Surface altered copper oxide ore flotation composite regulator, application and recovery method

Abstract

The invention relates to the technical field of copper oxide beneficiation, in particular to a surface altered copper oxide ore flotation composite regulator and application and recovery methods thereof. The composite regulator is composed of sodium pyrophosphite, PAC, sulfonated tannin, sodium lignin sulfonate and sodium fluosilicate; the weight ratio of the sodium pyrophosphite to the PAC to the sulfonated tannin to the sodium lignin sulfonate to the sodium fluosilicate is (5-10): (1-3): (5-10): (15-20): (5-10); under the action of targeting of a composite regulator and surface active points of alkaline earth metal minerals and aluminosilicate minerals, the slime is selectively dispersed, gangue minerals are inhibited, attachment of the slime to the surfaces of the copper minerals is eliminated, and interference of the slime to the action of the copper minerals and agents and flotation is reduced; the recovery method is stable and reliable, the copper recovery rate is high, the cost is low, the process is easy to control, and the technical problem that surface altered copper oxide ore beneficiation and recovery are difficult is solved.

Description

Technical Field

[0001] The invention relates to the technical field of copper oxide beneficiation, and in particular to a composite flotation regulator for surface altered copper oxide ore, and an application and recovery method thereof. Background Art

[0002] The reserves of copper oxide resources are large. As far as the world's copper resources are concerned, copper oxide ores account for about 10-15% of all copper deposits, and copper metal accounts for about 25% of the total reserves. Copper oxide ores are difficult to select, and only a very small part of the original gangue type is easy to select and recover, and has achieved successful production practice. Most of them are located on the surface. Due to long-term influence of factors such as weathering and water seepage alteration, the crystal lattice is incomplete, the degree of silicification is high, the ore mud content is high, the copper mineral floatability is poor, and some clay-type ore muds have good floatability when adsorbing copper ions, making it difficult to select and recover. The selection technology of complex altered high-mud difficult-to-select copper oxide ores is a global problem.

[0003] On the one hand, with the increasing consumption of sulfide ore and rich ore resources, the development and utilization of oxide ore resources is imperative; second, with the development of my country's social economy, its demand continues to increase. However, under the current technical conditions in my country, the mineral resources available for industrial mining and utilization are seriously insufficient, and self-produced concentrates cannot meet the needs of smelting and consumption, and a large amount of imports are required. The breakthrough of difficult-to-select copper oxide technology can reduce my country's dependence on copper imports; third, most of the complex altered high-mud difficult-to-select copper oxide resources are currently on hold due to economic and technical indicators. It is of great significance to carry out technical research and master the development technology to make its resource utilization economically and technically feasible. Summary of the invention

[0004] The present invention provides a composite flotation regulator for surface altered oxidized copper ore, its application and recovery method, which overcomes the deficiencies of the above-mentioned prior art and can effectively solve the problem of difficulty in ore dressing and recovery of surface altered oxidized copper ore.

[0005] To solve the above problems, one of the technical solutions of the present invention is achieved in the following way: a composite flotation adjuster for surface altered oxidized copper ore, which is composed of sodium pyrophosphite, PAC, sulfonated tannin, sodium lignin sulfonate and sodium fluorosilicate; the weight ratio of the sodium pyrophosphite, PAC, sulfonated tannin, sodium lignin sulfonate and sodium fluorosilicate is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 5~10:1~3:5~10:15~20:5~10.

[0006] The second technical solution of the present invention is achieved by the following method: application of a composite flotation regulator for surface altered oxidized copper ore, wherein the composite regulator is used for recovering copper oxide from the oxidized copper ore.

[0007] The third technical solution of the present invention is achieved by the following method: a method for recovering copper oxide by flotation of a surface altered copper oxide ore using a composite regulator, comprising the following steps: The first step is ore grinding and slurry pH adjustment: the ore, pH adjuster and water are fed into the mill for grinding, and the copper oxide minerals and gangue mineral monomers are dissociated; the grinding fineness is -0.074mm, accounting for 70~80%; The second step is to adjust the slurry with an adjusting agent to suppress gangue: water is added to the grinding slurry product obtained in the first step to adjust the slurry concentration to 25-32%, and then 500-900g / t of ore of a composite adjusting agent is added to suppress gangue minerals, and at the same time, the ore mud attached to the surface of the copper mineral is cleaned by the dispersing effect of the adjusting agent; The third step is deep sulfidation of copper minerals: add ammonium salt and sulfiding agent to the slurry adjusted in the second step, among which the positioning ion NH4 + Used to adsorb on the active points of mineral surfaces, increase the zeta potential of copper oxide minerals, target the anions of the sulfiding agent, and improve the sulfidation efficiency and stability of the sulfidation layer; The fourth step is to eliminate the inhibitory effect of the sulfidation process: after the deep sulfidation in the third step, the residual sulfiding agent in the pulp has a strong reducing property, which reduces the redox potential of the pulp and inhibits the oxidation of copper minerals. The inhibitory effect of the sulfidation process is eliminated by adding a weak oxidant to adjust the redox potential; The fifth step is to capture and recover copper minerals: After the inhibition of the sulfidation process in the fourth step is eliminated, collectors and frothers are added to carry out flotation recovery of oxidized copper ore using conventional flotation processes.

[0008] The pH adjuster is lime or sodium hydroxide.

[0009] In the third step, the amount of sulfiding agent is 25%-50% of the copper metal amount per ton of ore; the amount of ammonium salt is 60%-100% of the amount of sulfiding agent; the ammonium salt is ammonium sulfate or ammonium chloride; the sulfiding agent is one of sodium sulfide, sodium hydrosulfide or sodium polysulfide.

[0010] In the fourth step, when the inhibitory effect of the sulfidation process is eliminated by adding a weak oxidant, the operation method is different according to the type of the weak oxidant. If the weak oxidant is a gas, the slurry is aerated. If the weak oxidant is a solid, a solution is prepared and added. The oxidant is one of air, sodium persulfate, and ammonium persulfate.

[0011] Compared with the prior art, the present invention has the following advantages: 1. The present invention aims at the technical problem that the surface altered and difficult-to-select oxidized copper ore is affected by weathering, water immersion, etc., the loss of metal ions on the surface of copper minerals weakens its activity, the adsorption and self-activation of copper ions in gangue minerals, the similarity of mineral floatability and the deterioration of mudification make the separation and enrichment of copper minerals difficult. The present invention adopts a composite regulator to target the surface active points of alkaline earth metal minerals and aluminosilicate minerals, selectively disperses the ore mud, inhibits the gangue minerals, eliminates the adhesion of the ore mud on the surface of the copper mineral, and reduces the interference of the ore mud on the copper mineral and the reagent and flotation. Therefore, the recovery method of the present invention is stable and reliable, with a high copper recovery rate, low cost, and easy process control, which solves the technical problem of difficult ore dressing and recovery of surface altered oxidized copper ore. In addition, the composite regulator of the present invention has the advantages of low toxicity, good selectivity, good dispersion effect of gangue minerals and ore mud inhibition, and low reagent cost.

[0012] 2. The present invention uses the copper-ammonium complexing property to target and increase the zeta potential of copper minerals, attract the anions of the sulfiding agent, improve the sulfidation efficiency and the stability of the sulfidation layer, and achieve the purpose of deep sulfidation.

[0013] 3. The present invention eliminates the influence of residual sulfiding agent on the redox potential of the pulp through weak oxidation, eliminates the inhibitory effect of the sulfiding agent in the deep sulfidation process, indirectly improves the floatability of copper oxide minerals, and provides guarantee for subsequent efficient recovery. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0015] Figure 1 The present invention is a flow chart of a method for recovering copper oxide in an embodiment of the present invention. DETAILED DESCRIPTION

[0016] The present invention is not limited by the following embodiments, and specific implementation methods can be determined based on the technical solution of the present invention and actual conditions.

[0017] Example 1: The embodiment of the present invention discloses a composite flotation adjuster for surface altered oxidized copper ore, which is composed of sodium pyrophosphite, PAC, sulfonated tannin, sodium lignin sulfonate and sodium fluorosilicate; the weight ratio of the sodium pyrophosphite, PAC, sulfonated tannin, sodium lignin sulfonate and sodium fluorosilicate is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 5~10:1~3:5~10:15~20:5~10.

[0018] Example 2: The embodiment of the present invention discloses the application of a composite flotation regulator for surface altered oxidized copper ore, wherein the composite regulator is used for recovering copper oxide from the oxidized copper ore.

[0019] Example 3: The present invention discloses a method for recovering copper oxide by flotation of a surface altered copper oxide ore using a composite regulator, comprising the following steps: The first step is ore grinding and pulp pH adjustment: feed ore, pH adjuster and water into the mill for grinding, and separate copper oxide minerals from gangue mineral monomers; the grinding fineness is -0.074mm, accounting for 70~80%. During the grinding process, the pH adjuster fully reacts with the pulp to adjust the pH of the grinding product pulp to 7-9, wherein the pH adjuster is a conventional pH adjuster, such as lime, sodium hydroxide, etc.

[0020] The second step is to adjust the slurry with an adjusting agent to inhibit gangue: add water to the grinding slurry product obtained in the first step to adjust the slurry concentration to 25-32%, then add 500-900g / t of ore of a composite adjusting agent to inhibit gangue minerals, and at the same time, clean the sludge attached to the surface of the copper mineral through the dispersing effect of the adjusting agent; the adjusting agent adjusts the slurry to inhibit gangue for 3 minutes.

[0021] The third step is deep sulfidation of copper minerals: add ammonium salt and sulfiding agent to the slurry adjusted in the second step, among which the positioning ion NH4 + It is used to adsorb on the active points of the mineral surface, increase the zeta potential of copper oxide minerals, target the anions of the sulfiding agent, and improve the sulfidation efficiency and the stability of the sulfidation layer; thereby, a deep sulfidation effect is achieved; the sulfidation time of the sulfiding agent is 2-3 minutes; among them, the ammonium salt is a conventional ammonium salt, such as ammonium sulfate, ammonium chloride, etc., and the sulfiding agent is a conventional sulfiding agent, such as sodium sulfide, sodium hydrosulfide, sodium polysulfide, etc.; the amount of sulfiding agent is 25%-50% of the amount of copper metal per ton of ore; the amount of ammonium salt is 60%-100% of the amount of sulfiding agent.

[0022] The fourth step is to eliminate the inhibitory effect of the sulfidation process: After the deep sulfidation in the third step, the strong reducing property of the residual sulfiding agent in the slurry reduces the redox potential of the slurry, and the oxidation of copper minerals is inhibited. The inhibitory effect of the sulfidation process is eliminated by adjusting the redox potential by adding a weak oxidant; wherein, the time for adding a weak oxidant to adjust the redox potential to eliminate the inhibitory effect of the sulfidation process is 2-5 minutes.

[0023] The fifth step is to capture and recover copper minerals: After the inhibition of the sulfidation process in the fourth step is eliminated, collectors and frothers are added to carry out flotation recovery of oxidized copper ore using conventional flotation processes.

[0024] Among them, in the fourth step, when the inhibitory effect of the sulfidation process is eliminated by adding a weak oxidant, the operation method is different according to the type of the weak oxidant. If the weak oxidant is a gas, the slurry is aerated, and if the weak oxidant is a solid, a solution is prepared and added; the oxidant is one of air, sodium persulfate, and ammonium persulfate.

[0025] Example 2: The surface of an open pit of a copper mine in Xinjiang is covered with oxidized copper ore, with a copper grade of 1.02% and a copper oxidation rate of 93.40%, of which free oxidized copper accounts for 72.20% and combined oxidized copper accounts for 21.20%. The gangue minerals are mainly epidote, garnet, potassium feldspar, calcite, and dolomite. The conventional sulfide flotation copper recovery rate is only 28%, and the environmental risk of stockpiling is too high, so a flotation recovery test of oxidized copper was carried out. The details are as follows: The ratio of the composite regulator is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 7:3:10:15:5. Add 7 units of sodium pyrophosphite, 3 units of PAC, 10 units of sulfonated tannin, 15 units of sodium lignin sulfonate and 5 units of sodium fluorosilicate into a beaker, then add 960 units of water, stir and dissolve to prepare a 4% concentration.

[0026] First, add 200g / t lime to the ore and then add water to grind the ore to a fineness of -0.074mm, accounting for 80%.

[0027] Water was added to the grinding slurry to adjust the slurry concentration to 32%, and 500 g / t of composite adjusting agent was added, and the slurry was adjusted for 3 minutes.

[0028] Then add 1500g / t ore ammonium sulfate and 2600g / t ore sodium hydrosulfide, and perform deep sulfidation for 3 minutes.

[0029] Then add 100g / t sodium persulfide to eliminate the inhibition of copper minerals by residual sodium hydrosulfide in the slurry for 2 minutes.

[0030] Then, 30g / t alkyl hydroxamic acid and 200g / t amyl xanthate were added as collectors, and 50g / t 2# oil was used as a frother. After one roughing, two cleanings and one scavenging, the copper concentrate with a copper grade of 18.89% and a recovery rate of 63.56% was finally produced, achieving efficient recovery of the ore.

[0031] Example 3: A copper-gold-silver oxidized mine in Kyrgyzstan, with a copper grade of 0.68%, an oxidation rate of 98.54%, 76.44% of free oxidized copper, 22.10% of combined oxidized copper, a gold grade of 1.5 g / t, and a silver grade of 5.2 g / t. The gangue minerals are mainly diopside and garnetite, and contain a large amount of talc, chlorite and serpentine. A comprehensive recovery study of copper, gold and silver was conducted, as follows: The ratio of the composite adjusting agent is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 10:2:5:20:10. The preparation method is as shown in Example 2.

[0032] First, add 500g / t lime to the ore and then add water to grind the ore to a fineness of -0.074mm, accounting for 70%.

[0033] Water was added to the grinding slurry to adjust the slurry concentration to 27%, MIBC 40g / t ore was added for desliming flotation, and a composite adjuster 800g / t ore was added to the bottom of the desliming flotation tank, and the slurry was adjusted for 3 minutes.

[0034] Then add 1000g / t ore ammonium sulfate and 1600g / t ore sodium hydrosulfide and perform deep sulfidation for 2 minutes.

[0035] Air is then added through aeration and stirring to eliminate the inhibition of the copper minerals by the residual sodium hydrosulfide in the slurry for 5 minutes.

[0036] 20g / t butyl ammonium black powder, 220g / t amyl xanthate, and 25g / t kerosene were added as collectors, and 10g / t MIBC was used as a frother. After two roughing selections, two cleaning selections, and one scavenging selection, the final concentrate produced had a copper grade of 16.02% and a recovery rate of 46.56%, a gold grade of 48.69g / t, and a recovery rate of 64.15%, and a silver grade of 94.5g / t, with a recovery rate of 58.36%, thus achieving efficient recovery of the ore resources.

[0037] Example 4: A copper-gold oxidized mine in Kyrgyzstan, with a copper grade of 0.42%, an oxidation rate of 99.01%, 82.61% free oxidized copper, 6.40% combined oxidized copper, 2.85g / t gold grade, and 5.2g / t gold grade. The gangue minerals are mainly hematite, limonite, and quartz. A study on the comprehensive recovery of copper and gold is conducted as follows: The ratio of the composite adjusting agent is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 5:1:7:18:6. The preparation method is as shown in Example 2.

[0038] First, add 300g / t ore sodium hydroxide and water to grind the ore to a fineness of -0.074mm, accounting for 75%.

[0039] Water was added to the grinding slurry to adjust the slurry concentration to 27%, and 650 g / t of composite adjusting agent was added to the ore, and the slurry was adjusted for 3 minutes.

[0040] Then add 1700g / t ore ammonium sulfate and 1700g / t ore sodium sulfide, and perform deep sulfidation for 3 minutes.

[0041] Air is then added through aeration and stirring to eliminate the inhibition of the copper minerals by the residual sodium hydrosulfide in the slurry for 5 minutes.

[0042] 50g / t butyl ammonium black powder, 120g / t butyl xanthate, 15g / t light white oil were added as collectors, and 20g / t 2# oil was used as a frother. After two roughing selections, two fine selections and one scavenging selection, the final output was a concentrate with a copper grade of 11.04% and a recovery rate of 61.21%, a gold grade of 88.19g / t and a recovery rate of 72.06%.

[0043] Example 5: A copper oxide mine in Tibet, with a copper grade of 1.85%, an oxidation rate of 72.00%, 50.32% of free copper oxide, and 21.68% of combined copper oxide. The gangue mineral is mainly hornblende. The recovery study is as follows: The ratio of the composite adjusting agent is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 8:2:8:16:7. The preparation method is as shown in Example 1.

[0044] First, add 1000g / t sodium carbonate to the ore and grind it with water to a fineness of -0.074mm, accounting for 70%.

[0045] Water was added to the grinding slurry to adjust the slurry concentration to 27%, and 750 g / t of composite adjusting agent was added to the ore, and the slurry was adjusted for 3 minutes.

[0046] Then add 3300g / t ore ammonium sulfate and 5000g / t ore sodium polysulfide, and perform deep sulfidation for 3 minutes.

[0047] Air is then added through aeration and stirring to eliminate the inhibition of the copper minerals by the residual sodium hydrosulfide in the slurry for 4 minutes.

[0048] Then 120g / t butyl xanthate and 20g / t mercaptobenzothiazole were added as collectors, and 30g / t 2# oil was used as a frother. After two roughing selections, two cleaning selections and two scavenging selections, the final output was a concentrate with a copper grade of 23.04% and a recovery rate of 67.45%.

[0049] Example 6: A copper oxide mine in Tibet, with a copper grade of 0.78%, an oxidation rate of 85.29%, 82.19% of free copper oxide, and 3.10% of combined copper oxide. The gangue minerals are mainly diopside, quartz, and epidote. The recovery research is as follows: The ratio of the composite adjusting agent is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 9:1:6:15:5. The preparation method is as shown in Example 1.

[0050] First, add 200g / t ore lime and water to grind the ore to a fineness of -0.074mm accounting for 74%.

[0051] Water was added to the grinding slurry to adjust the slurry concentration to 31%, and 800 g / t of composite adjusting agent was added, and the slurry was adjusted for 3 minutes.

[0052] Then add 1500g / t ore ammonium sulfate and 2000g / t ore sodium polysulfide, and perform deep sulfidation for 2 minutes.

[0053] Then add 150g / t sodium persulfide to eliminate the inhibition of copper minerals by residual sodium hydrosulfide in the slurry for 3 minutes.

[0054] Then, 120 g / t butyl xanthate and 30 g / t salicylic acid were added as collectors, and 30 g / t MIBC was used as a frother. After one roughing, two cleaning and two scavenging processes, the final copper concentrate was 21.16% and the recovery rate was 54.29%.

[0055] The invention can be widely applicable to the comprehensive recovery of copper, gold and silver when the ores are associated with gold, silver and other metals, and the ores are oxidized copper-gold ore, oxidized copper-silver ore and oxidized gold-silver-copper ore.

[0056] In summary, the embodiments of the present invention target the technical problems that the surface altered and difficult-to-select oxidized copper ore is affected by weathering, water immersion, etc., the loss of metal ions on the surface of copper minerals weakens its activity, the adsorption and self-activation of copper ions in gangue minerals, the similarity of mineral floatability and the deterioration of mudification make the separation and enrichment of copper minerals difficult. The present invention adopts a composite regulator to target the surface active points of alkaline earth metal minerals and aluminosilicate minerals, selectively disperses the ore mud, inhibits gangue minerals, eliminates the adhesion of ore mud on the surface of copper minerals, and reduces the interference of ore mud on the action of copper minerals with reagents and flotation; therefore, the recovery method of the present invention is stable and reliable, with high copper recovery rate, low cost, and easy process control, which solves the technical problem of difficult ore dressing and recovery of surface altered and oxidized copper ore; and the composite regulator of the present invention has the advantages of low toxicity, good selectivity, good dispersion effect of gangue minerals and ore mud inhibition, and low reagent cost.

[0057] In addition, the present invention uses the copper-ammonium complexing property to improve the zeta potential of copper minerals in a targeted manner, attract the anions of the sulfiding agent, improve the sulfidation efficiency and the stability of the sulfidation layer, and achieve the purpose of deep sulfidation.

[0058] Furthermore, the present invention eliminates the influence of residual sulfiding agent on the redox potential of the pulp through weak oxidation, eliminates the inhibitory effect of the sulfiding agent in the deep sulfidation process, indirectly improves the floatability of copper oxide minerals, and provides a guarantee for subsequent efficient recovery.

Claims

1. A composite flotation regulator for surface altered copper oxide ore, characterized in that: The composite regulator is composed of sodium pyrophosphite, PAC, sulfonated tannin, sodium lignin sulfonate and sodium fluorosilicate; the weight ratio of the sodium pyrophosphite, PAC, sulfonated tannin, sodium lignin sulfonate and sodium fluorosilicate is: sodium pyrophosphite: PAC: sulfonated tannin: sodium lignin sulfonate: sodium fluorosilicate = 5~10:1~3:5~10:15~20:5~10.

2. Application of a composite flotation regulator for surface altered copper oxide ore, characterized in that: The composite adjusting agent is used for recovering copper oxide from copper oxide ore.

3. A method for recovering copper oxide from surface altered copper oxide ore by flotation of composite regulator, characterized in that: The following steps are involved: The first step is ore grinding and slurry pH adjustment: the ore, pH adjuster and water are fed into the mill for grinding, and the copper oxide minerals and gangue mineral monomers are dissociated; the grinding fineness is -0.074mm, accounting for 70~80%; The second step is to adjust the slurry with an adjusting agent to suppress gangue: water is added to the grinding slurry product obtained in the first step to adjust the slurry concentration to 25-32%, and then 500-900g / t of ore of a composite adjusting agent is added to suppress gangue minerals, and at the same time, the ore mud attached to the surface of the copper mineral is cleaned by the dispersing effect of the adjusting agent; The third step is deep sulfidation of copper minerals: add ammonium salt and sulfiding agent to the slurry adjusted in the second step, among which the positioning ion NH4 + Used to adsorb on the active points of mineral surfaces, increase the zeta potential of copper oxide minerals, target the anions of the sulfiding agent, and improve the sulfidation efficiency and stability of the sulfidation layer; The fourth step is to eliminate the inhibitory effect of the sulfidation process: after the deep sulfidation in the third step, the residual sulfiding agent in the pulp has a strong reducing property, which reduces the redox potential of the pulp and inhibits the oxidation of copper minerals. The inhibitory effect of the sulfidation process is eliminated by adding a weak oxidant to adjust the redox potential; The fifth step is to capture and recover copper minerals: After the inhibition of the sulfidation process in the fourth step is eliminated, collectors and frothers are added to carry out flotation recovery of oxidized copper ore using conventional flotation processes.

4. The method for recovering copper oxide by using a composite flotation regulator for surface altered copper oxide ore according to claim 3, characterized in that: The pH adjuster is lime or sodium hydroxide.

5. The method for recovering copper oxide by using a composite flotation regulator for surface altered copper oxide ore according to claim 3, characterized in that: In the third step, the amount of sulfiding agent used is 25%-50% of the amount of copper metal per ton of ore; the amount of ammonium salt used is 60%-100% of the amount of sulfiding agent used; the ammonium salt is ammonium sulfate or ammonium chloride; and the sulfiding agent is one of sodium sulfide, sodium hydrosulfide or sodium polysulfide.

6. The method for recovering copper oxide by using a composite flotation regulator for surface altered copper oxide ore according to claim 3, characterized in that: In the fourth step, when the inhibitory effect of the sulfidation process is eliminated by adding a weak oxidant, the operation method is different according to the type of the weak oxidant. If the weak oxidant is a gas, the slurry is aerated, and if the weak oxidant is a solid, a solution is prepared and added; the oxidant is one of air, sodium persulfate, and ammonium persulfate.

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