration is 1.28 g / L, the magnesium ion concentration is 1.80 g / L, and the flotation process is as follows:

[0105] (1) Grinding and slurrying: The test sample ore is ground to a fineness of less than 0.074 mm and the product accounts for 75% of the total weight. Then, tailing water is added to adjust the slurry to a concentration of 35% to obtain 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 2# oil were added in sequence, and the mixture was stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain a first roughing concentrate and a first roughing tailings. 250 g of carboxymethyl cellulose was added to the first roughing concentrate, and two rounds of flotation were performed to obtain an oxidized concentrate I.

[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 the second rougher concentrate and the 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 the third rougher concentrate and the third rougher tailings. The second rougher concentrate and the third rougher concentrate were combined to obtain the oxidized concentrate II.

[0108] (4) 500 g of sodium sulfide, 400 g of ammonium bicarbonate, 40 g of benzohydroxamic acid, and 10 g of 2# oil were added to the third rougher tailings slurry in sequence, stirred, and aerated flotation was performed to obtain the fourth rougher concentrate and the fourth rougher tailings; 300 g of sodium sulfide and 40 g of benzohydroxamic acid were added to the fourth rougher tailings slurry in sequence, stirred, and aerated flotation was performed to obtain the fifth rougher concentrate and the fifth rougher tailings. After the fourth and fifth rougher concentrate slurries were combined, 200 g of carboxymethyl cellulose was added and then the oxidized concentrate III was obtained.

[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 the amount of the composite auxiliary agent in Example 1, and the other operations and parameters are also the same as 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 the amount of the composite auxiliary agent in Example 1, and the other operations and parameters are also the same as 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 xanthate collector (including butyl xanthate and pentyl xanthate in a weight ratio of 1:1), and the other operations and parameters are the same as 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] It can be seen from Examples 1 to 2 and Comparative Examples 1 to 3 that the combination of component A and component B as a composite auxiliary agent can solve the flotation degradation problem caused by the reuse of magnesium-containing tailings water. In addition, it can be seen from Examples 1 and 3 that when component A in the composite auxiliary agent is ammonium bicarbonate, a better composite auxiliary agent synergistic advantage can be obtained. In addition, it can be seen from Example 2 and Comparative Example 4 that the use of xanthate and hydroxamic acid collectors in the roughing process can be further combined with the composite auxiliary agent to further solve the degradation 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 process of flotation of copper-cobalt oxide ore using magnesium-containing tailings water as flotation water comprises the following steps: Step (1): The raw ore of the cobalt oxide copper ore is crushed, ground and then slurried 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 flotation collector a includes xanthate collectors and thiocarbamate collectors; Step (3): The first roughing tailings are subjected to a second stage of roughing in a flotation reagent b containing a composite auxiliary agent, a sulfiding agent b, and a composite collector b to obtain a second roughing concentrate and a second roughing tailings; the second roughing tailings are subjected to a third stage of roughing in a flotation reagent c containing a composite collector b and a sulfiding agent b to obtain a third roughing concentrate and a third roughing tailings; the second roughing concentrate and the third flotation concentrate are combined to obtain an oxidized concentrate II; The flotation aid comprises 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 which at least one substituent is a C1-C3 alkyl or aminoalkyl group, and the remaining substituents are H, a C1-C3 alkyl or 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; The water used in slurry preparation and roughing in step (1) to step (4) is the magnesium-containing tailings water.

2. The method according to claim 1, characterized in that The copper grade in the oxidized copper-cobalt 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%; Preferably, in step (1), the raw ore is crushed to a fineness of 2-4 mm; Preferably, 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%; Preferably, the sulfiding agent a and the sulfiding agent b are at least one of NaHS and Na2S; Preferably, the xanthate collector is a compound having a structure of Formula 2; Formula 2 The R1 is solely a C2~C8 alkyl group; Preferably, the thiocarbamate 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 The alkyl group; Preferably, the hydroxamic acid collector is a compound having a structure of Formula 4; Formula 4 Preferably, the R5 is C2~C 10 alkyl, substituted alkyl, phenyl or substituted phenyl; Preferably, the foaming agent includes at least one of 2# oil and methyl isobutyl carbinol.

3. The method according to claim 1 or 2, characterized in that 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.

4. The method according to claim 3, characterized in that 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; Preferably, the inhibitor comprises at least one of CMC and water glass; Preferably, the amount of inhibitor added is 100-300 g / t; Preferably, the concentrated tailings are returned to the previous flotation process.

5. The method according to claim 1, characterized in that In the composite auxiliary agent, the component A is ammonium bicarbonate; Preferably, the component B is ethylenediamine phosphate; 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; Preferably, in the second roughing stage, the dosage of the composite auxiliary agent is 300-450 g / t ore, the dosage of the sulfiding agent b is 600-1200 g / t 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; Preferably, in the third roughing stage, the dosage of the components in the flotation reagent c is 30-110% of that in the flotation reagent b.

6. The method according to claim 1, characterized in that In step (4), the roughing process includes two roughing processes, and the steps are: subjecting the third roughing tailings to a fourth 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 roughing process to obtain a fifth roughing concentrate and a fifth roughing tailings; and combining the fourth roughing concentrate and the fifth roughing concentrate to obtain the roughing concentrate a, and the fifth roughing tailings to obtain the roughing tailings b.

7. The method according to claim 6, characterized in that In step (4), a sulfiding agent c, a regulator and a frother are added to the flotation reagent d in the fourth roughing process; the regulator includes ammonium bicarbonate; Preferably, in the fourth roughing stage, the amount of the sulfiding agent c added is 200-500 g / t ore, the amount of the regulator added is 200-400 g / t ore; the amount of the hydroxamic acid collector added is 30-100 g / t ore; the amount of the frother added is 10-20 g / t ore; Preferably, in the fifth roughing stage, the amount of hydroxamic acid collector added is 20-50 g / t ore.

8. The method according to claim 1, characterized in that In step (4), the rougher concentrate a is subjected to two-stage cleaning treatment to obtain the oxidized concentrate III; Preferably, an inhibitor is added during the first cleaning process of the cleaning treatment stage; Preferably, the inhibitor comprises at least one of CMC and water glass; Preferably, the dosage of the inhibitor is 100-300 g / t; Preferably, the concentrated tailings are returned to the previous flotation process.

9. The method according to claim 1, characterized in that 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; Preferably, the dosage of the hydroxamic acid collector in the scavenging stage is 20-50 g / ton of ore.

10. The method according to any one of claims 1 to 9, characterized in that: The magnesium-containing tailings water is high-magnesium tailings water with a magnesium ion content of 0.3-2.5 g / L; Preferably, calcium ions also exist in the magnesium-containing tailings water; Preferably, the concentration of calcium ions in the magnesium-containing tailings water is 0.3-2.0 g / L.

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