A high-efficiency combined regulator for easily muddy copper-cobalt oxide ore and a beneficiation method

Abstract

The invention discloses a kind of efficient combination regulator and beneficiation method of easily muddy copper-cobalt oxide ore, and the efficient combination regulator includes 250 350 parts of sodium citrate and 1100 1200 parts of sodium hydrosulfide by weight.Sodium citrate has stronger dispersibility, can improve the efficiency of selective adsorption between muddy copper-cobalt ore and reagent;Meanwhile, sodium citrate is stronger to the complexing ability of the ion that affects reagent adsorption such as ore surface Fe, Ca and Mg, and, the product after complexing Fe, Ca and Mg ions is soluble in water, for the selective adsorption of sulfiding agent (NaHS) and collector amyl xanthate (PAX) provides action site.Combination regulator proposed in the present invention and beneficiation method can significantly improve the problem of poor selectivity of muddy copper-cobalt ore flotation process reagent, strengthen the sulfiding effect of sulfiding agent, promote the selective adsorption of collector, so as to improve the recovery of copper-cobalt metal in copper-cobalt oxide ore under the serious condition of ore mudification.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to a high-efficiency combined regulator for easily muddy copper-cobalt oxide ore and a beneficiation method. Background Art

[0002] Sulfide flotation is one of the important processes for treating copper-cobalt oxide ores. The specific process is to first sulfide the copper-cobalt oxide ores with a sulfiding agent to enhance their affinity with the collector, and then use a sulfide collector such as xanthate to selectively float out the valuable minerals. The sulfide flotation process has the problems of poor sorting efficiency and low copper-cobalt recovery rate when flotating copper-cobalt ores that are prone to muddling. However, with the continuous development and utilization of high-quality resources, copper-cobalt oxide ores that are prone to muddling have gradually become the main force in the production of copper and cobalt metals (Lin Yuemeng, Han Baisui, Jiang Lishuai, et al., Research Status and Prospects of Flotation Methods and Reagents for Copper Oxide Ores, Comprehensive Utilization of Minerals, 2024, 45(3):112-120.). Therefore, the efficient recovery technology of copper-cobalt oxide ores that are prone to muddling needs to be further improved.

[0003] The quality of flotation index depends on the physical and chemical properties of the ore (Chen Haijun. Experimental study on optimization of parameters for sulfuric acid pre-oxidation-flotation separation of copper-lead mixed concentrate [J]. Nonferrous Metals Engineering, 2024, 15(5): 95-103.). The solution ions in the slurry easily react with the mud particles, causing the mud fine particles to non-selectively deposit on the ore surface, resulting in a homogenization effect between useful minerals and gangue minerals, affecting the non-selective adsorption of the collector, and thus worsening the separation between ores (Zhao Haiping, Liu Jingzhi, Hu Xueping, et al. Application of sodium aminophosphate in efficient separation of Carlin-type gold deposits [J]. Nonferrous Metals Engineering, 2024, 14(6): 90-98.). In summary, the efficient separation of easily muddy copper-cobalt ores should start with the development of efficient adjusters, and develop more efficient adjusters to improve the selective adsorption effect of sulfiding agents and collectors on the mineral surface (Wei Zhao, Sun Wei, Zhang Qingpeng, et al. Flotation separation of fine-grained copper sulfide ores and easily muddy calcium magnesium minerals [J]. Nonferrous Metals Engineering, 2017, 7(4): 64-69.).

[0004] In current research, the improvement of flotation effect of easily muddy copper-cobalt ores is mainly focused on enhancing the sulfiding effect of sulfiding agents. For example, Chen Daixiong et al. (Chen Daixiong, Liu Mengfei, Li Songjiang, et al. Activation sulfidation flotation mechanism of copper oxide ore and its industrial application [J]. Journal of the Chinese Society of Nonferrous Metals, 2022 (8): 2393-2404.) added NH4 +To increase the effect of sulfiding agent, but this technology has the problem of difficult to control the dosage of sulfiding agent. Too much sulfiding agent may produce the opposite effect. More importantly, this technology also does not solve the problem of large dosage of reagents and poor sorting efficiency. At the same time, for ores that are prone to mudification, some researchers recommend the use of desludging methods (Lin Yuemeng, Han Baisui, Jiang Lishuai, et al., Research Status and Prospect of Flotation Methods and Reagents for Copper Oxide Ores, Comprehensive Utilization of Minerals, 2024, 45(3): 112-120.). Although this process can improve the quality of concentrate to a certain extent, the removed fine particles still contain a part of copper and cobalt metals, resulting in a waste of ore resources. Therefore, the development of efficient adjusters that can promote the selective adsorption of sulfiding agents and collectors is an effective way to solve the problem of difficult flotation recovery of easily muddy ores. However, currently available copper oxide mineral conditioning agents, such as lignin sulfonate (Chinese patent application CN103480500A) and imidazole hydroxide + sodium sulfite (Chinese patent application CN117380401A), suffer from high reagent costs and poor performance when flotating easily slimed copper-cobalt ores. Consequently, further optimization of efficient conditioning agents for easily slimed copper-cobalt ores is needed. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the present invention aims to provide a high-efficiency combined regulator and a beneficiation method for easily muddy copper-cobalt oxide ores.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The invention provides a high-efficiency combined regulator for easily muddy copper-cobalt oxide ore. The high-efficiency combined regulator comprises 250-350 parts of sodium citrate and 1100-1200 parts of sodium hydrosulfide in parts by weight.

[0008] The present invention also provides a beneficiation method for easily muddy copper-cobalt oxide ore using the above-mentioned high-efficiency combined regulator, comprising the following steps:

[0009] S1, crush the raw ore and set aside;

[0010] S2, taking the crushed ore obtained in step S1, mixing it with water and grinding it to obtain a floatable product;

[0011] S3, subjecting the floatable product obtained in step S2 to multi-stage mixed flotation of sulfide ore and oxide ore; in the first stage of flotation, a regulator NaHS, a collector and a frother are added to pre-float out a portion of fine mud;

[0012] After the first stage of flotation is completed, the tailings remaining after a portion of fine mud is floated out are subjected to subsequent flotation; before each subsequent stage of flotation, the high-efficiency combined adjuster and collector are pre-added, and after stirring and slurrying, flotation is performed to obtain concentrate and tailings. The tailings remaining in each stage of flotation enter the next stage of flotation, and the concentrates obtained in each stage of flotation are mixed to obtain the final copper-cobalt oxide concentrate. The tailings remaining after the fifth stage of flotation are the final tailings.

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

[0014] Furthermore, in step S2, the grinding is performed using a ball mill, the ball mill uses iron ball media, and the filling rate of the iron ball media is 32%.

[0015] Furthermore, in the floatable product obtained in step S2, the portion with a particle size of ≤74 μm accounts for 67-77% of the total mass of the floatable product.

[0016] Furthermore, in step S3, in the first stage of flotation, the pH of the pulp is 9-10, and the mass concentration of the pulp is 28-34%; in the first stage of flotation, the amount of the adjusting agent NaHS is 500-700 g / t of the dry weight of the original ore, the collector used includes amyl xanthate, the amount of which is 500-700 g / t of the dry weight of the original ore, and the frother used includes 2 # Oil, the dosage is 20-40g / t dry weight of the original ore.

[0017] Furthermore, in step S3, in each flotation stage after the first flotation stage, the collector used includes amyl xanthate.

[0018] Furthermore, in step S3, the total amount of amyl xanthate used as the collector in all flotation stages is 1800-1900 g / t dry weight of the raw ore.

[0019] Furthermore, in step S3, the total amount of the high-efficiency combined adjusting agent used in all flotation stages is 250-350 g of sodium citrate and 1100-1200 g of sodium hydrosulfide per ton of dry weight of the raw ore.

[0020] The beneficial effects of the present invention are as follows: mineral sliming causes non-selective adsorption of sulfiding agent (NaHS) and collector amyl xanthate (PAX) on the surfaces of useful ores and gangue, resulting in high reagent costs, poor separation efficiency of useful minerals and gangue minerals in flotation concentrates, and low flotation recovery efficiency of copper and cobalt metals in the flotation process of copper-cobalt oxide ores. In this regard, the present invention provides a high-efficiency combined adjusting agent of sodium citrate and sodium hydrosulfide. Sodium citrate has strong dispersing ability and can improve the efficiency of selective adsorption between muddy copper-cobalt ore and reagents. At the same time, sodium citrate has strong complexing ability for ions such as Fe, Ca and Mg on the ore surface that affect the selective adsorption of the reagent. The product after complexing Fe, Ca and Mg ions is soluble in water, providing action sites for the selective adsorption of the sulfiding agent (NaHS) and the collector amyl xanthate (PAX). This can significantly improve the problem of poor reagent selectivity, enhance the effect of the sulfiding agent, promote the selective adsorption of the collector, and thus improve the recovery rate of copper and cobalt metals in oxidized copper-cobalt ore under conditions of severe ore muddiness. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a flow chart of the method of Examples 1-3 of the present invention. DETAILED DESCRIPTION

[0022] The present invention will be further described below in conjunction with the accompanying drawings. It should be noted that this embodiment is based on the technical solution and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to this embodiment.

[0023] Example 1

[0024] This embodiment provides a beneficiation method for easily muddy copper-cobalt oxide ore, such as Figure 1 As shown, the specific process is:

[0025] The raw ore was crushed to a particle size of ≤2 mm using a New Zealand crusher, mixed evenly, and set aside. A 500 g sample of the mixed mixture was mixed with 215 mL of water and placed in a ball mill with an iron ball filling rate of 32%. The ore was ground for 3.5 minutes to obtain a flotation product, of which the fraction with a particle size of ≤74 μm accounted for 72% of the total mass.

[0026] The flotation products obtained above were subjected to five-stage fully open-circuit sulfur-oxygen mixed flotation. Considering the serious muddiness of the ore, the first stage flotation process did not add the combined regulator, but added the regulator sodium hydrosulfide 600g / t dry weight of the ore (stirred for 2 minutes), the collector amyl xanthate 600g / t dry weight of the ore (stirred for 2 minutes) and 2 #The oil content is 30g / t dry weight of the ore (stirring for 1 minute). Pre-flotation removes a portion of fine mud (the first flotation period is 5 minutes). This reduces the impact of fine mud on subsequent flotation and reduces the amount of high-efficiency combined modifiers, thereby reducing reagent costs. During the first flotation stage, the slurry pH is maintained at an alkaline environment of 9.5, and the slurry mass concentration is approximately 30%.

[0027] Before the second and third stages of flotation, a high-efficiency combined adjuster (sodium citrate 100g / t dry weight of the raw ore + sodium hydrosulfide 400g / t dry weight of the raw ore) was first added and stirred for 2 minutes. Then, a collector of amyl xanthate (PAX) 400g / t dry weight of the raw ore was added and stirred for 2 minutes before starting flotation. The second and third flotation stages each last 5 minutes. Before the fourth flotation stage, a high-efficiency combined collector (50 g sodium citrate / t dry weight of the ore + 300 g sodium hydrosulfide / t dry weight of the ore) is added and stirred for 2 minutes, followed by the addition of 300 g amyl xanthate (PAX) and stirring for 2 minutes. The flotation time is 4 minutes. Before the fifth flotation stage, a high-efficiency combined collector (50 g sodium citrate / t dry weight of the ore + 50 g sodium hydrosulfide / t dry weight of the ore) is added and stirred for 2 minutes. The flotation time is 3 minutes. The tailings remaining from each flotation stage are fed to 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 fifth flotation stage are the final tailings.

[0028] In this embodiment, during the entire flotation process, the total dosage of the high-efficiency combined adjuster is 1450 g / t of the dry weight of the raw ore, including 300 g / t of sodium citrate and 1150 g / t of the dry weight of the raw ore, and the total dosage of the collector amyl xanthate (PAX) is 1900 g / t of the dry weight of the raw ore.

[0029] In the above method, under a flotation environment with severe ore sliming, conventional adjusting agent sodium hydrosulfide, collector and frother are first used to float out a portion of fine mud. Starting from the second flotation stage, a high-efficiency combined adjusting agent (sodium citrate + sodium hydrosulfide) is first added for activation and slurry adjustment, and then amyl xanthate collector is added. After five full open-circuit sulfur-oxygen mixed flotation processes, copper-cobalt oxide concentrate is obtained.

[0030] Example 2

[0031] The method flow of this embodiment is the same as that of Example 1, with the main difference being that the total amount of the high-efficiency combined adjusting agent used is 1450 g / t of the dry weight of the original ore, which includes 350 g / t of sodium citrate and 1100 g / t of the dry weight of the original ore.

[0032] Before the second and third stages of flotation, a high-efficiency combined adjuster (sodium citrate 100g / t dry weight of the raw ore + sodium hydrosulfide 400g / t dry weight of the raw ore) was first added and stirred for 2 minutes. Then, a collector of amyl xanthate (PAX) 400g / t dry weight of the raw ore was added and stirred for 2 minutes before starting flotation. The second and third flotation stages each last 5 minutes. Prior to the fourth flotation stage, a high-efficiency combined collector (100g / t sodium citrate + 200g / t sodium hydrosulfide) is added and stirred for 2 minutes, followed by the addition of 300g / t amyl xanthate (PAX) and stirring for 2 minutes. The flotation process lasts for 4 minutes. Prior to the fifth flotation stage, a high-efficiency combined collector (50g / t sodium citrate + 100g / t sodium hydrosulfide) is added and stirred for 2 minutes. The addition of 200g / t amyl xanthate (PAX) and stirring for 2 minutes are followed by the addition of 3 minutes. The tailings remaining from each flotation stage are fed to the next flotation stage. The concentrates from each flotation stage are mixed to form the final copper-cobalt oxide concentrate. The tailings remaining after the fifth flotation stage are the final tailings.

[0033] Example 3

[0034] The method flow of this embodiment is the same as that of Example 1, with the main difference being that the total amount of the high-efficiency combined adjusting agent used is 1450 g / t dry weight of the original ore, which includes 250 g / t dry weight of sodium citrate and 1200 g / t dry weight of sodium hydrosulfide.

[0035] Before the second and third stages of flotation, a high-efficiency combined adjuster (sodium citrate 100g / t dry weight of the raw ore + sodium hydrosulfide 400g / t dry weight of the raw ore) was first added and stirred for 2 minutes. Then, a collector of amyl xanthate (PAX) 400g / t dry weight of the raw ore was added and stirred for 2 minutes before starting flotation. The second and third flotation stages each last 5 minutes. Prior to the fourth flotation stage, a high-efficiency combined collector (30 g sodium citrate / t dry weight of the ore + 200 g sodium hydrosulfide / t dry weight of the ore) is added and stirred for 2 minutes, followed by the addition of 300 g amyl xanthate (PAX) collector and stirring for 2 minutes. The flotation time is 4 minutes. Prior to the fifth flotation stage, a high-efficiency combined collector (20 g sodium citrate / t dry weight of the ore + 200 g sodium hydrosulfide / t dry weight of the ore) is added and stirred for 2 minutes. Subsequently, 200 g amyl xanthate (PAX) collector is added and stirred for 2 minutes. The flotation time is 3 minutes. The tailings remaining from each flotation stage are fed to the next flotation stage. The concentrates from each flotation stage are mixed to form the final copper-cobalt oxide concentrate. The tailings remaining after the fifth flotation stage are the final tailings.

[0036] Comparative Example 1

[0037] A copper-cobalt oxide ore, with a raw ore content of approximately 2.30% copper and 0.20% cobalt, has the following characteristics: ① a high oxidation rate of approximately 95%; ② severe mudification, poor separation efficiency between useful minerals and gangue minerals, and low copper and cobalt metal recovery rates. The copper metal in the ore is primarily found in malachite, chalcocite, and chalcocite, while the cobalt metal is primarily distributed in hydrocobaltite, pyrocobaltite, and styraxite. The gangue minerals, primarily dolomite, quartz, and chlorite, are severely muddied. Due to this muddiing, the separation efficiency of the flotation concentrate using conventional conditioning agents is poor, resulting in low copper and cobalt recovery rates. The ore was treated using the mineral processing method described in Example 1 of the present invention, and the resulting indicators are shown in Table 1.

[0038] Using the same ore as above, the high-efficiency combined regulator in Example 1 was replaced with a conventional regulator, sodium hydrosulfide, as Comparative Example 1. The total amount of the conventional regulator was 2050 g / t dry weight of the ore.

[0039] The process indicators of Example 1 and Comparative Example 1 are shown in Table 1

[0040] Table 1

[0041]

[0042] As can be seen from Table 1, this embodiment achieves better mineral processing indicators. The test results show that the copper recovery rate of the method of Example 1 is increased by 4.66%, the cobalt recovery rate is increased by 1.64%, the copper grade is increased by 0.55%, and the cobalt grade is increased by 0.09%.

[0043] Comparative Example 2

[0044] A copper-cobalt oxide ore contains approximately 2.00% copper and 0.10% cobalt. Its characteristics are: ① a high oxidation rate, approximately 96% for copper and cobalt; ② low copper and cobalt metal recovery efficiencies. The copper mineral in the ore is primarily malachite; the iron mineral is primarily limonite; other metals include cobaltite and a small amount of pyrocobaltite; and non-metallic cobalt minerals include quartz, dolomite, and chlorite. Conventional conditioning agents result in low copper and cobalt recovery.

[0045] The ore was processed by the ore dressing method in Example 2 of the present invention, and the obtained process indicators are shown in Table 2.

[0046] Using the same ore as above, the high-efficiency combined regulator in Example 2 was replaced by the conventional regulator sodium hydrosulfide as Comparative Example 2. The total amount of the conventional regulator was 2050 g / t dry weight of the ore.

[0047] The process indicators of Example 2 and Comparative Example 2 are shown in Table 1

[0048] Table 2

[0049]

[0050] As can be seen from Table 2, the method of Example 2 achieved better mineral processing indicators. The test results showed that the copper recovery rate of the method of Example 2 increased by 1.99%, and the cobalt recovery rate increased by 0.24%.

[0051] Those skilled in the art can make various corresponding changes and modifications based on the above technical solutions and concepts, and all of these changes and modifications should be included in the scope of protection of the claims of the present invention.

Claims

1. A beneficiation method for easily muddy copper-cobalt oxide ore using a high-efficiency combined regulator, characterized in that: The high-efficiency combined regulator comprises 250-350 parts of sodium citrate and 1100-1200 parts of sodium hydrosulfide in parts by weight; The mineral processing method comprises the following steps: S1, crush the raw ore and set aside; S2, taking the crushed ore obtained in step S1, mixing it with water and grinding it to obtain a floatable product; S3, the floatable product obtained in step S2 is subjected to multi-stage mixed flotation of sulfide ore and oxide ore; in the first stage flotation process, a regulating agent NaHS, a collector and a frother are added to pre-float out a portion of fine mud; in the first stage flotation, the pH of the ore pulp is 9-10, and the mass concentration of the ore pulp is 28-34%; in the first stage flotation, the amount of regulating agent NaHS is 500-700g / t dry weight of the original ore, the collector used includes amyl xanthate, the amount used includes 2 # Oil, the dosage is 20-40g / t dry weight of ore; After the first stage of flotation is completed, the tailings remaining after a portion of fine mud is floated out are subjected to subsequent flotation; before each subsequent stage of flotation, the high-efficiency combined adjuster and the collector amyl xanthate are pre-added, and after stirring and slurrying, flotation is performed to obtain concentrate and tailings. The tailings remaining in each stage of flotation enter the next stage of flotation, and the concentrates obtained in each stage of flotation are mixed to obtain the final copper-cobalt oxide concentrate. The tailings remaining after the fifth stage of flotation are the final tailings; The total amount of the high-efficiency combined adjusting agent used in all stages of flotation is 250-350 g / t of raw ore dry weight of sodium citrate and 1100-1200 g / t of raw ore dry weight of sodium hydrosulfide.

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

3. The method according to claim 1, characterized in that In step S2, the ore is ground using a ball mill, which uses iron ball media and has a filling rate of 32%.

4. The method according to claim 1, wherein In the floatable product obtained in step S2, the portion with a particle size of ≤74 μm accounts for 67-77% of the total mass of the floatable product.

5. The method according to claim 1, wherein In step S3, the total amount of amyl xanthate used as the collector in all flotation stages is 1800-1900 g / t dry weight of the raw ore.

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