Our iron sphalerite very rich in resources, reserves only iron sphalerite Yunnan region amounted to 700 million t. Our MARMATITE very wide distribution of resources, such as mining Yunnan Wenshan Dulong, Lancang Lead Mine old factories, mines and mining areas and Mongolian cattle confession, Dachang lead, complex multi-antimony, zinc, tin metal ore Hehe three lead-zinc mine, Hunan Huangshaping, Panjiachong and Yejiwei lead-zinc mine, Guizhou Hezhang lead-zinc mine, Qinghai Xitieshan lead-zinc mine, Heilongjiang Xilin lead-zinc mine, Jilin Fangniugou and the former cattle scouring lead and zinc The mine, as well as the Guangdong Fupoyu lead-zinc mine, etc., contain iron sphalerite in the ore. The iron content of iron sphalerite in these mines is generally 6% to 12%, and some are as high as 20% or more, and often associated with rare and rare metals such as silver , indium , cadmium and antimony , the research value and economic value are very high. .

Iron sphalerite is an iron-rich sphalerite, which is usually mixed into sphalerite by the same type. The zinc atom on the zinc blende crystal lattice is replaced by iron, which reduces the hole concentration and increases the electron density, making the sphalerite become the N-type semiconductor mineral iron sphalerite, which affects its floatability, adsorption, redox State and interface electrochemical reactions. In actual production, iron sphalerite is less soluble than ordinary sulfide minerals, and is difficult to separate from pyrite, pyrrhotite, arsenopyrite and other planktonic gangue minerals. Generally, it needs to be activated or long carbon chain. Yellow medicine can be harvested.

Due to poor natural floatability, activation is a prerequisite for iron sphalerite flotation, and has been one of the hot spots in domestic and international mineral processing research. The xanthogenates formed by heavy metal cations such as Cu ²⁺ , Ag ⁺ , Pb ²⁺ and Hg ²⁺ are smaller than the solubility products of zinc xanthate. Therefore, these heavy metal ions can be used as the activation of iron sphalerite. Agent. After activation of the iron sphalerite, its flotation performance is similar to that of the metal sulfide corresponding to the activator used.

In the production practice, Copper sulfate is the most common Marmatite activator. However, there are some problems in the activation of iron sphalerite with copper sulfate. There are three main aspects: 1 The activation of copper sulfate increases with the enhancement of alkalinity. Therefore, the activation needs to be carried out in a highly alkaline environment, that is, it needs to be added. The amount of large lime will inhibit the low-volume iron sphalerite, and it will not be conducive to the recovery of rare metals such as gold, silver, indium and cadmium. 2 Increase the amount of lime from the perspective of comprehensive recovery. It is also unreasonable to talk about it. Especially for tin-containing polymetallic ores, it will cause scaling of re-election equipment, which will seriously affect the recovery and utilization of tin. 3 Copper sulfate will activate the iron sphalerite and activate it. The iron sulfide minerals such as pyrite and pyrrhotite increase the content of impurities in the zinc concentrate and reduce the grade of the zinc concentrate, which is very disadvantageous for further separation of zinc and indium.

Therefore, it is very important to study the selective high-efficiency activator to reduce the production cost and ensure the comprehensive recovery and subsequent separation of zinc minerals and co-associated rare metals.

This experiment investigated the activation properties of several flotation activators on iron sphalerite.

1. Test samples and medicaments

Lancang ore samples taken from lead, wherein the metal minerals galena, iron sphalerite, pyrite, pyrrhotite and sphalerite main gangue minerals are quartz, calcite, sericite, green Mudstone, dolomite, diopside and tremolite . After the original ore sample was crushed and mixed, the experts of the Department of Geology of Kunming University of Science and Technology were entrusted to select the pure iron sphalerite single mineral, and then the single mineral crushing sieve was divided into different grades and stored separately. The study took -80+200 The single-bubble flotation test was carried out on the order of (74-175 μm). The chemical multi-element analysis results of iron-sphalerite single minerals are shown in Table 1.

Table 1 Multi-element analysis results of single mineral chemistry of iron sphalerite

Note: The content of Ag is in g/t.

Test adjusting agent using concentrated sulfuric acid or sodium hydroxide; activators are copper sulfate, ammonium chloride, lead nitrate, and T-1, T-1 where the present research group developed new efficient activator zinc; collector using Ding Huang medicine. These agents are analytical grade reagents except Dinghuang and T-1 are industrial grade. The test water is distilled water.

Second, the test method

Each time, 1.0 g of iron sphalerite single mineral sample was weighed into a 45 mL single bubble tube (Halimond tube) with an analytical balance, and an appropriate amount of distilled water was added to open a nitrogen bottle, and the nitrogen gas was charged at a filling rate of 35 mL/min, and then according to the graph. The process shown in 1 is slurrying and flotation. Since the flotation process uses mandatory inflation, no foaming agent is required. After the flotation is completed, the foam product is filtered, dried, weighed, and the recovery rate is calculated according to its mass.

Third, test results and analysis

(1) Natural floatability of iron sphalerite

Without flotation agent, 1.0g of iron sphalerite single mineral flotation was carried out for 12min, and the foam product was 15mg, that is, the flotation recovery rate was only 1.5%, indicating that the natural floatability of the test iron sphalerite single mineral was very poor. .

Figure 1 Test procedure

(II) Effect of Dinghuang on the floatability of iron sphalerite

At the natural pH (pH=7) and without the addition of activator, different amounts of butyl xanthate were used for flotation of 1.0 g of iron sphalerite single mineral for 12 min. The test results are shown in Fig. 2. It can be seen that under the action of butyl sulphate, the floatability of iron sphalerite has improved, but it is still poor; the flotation recovery rate of iron sphalerite increases with the increase of medicinal amount of butyl yellow, but when After the yellow medicinal amount reached 100g/t, the upward trend was not obvious, so the following test added 100g/t of butyl yellow drug.

Fig. 2 Effect of Dinghuang on the floatability of iron sphalerite

(3) Activation test

1. Copper sulfate activation test

(1) Copper sulfate dosage test

Under the conditions of natural pH (pH=7) and medicinal amount of Dinghuang 100g/t, different amounts of copper sulfate were added and floated for 12min. The change of flotation recovery of iron sphalerite is shown in Fig. 3. 3 shows that: when the amount is less than CuSO ₄ 600g / t, the iron recovery sphalerite flotation with the increase of the amount of CuSO ₄ is increased; when the amount is more than CuSO ₄ 600g / t, due to the activation of the pulp from The metal cations are excessively excessive, and these metal cations are easily reacted with the collector to form a collector-metal salt precipitate having a small solubility product, thereby causing unnecessary consumption of the collector, and the iron sphalerite recovery rate is rather decreased. Therefore, a suitable amount of CuSO ₄ is 600 g/t, and the flotation recovery of the iron sphalerite is 35.30%.

Figure 3 results of copper sulfate dosage test

(2) Effect of pH on the activation performance of copper sulfate

Under the condition of CuSO ₄ dosage of 600g / t, Ding Huang pharmaceutical dosage of 100g / t, flotation time of 12min, adjust the pH of the slurry with concentrated sulfuric acid or sodium hydroxide, and investigate the effect of pH on the activation performance of copper sulfate. The results are shown in Figure 4. It can be seen from Fig. 4 that when the slurry pH=13, the activation effect of copper sulfate is the best, and the flotation recovery rate of iron sphalerite is the highest, reaching 61.30%; in addition, when the slurry pH=5.5, the curve has a peak, iron The recovery rate of sphalerite is 60.20%, which may be the result of self-induced flotation of iron sphalerite under acidic conditions.

Figure 4 Effect of pH on the activation performance of copper sulfate

2. Ammonium chloride activation test

(1) Ammonium chloride dosage test

Under the conditions of natural pH (pH=7) and medicinal amount of Dinghuang 100g/t, different amounts of ammonium chloride were added and floated for 12min. The change of flotation recovery of iron sphalerite is shown in Fig. 5. It can be seen from Fig. 5 that the flotation recovery of iron sphalerite increases with the increase of ammonium chloride dosage, but in general, the activation of iron sphalerite by ammonium chloride is weaker than that of copper sulfate; After reaching 960g/t, the recovery rate of iron sphalerite is not obvious. Therefore, the following test ammonium chloride dosage is 960g/t. Under the ammonium chloride dosage, the flotation recovery rate of iron sphalerite in natural pH environment is 15.95%.

Figure 5 results of ammonium chloride dosage test

(2) Effect of pH on the activation performance of ammonium chloride

Under the condition of ammonium chloride dosage of 960g/t, Dinghuang pharmaceutical dosage of 100g/t and flotation time of 12min, the pH of the slurry was adjusted with concentrated sulfuric acid or sodium hydroxide to investigate the effect of pH on the activation performance of ammonium chloride. The test results are shown in Figure 6. It can be seen from Fig. 6 that changing the pH of the slurry can not effectively improve the activation ability of ammonium chloride to iron sphalerite. In the test range, when pH=5.5, the flotation recovery of iron sphalerite under the action of ammonium chloride The rate is the highest, but only 22.10%.

Figure 6 Effect of pH on the activation performance of ammonium chloride

3. Lead nitrate activation test

(1) Lead nitrate dosage test

Under the conditions of natural pH (pH=7) and Dinghuang medicinal amount of 100g/t, different amounts of lead nitrate were added and floated for 12min. The flotation recovery of iron sphalerite was shown in Fig. 7. It can be seen from Fig. 7 that the flotation recovery of iron sphalerite increases with the increase of lead nitrate content, but in general, the activation of lead nitrate to iron sphalerite is weaker than that of copper sulfate; when the amount of lead nitrate reaches 6000g After /t, the recovery rate of iron sphalerite is obviously smaller, so the following test lead lanthanum nitrate is 6000g/t. Under the lead nitrate dosage, the flotation recovery rate of iron sphalerite in natural pH environment is 13.40. %.

Figure 7 Results of lead nitrate test

(2) Effect of pH on the activation performance of lead nitrate

Under the condition of the dosage of lead nitrate being 6000g/t, the dosage of Dinghuang being 100g/t and the flotation time being 12min, the pH of the slurry was adjusted with concentrated sulfuric acid or sodium hydroxide to investigate the effect of pH on the activation performance of lead nitrate. The results are shown in Figure 8. It can be seen from Fig. 8 that changing the pH of the slurry can not effectively improve the activation ability of lead nitrate to iron sphalerite. In the test range, when pH=5.5, the flotation recovery rate of iron sphalerite is the highest under the action of lead nitrate. But only 28.10%.

Figure 8 Effect of pH on the activation of lead nitrate

4, T-1 activation test

(1) T-1 dosage test

Under the conditions of natural pH (pH=7) and medicinal amount of Dinghuang 100g/t, different amounts of the new zinc activator T-1 developed by our research group were added and floated for 12min, and the flotation recovery of iron sphalerite was carried out. The rate change is shown in Figure 9. It can be seen from Fig. 9 that T-1 activates iron sphalerite at natural pH significantly better than ammonium chloride and lead nitrate; when T-1 is used at 700g/t, flotation recovery of iron sphalerite A peak of 28.10% appeared, ie a suitable amount of T-1 activated iron sphalerite was 700 g/t.

Figure 9 T-1 test results

(2) Effect of pH on the activation performance of T-1

Under the condition of T-1 dosage of 700g/t, Dinghuang medicinal amount of 100g/t and flotation time of 12min, the pH of the slurry was adjusted with concentrated sulfuric acid or sodium hydroxide to investigate the effect of pH on the activation performance of T-1. The test results are shown in Figure 10. It can be seen from Fig. 10 that T-1 has the best activation effect at pH=10, and the flotation recovery rate of iron sphalerite can reach 64.10%, which exceeds the recovery rate obtained by copper sulfate at the optimum pH.

Figure 10 Effect of pH on the activation performance of T-1

5. Comparison of several activators under suitable conditions

After activation of the iron sphalerite with several activators according to the appropriate dosage and pH conditions determined by the above test, the activation performance of several activators was further compared with 100 g/t of the yellowing agent for different time. The test results are shown in the figure. 11 is shown. It can be seen that in the extensive flotation time range of 2-20 min, the order of recovery of iron sphalerite obtained by several activators is always T-1>CuSO ₄ >PbNO ₃ >NH ₄ Cl, indicating T-1 pair The activation properties of iron sphalerite are better than copper sulfate. In addition, based on the determined appropriate conditions, the activation of iron sphalerite with T-1 can be as much as 20% cheaper than copper sulfate.

Figure 11 Variation of flotation recovery over time with different activators

â—‹-T-1700g/t, pH=10; â–²-copper sulfate 700g/t, pH=13;

● - lead nitrate 6000g / t, pH = 5.5; ■ - ammonium chloride 960g / t, pH = 5.5

Fourth, the conclusion

(1) Copper sulfate has the best activation effect on iron sphalerite at pH=13, and the recovery rate of iron sphalerite can reach 61.30%.

(2) The new activator T-1 has the best activation effect on iron sphalerite at pH=10, which can make the recovery rate of iron sphalerite reach 64.10%, and the activation effect of copper sulfate at pH=13. Compared with the recovery rate of iron sphalerite, it increased by 2.80 percentage points.

(3) The new activator T-1 not only has better activation effect on iron sphalerite than copper sulfate, but also can be activated in a lower pH environment, thus creating a prerequisite for reducing the amount of lime and reducing the production cost.

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