A plurality of metallic zinc copper sulfide ore, copper ore, zinc, sulfur-based, associated copper, gold, silver and the like. Since it was put into production, due to the high copper content of the ore, the zinc mineral contains opal-like chalcopyrite, which causes the zinc recovery index to fluctuate greatly. The zinc concentrate contains copper exceeding the standard and the zinc recovery rate is low. The purpose of the research is to improve the process, improve the separation efficiency of copper and zinc, improve the recovery index of useful metals, and enable zinc concentrate to be produced as qualified products. Taking into account the high content of silver in the ore, reaching nearly 80g / t, its industrial value can not be ignored, in order to reduce the content of silver in the sulfur concentrate, so that it into the copper, zinc concentrate products, thereby reducing the loss of silver, the test program It adopts the process of preferential floating copper, zinc-sulfur mixed floatation, and mixed concentrate re-grinding and sorting. Through a large number of conditional tests, the floatability rules of copper, zinc and sulfur were found, and the suitable process parameters and chemical system for the treatment of the ore were determined. The closed-line test verified that satisfactory sorting indicators were obtained.
I. Process mineralogy research
(1) Multi-element analysis and relative mineral content
The results of multi-element analysis of ore are shown in Table 1. The relative content of minerals is shown in Table 2.
Table 1 Results of multi-element analysis of raw ore
Table 2 Relative content of minerals
(2) Phase analysis of copper and zinc
The phase analysis results of copper and zinc are shown in Tables 3 and 4.
Table 3 Results of chemical phase analysis of copper
Table 4 Results of chemical phase analysis of zinc
(3) Process characteristics of major minerals
The ore body is a complex polymetallic sulfide ore. The process characteristics of the main minerals are as follows:
Chalcopyrite: The main copper-bearing mineral, containing 80% of the total copper. Irregular granular aggregates chalcopyrite and pyrite, marcasite, sphalerite, galena closely fitted green compact block body composition, or irregular particles embedded in raw dolomite, quartz gangue minerals in. The chalcopyrite is filled into a grid-like structure along the fractures of the broken pyrite particles, and the pulse width is 0.04 to 0.008 mm, which is difficult to dissociate. A small amount of chalcopyrite has secondary changes, and the formation of chalcopyrite, blue-copper ore, porphyrite and copper blue is filled in the gaps or fissures of pyrite particles. Chalcopyrite has a wide range of natural particle sizes, but it is mainly concentrated in the grade of 1 to 0.037 mm. The particles below 0.074 mm are mainly encapsulated in sphalerite in the form of emulsified and short velvet.
Sphalerite: The main zinc-containing mineral, which contains more than 80% of total zinc. Sphalerite is mainly composed of irregular granular aggregates embedded in pyrite, carbonate minerals and quartz veins in various ores. It is closely embedded with chalcopyrite and galena, and a small amount is self-formed and semi-self. The shaped crystal particles are embedded in the gangue mineral. In the dense massive ore, the sphalerite is irregularly shaped, and the chalcopyrite is closely embedded with the chalcopyrite or aggregated with chalcopyrite and galena, filled in the interstitial space of the pyrite particles, and the particle size is generally greater than 50 μm. It is easy to dissociate; most of the sphalerite in the disseminated ore is irregularly granular, and a small amount of semi-self-shaped particles are infiltrated into carbonate minerals and quartz, which are interlaced with canine teeth and the particles are relatively thin. Most of the sphalerite particles contain opal-like chalcopyrite, as well as individual fine pyrite and galena particles. The sphalerite and pyrite contact interface is sometimes filled with a layer of chalcopyrite and porphyrite. Thus, the zinc and sulfur minerals are separated, and the torsion cracks of the sphalerite are sometimes filled with quartz or calcite .
Pyrite: self-formed, semi-automorphic or enamel granules and chalcopyrite, sphalerite, galena ore, or embedded aggregates in the gangue. The pyrite embedded in the quartz vein is surrounded or filled with common calcite in the fissure. Otherwise, the pyrite or the fissure embedded in the carbonate gangue is surrounded or filled with quartz. The boundary between these minerals Smooth, because the hardness index of quartz and calcite differs greatly, which is good for dissociation. In addition, some pyrites are fractured after they are formed, and their fissures are filled with chalcopyrite and porphyrite. A small amount of pyrite particles are coated with particulate chalcopyrite, porphyrite or sphalerite, and a small amount of fine pyrite. Also included in the chalcopyrite particles.
Second, the flotation condition test
The sorting of complex copper-zinc-sulfur polymetallic sulfide ore is widely considered by the mining industry at home and abroad to be one of the more difficult topics. The reason why it is difficult to sort is that the sphalerite has been activated by long-term weathering and leaching in the deposit, and has been activated by soluble copper ions or encapsulated by copper ions. This sphalerite has very similar to copper minerals. It is difficult to sort by buoyancy; the second is when the copper-zinc minerals are closely symbiotic, and the chalcopyrite is fine droplets of fine particles below 5μm. When the stars are scattered in the sphalerite, the ore is difficult to pass through after grinding. Dissociation. Through the study of the mineralogy of the ore and the consideration of various factors, it is decided to adopt the process of preferential floating copper, zinc-sulfur mixing, mixing and re-grinding. The first stage of copper float is only to obtain high quality copper essence. The ore, copper and other minerals are treated in the second stage of regrind.
(1) Priority float copper grinding fineness test
The coarse grinding fineness is determined to achieve the following objectives: the copper mineral is substantially dissociated, and the high-quality copper concentrate is recovered to the utmost extent, and the zinc content in the copper concentrate is low. The test procedure is shown in Figure 1 (the dosage unit is g/t), and the test results are shown in Figure 2.
Figure 1 Priority float copper condition test procedure
Fig. 2 Effect of grinding fineness on copper concentrate grade and recovery rate
1-Cu grade; 2-Cu recovery
The test results show that with the increase of grinding fineness, the grade of copper is improved, the recovery rate of copper is not much increased, but the zinc content of copper concentrate is decreased. According to the load capacity of a ball mill, the suitable grinding fineness is less than 0.074 mm and the content is 65% to 75%. The following rough grinding fineness is less than 0.074 mm and 70%.
(2) Priority float copper lime dosage test
Lime is the most commonly used pulp pH adjuster and pyrite inhibitor. Especially in the preferential flotation operation, the suitable pulp alkalinity can improve the sorting effect of copper and zinc minerals. The test procedure is shown in Figure 1, and the results are shown in Figure 3.
Figure 3 Effect of lime dosage on copper concentrate grade and recovery
1-Cu grade; 2-Cu recovery
The test shows that with the increase of the amount of lime, the grade of copper concentrate is obviously improved, the recovery rate of copper is reduced, the pyrite is inhibited, but the sphalerite is enhanced in floatability, and the suitable amount of lime is 1000g/t. The pH of the pulp is about 8.5.
(III) Priority float copper collector selection test
At present, the commonly used collectors for copper flotation are: butylamine black medicine, Z-200 # , thyroid yellow medicine, butyl yellow medicine, etc. The experiment has examined in detail the collection effect of several commonly used collectors alone or in combination. The test procedure is shown in Figure 1, and the results are shown in Table 5.
Table 5 Preferred floating copper collector selection test results
The test results showed that Dinghuang and butylamine black drugs were mixed in a ratio of 1:1. When the dosage was 20g/t, the selectivity and the harvesting ability were better. Therefore, the collectors were treated with Dinghuang and butylamine. Mixing 1:1, hereinafter referred to as a mixture.
(4) Test of the dosage of zinc-sulfur mixed float collector
Zinc flotation uses the most commonly used collector Dinghuang. The test procedure is shown in Figure 4 (the dosage unit is g/t), and the test results are shown in Figure 5.
Figure 4 Zinc-sulfur mixing test procedure
Fig. 5 Effect of medicinal amount of zinc-sulfur mixed shuanghuang on zinc grade and recovery rate
1-Zn grade; 2-Zn recovery
The test shows that with the increase of the amount of collector, the grade of zinc in zinc-sulfur mixture is reduced, and the recovery rate of zinc is obviously improved. A suitable collector is used in an amount of 80 g/t.
(5) Determination of fineness of re-grinding of zinc-sulfur mixture
In the zinc-sulfur mixture, some of the fine-grained copper has not been dissociated from the monomer. This part of the copper that has not been dissociated by the monomer needs to be dissociated during the regrind process, and the zinc and sulfur are embedded in the zinc-sulfur mixture. The cloth is much coarser than copper. Therefore, the regrind fineness of zinc-sulfur mixture is mainly determined by the dissociation of copper in the zinc-sulfur mixture. The test procedure is shown in Figure 6 (the dosage unit is g/t), and the test results are shown in Figure 7.
Figure 6 Mixing regrind condition test procedure
Fig.7 Effect of regrind on copper recovery and zinc content of copper concentrate II
1-Zn grade; 2-Zn recovery
The test results show that the recovery rate of copper decreases slightly with the increase of regrind fineness, while the content of zinc in copper concentrate is higher when the regrind fineness is coarse or too fine, because regrind fineness When it is thicker, copper and zinc have not been dissociated from the monomer, and when the fineness is too fine, the entrainment of fine-grained zinc is more in the process of floating copper, resulting in higher zinc content. The suitable fineness of the zinc-sulfur mixture is less than 0.045 mm and accounts for 82%.
(6) Mixing and re-grinding activated carbon dosage test
In order to reduce the adverse effect of the upper flotation residual agent on the lower stage flotation, in the process of remixing and re-grinding, an appropriate amount of activated carbon must be added for drug removal. The test procedure is shown in Figure 6, and the test results are shown in Figure 8.
Figure 8 Effect of the amount of activated carbon on the copper grade, recovery and zinc content of copper concentrate II
1-Cu grade; 2-Cu recovery; 3-Zn recovery
The test shows that the effect of adsorption of residual agent on activated carbon is obvious. With the increase of dosage, the flotation foam becomes brittle, the grade of copper concentrate increases, and the recovery rate of copper decreases slightly, but the loss of zinc in copper concentrate is Significantly lower. A suitable amount of activated carbon is 300 g/t.
(7) Mixing and re-grinding sodium sulfide dosage test
The test procedure is shown in Figure 6, and the results are shown in Figure 9.
Fig.9 Effect of Na 2 S dosage on copper recovery and zinc content of copper concentrate II
1- Cu recovery; 2-Zn recovery
The test results show that the amount of sodium sulfide is less than 500g/t, which has no obvious effect on the recovery rate of copper, but significantly inhibits zinc, and the dosage is above 600g/t, which has inhibitory effect on copper and zinc. A suitable amount of sodium sulfide is 500 g/t.
Third, the whole process closed circuit test
Based on the process parameters determined by a large number of conditional tests, the laboratory full-process closed-circuit test is carried out to simulate the dynamic process of continuous operation at the production site, to examine the cumulative situation of each operation, the distribution of the mineral products and the possible sorting indicators. . The process flow and the pharmaceutical system of the full-process closed-circuit test are shown in Figure 10 (the dosage unit is g/t), and the final test results are listed in Table 6.
Figure 10 full process closed circuit test process
Table 6 % of closed-circuit test results of the whole process
Fourth, the conclusion
1. Process mineralogical research shows that the ore is a polymetallic sulfide ore mainly composed of copper, zinc and sulfur. The useful minerals are extremely irregular granular aggregates embedded in the fractures of gangue minerals, and the mosaic relationship is extremely complicated.
2. The experimental research shows that the process of preferential float copper, zinc-sulfur mixed floatation, mixing and re-grinding and sorting is preferred. The priority float copper operation adopts the method of “light pull and light pressureâ€, which is the mixing of zinc and sulfur and re-grinding copper. Job creation conditions. Copper is selected at the stage to make the recovery index of copper concentrate relatively stable, thus ensuring the quality of zinc concentrate. Zinc-sulfur mixture can be produced by fine grinding and activated carbon, and can produce qualified zinc concentrate, sulfur concentrate and a small amount of copper concentrate. The silver in the ore is mainly concentrated in copper concentrate and zinc concentrate, thus The valuable metals in the ore are effectively and comprehensively recovered.
3. The mineral processing drugs used in the test are conventional agents with no toxicity and a wide range of sources. The medium and mine adopts the sequential return mode, and the process flow structure is simple and reasonable, which is conducive to on-site production implementation.
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