Research progress on flotation process technology of copper oxide ore

Vulcanization flotation is currently the main method for the treatment of copper oxide ore in the industry. It is suitable for carbonate-bearing copper oxide ore, such as malachite, azurite, ortho-copper, etc., while the chrysocolla is not specially treated in advance. , the vulcanization effect is very poor, the base can not be vulcanized. The key to vulcanization flotation is to strictly control the amount of sodium sulfide. The appropriate amount of sodium sulfide is the copper oxide mineral activator. After exceeding the critical amount, sodium sulfide is the inhibitor of copper sulfide mineral. In order to reduce or prevent this inhibition, segmentation dosing is often used in industrial production to control the concentration of vulcanizing agent in the slurry. At present, the application sulfide flotation beneficiation plant in Hubei Tonglushan concentrator, Tongling Chemical Industry Group Xinqiao mining companies.

Jiang Taiguo et al. studied the effect of ammonium (amine) salt on the sulfide flotation behavior of copper oxide ore in the low-grade high oxidation rate refractory copper ore in Sichuan. The results show that ethylenediamine phosphate and ammonium bicarbonate in a 1: 3 best combination, closed-circuit test obtained copper concentrate grade of 19.01% copper, 83.31% copper recovery, compared to the direct flotation of sulfide, copper concentrate The copper grade and recovery rate in the mine increased by 4.05% and 12.42%, respectively. Liu Dianwen et al. studied the vulcanization promoting effect of ammonium sulfate in the vulcanization flotation process of malachite. It was found that in the case of ammonium sulfate, the inhibition effect of excessive sodium sulfide on malachite can be avoided. Studies have shown that with the promotion of ammonium sulfate, the copper recovery rate can be increased by 8% to 10%, or even 20%; at the same time, the copper grade of the concentrate is significantly improved, and when the amount of ammonium sulfate and sodium sulfide is approximately equal, the recovery rate is highest. point.

A copper oxide ore has a high copper content, the oxidation rate reaches 90.58% and the combined copper content accounts for 28.92%, which is a difficult to choose copper oxide ore. Gu Qingxiang uses a vulcanization flotation process and is divided into eight sections to be selected. A copper concentrate with a copper grade of 25.61% and a copper recovery of 74.79% was obtained. Ye Fuxing et al. analyzed the adverse effects of a large amount of sodium sulfide added to the flotation system in a complex copper oxide ore flotation study with silver . The method of adding sodium sulfide in three stages, the recovery rate of copper and one-off Compared with dosing, it increased by 2.68%. A large-scale iron ore deposit in Yunnan is associated with low-grade copper oxide ore. The copper grade of ore is 0.34%. It is a complex refractory copper oxide with low grade, high copper oxidation rate, high secondary copper content, high combined copper oxide content and many copper minerals. ore. Luo Liangfei et al. added a small amount of salicyl hydroxamic acid as an auxiliary collector on the basis of the traditional vulcanization flotation process, and heated the slurry to 30 ° C. After three-stage vulcanization flotation, the copper concentrate contained 21.48% copper in the closed circuit test. The copper recovery rate is 70.33% of the test index.

Chen Jinghua et al. proposed a simultaneous flotation process for copper sulfide ores, and proposed a synchronous flotation process and an asynchronous flotation process. The key to synchronous flotation and asynchronous flotation is the matching of process flow and pharmaceutical system. In the formulation of the copper oxide ore beneficiation process, it is necessary to rely on the nature of the ore, especially the type and floatability of the copper mineral. 1. N.Babich et al. discussed the separation process of Udokan mixed copper ore, and obtained the best pH value of flotation copper sulfide minerals, and the best flotation copper oxide minerals. The pH value is 10, and the staged flotation process of copper sulfide ore and copper oxide ore is used to obtain a copper recovery rate of 89%, which is 4.8% higher than that of the mixed flotation. A copper oxide ore in Shanxi has high oxidation rate and high mud content. It is a refractory copper oxide ore. Tang Pingyu et al. used a synchronous flotation process of sulfide ore oxidized ore, supplemented with high-efficiency copper oxide ore activator JH, and closed copper test to obtain copper fines. The mine contains 18.34% copper and 81.36% copper recovery.

Direct flotation methods include organic acid flotation and amine collector flotation. Organic acid flotation method is also called fatty acid flotation method. This method is suitable for the selection of copper oxide minerals with malachite as the main copper-bearing mineral and gangue as the main gangue. The flotation rule of amine collector suitable for flotation of lead oxide, copper oxide, zinc, copper oxide ore as compared to sulfide flotation, flotation applications less direct, but accompanied by continued exploitation of copper resources, direct flotation method has broad application prospect.

The organic acid collector can be physically adsorbed or chemically adsorbed on the surface of the mineral. It is generally in a multi-layer adsorption state, and the organic acid collector is easily adsorbed on the surface of the silicate mineral to improve the growth of the malachite. Floatability. When flotation is carried out using fatty acids and their soaps as collectors, it is usually necessary to add gangue mineral inhibitor water glass, phosphate and slurry adjuster sodium carbonate. The Zambia Sichangjia Concentrator handles the sulfide-oxidized mixed copper ore containing carbonate gangue. The ore contains 4.7% copper. The flotation of the copper sulfide ore and the sulfided copper oxide is first carried out by vulcanization flotation. The fatty acid (palmitic acid) recovers the residual copper oxide ore to obtain a concentrate containing 50% to 55% of copper. The reagents used in the flotation method of the amine collector are mainly organic amines, and the commonly used amine collectors are cocoamine and laurylamine. Since amines can capture gangue in copper oxide ore, in order to make the flotation process more selective, the choice of gangue inhibitors is very important. In addition to common inhibitors, sodium alginate and polyacrylic acid can be used. , cellulose lignosulfonate or lignosulfonate.

After pretreatment flotation method is to use a chemical or metallurgical processes copper oxidation pretreatment, and then using a conventional flotation process for the recovery of the copper is selected from copper oxide ore beneficiation difficult process which comprises mainly ammonia leaching - Sulfide precipitation - flotation, separation - flotation, vulcanization roasting - flotation, chemical pretreatment - flotation. Due to the complexity of the process and high cost of mineral processing, it has restricted the pace of industrial application.

Ammonia leaching - sulphide precipitation - flotation method is the addition of elemental sulphur (sulfur powder) during the pressure leaching process. After the copper oxide ore is dissolved by ammonia and carbon dioxide, it is precipitated into copper sulphide immediately. The slurry does not undergo solid-liquid separation. directly distilled after the recovery of NH ₃ and CO _2, for the recovery of copper sulfide precipitated synthetic and natural ores existing conventional copper sulfide flotation. This method is suitable for the inlay of very fine copper oxide ore. It has obtained a good sorting index in the experimental study of Tangdan refractory copper oxide. The copper recovery rate has increased by 17% and the concentrate grade has also been improved by one time.

Chemical pretreatment - flotation method is to add sulfuric acid to the selected slurry to leaching copper ions in the form of copper sulfate, then adding iron powder to replace copper, and using yellow medicine to collect flotation copper. This method is suitable for complex refractory oxidation. Copper ore sorting, such as non-floating minerals such as chrysocolla; or extremely high mud content, gangue containing carbonate and iron, manganese compounds, fine-grained, easy to mud, refractory copper oxide, chemical Pretreatment-flotation has been successfully applied to the US Butte Concentrator. Some scholars have studied the chemical pretreatment and flotation process of refractory copper oxide ore with deep oxidation and poor floatability in a copper mine in Xinjiang, and obtained copper concentrate with copper content of 45.09% and copper recovery rate of 84.22%.

The author first proposed the academic idea of ​​dip-dyed body combined with copper polymer bridge flotation, invented sodium polyethyldithiocarbamate as a polymer bridging agent, copper ion as a bridging ion, and xanthate as a bridge. The bridging flotation method of the receiving agent shows that the bridging flotation method can greatly improve the copper recovery rate by 8%~30% through the practice of mixed copper ore with different oxidation rates.

For some complex refractory copper oxide ore that is difficult to handle by flotation, it is an effective method to use the combined metallurgy or hydrometallurgical process. The low-grade copper oxide ore in Lanping, Yunnan is mainly composed of malachite and azurite. The gangue minerals are mainly quartz , kaolinite and mica . The ore contains a large amount of mud, and the pre-dewatering-flotation method is only used. Obtaining copper concentrate with copper grade of 23.35% and copper recovery rate of 43.02%; while using acid leaching process, the copper leaching rate is 92.08% after acid leaching at 85% of human immersion particle size, 0.074mm, and the leaching time is short and the efficiency is high. . Yuan Minghua et al. studied the combined process of copper oxide ore with 1.2% copper and 89.16% oxidation rate in Yunnan. After three rough selections, two selections and one sweep, the copper grade of copper concentrate was 27.68%. The copper recovery rate is 61.33%; the tailings contain 0.477% copper, and the flotation tailings are treated by acid leaching, which can make the comprehensive recovery rate of copper reach 88%.

In order to solve the problem of permeability during the acid leaching process of copper oxide ore and increase the leaching rate of copper ore, in recent years, new technologies such as concentrated sulfuric acid leaching, granulation pretreatment, heap leaching and fractional leaching have been proposed and applied. A high-mud copper oxide ore in Yunnan is a typical surface oxide ore, with a degree of muddyity of more than 70%. To this end, Yuan Minghua and others have broken the relationship between sulfuric acid concentration and leaching effect, and proposed that the use of concentrated sulfuric acid for enhanced leaching is not only conducive to increasing the permeability of ore, but also beneficial to improve the leaching rate of ore and the leaching liquid grade and reduce the acid consumption of leaching. The 40t-level on-site expansion test of the mud-containing oxidized ore of Daye Xintai Co., Ltd. using granulation pretreatment and heap leaching process. The ore is piled up by granulation pretreatment, and leached by leaching for 27 days. The leaching rate of slag meter is 75.11. %.

When vulcanization flotation of high-content copper oxide ore, the slime has an adverse effect on the flotation process, and the serious time difference may make the flotation impossible. At present, the following measures are taken to eliminate the adverse effects of the slime: (1) Washing and de-slipping; (2) selective flocculation flotation sludge; (3) adding dispersant to disperse the slime, wherein the water glass is widely used because of its low cost and effective inhibition of common slime. The useful minerals in a refractory copper oxide ore in Yunnan are unevenly embedded, and the symbiotic relationship with the gangue is complicated. The copper oxidation rate is 52.94%. Du Shuhua et al. added sodium humate and water glass to suppress the gangue and ore during the flotation flotation process. Mud, adding ethylenediamine phosphate as auxiliary activator, sulfide flotation obtained copper concentrate containing 20.54% copper, copper recovery rate of 80.57%. Li Rongchang and others used the process of “pre-dewatering-Na ₂ S induced flotation” on a copper oxide ore to effectively avoid the adverse effects of the slime. The obtained copper concentrate copper grade was 21.24%, and the copper recovery rate was 81.80. %.

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