High-efficiency combined collector for copper-cobalt oxide ore under high-magnesium backwater system and mineral processing method

Abstract

The application discloses a high-efficiency combined collector for oxidized copper-cobalt ore under a high-magnesium backwater system and a beneficiation method. The high-efficiency combined collector comprises, in terms of weight parts, 200-300 parts of sulfosalicylic acid, 650-900 parts of butyl ammonium black medicine and 650-900 parts of butyl xanthate. The high-efficiency combined collector for oxidized copper-cobalt ore and the beneficiation method can improve the foaming performance in the flotation process of the oxidized copper-cobalt ore under the high-magnesium backwater system, and can obviously improve the recovery rate of copper and cobalt metals in the oxidized copper-cobalt concentrate.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, specifically to a highly efficient combined collector and mineral processing method for copper-cobalt oxide ore in a high-magnesium reflux system. Background Technology

[0002] More than 50% of the world's Co metal originates from the copper-cobalt metallogenic belt in the Democratic Republic of Congo (TIJSSELING LT, DEHAINE Q, ROLLINSON GK, et al. Flotation of mixed oxide sulphide copper-cobalt minerals using xanthate, dithiophosphate, thiocarbamate and blended collectors[J]. Minerals Engineering, 2019, 138: 246-256.). With the commissioning of the Luoyang Molybdenum KFM project, this figure has lagged behind the actual expansion speed of its business. Copper-cobalt oxide ores are among the important cobalt-bearing ores. With the continuous development of high-quality resources, low-grade copper-cobalt oxide ores are gradually becoming the main copper-cobalt minerals for producing copper-cobalt metal.

[0003] Currently, there are generally two flotation technologies for the efficient recovery of copper-cobalt oxide ores: First, the oxygen-sulfur mixed flotation process: the minerals are first sulfidated with sulfiding agents such as sodium hydrosulfide (NaHS) or sodium sulfide (Na2S), and then both sulfide copper-cobalt ore and copper-cobalt oxide ore are floated together in the ore; Second, the sulfur-first-oxygen flotation process: butyl xanthate or pentyl xanthate is first used to float the sulfide ores present in the minerals, and then sulfiding agents are used to sulfide the oxide ores in the ore, thereby recovering the remaining copper and cobalt metals in the ore. The choice between these two processes depends on the properties of the ore. It is worth noting that, since Co-bearing minerals are not easily sulfided by sulfiding agents, this technology still has corresponding limitations (TIJSSELING LT, DEHAINE Q, ROLLINSON GK, et al. Flotation of mixed oxide sulphide copper-cobalt minerals using xanthate, dithiophosphate, thiocarbamate and blended collectors[J]. MineralsEngineering, 2019, 138: 246-256; Liu Jun. Research on recovery technology of valuable metals in low-grade cobalt ore[D]. Wuhan University of Technology, 2011.).

[0004] Generally, Cu is well recovered by flotation in copper-cobalt oxide ores, while Co has a weaker effect with traditional collectors (BUCKLEY. The Surface Oxidation of Cobaltite[J]. Australian Journal of Chemistry, 1987, 40(2): 231-239.). Therefore, Co metal is usually produced as a by-product (RAO GV. Nickel and cobalt ores: flotation[J]. Encyclopedia of Separation Science, 2000: 3491-3500.). However, in high-magnesium reflux water (around 1 g / L) systems (during the combined beneficiation and metallurgical production process, to ensure washing efficiency, a cobalt-precipitated liquid with high magnesium ion content is usually generated; this liquid cannot be discharged and, to reduce environmental pollution, can only be reused in the flotation system), traditional oxygen-sulfur mixed flotation or sulfur-first-oxygen flotation processes suffer from poor sulfidation effects and poor foaming properties, reducing copper-cobalt metal recovery rates (copper recovery rate decreases by 5-6 percentage points). Furthermore, traditional copper-cobalt oxide ore collector combinations such as benzoyl acetone + styrene phosphoric acid + butyl xanthate (Chinese patent application CN102218377A) and butyl xanthate + butylammonium black powder (Chinese patent application CN110898985A) show poor recovery effects on copper-cobalt oxide ore in high-magnesium reflux water (around 1 g / L) systems, and research on this technology is limited. Therefore, efficient recovery technology for copper-cobalt oxide ore in high-magnesium reflux water (1 g / L) systems requires further optimization. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention aims to provide a highly efficient combined collector and beneficiation method for copper-cobalt oxide ore in a high-magnesium reclaimed water system.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A highly efficient combined collector for oxidized copper-cobalt ore in a high-magnesium reflux system, comprising, by weight: 200-300 parts of sulfosalicylic acid, 650-900 parts of butylammonium xanthate and 650-900 parts of butyl xanthate.

[0008] This invention also provides a method for beneficiating copper-cobalt oxide ore in a high-magnesium reclaimed water system using the above-mentioned highly efficient combined collector, comprising the following steps:

[0009] S1. Crush the raw ore and set it aside for later use;

[0010] S2. The crushed ore obtained in step S1 is mixed with water and then ground to obtain a flotation product.

[0011] S3. The flotation product obtained in step S2 is subjected to mixed flotation of sulfide and oxide ores;

[0012] Before each flotation stage, a sulfiding agent is added to the floatable product and stirred to adjust the slurry. Then, the above-mentioned high-efficiency combined collector is added to the slurry obtained by slurry adjustment. After stirring and adjusting the slurry, flotation is carried out to obtain concentrate and tailings. The tailings remaining after each flotation stage enter the next flotation stage. The concentrates obtained from each flotation stage are mixed to form the final copper-cobalt oxide concentrate. The tailings remaining after the sixth flotation stage are the final tailings.

[0013] Further, in step S1, the raw ore is crushed to a particle size ≤ 2 mm.

[0014] Furthermore, in step S2, the grinding is carried out in a ball mill filled with iron ball media and the filling rate of the iron ball media is 30%.

[0015] Furthermore, in step S2, the portion of the floatable product with a particle size ≤74 μm accounts for 65-75% of the total mass of the floatable product.

[0016] Further, in step S3, the pH of the slurry obtained after slurry conditioning is 8.5-9.5, and the slurry mass concentration is 30-35%; the sulfiding agent is sodium hydrosulfide, and the total amount of sodium hydrosulfide used in all flotation stages is 1900-2100 g / t of raw ore dry weight.

[0017] Further, in step S3, the total amount of the high-efficiency combined collector used in all flotation stages is 200-300 g / t dry weight of sulfosalicylic acid, 650-900 g / t dry weight of butylammonium black powder, and 650-900 g / t dry weight of butyl xanthate.

[0018] Furthermore, in the first stage of flotation, after adding a highly efficient combined collector, a frother 2 was also added. # The dosage of oil is 30-40 g / t of dry weight of raw ore.

[0019] The beneficial effects of this invention are as follows:

[0020] 1. The efficient combined collector and beneficiation method for copper-cobalt oxide ore proposed in this invention can significantly improve the recovery rate of copper and cobalt metals in copper-cobalt oxide concentrate;

[0021] 2. The highly efficient combined collector proposed in this invention can improve the foaming performance during the flotation of copper-cobalt oxide ore in a high-magnesium reflux water system (around 1 g / L). Magnesium ions have the ability to affect mineral sulfidation and inhibit foaming. The combination of sulfosalicylic acid, butylammonium black powder, and butyl xanthate, which have strong chelating ability with metal ions and stronger foaming properties, can significantly improve the foam state during the flotation process, increasing the foam layer from 1 cm to about 4 cm. Attached Figure Description

[0022] Figure 1 This is a flowchart illustrating the implementation of the method in Embodiment 1 of the present invention. Detailed Implementation

[0023] The present invention will be further described below with reference to the accompanying drawings. It should be noted that this embodiment is based on the present technical solution and provides detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to this embodiment.

[0024] Example 1

[0025] This embodiment provides a beneficiation method for copper-cobalt oxide ore in a high-magnesium reclaimed water (approximately 1 g / L) system, for processing the aforementioned ore. Figure 1 As shown, it includes:

[0026] The raw ore was crushed to a particle size ≤2 mm using a double roll crusher and mixed evenly for later use. 500 g of the evenly mixed crushed ore was mixed with 335 mL of water and then placed in a ball mill with iron ball media at a filling rate of 30% and ground for 4 minutes to obtain a flotationable product. The portion of the flotationable product with a particle size ≤74 μm accounted for 69% of the total product.

[0027] The flotationable product obtained above is subjected to mixed flotation of sulfide and oxide ores. In this embodiment, a total of six open-circuit oxygen-sulfur mixed flotation processes are performed. The tailings obtained from each flotation process enter the next flotation process. The concentrates obtained from each flotation process are mixed to obtain the final copper-cobalt oxide concentrate product, and the tailings obtained from the last flotation process are the final tailings.

[0028] Before each flotation stage, a sulfiding agent (NaHS) is added to condition the slurry (the amounts of sulfiding agent used in the first to sixth stages are 1000 g / t dry weight of raw ore, 400 g / t dry weight of raw ore, 300 g / t dry weight of raw ore, 150 g / t dry weight of raw ore, 100 g / t dry weight of raw ore and 50 g / t dry weight of raw ore, respectively; the conditioning times are 5 minutes, 2 minutes, 2 minutes, 2 minutes, 2 minutes and 2 minutes, respectively), so that the slurry pH is maintained in an alkaline environment of 9 and the slurry mass concentration is about 32%.

[0029] Subsequently, a high-efficiency combined collector (sulfosalicylic acid, butylammonium black powder, and butyl xanthate) was added to the slurry and stirred to adjust the consistency. In the first flotation stage, the dosage of the high-efficiency combined collector was 25 g / t dry weight of sulfosalicylic acid + 250 g / t dry weight of butylammonium black powder + 250 g / t dry weight of butyl xanthate. The dosage was the same in the second and third stages, specifically: 50 g / t dry weight of sulfosalicylic acid + 125 g / t dry weight of butylammonium black powder + 125 g / t dry weight of butyl xanthate. The dosage was also the same in the fourth to sixth stages of flotation, specifically: 25 g / t dry weight of sulfosalicylic acid + 62.5 g / t dry weight of butylammonium black powder + 62.5 g / t dry weight of butyl xanthate. The stirring and slurry conditioning time after adding the high-efficiency combined collector in the first to sixth flotation stages is 2 minutes.

[0030] After adding a high-efficiency combined collector and stirring to adjust the slurry, flotation was performed. The flotation times for the first to sixth stages were 5 minutes, 5 minutes, 5 minutes, 3 minutes, 2 minutes, and 1 minute, respectively. In this embodiment, in the first stage of flotation, a frother 2 was also added after the high-efficiency combined collector. # Oil, dosage is 30 g / t of raw ore dry weight (stirring time is 1 minute).

[0031] In this embodiment, during the six flotation processes, the total amount of sodium hydrosulfide sulfide as the sulfiding agent is 2000 g / t of dry ore; the total amount of the high-efficiency combined modifier is 1575 g / t of dry ore, specifically including: 200 g / t of sulfosalicylic acid, 687.5 g / t of butylammonium black powder, and 687.5 g / t of butyl xanthate.

[0032] Example 2

[0033] The method in this embodiment is basically the same as that in embodiment 1. The main difference is that the total amount of the high-efficiency combined collector is 1725 g / t of dry ore, which specifically includes: 250 g / t of sulfosalicylic acid, 737.5 g / t of butylammonium black powder and 737.5 g / t of butyl xanthate.

[0034] The amount of high-efficiency combined collector added to the slurry is changed as follows: the amount of high-efficiency combined collector used in the second and third flotation stages is the same, specifically including: 75 g / t dry weight of sulfosalicylic acid + 150 g / t dry weight of butylammonium black powder + 150 g / t dry weight of butyl xanthate.

[0035] Example 3

[0036] The method in this embodiment is basically the same as that in embodiment 1. The main difference is that the amount of the high-efficiency combined collector is 1875 g / t of dry ore, which specifically includes: 300 g / t of sulfosalicylic acid, 787.5 g / t of butylammonium black powder and 787.5 g / t of butyl xanthate.

[0037] The amount of high-efficiency combined collector added to the slurry is changed as follows: the amount of high-efficiency combined collector used in the second and third flotation stages is the same, specifically including: 100 g / t dry weight of sulfosalicylic acid + 175 g / t dry weight of butylammonium black powder + 175 g / t dry weight of butyl xanthate.

[0038] Comparative Example 1

[0039] A certain copper-cobalt oxide ore contains approximately 2.19% copper and 0.12% cobalt in its raw form. The ore is characterized by: ① a high oxidation rate, around 90%; ② high Mg content in the beneficiation water (around 1 g / L), resulting in poor sulfidation, weak foaming, and significant recovery difficulty. The main copper mineral in the ore is malachite, followed by native copper and chalcocite, while the main cobalt mineral is cobaltite. The non-metallic gangue is primarily quartz and dolomite, followed by muscovite, chlorite, talc, and pyroxene, with a small amount of apatite, etc. Under a high-Mg reflux water system (around 1 g / L), the recovery rate using conventional collectors is low.

[0040] The above-mentioned ore was treated using the high-efficiency combined collector and beneficiation method described in Example 1, and the resulting indicators are shown in Table 1.

[0041] Using the same ore, the high-efficiency combined collector in Example 1 was replaced with a combination of conventional collectors butyl xanthate and pentyl xanthate (butyl xanthate: pentyl xanthate = 1:1) as a comparative test. The total amount of conventional collector used was 1575 g / t of dry ore, specifically including 787.5 g / t of dry ore butyl xanthate and 787.5 g / t of dry ore pentyl xanthate.

[0042] The process parameters of Example 1 and the comparative test are shown in Table 1.

[0043] Table 1

[0044]

[0045] As can be seen from Table 1, Example 1 achieved better mineral processing indicators. Compared with the comparative test, the recovery rate of copper increased by 5.87% and the recovery rate of cobalt increased by 6.96%.

[0046] Comparative Example 2

[0047] The raw copper-cobalt oxide ore contains approximately 2.40% copper and 0.22% cobalt. The ore's characteristics are: ① High oxidation rate, with copper and cobalt oxidation rates around 98%; ② High Mg content in the beneficiation water (around 1 g / L), resulting in poor sulfidation, poor foaming, and significant recovery difficulty. The copper minerals in the ore are mainly malachite and azurite, while the cobalt minerals are mainly cobaltite and cobaltite. The ore primarily contains carbonaceous dolomitic shale, silicified crystalline dolomite, layered dolomite, banded silicified dolomite, and completely weathered dolomite. Under a high-Mg reclaimed water system (around 1 g / L), conventional collectors result in low recovery rates.

[0048] The above-mentioned ore was treated using the efficient combined collector and beneficiation method described in Example 2, and the resulting indicators are shown in Table 2.

[0049] Using the same ore, the high-efficiency combined collector in Example 2 was replaced with a combination of conventional collectors butyl xanthate and pentyl xanthate (butyl xanthate: pentyl xanthate = 1:1) as a comparative experiment. The total amount of conventional collector used was 1725 g / t of dry ore, specifically including 862.5 g / t of dry ore butyl xanthate and 862.5 g / t of dry ore pentyl xanthate.

[0050] The process parameters for Example 2 and the comparative experiment are shown in Table 2.

[0051] Table 2

[0052]

[0053] As can be seen from Table 2, Example 2 achieved better mineral processing indicators. Compared with the comparative experiment, the copper recovery rate was 2.97% higher and the cobalt recovery rate was 3.18% higher.

[0054] For those skilled in the art, various corresponding changes and modifications can be made based on the above technical solutions and concepts, and all such changes and modifications should be included within the protection scope of the claims of this invention.

Claims

1. A beneficiation method for copper-cobalt oxide ore using a high-magnesium reclaimed water system with a highly efficient combined collector, characterized in that, The highly efficient combined collector for copper-cobalt oxide ore under the high magnesium backwater system comprises, by weight: 200-300 parts of sulfosalicylic acid, 650-900 parts of butylammonium xanthate, and 650-900 parts of butyl xanthate. The mineral processing method includes the following steps: S1. Crush the raw ore and set it aside; S2. The crushed ore obtained in step S1 is mixed with water and then ground to obtain a flotation product. S3. The flotation product obtained in step S2 is subjected to multi-stage mixed flotation of sulfide and oxide ores. Before each flotation stage, a sulfiding agent is added to the floatable product and stirred to adjust the slurry. Then, the above-mentioned high-efficiency combined collector is added to the slurry obtained by slurry adjustment. After stirring and adjusting the slurry, flotation is carried out to obtain concentrate and tailings. The tailings remaining after each flotation stage enter the next flotation stage. The concentrates obtained from each flotation stage are mixed to form the final copper-cobalt oxide concentrate. The tailings remaining after the sixth flotation stage are the final tailings.

2. The method according to claim 1, characterized in that, In step S1, the raw ore is crushed to a particle size ≤ 2 mm.

3. The method according to claim 1, characterized in that, In step S2, the grinding is carried out in a ball mill filled with iron ball media and the filling rate of the iron ball media is 30%.

4. The method according to claim 1, characterized in that, In step S2, the portion of the floatable product with a particle size ≤74 μm accounts for 65-75% of the total mass of the floatable product.

5. The method according to claim 1, characterized in that, In step S3, the pH of the slurry obtained after slurry conditioning is 8.5-9.5, and the slurry mass concentration is 30-35%; the sulfiding agent is sodium hydrosulfide, and the total amount of sodium hydrosulfide used in all flotation stages is 1900-2100 g / t of raw ore dry weight.

6. The method according to claim 1, characterized in that, In step S3, the total amount of the high-efficiency combined collectors used in all flotation stages is 200-300 g / t dry weight of sulfosalicylic acid, 650-900 g / t dry weight of butylammonium black powder, and 650-900 g / t dry weight of butyl xanthate.

7. The method according to claim 1, characterized in that, In the first stage of flotation, after adding a high-efficiency combined collector, a frother 2 was also added. # The dosage of oil is 30-40 g / t of dry weight of raw ore.

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