Study on Separation of Copper and Lead Sulfide Ore

By adsorption density measurements to study the mechanism of inhibition of sodium silicate other lead mines. The inhibition of water glass is related to its prevention or reduction of the adsorption of the collector . It completely prevents the adsorption of thiol esters on galena, but does not completely prevent the adsorption of butyl xanthate, indicating collectors and inhibitors. There is a weak-weak, strong-strong match between the two.

I. Introduction

Copper and lead separation is one of the main problems in complex sulfide ore dressing . Copper cyanide inhibition flying lead or lead chromate heavy copper depressants commonly used in practice is the production of two typical separation scheme of copper and lead. However, both cyanide and dichromate are highly toxic agents. With the increasing emphasis on environmental protection, their use has been limited, resulting in a decline in copper and lead sorting indicators. Therefore, many researchers have studied the separation of copper and lead from the search for non-toxic inhibitors, highly selective collectors and methods to enhance the flotation process.

Thiocarboxylate is a highly selective collector of sulfide minerals and has been initially used in production practice. The results show that it has the advantages of good selectivity, low dosage and foaming. Nevertheless, the current sulfur ester carbonyl sulphide is still mainly used to separate copper and iron sulfide ore, copper and lead separation, only the United States, Canada and Australia a few Concentrator successfully applied thiocarbonyl ester, and most of them will It is mixed with a yellow drug plasma agent. According to our analysis, there are three possible reasons for the difficulty in promoting the application of such agents:

When (a) when dealing with complex sulphide ore, more particularly containing metals processing symbiotic dense ore, even if the application of such agents, to be effective must be sorted so that the appropriate angle adjusting agent. The characteristics of thiol esters are different from those of xanthate. If the conditioning agent combined with xanthate is used directly with such agents without research, it is difficult to obtain satisfactory enchantment. Practice from abroad successfully applied thiocarbonyl ester separating lead and copper in the copper-zinc mixed concentrate of view, thiono esters are generally fitted with a weak inhibitor will be used. When the Z-200 is used as a collector to separate the copper-lead mixed concentrate, the lime can effectively inhibit the galena, the Nanivik concentrator in Canada and the concentrating plant of the Brahruic Mining and Metallurgical Company. Both use dextrin as an effective inhibitor of galena, and the amount of dextrin is only about 40g/t. When using the Z-200 to separate copper and zinc, the Bluehill Concentrator can suppress sphalerite by using sodium sulfite alone. Lime, dextrin and sodium sulfite are weak inhibitors.

However, when xanthate is used as a collector, the effects of the above inhibitors are very poor, and only a significant inhibitory effect is obtained at a higher dosage. When the Selinanov concentrator of the Soviet Union used a yellow drug to separate the copper-lead mixed concentrate, the lead was inhibited by FeC1 3 and Na 2 S 2 O 3 , the amount of FeCl 3 was as high as 8 kg/t, and the amount of Na 2 S 2 O 3 was as high as 2 kg/t. . When the water glass mixture of Guangxi Heshan Lead-Zinc Mine is used as an inhibitor to separate copper-lead mixed concentrate, the dosage of the mixture is above 12kg/t concentrate. The use of lime as an inhibitor of galena has not been seen with xanthate ionic collectors. The above facts indicate that there is a certain matching relationship between the collector and the inhibitor. According to the competitive adsorption theory, the ratio of the solubility product of the inhibitor to the metal ion compound and the solubility product of the collector and the metal ion compound must be moderate. When it is too large, it may cause an increase or failure of the amount of the collector. In hours, the suppression effect is poor. In addition, if the collector has a strong ability to capture, it can produce a highly hydrophobic mineral surface, thus requiring a strong hydrophilicity to balance and inhibit the mineral, that is, using a strong inhibitor or a large inhibitor. . In contrast, if the collector's ability to capture is weak, it generally only produces a weakly hydrophobic mineral surface, so only a weak hydrophilicity is needed to balance, cyanide and dichromate are two strong inhibitors. Their use in combination with chemically active thiocarbonyl esters may cause an increase or even failure in the amount of collector. Weak inhibitors such as carboxymethyl cellulose and water glass are used in combination with chemically active xanthate collectors, and the inhibitory effect is relatively poor. If they are used in combination with a thiol ester, it may increase their inhibitory effect or reduce their amount. Here we use the terms strong (catch)-strong (suppression) and weak-weak match to summarize this idea.

(2) The corresponding cooperation of other conditions (such as process structure, stirring and aeration) other than the agent.

(III) There are few studies on the mechanism of action of thiocarbonyl esters. The mechanism is unclear and the control of the production process has a certain blindness.

It can be seen that to promote the application of thiol esters, it is necessary to find the modifiers and process conditions with which it is combined and to study its mechanism of action.

In this paper, we explored the separation of copper and lead by the combination of weak inhibitor monohydrate glass and thiol ester, studied the inhibition mechanism of water glass, and explained the matching relationship between collector and inhibitor.

Second, the test method

(1) Mineral sample

The pure mineral chalcopyrite used in the test was collected from the Hebei Wuyuan copper mine, and the galena was collected from the Shuikoushan lead-zinc mine. The coarse-grained pure ore sample is batch-scale porcelain mill, wet sieve, and the required size grade (-200+400 mesh) is dried in a vacuum drying oven. The dried sample is stored in a desiccator for use. The purity of minerals is calculated based on the main element content, and its purity is:

Chalcopyrite containing copper 31.26% purity 90.29%

Galena lead 84.64% purity 97.74%

(2) Pharmacy

The collectors used are all industrial products. Butyl xanthate (BuX, butyl xanthate) is a product of Zhuzhou Mineral Processing Pharmacy, with a purity of about 85%: Z-200, ethyl isopropyl thionocarbamate is a product of Shenyang Institute of Mining and Metallurgy, and its purity is greater than 90%; diethylamino ethyl plug dithiocarbamate carbonitrile (E105.diethyl propyluitrite dithiocarbamate) white silver pharmaceutical plant product, purity of about 80%; xanthan nitrile butyl acrylate (OS-43, butyl propyluitrite xanthic Ester) is a product of Kunming Metallurgical Institute with low purity, about 60-80%. Water glass (WG, Water glass) is an industrial product with a modulus of 2.3. The other agents were analytically pure reagents and the foaming agent was n-octanol (OA, octyl alcoh ol). The test used one distilled water.

(3) Treatment of mineral samples

The samples were ultrasonically cleaned for 5 minutes before the test. The instrument used was a CQ50 ultrasonic cleaner.

(4) Flotation test

The flotation test was carried out in a 50 m1 hanging trough flotation machine. The chalcopyrite flotation is 2g per mineral sample. The galena flotation is 3g per ore sample, and the artificial mixed ore is separated by 4g (chalcopyrite: galena = 1..1). 50 ml of distilled water, the speed of the flotation machine impeller was 1600 rpm, and the foaming was carried out for 4 minutes.

(5) Determination of adsorption density

The residual concentration of the collector in the slurry concentrate was determined by a 751 spectrophotometer, and the adsorption density of the collector on the mineral surface was determined indirectly. The solid-liquid ratio (weight ratio) was 6.50 in the measurement, and the initial concentration of the collector was 10 mg/1. Minerals and agents work for 3 hours. During the action process, the slurry is stirred intermittently with a glass rod to ensure that the ore and the agent fully function.

Third, the test results and discussion

(1) Flotation activity of thiol esters to chalcopyrite and galena

Figures 1 and 2 show the relationship between the float rate and the pH of chalcopyrite and galena when using four agents BuX, Z-200, E105 and OS-43 as collectors. The results show:

1. The ability of thiocarbonyl ester to capture chalcopyrite is slightly lower than that of butyl xanthate. When BuX, Z-200, OS-43 and E105 are both used at 5 mg/l, the uplift rate of chalcopyrite is about 90%, 85%, 85% and 75%, respectively;

2. The ability of thiocarbonyl ester to lead ore is much weaker than that of butyl xanthate. When butyl xanthate is used as a collector, galena is easy to float in the whole pH range of the test. When the dosage is 5 mg/l, the leaching rate of galena is more than 92%; when using thiol ester, leaching The mine has a weak floatability only near pH=9. At pH=9, when the amount of Z-900, OS-43 and E105 is 5 mg/l, the leaching rate of galena is about 60%, 62% and 38%, respectively.

In summary, the selectivity of thiocarbonyl esters is higher than that of butyl xanthate.

(2) Effect of water glass on the floatability of chalcopyrite and galena

The effect of the flotation behavior of the water glass on the lead ore with or without the addition of copper ions is shown in Fig. 3 and Fig. 4, and the effect on the floatability of the chalcopyrite is shown in Fig. 5. The results shown in the figure indicate:

1. Compared with the use of butyl xanthate as a collector, the use of thiocarbonate is a strong inhibitor of water glass. When Z-200 is used as a collector, water glass can effectively inhibit galena in weak alkaline conditions. When butyl xanthate is used, water glass can effectively inhibit galena when pH>11. Mine, water glass has an excellent inhibitory effect on the lead ore near pH=6;

2, the presence of copper ions reduces the inhibitory effect of the water glass on the other side of the lead ore, in order to effectively suppress the galena must increase the pulp pH;

3. Whether using butyl xanthate or Z-200 as a collector, water glass has basically no effect on the floatability of chalcopyrite. Obviously, replacing the butyl xanthate-water glass prescription with a thiocarbonyl ester-water glass prescription may improve the separation effect of copper and lead.

(3) Separation of artificial mixed ore

The separation of copper-lead artificial mixed ore was tested on the basis of single mineral flotation research. The sorting index is calculated based on the test value of the flotation foam product. When separating, the amount of water glass is 90 mg/l, and the slurry is slurried for 3 minutes. The separation results shown in Figure 6 indicate that the separation of copper and lead by Z-200 is the best, followed by OS-43 and E105, and the butyl yellow is the worst. In order to more clearly illustrate the difference in each agent, the sorting effect was expressed by the Gauteng selectivity index i = εCu / εPb and the recovery of chalcopyrite. The sorting index of the artificial mixed ore at pH = 10.60 is shown in Table 1.

Table 1 Artificial mixed ore sorting index

index

Z-200 (5mg/l)

OS-43 (5mg/l)

E105 (5mg/l)

BuX (5mg/l)

εCu

90.0

84.0

84.0

90.0

i

45.0

21.0

10.5

9.0

The data in the table indicates that the selective order of separation of copper-lead mixed ore by various agents is: Z-200>OS-43>E105>BuX, and Z-200-water glass is expected to be a good prescription for copper-lead separation. If the prescription is successfully used to replace the two common copper-lead separation schemes of cyanide copper-lead float and dichromate-lead float copper, it is expected to solve the problems of high cost and high toxicity in production practice. Water glass has the advantages of wide source, easy preparation, low price and low toxicity.

(IV) Effect of water glass on the adsorption of collector on galena

In order to discuss the mechanism of water glass inhibiting galena, its effect on the adsorption of thiocarbonyl ester (Z-200) and butyl xanthate was studied. The results are shown in Fig. 7, Fig. 8, Fig. 9 and Fig. 10. The results of Fig. 7 and Fig. 8 show that the adsorption density of Z-200 on galena is small in the presence or absence of copper ions, and the water glass can completely prevent its adsorption on galena, thus lead The mine is completely suppressed. However, under the same conditions, although water glass reduces the adsorption density of butyl xanthate, its density is still very large, especially when copper ions are present. Therefore, galena cannot be completely suppressed. This indicates:

1. Water glass inhibits galena from being adsorbed on the mineral surface to prevent the collector from adsorbing or reducing its density.

2. When thiocarbonyl ester is used as collector, the inhibitory effect of water glass on lead ore is better than that of butyl xanthate, because thiocarbonyl ester is lower than butyl xanthate, and its sputum is affected by water glass. Big. That is, there is a weak-weak, strong-strong matching phenomenon in the reasonable matching of collectors and inhibitors.

Fourth, the conclusion

(1) Thiocarboxylate-water glass may be a good prescription for copper and lead separation.

(b) When thiocarbonyl ester is used as a collector, the water glass has a sufficient inhibitory effect on the lead ore, and the butyl yellow drug is only slightly inhibited when used as a collector.

(3) Water glass can completely prevent the adsorption of thiol ester on galena, and can not completely prevent the adsorption of butyl xanthate, indicating that there is a weak-weak, strong-strong matching relationship between collector and inhibitor.

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