Flotation method of high calcium magnesium oxide copper cobalt ore

Abstract

The present invention belongs to the field of mineral flotation and specifically relates to a flotation method for high-calcium-magnesium copper-cobalt oxide ore. The high-calcium-magnesium copper-cobalt oxide ore to be selected is crushed, ground, and slurried to obtain a raw ore pulp. The raw ore pulp is subjected to roughing separation using a flotation reagent A, and a roughing concentrate and roughing tailings are collected. The flotation reagent A comprises a water-soluble sulfide salt A and a xanthate collector A. The roughing concentrate is then concentrated using a flotation reagent B, and a copper-cobalt concentrate and concentrated tailings are collected. The concentrated tailings are returned to the roughing and / or concentrating stages. The roughing tailings are scavenged using a flotation reagent C, and scavenged tailings and a scavenged concentrate are returned to the roughing process. The flotation reagent C comprises a water-soluble sulfide salt C and a combined collector. The combined collector comprises a xanthate collector C and a salicylic hydroxamic acid collector. The process described in the present invention can achieve excellent collection 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 flotation process for treating high-calcium-magnesium-containing copper-cobalt oxide ores. Background Art

[0002] The development and utilization of copper and cobalt resources is extremely important. However, most copper and cobalt ores in nature exist as copper-cobalt oxide ores, which have high oxidation rates, complex ore properties, and are rich in calcium, magnesium, and aluminum impurities. Treating these high-calcium-magnesium gangue copper-cobalt ores with traditional direct acid leaching processes consumes large amounts of sulfuric acid, significantly increasing production costs and reducing economic efficiency. Furthermore, these ores are prone to mudification, and high gangue content reduces the overall settling performance of the leached slurry, affecting the efficiency of solid-liquid separation after leaching and reducing copper and cobalt metal recovery. Copper-cobalt oxide ores with high calcium and magnesium contents have low copper and cobalt grades, making efficient copper and cobalt metal recovery difficult to achieve using any leaching process alone. Separating minerals containing calcium and magnesium impurities through flotation processes and improving the copper and cobalt grades is an important way to reduce acid consumption in subsequent processing and improve the utilization rate of copper and cobalt in the ore.

[0003] After searching the literature on the prior art, it was found that patent CN 110681477 A discloses a combined beneficiation and smelting process for recovering complex copper oxide ores. This patent first uses a copper sulfide flotation process to recover the sulfide ore from the complex copper oxide ores. The muddy oxide ore is first deslimed and then the oxide ore is flotated, achieving efficient recovery of the copper oxide ore. However, the process is relatively complex and is mainly targeted at mixed oxide ores with a copper grade of about 5.3%. For low-grade copper-cobalt oxide ores with a high calcium-magnesium oxidation rate of more than 90%, due to the presence of more impurity minerals such as calcium-magnesium gangue and talc, the ore is severely muddied, flotation is difficult, the copper concentrate yield is high, and the consumption of sulfuric acid for post-acid leaching is large. Patent CN 114054211 A discloses a combined beneficiation and smelting process for copper-cobalt oxide ores. This process involves sulfiding the oxide ore surface with sodium hydrosulfide, followed by the synergistic capture of sodium amyl xanthate and benzohydroxamic acid. This process employs an extended flotation time and five consecutive roughing cycles. While the overall recovery of copper and cobalt is acceptable, even with desludging, the concentrate yield remains at 26.27%, resulting in excessive acid consumption. Therefore, developing a flotation process capable of effective desludging would improve copper and cobalt recovery while effectively reducing the concentrate yield of copper-cobalt oxide ores, thereby increasing copper and cobalt metal grades and potentially reducing the amount of sulfuric acid used in subsequent acid leaching. Summary of the Invention

[0004] Aiming at the problem that the copper-cobalt flotation recovery rate and grade of high-calcium-magnesium-oxide copper-cobalt ore are not high, the present invention provides a flotation process for high-calcium-magnesium-oxide copper-cobalt ore, aiming to improve the copper-cobalt flotation recovery rate and grade while simplifying the process.

[0005] High-calcium-magnesium oxide copper-cobalt ore has a high gangue content and low copper and cobalt contents. The gangue also intersperses and envelops the copper and cobalt, significantly increasing the flotation recovery rate, grade, and efficiency of the copper and cobalt. To address this issue, the present invention, after in-depth research, provides the following improved solutions:

[0006] A flotation method for high-calcium-magnesium copper-cobalt oxide ore, comprising crushing, grinding and slurrying the high-calcium-magnesium copper-cobalt oxide ore to be selected to obtain raw ore slurry;

[0007] The raw ore pulp is subjected to rough separation using flotation reagent A to collect rougher concentrate and rougher tailings; wherein the flotation reagent A comprises a water-soluble sulfide salt a and a xanthate collector a;

[0008] The roughing concentrate is beneficiated using flotation agent B to collect copper-cobalt concentrate (final concentrate) and beneficiated tailings, and the beneficiated tailings are returned to the roughing and / or beneficiation stages; the flotation agent B comprises a combination of additives, a water-soluble sulfide salt b, and a xanthate collector b, wherein the combination of additives comprises additives A and additives B, wherein additive A comprises hexametaphosphoric acid and a water-soluble salt thereof; and the additive B comprises carboxymethyl cellulose and a water-soluble salt thereof;

[0009] The roughing tailings are scavenged using a flotation agent C to obtain scavenged tailings (final tailings) and scavenged concentrates, and the scavenged concentrates are returned to the roughing process, wherein the flotation agent C comprises a water-soluble sulfide salt C and a combined collector; the combined collector comprises a xanthate collector C and a salicylic hydroxamic acid collector.

[0010] To address the problem of unsatisfactory flotation recovery and selectivity of copper and cobalt due to high gangue embedding and encapsulation in high-calcium-magnesium oxide copper-cobalt ore, the present invention innovatively adopts flotation agent A for roughing, combines it with components containing a combination auxiliary agent for fine separation, and further combines it with a combined collector containing xanthate and salicylic hydroxamic acid for scavenging. This unexpected synergy can be achieved, solving the problem of difficulty in selective recovery and separation caused by the embedding and encapsulation of cobalt and copper by high-content gangue, and improving the flotation recovery and selectivity of copper and cobalt.

[0011] In the present invention, the selection process involving the combined auxiliary agent and the scavenging process involving the combined collector are the key to synergistically improving the mineralization adaptability of high-calcium-magnesium copper-cobalt oxide and improving the flotation recovery rate, selectivity and efficiency of copper and cobalt.

[0012] In the present invention, the crushing fineness of the raw ore is 2-4 mm; the grinding fineness of the product less than 0.074 mm accounts for 55%-90% of the total mass; the raw ore pulp concentration is 30%-35%;

[0013] In the present invention, the copper grade of the high calcium and magnesium oxide copper-cobalt ore is 1.5% to 3.5%, the cobalt grade is not less than 0.12%, and the cobalt-copper oxidation rate is greater than 90%. Furthermore, the copper grade of the high calcium and magnesium oxide copper-cobalt ore is 1.5% to 3.5%, the cobalt grade is 0.12% to 0.25%, and the cobalt-copper oxidation rate is greater than 90%.

[0014] In the present invention, in the flotation reagent A, the water-soluble sulfide salt a includes at least one of sodium hydrosulfide and sodium sulfide; further includes sodium hydrosulfide and sodium sulfide in a weight ratio of 1 to 10:1 to 10;

[0015] In the present invention, the xanthate collector a comprises at least one of ethyl xanthate, propyl xanthate, butyl xanthate and pentyl xanthate; preferably, the weight ratio of butyl xanthate to pentyl xanthate is 1:0.5-5.

[0016] In the present invention, the roughing stage includes a three-stage roughing process, which includes the following steps: subjecting the raw ore pulp to a first stage roughing to obtain a first roughing concentrate and a first roughing tailing; subjecting the first roughing tailing to a second stage roughing to obtain a second roughing concentrate and a second roughing tailing; subjecting the second roughing tailing to a third stage roughing to obtain a third roughing concentrate and a third roughing tailing;

[0017] The first rougher concentrate, the second rougher concentrate and the third rougher concentrate are combined to produce a rougher concentrate; and the third rougher tailings are used as rougher tailings for scavenging treatment.

[0018] In the present invention, in the flotation reagent A of the first roughing stage, the amount of the water-soluble sulfide salt a is 800-2000 g / t, and the amount of the xanthate collector a is 150-400 g / t. Further, the amount of the water-soluble sulfide salt a is 900-1600 g / t, and the amount of the xanthate collector a is 200-300 g / t. Preferably, a foaming agent is further added to the flotation reagent A of the first roughing stage, and the foaming agent includes at least one of 2# oil or methyl isobutyl carbinol. The amount of the foaming agent is 20-50 g / t, and further 30-40 g / t.

[0019] In the present invention, the amount of flotation reagent A used in the first roughing stage and the second roughing stage is 35-100% of the amount used in the first roughing stage, and can further be 45-55%;

[0020] In the present invention, the amount of the foaming agent added in the second roughing stage and the third roughing stage is less than or equal to 50 wt.% of the amount in the first roughing stage. Furthermore, it is not necessary to add the foaming agent.

[0021] In the present invention, the scraping time of each rough selection is 4 to 6 minutes.

[0022] In the present invention, in the flotation reagent B, the water-soluble sulfide salt b includes at least one of sodium hydrosulfide and sodium sulfide;

[0023] In the present invention, the xanthate collector b comprises at least one of ethyl xanthate, propyl xanthate, butyl xanthate and amyl xanthate; preferably, butyl xanthate and amyl xanthate in a weight ratio of 1:1 to 2;

[0024] In the present invention, the auxiliary agent A comprises sodium hexametaphosphate, and the auxiliary agent B comprises carboxymethyl cellulose. In the combined auxiliary agent, the weight ratio of the auxiliary agent A to the auxiliary agent B is 1-2:1-2.

[0025] In the present invention, the beneficiation process includes two beneficiation processes, and the steps are: subjecting the roughing concentrate to a first beneficiation to obtain a first beneficiation concentrate and a first beneficiation tailings, returning the first beneficiation tailings to the roughing process, subjecting the first beneficiation concentrate to a second beneficiation to obtain a second beneficiation concentrate and a second beneficiation tailings; the second beneficiation concentrate is the copper-cobalt concentrate; and returning the second beneficiation tailings to the first beneficiation process.

[0026] In the present invention, in the first beneficiation process, the dosage of auxiliary agent A is 100-200 g / t, the dosage of auxiliary agent B is 100-200 g / t, the dosage of water-soluble sulfide salt b is 100-200 g / t, and the dosage of xanthate collector b is 40-100 g / t;

[0027] In the present invention, in the second beneficiation process, the amount of auxiliary agent A and auxiliary agent B is 35 to 65 wt.% of the amount used in the first beneficiation; the amount of water-soluble sulfide salt b and xanthate collector b is less than or equal to 20 wt.% of the amount used in the first beneficiation; considering the cost, it is not necessary to add water-soluble sulfide salt b and xanthate collector b.

[0028] In the present invention, the time of each concentrating stage is 3 to 4 minutes.

[0029] In the present invention, the water-soluble sulfide salt c includes at least one of sodium hydrosulfide and sodium sulfide;

[0030] In the present invention, in the combined collector, the xanthate collector c comprises at least one of ethyl xanthate, propyl xanthate, butyl xanthate and pentyl xanthate; preferably, butyl xanthate and pentyl xanthate in a weight ratio of 1:1 to 2;

[0031] In the present invention, in the combined collector, the weight ratio of the xanthate collector c to the salicylic hydroxamic acid collector is 1 to 10:1, further 2 to 6:1.

[0032] In the present invention, the scavenging process includes two scavenging processes, the steps of which are: subjecting the rougher tailings to a first scavenging process to obtain a first scavenged concentrate and a first scavenged tailings; subjecting the first scavenged tailings to a second scavenging process to obtain a second scavenged concentrate and a scavenged tailings;

[0033] mixing the first scavenged concentrate and the second scavenged concentrate and returning the mixture to the roughing process;

[0034] In the present invention, in the first scavenging stage, the dosage of water-soluble sulfide salt C is 100-200 g / t; the dosage of xanthate collector is 40-100 g / t; the dosage of salicylic hydroxamic acid collector is 10-20 g / t; the addition ratio of butyl xanthate and amyl xanthate is 1:1-1:2;

[0035] In the present invention, a foaming agent is further added in the first scavenging stage, wherein the foaming agent comprises at least one of 2# oil or methyl isobutyl carbinol; and the amount thereof is 5-20 g / t;

[0036] In the present invention, the dosage of the reagent in the second scavenging stage is 35-65 wt% of the dosage of the reagent in the first stage; the dosage of the foaming agent is less than 10 wt.% of the dosage of the reagent in the first stage;

[0037] In the present invention, the duration of each scanning stage is 3 to 4 minutes.

[0038] Beneficial effects:

[0039] The present invention innovatively adopts flotation reagent A for roughing, and combines it with a component containing a combination auxiliary agent for fine separation, and further combines it with a combined collector containing xanthate and salicylic hydroxamic acid for scavenging. This can unexpectedly achieve synergy, solve the problem of difficulty in selective recovery and separation caused by the embedding of high-content gangue on cobalt and copper, and improve the flotation recovery rate and selectivity of copper and cobalt.

[0040] The purpose of this flotation process is to enhance the flotation of copper-cobalt oxide ore to improve the copper-cobalt recovery rate, while inhibiting the flotation of calcium and magnesium impurity minerals. Through a closed-circuit process, the recovery rate of copper-cobalt metals is greatly improved, and the loss of copper-cobalt metals from tailings is minimized, the yield of copper-cobalt oxide ore concentrate is reduced, and the copper-cobalt metal grade is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a flotation process flow chart for high-calcium-magnesium copper-cobalt oxide ore according to Examples 1-3 of the present invention. The reagent abbreviations in the figure mean: SIBX represents butyl xanthate; PAX represents amyl xanthate; SHA represents salicylic hydroxamic acid; MIBC represents methyl isobutyl carbinol; SHMP represents sodium hexametaphosphate; and CMC represents carboxymethyl cellulose. DETAILED DESCRIPTION

[0042] 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 the accompanying drawings and specific embodiments.

[0043] 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.

[0044] The optional flotation process for treating high calcium magnesium copper oxide cobalt ore of the present invention comprises the following steps:

[0045] (1) Grinding and slurrying: The raw cobalt copper oxide ore is crushed, ground and slurried to obtain raw ore slurry.

[0046] (2) Oxide ore roughing 1: NaHS and Na2S, butyl xanthate and amyl xanthate, 2 # Oil / methyl isobutyl carbinol is then subjected to aeration flotation to obtain the first rougher concentrate and the first rougher tailings of the oxide ore.

[0047] (3) Oxide ore roughing 2: NaHS and Na2S, butyl xanthate and amyl xanthate, 2 # The oil / methyl isobutyl carbinol is then subjected to aeration flotation to obtain the second rougher concentrate and the second rougher tailings of the oxide ore.

[0048] (4) Oxide ore roughing third: NaHS and Na2S, butyl xanthate and amyl xanthate are sequentially added to the second roughing tailings slurry in step (3) and then aerated flotation is performed to obtain the oxide ore third roughing concentrate and the third roughing tailings.

[0049] (5) Oxide ore scavenging: NaHS, butyl xanthate-amyl xanthate-salicylic hydroxamic acid agent combination, 2 # After oil / methyl isobutyl carbinol, aeration flotation is carried out, and scavenging operations are carried out twice. The scavenging concentrate enters the first roughing operation, and the scavenging tailings are the final tailings.

[0050] (6) Oxide ore concentration 1: The first, second and third roughing concentrate pulps in steps (2) (3) (4) are combined, and sodium hexametaphosphate and carboxymethyl cellulose, NaHS and Na2S, butyl xanthate and amyl xanthate are added in sequence, and then aeration flotation is performed to obtain the first concentrated ore and the first concentrated tailings. The first concentrated tailings enter the roughing operation 1.

[0051] (7) Oxide ore selection 2: Sodium hexametaphosphate and carboxymethyl cellulose are added to the first selected tailings slurry in step (6) for aeration flotation to obtain a second selected concentrate and a second selected tailings. The second selected concentrate is the final copper-cobalt oxide ore concentrate, and the second selected tailings enter the first selection operation.

[0052] Furthermore, in step 1, the raw ore is crushed to a fineness of 2-4 mm, and the product with a grinding fineness of less than 0.074 mm accounts for 55%-90% of the total mass.

[0053] Furthermore, the concentration of the raw ore pulp in step 2 is 30%-35%.

[0054] Furthermore, in the step (2), the amount of NaHS added is 500-1000 g / ton of ore, the amount of Na2S added is 500-1000 g / ton of ore, the ratio of NaHS and Na2S added is 1:1 to 1:3, the amount of butyl xanthate added is 100-200 g / ton of ore, the amount of amyl xanthate added is 100-200 g / ton of ore, the ratio of butyl xanthate to amyl xanthate added is 1:1 to 1:2, and the amount of 2# oil or methyl isobutyl carbinol added is 30-40 g / ton of ore.

[0055] Furthermore, in the step (3), the amount of NaHS added is 200-500 g / ton of ore, the amount of Na2S added is 200-500 g / ton of ore, the ratio of NaHS and Na2S added is 1:1 to 1:3, the amount of butyl xanthate added is 50-100 g / ton of ore, the amount of amyl xanthate added is 50-100 g / ton of ore, the ratio of butyl xanthate to amyl xanthate added is 1:1 to 1:2, and the amount of 2# oil or methyl isobutyl carbinol added is 10-20 g / ton of ore.

[0056] Furthermore, in step (4), the amount of NaHS added is 200-400 g / ton of ore, the amount of Na2S added is 200-400 g / ton of ore, the ratio of NaHS and Na2S added is 1:1 to 1:3, the amount of butyl xanthate added is 50-100 g / ton of ore, the amount of amyl xanthate added is 50-100 g / ton of ore, and the ratio of butyl xanthate to amyl xanthate added is 1:1 to 1:2.

[0057] Furthermore, in the step (5), the amount of NaHS added is 100-200 g / ton of ore, the amount of butyl xanthate added is 20-50 g / ton of ore, the amount of amyl xanthate added is 20-50 g / ton of ore, and the amount of salicylic acid is 10-20 g / ton of ore. The ratio of butyl xanthate to amyl xanthate is 1:1 to 1:2, the ratio of the xanthate combination to salicylic acid is 3:1 to 5:1, and the amount of 2# oil or methyl isobutyl carbinol added is 10-20 g / ton of ore.

[0058] Furthermore, in the second sweep in step (5), no 2# oil or methyl isobutyl carbinol is added, and the amount of other reagents added is halved compared to the amount of the first sweep.

[0059] Furthermore, in the step (6), the sodium hexametaphosphate is 100-200 g / ton of ore, the carboxymethyl cellulose is 100-200 g / ton of ore, the NaHS addition amount is 100-200 g / ton, the butyl xanthate addition amount is 20-50 g / ton of ore, and the amyl xanthate addition amount is 20-50 g / ton of ore, and the butyl xanthate and amyl xanthate addition ratio is 1:1 to 1:2.

[0060] Furthermore, in the step (7), the sodium hexametaphosphate is 50-100 g / ton of ore and the carboxymethyl cellulose is 50-100 g / ton of ore.

[0061] Furthermore, the scraping time of the roughing operation is 4 to 6 minutes, and the scraping time of the sweeping operation and the fine selection operation is 3 to 5 minutes.

[0062] The invention is used for processing high-calcium-magnesium copper-cobalt oxide ore, wherein the copper grade in the copper-cobalt oxide ore is 1.5% to 3.5%, the cobalt grade is not less than 0.12%, and the cobalt-copper oxidation rate is greater than 90%.

[0063] In the following cases, the dosage of reagents refers to the weight of reagents used per ton of ore.

[0064] Example 1

[0065] Test sample 1 is a high calcium and magnesium impurity cobalt-copper oxide ore. The copper and cobalt grades are 1.98% and 0.16% respectively. The contents of calcium oxide and magnesium oxide are 15.62% and 14.23% respectively. It is a typical high calcium and magnesium impurity copper-cobalt oxide ore. The beneficiation process is as follows:

[0066] (1) Grinding and slurrying: The raw ore of the test sample cobalt oxide copper ore was ground to a fineness of less than 0.074 mm, and the product accounted for 75% of the total weight. Then water was added to adjust the slurry to a concentration of 30% to obtain raw ore slurry.

[0067] (2) Roughing operation: 500 g of NaHS, 500 g of Na2S, 100 g of butyl xanthate, 100 g of amyl xanthate, and 30 g of No. 2 oil were added to each ton of raw ore pulp in sequence, and stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain the first roughing copper-cobalt oxide concentrate and the first roughing copper-cobalt oxide tailings (first tailings);

[0068] Second roughing of the first tailings: 300 g of NaHS, 300 g of Na2S, 50 g of butyl xanthate, and 50 g of amyl xanthate were added to the first roughing tailings slurry in sequence, stirred, and the easily floatable copper and cobalt minerals were subjected to aeration flotation to obtain the second concentrate and the second tailings;

[0069] The second tailings were subjected to the third roughing: 200g of NaHS, 300g of Na2S, 50g of butyl xanthate and 50g of amyl xanthate were added to the second roughing tailings slurry in sequence, and stirred. The easily floatable copper and cobalt minerals were subjected to aeration flotation. The copper oxide concentrates from the first, second and third roughing were combined to obtain the roughing concentrate.

[0070] (3) Scavenging operation: 100 g of NaHS, a combined collector (including 40 g of butyl xanthate, 40 g of amyl xanthate, and 20 g of salicylic acid), and 10 g of No. 2 oil were sequentially added to the slurry of the third roughing copper-cobalt oxide tailings (the third tailings of step 2), stirred, and the first scavenging operation was performed to obtain the first scavenged concentrate and the first scavenged tailings;

[0071] Second scavenging: 50g of NaHS, 20g of butyl xanthate, 20g of amyl xanthate and 10g of salicylic hydroxamic acid were added to the slurry of the copper-cobalt oxide ore tailings from the first scavenging. The first scavenging concentrate and the second scavenging concentrate entered the first roughing operation, and the second scavenging tailings were discarded to obtain scavenging tailings.

[0072] (4) Concentration operation: adding a combination of additives (sodium hexametaphosphate (auxiliary agent A) and carboxymethyl cellulose (auxiliary agent B)) to the combined pulp of the first, second and third roughing copper-cobalt oxide concentrates (roughing concentrate) in step 2, wherein 100 g of sodium hexametaphosphate, 100 g of carboxymethyl cellulose, 100 g of NaHS, 20 g of butyl xanthate, and 20 g of amyl xanthate are added, stirred, and the first concentrating operation is performed to obtain a first concentrating concentrate and a first concentrating tailing;

[0073] Second concentration: 50g of sodium hexametaphosphate and 50g of carboxymethyl cellulose are added to the first concentrated ore slurry in sequence. The first concentrated tailings enter the first roughing selection, and the second concentrated tailings return to the first selection. The second concentrated concentrate is the final copper-cobalt oxide concentrate.

[0074] Example 2

[0075] Test sample 2 is a cobalt-copper ore with high calcium and magnesium impurities. The copper and cobalt grades are 2.85% and 0.24% respectively. The contents of calcium oxide and magnesium oxide are 9.46% and 10.72% respectively. The beneficiation process is as follows:

[0076] (1) Grinding and slurrying: The raw ore of the test sample cobalt oxide copper ore was ground to a fineness of less than 0.074 mm, and the product accounted for 75% of the total weight. Then water was added to adjust the slurry to a concentration of 35% to obtain raw ore slurry.

[0077] (2) Roughing operation: 800 g of NaHS, 800 g of Na2S, 150 g of butyl xanthate, 150 g of amyl xanthate, and 40 g of No. 2 oil were added to each ton of raw ore pulp in sequence, and stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain the first roughing copper-cobalt oxide concentrate and the first roughing copper-cobalt oxide tailings (first tailings);

[0078] Second roughing: 400 g of NaHS, 400 g of Na2S, 75 g of butyl xanthate, and 75 g of amyl xanthate were sequentially added to the slurry of the first roughing tailings (first tailings), stirred, and the easily floatable copper and cobalt minerals were subjected to aeration flotation to obtain a second roughing concentrate and a second roughing tailings;

[0079] Third roughing: 300g of NaHS, 300g of Na2S, 75g of butyl xanthate, and 75g of amyl xanthate are stirred and the easily floatable copper-cobalt minerals are subjected to aeration flotation to obtain the third roughing concentrate and the third roughing tailings;

[0080] (3) Scavenging operation: 200 g of NaHS, 50 g of butyl xanthate, 50 g of amyl xanthate, 20 g of salicylic hydroxamic acid, and 10 g of No. 2 oil were sequentially added to the third roughing copper-cobalt oxide tailings slurry, stirred, and the first scavenging operation was performed to obtain the first scavenged concentrate and the first scavenged tailings;

[0081] Second scavenging: 100g of NaHS, 25g of butyl xanthate, 25g of amyl xanthate and 10g of salicylic hydroxamic acid were added to the slurry of the copper-cobalt oxide ore tailings from the first scavenging. The first scavenging concentrate and the second scavenging concentrate entered the first roughing operation, and the second scavenging tailings were discarded to obtain scavenging tailings.

[0082] (4) Concentration operation: 200 g of sodium hexametaphosphate (auxiliary agent A), 200 g of carboxymethyl cellulose (auxiliary agent B), 200 g of NaHS, 40 g of butyl xanthate, and 40 g of amyl xanthate were added to the combined pulp of the first, second, and third rough copper-cobalt oxide concentrates in step 2 in sequence, and stirred to perform the first concentrating operation to obtain a first concentrating concentrate and a first concentrating tailings;

[0083] Second concentration: 100g of sodium hexametaphosphate and 100g of carboxymethyl cellulose are added to the first concentrated ore slurry in sequence. The first concentrated tailings enter the first roughing selection, and the second concentrated tailings return to the first selection. The second concentrated concentrate is the final copper-cobalt oxide concentrate.

[0084] Example 3

[0085] The quality of the raw ore used in Example 3 is the same as that in Example 2, and the mineral processing process is as follows:

[0086] (1) Grinding and slurrying: The raw ore of the test sample cobalt oxide copper ore was ground to a fineness of less than 0.074 mm, and the product accounted for 70% of the total weight. Then water was added to adjust the slurry to a concentration of 30% to obtain raw ore slurry.

[0087] (2) Roughing operation: add 800g of NaHS, 1000g of Na2S, 100g of butyl xanthate, 200g of amyl xanthate and 30g of methyl isobutyl carbinol to each ton of raw ore pulp, stir, and carry out aeration flotation on the easily floatable copper-cobalt minerals to obtain the first roughing copper-cobalt oxide concentrate and the first roughing copper-cobalt oxide tailings. Roughing operation is carried out 3 times. The second roughing of copper-cobalt oxide ore: add 400g of NaHS, 500g of Na2S, 50g of butyl xanthate and 100g of amyl xanthate to the first roughing tailings pulp, stir, and carry out aeration flotation on the easily floatable copper-cobalt minerals. The third roughing of copper-cobalt oxide ore: add 300g of NaHS, 400g of Na2S, 50g of butyl xanthate and 100g of amyl xanthate to the first roughing tailings pulp, stir, and carry out aeration flotation on the easily floatable copper-cobalt minerals. The first, second and third roughing copper oxide concentrates are subjected to two concentration operations to obtain oxide concentrate.

[0088] (3) Scavenging operation: 150 g of NaHS, 30 g of butyl xanthate, 50 g of amyl xanthate, 15 g of salicylic acid and 10 g of methyl isobutyl carbinol were added to the third roughing copper-cobalt oxide tailings slurry in sequence, stirred, and scavenging operation was carried out twice. Second scavenging: 75 g of NaHS, 15 g of butyl xanthate, 25 g of amyl xanthate and 7.5 g of salicylic acid were added to the first scavenging copper-cobalt oxide tailings slurry in sequence. The first scavenging concentrate and the second scavenging concentrate entered the first roughing operation, and the second scavenging tailings were discarded to obtain scavenging tailings.

[0089] (4) Concentration operation: 150g of sodium hexametaphosphate, 150g of carboxymethyl cellulose, 150g of NaHS, 30g of butyl xanthate and 30g of amyl xanthate were added to the combined pulp of the first, second and third roughing copper-cobalt oxide concentrates in sequence, stirred and subjected to concentration operation. The concentration operation was carried out twice. Second concentration: 75g of sodium hexametaphosphate and 75g of carboxymethyl cellulose were added to the pulp of the first concentrated concentrate in sequence. The tailings of the first concentration entered the first roughing, and the tailings of the second concentration returned to the first concentration. The concentrate of the second concentration was the final copper-cobalt oxide concentrate.

[0090] Comparative Example 1:

[0091] Compared with Example 2, the only difference is that the combined auxiliary agent in step 4 is changed. The experimental groups are:

[0092] Group A: The combined auxiliary agent is only auxiliary agent A, and the amount of the remaining auxiliary agents is the same as the total amount of the combined auxiliary agents in Example 1:

[0093] Group B: The combined auxiliary agent is only auxiliary agent B, and the amount of the remaining auxiliary agents is the same as the total amount of the combined auxiliary agents in Example 1: 1;

[0094] Other operations and parameters are the same as in Example 1.

[0095] Comparative Example 2:

[0096] Compared with Example 2, the only difference is that the type of combined collector is changed. The experimental groups are:

[0097] Group A: In the combined collector, salicylic acid was absent and only xanthate collector (butyl xanthate and amyl xanthate in a weight ratio of 1:1) was used. The total weight of the remaining collector was the same as the total amount of the combined collector in Example 1.

[0098] Group B: In the combined collection, the xanthate collector is absent and only salicylic acid is used, wherein the total weight of the remaining collectors is the same as the total amount of the combined collectors in Example 1;

[0099] Other operations and parameters are the same as in Example 2.

[0100] Comparative Example 3:

[0101] The quality of the raw ore used is the same as that in Example 2. The difference between the ore dressing process and that in Example 2 is that this embodiment adopts the six-stage roughing open circuit process commonly used in industry to collect all the concentrates. The specific implementation process is as follows:

[0102] (1) Grinding and slurrying: The raw ore of the test sample cobalt oxide copper ore was ground to a fineness of less than 0.074 mm, and the product accounted for 70% of the total weight. Then water was added to adjust the slurry to a concentration of 30% to obtain raw ore slurry.

[0103] (2) Roughing operation: add 800g NaHS, 800g Na2S, 250g butyl xanthate, 250g amyl xanthate, and 30g 2# oil to each ton of raw ore pulp, stir, and aerate the easily floatable copper-cobalt minerals for 5 minutes to obtain the first roughing copper-cobalt oxide concentrate and the first roughing copper-cobalt oxide tailings. Roughing operation is carried out 6 times. The second roughing of copper-cobalt oxide: add 400g NaHS, 400g Na2S, 200g butyl xanthate, and 200g amyl xanthate to the first roughing tailings pulp, stir, and aerate the easily floatable copper-cobalt minerals for 5 minutes. The third roughing of copper-cobalt oxide: 300g NaHS, 400g Na2S, 200g butyl xanthate, and 200g amyl xanthate. 300g, butyl xanthate 200g, amyl xanthate 200g, stirring, the easy-floating copper-cobalt minerals are aerated for flotation for 5min, the fourth roughing of copper-cobalt oxide ore: NaHS200g, butyl xanthate 100g, amyl xanthate 100g, salicylic acid 30g, 2 #Oil 10g, stirring, the difficult-to-float copper-cobalt minerals are subjected to aeration flotation for 3min, the fifth roughing of copper-cobalt oxide ore: NaHS200g, butyl xanthate 100g, amyl xanthate 100g, salicylic hydroxamic acid 30g, stirring, the difficult-to-float copper-cobalt minerals are subjected to aeration flotation for 2min, the sixth roughing of copper-cobalt oxide ore: NaHS100g, butyl xanthate 100g, amyl xanthate 100g, salicylic hydroxamic acid 30g, stirring, the difficult-to-float copper-cobalt minerals are subjected to aeration flotation for 1min, the sixth roughing tailings are the final tailings, and the first to sixth roughing concentrates are combined into the final copper concentrate.

[0104] Table 1 Flotation test results of different processes (%)

[0105]

[0106] Analysis and testing: The concentrate yields and concentrate copper and cobalt recoveries of Examples 1 to 3 and Comparative Examples 1 to 3 were measured, and the results are recorded in Table 1. The above results show that the flotation process of the present invention can effectively improve the copper and cobalt recovery rate, significantly reduce the yield, and improve the concentrate grade.

Claims

1. A flotation method for high calcium magnesium copper-cobalt oxide ore, characterized in that: The high calcium magnesium copper-cobalt oxide ore to be selected is crushed, ground and slurried to obtain raw ore slurry; The raw ore pulp is subjected to rough separation using flotation reagent A to collect rougher concentrate and rougher tailings; wherein the flotation reagent A comprises a water-soluble sulfide salt a and a xanthate collector a; The roughing concentrate is beneficiated using flotation agent B to collect copper-cobalt concentrate and beneficiated tailings, and the beneficiated tailings are returned to the roughing and / or beneficiation stages; the flotation agent B comprises a combination of additives, a water-soluble sulfide salt b, and a xanthate collector b, wherein the combination of additives comprises additives A and additives B, wherein additive A comprises hexametaphosphoric acid and a water-soluble salt thereof; and additive B comprises carboxymethyl cellulose and a water-soluble salt thereof; The roughing tailings are scavenged using a flotation agent C to obtain scavenged tailings and scavenged concentrates, and the scavenged concentrates are returned to the roughing process, wherein the flotation agent C comprises a water-soluble sulfide salt C and a combined collector; the combined collector comprises a xanthate collector C and a salicylic hydroxamic acid collector.

2. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 1, wherein: The crushing fineness of the raw ore is 2~4mm; the products with grinding fineness less than 0.074mm account for 55%~90% of the total mass; the raw ore slurry concentration is 30%~35%.

3. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 1, wherein: The copper grade in high calcium magnesium oxide copper cobalt ore is 1.5%~3.5%, the cobalt grade is not less than 0.12%, and the cobalt-copper oxidation rate is greater than 90%.

4. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 1, wherein: In the flotation reagent A, the water-soluble sulfide salt a includes at least one of sodium hydrosulfide and sodium sulfide.

5. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 4, characterized in that: In the flotation reagent A, the water-soluble sulfide salt a comprises sodium hydrosulfide and sodium sulfide in a weight ratio of 1-10:1-10.

6. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 1, characterized in that: The xanthate collector a includes at least one of ethyl xanthate, propyl xanthate, butyl xanthate and pentyl xanthate.

7. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 6, characterized in that: The xanthate collector a comprises butyl xanthate and amyl xanthate in a weight ratio of 1:0.5-5.

8. The flotation method of high calcium magnesium copper-cobalt oxide ore according to any one of claims 1, 4 to 7, characterized in that: The roughing stage includes three roughing processes, including: subjecting the raw ore pulp to the first roughing stage to obtain the first roughing concentrate and the first roughing tailings; subjecting the first roughing tailings to the second roughing stage to obtain the second roughing concentrate and the second roughing tailings; subjecting the second roughing tailings to the third roughing stage to obtain the third roughing concentrate and the third roughing tailings; The first rougher concentrate, the second rougher concentrate and the third rougher concentrate are combined to produce a rougher concentrate; and the third rougher tailings are used as rougher tailings for scavenging treatment.

9. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 8, characterized in that: In the first roughing stage, the amount of water-soluble sulfide salt a in the flotation reagent A is 800~2000g / t, and the amount of xanthate collector a is 150~400g / t.

10. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 9, characterized in that: A foaming agent is also added to the flotation reagent A in the first roughing stage. The foaming agent includes at least one of 2# oil or methyl isobutyl carbinol. The amount of the foaming agent is 20-50 g / t. No additional foaming agent is required in the second and third roughing stages.

11. The flotation method of high calcium magnesium copper oxide cobalt ore according to claim 10, characterized in that: The dosage of flotation reagent A in the second and third roughing stages is 35~100% of that in the first roughing stage.

12. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 10, characterized in that: The scraping time for each rough selection is 4 to 6 minutes.

13. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 1, characterized in that: In the flotation reagent B, the water-soluble sulfide salt b includes at least one of sodium hydrosulfide and sodium sulfide.

14. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 1, characterized in that: The xanthate collector b includes at least one of ethyl xanthate, propyl xanthate, butyl xanthate and pentyl xanthate.

15. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 14, characterized in that: The xanthate collector b comprises butyl xanthate and amyl xanthate in a weight ratio of 1:1-2.

16. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 14, characterized in that: The auxiliary agent A includes sodium hexametaphosphate; and the auxiliary agent B includes carboxymethyl cellulose.

17. The flotation method of high calcium magnesium copper-cobalt oxide ore according to any one of claims 13 to 16, characterized in that: The beneficiation process includes two beneficiation processes, and its steps are: subjecting the roughing concentrate to a first beneficiation to obtain a first beneficiation concentrate and a first beneficiation tailings, returning the first beneficiation tailings to the roughing process, subjecting the first beneficiation concentrate to a second beneficiation to obtain a second beneficiation concentrate and a second beneficiation tailings; the second beneficiation concentrate is the copper-cobalt concentrate; and returning the second beneficiation tailings to the first beneficiation process.

18. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 17, characterized in that: In the first selection process, the dosage of auxiliary agent A is 100~200g / t, the dosage of auxiliary agent B is 100~200g / t, the dosage of water-soluble sulfide salt b is 100~200g / t, and the dosage of xanthate collector b is 40~100g / t.

19. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 18, characterized in that: During the second selection process, the dosage of auxiliary agent A and auxiliary agent B is 35-65% of the dosage of the first selection process; the dosage of water-soluble sulfide salt b and xanthate collector b is less than or equal to 20% of the dosage of the first selection process.

20. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 18, characterized in that: Each selection stage takes 3 to 4 minutes.

21. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 1, characterized in that: The water-soluble sulfide salt c includes at least one of sodium hydrosulfide and sodium sulfide.

22. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 21, characterized in that: In the combined collector, the xanthate collector C includes at least one of ethyl xanthate, propyl xanthate, butyl xanthate and pentyl xanthate.

23. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 22, characterized in that: The xanthate collector C is butyl xanthate and amyl xanthate in a weight ratio of 1:1-2.

24. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 22, characterized in that: In the combined collector, the weight ratio of the xanthate collector c to the salicylic hydroxamic acid collector is 1-10:

1.

25. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 24, characterized in that: In the combined collector, the weight ratio of the xanthate collector c to the salicylic hydroxamic acid collector is 2-6:

1.

26. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 1, characterized in that: The scavenging process includes two stages of scavenging, which include: subjecting the rougher tailings to the first stage of scavenging to obtain the first scavenged concentrate and the first scavenged tailings; subjecting the first scavenged tailings to the second stage of scavenging to obtain the second scavenged concentrate and the scavenged tailings; The first scavenged concentrate and the second scavenged concentrate are mixed and returned to the roughing process.

27. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 26, characterized in that: In the first scavenging stage, the dosage of water-soluble sulfide salt C is 100~200g / t; the dosage of xanthate collector is 40~100g / t; the dosage of salicylic hydroxamic acid collector is 10~20g / t; the addition ratio of butyl xanthate and amyl xanthate is 1:1~1:

2.

28. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 27, characterized in that: A foaming agent is also added in the first scavenging stage. The foaming agent includes at least one of 2# oil or methyl isobutyl carbinol; the amount of the foaming agent is 5-20 g / t.

29. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 26, characterized in that: The dosage of the chemical in the second sweeping stage is 35~65% of the dosage in the first stage; the dosage of the foaming agent is less than 10% of the dosage in the first stage.

30. The flotation method of high calcium magnesium copper-cobalt oxide ore according to claim 26, characterized in that: Each scanning stage takes 3 to 4 minutes.

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