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Characteristics of lead zinc copper sulfide ores are many kinds of minerals; useful minerals dissemination size fine, and dense symbiotic; floatability of galena and copper sulphide minerals is very close; sphalerite, pyrite and pyrrhotite It is easily activated by copper ions eluted from secondary copper minerals in the ore; even if the same mineral is often affected by the degree of oxidation, its floatability is difficult, so it is difficult to sort the ore.
1 Example of copper sulfide lead-zinc ore flotation
A lead-zinc ore fluorite mine genus warmed liquid metal filling the plurality of low-grade deposit metallic minerals galena, sphalerite and chalcopyrite, and small amounts of pyrite. The non-metallic mineral is fluorite, and the gangue mineral is mainly quartz . Metallic minerals have a coarser grain size and are a better choice of ore. The mine selection plant uses copper and lead partial mixing to separate and mix and select tailings to sequentially float zinc and float fluorite, and recover four useful components of copper, lead, zinc and fluorite. The principle process of the factory production is shown in Figure 1.
When copper and lead are mixed, ZrISO 4 + Na 2 S 2 O 3 is mainly used to suppress sphalerite. Tests and production have shown that the addition of a small amount of cyanide (about 5 g/t) has a significant effect on reducing the zinc content of the mixed concentrate. In the sweeping operation of the mixing cycle, the addition of 30 g/t of activated lead oxide to promote the recovery of lead is advantageous. When separation of copper and lead, after removal of activated carbon by weight sodium inhibitory drug of chromium, lead, supplemented with a small amount of copper floating pine oil, activated charcoal and sodium dichromate as long as there is sufficient duration of action (approximately for 30 min), the copper can be more Good separation.
2 copper lead separation method
(1) Common copper and lead separation methods. The separation method is shown in Table 1.
The inhibitor schemes listed in Table 1 can be summarized into three methods: the cyanide method, the dichromate method, and the sulfurous acid and its salt method, and other compounds are more or less used in each method. Copper and lead separation by copper cyanide method (or dichromate method), good separation effect, stable operation, but both are toxic. There are more people using sulfite and its salt methods today. Sulfuric acid does not inhibit chalcopyrite, porphyrite and chalcopyrite. Because it can clean the surface of copper minerals, it has the function of activating copper minerals. Sulfuric acid and its salts are combined with sodium sulfide or starch. Lead-free copper floatation is beneficial to improve sorting effect and stability. Some people use the "Nuchar method" - silicon chromium cellulose composition method to remove copper and lead mixed concentrate with activated carbon, add an equal amount of sodium chromate and water glass to stir, and then add carboxymethyl cellulose (CMC ) lead-free float copper.
(2) The principle of separation method selection. In the polymetallic sulfide ore flotation, whether it is lead-zinc separation, zinc-sulfur separation, copper-zinc separation or copper-lead separation, there are many separation methods (including process and chemical solutions), especially copper-zinc separation and copper-lead separation. The suppression scheme is more, and the principle of selection can be considered from the following aspects:
1) The mineral composition and floatability of the ore or mixed concentrate are the main basis for the separation method. There are many types of copper minerals. The primary copper minerals dominated by chalcopyrite are easily inhibited by cyanide. The free Cu 2+ is less in the pulp, and the galena and sphalerite are not easily activated by Cu 2+ . In this case, it is effective to use copper cyanide to suppress copper and lead separation, but it is not suitable to use zinc cyanide to inhibit copper and zinc separation, because chalcopyrite is susceptible to cyanide inhibition. The secondary copper minerals mainly composed of copper ore and copper blue are not easily inhibited by cyanide, and there are many free Cu 2+ in the pulp. The galena and sphalerite are easily activated by Cu 2+ . In this case, the cyanide method and the dichromate method are all inferior, and the sulfurous acid and its salt method are commonly used. For the lead ore, it is easy to be inhibited by dichromate and sulfite without Cu 2+ activation or surface oxidation. The galena activated by Cu 2+ is difficult to be inhibited by dichromate. Sulfuric acid is used in combination with sodium sulfide or sodium thiosulfate and ferrous sulfate (or ferric chloride) are used in combination with lead-free copper.
2) The mineral content ratio of the valuable components in the mixed concentrate. The general principle is to “suppress more and less floatâ€, which can reduce the inclusion of foam products and obtain better separation indicators.
3) The content of rare and precious metals in the original ore. When the lean ore, high precious metal content in the concentrate should be enriched (e.g., enriched in silver and gold, of copper and lead concentrates as much as possible, the possible enrichment of the cadmium zinc concentrate). In order to prevent the loss of gold and silver, the cyanide method is best not used.
4) The selection plan should be considered comprehensively from the aspects of mineral processing indicators, economic costs, environmental protection and labor conditions. For certain ores, the use of cyanide is indeed more effective, and the cyanide method is preferable when the economic benefits of increasing the index exceed the losses caused by cyanide. At present, in the industrial production at home and abroad, many manufacturers continue to use the cyanide dichromate method. In particular, it is more common in Western countries to use cyanide to preferentially float lead and zinc.
3 concentrate removal
In the flotation of polymetallic sulphide ore, due to the nature of the ore and the complexity of the process, various metal minerals are often poorly separated, resulting in the so-called "mutual inclusion" (ie, the concentrate contained in the concentrate, and the concentrate contained in the concentrate). The phenomenon that the mine is too high will not only reduce the quality of the concentrate, but also reduce the recovery rate. In order to solve this problem, the process of demineralization can be used. The so-called concentrate decontamination is to re-process the concentrate to reduce the content of impurities.
The process of demineralization of concentrates is often used for dezincification of lead concentrate, de-lead of zinc concentrate, de-lead of copper concentrate, copper removal by lead concentrate, and copper removal from zinc concentrate. The method of demineralization of concentrates is generally the reverse of the flotation process for obtaining coarse concentrates. For example, lead concentrate with excessive zinc content is obtained by the method of floating lead and zinc inhibition. When dephosphorization of lead concentrate, zinc should be used to suppress lead. That is, reverse flotation is generally used when removing impurities.
4 mixed concentrate detoxification
Before the separation of the concentrate, in order to improve the separation effect, it is often necessary to remove the drug in advance to remove the drug film on the mineral surface and the excess agent in the slurry.
There are several ways to remove the concentrate concentrate:
(1) Mechanical de-dosing method. The method includes multiple selection, re-grinding, concentration, scrubbing, filtration and washing options. Multiple selections are both a process to improve the grade of the mixed concentrate and a process of removing the drug. In the general selection process, the concentration of the slurry is very low, so that a part of the excess agent can be removed by desorption, but the effect is limited. The re-grinding of the mixed concentrate mainly promotes the further monomer dissociation of the continuum in the mixed concentrate, and at the same time, it can also peel off a part of the excess medicament. Concentrated concentrate concentrate can remove the agent from the water by dehydration, which can be carried out in a thickener or hydrocyclone. The scrubbing method is to stir in the thick slurry and to remove the medicine by friction between the ore particles. The application condition is that the mineral is not easily muddy. The filtration washing method is to filter the mixed concentrate, spray it on the filter, and then re-pulp the filter cake, which is the most thorough one in the mechanical de- ing method. However, the process is complicated, costly, and often limited by material conditions, and is rarely used.
(2) Desorption method. The desorption method is a method for desorbing the surface of the ore particles by utilizing the strong adsorption property of sodium sulfide on the surface of the mineral, and the agent adsorbed on the surface of the ore particles is returned to the slurry by the activated carbon adsorbing the agent in the slurry. These two methods can be used simultaneously. However, when the amount of sodium sulfide is large, it is necessary to use a thickener to remove the drug at the same time, which complicates the process.
(3) Heating and roasting methods. For example, the copper- molybdenum mixed concentrate is heated by steam in a lime medium to destroy the collector film on the mineral surface, and then diluted with water to separate. Or the copper-molybdenum mixed concentrate is calcined, the surface of the copper mineral is oxidized to become difficult to float, and then the molybdenum concentrate is floated and floated. Both methods are costly.
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