Shizhuyuan Mine is a large-scale study in which more than scheelite, wolframite metals mining, comprehensive utilization of its resources has always been a subject of great concern issues over the years have been listed as national key scientific and technological projects, Especially active. In recent years, the research on the ore dressing process of this mine has made breakthrough progress. Is selected from the original ore beneficiation processes do molybdenum sulphide sulfur full floating a bismuth molybdate with bismuth molybdenum sulfur separated from a separation process. During the "Eighth Five-Year Plan" period, the process of flotation of sulphide ore was improved, and a new sulphide ore separation process was determined, that is, a process of separating molybdenum and bismuth, such as molybdenum and bismuth, and separation of sulphur and sulphur. The molybdenum and bismuth sorting index has been greatly improved.

The current production process of molybdenum in the sulphide ore is carried out with or without the addition of a non-polar collector , with the addition of pine oil as a foaming agent, and the separation of molybdenum and the like, and the separation of molybdenum and rhodium. As a collector, it is used for the separation of sulphur and other sulphur and sulphur. At present, only the pine oil is added to the floating process such as molybdenum and rhodium. Because the flotation foam of the pine oil is relatively sticky and has poor selectivity, it is easy to cause foam entrainment, resulting in low grade of concentrate, resulting in high yield of molybdenum crucible and other coarse and coarse concentrates, and low grade of molybdenum tantalum. This not only makes it difficult to separate molybdenum and niobium and molybdenum niobium, but also brings losses to the subsequent tungsten ore and fluorite selection. At the same time, because of the hysteresis of the pine oil, the subsequent tungsten separation process is greatly disturbed, and the troughing phenomenon is likely to occur in the rough selection process of tungsten, which makes the rough selection of tungsten difficult to control and brings greater loss to tungsten. According to the good floatability of molybdenum-niobium minerals and the production status of molybdenum-niobium minerals, the study of high-selective agents for flotation of molybdenum-niobium minerals can not only make molybdenum-bismuth separation and molybdenum-niobium selection easier, And reduce the subsequent loss of tungsten ore and fluorite. Therefore, it is necessary to improve the flotation status of molybdenum-niobium sulfide ore in Shizhuyuan Mine. The new agent for flotation of molybdenum and rhodium is of great practical significance.

First, the nature of the ore

The Shizhuyuan Mine is a tungsten, molybdenum, niobium and fluorite polymetallic deposit. It is mainly composed of tungsten and rhenium, accompanied by polymetallic deposits of molybdenum, tin , fluorite and garnet. It is a rare extra-large polymetallic deposit in the world. It is also an important base for the comprehensive utilization of non-ferrous metal mineral resources under development in China.

The ore-rich ore that is currently being developed in production is the skarn-Yunyingyan tungsten-molybdenum ore. Wherein the tungsten minerals are scheelite, wolframite, artifacts semi illusion scheelite and tungsten China; bismuth minerals are bismuthinite, Nature, bismuth China and orthopyroxene lead-bismuth ore; Molybdenum molybdenite and molybdenum China. Other metallic minerals are cassiterite, yellow copper ore, bornite, pyrite, and magnetite. Garnet non-metallic minerals, fluorite, quartz, feldspar, mica, calcite, pyroxenes, chlorite, epidote, hornblende, apatite and the like.

Second, the characteristics of high efficiency flotation agent

In the research and production practice activities of the comprehensive utilization of polymetallic mineral resources in Shizhuyuan Mine, according to the nature of its molybdenum-niobium sulfide ore, the process of selecting the molybdenum-niobium sulfide ore has been continuously improved. At present, the new process of separation of molybdenum-ruthenium and other float-molybdenum ruthenium separation from bismuth-sulfur and other bismuth-sulfur-separation sulphur is used to replace the separation process of the original molybdenum, sulphur, sulphur, sulphur, and sulphur separation. Nature, significantly improved the selection of molybdenum bismuth. However, before the study, the agent used in the production was pine oil, and the flotation foam of the pine oil was more sticky and less selective, which easily caused foam entrainment, resulting in lower concentrate grade and selection of subsequent tungsten. Do not bring losses; at the same time, due to the hysteresis of the pine oil, the subsequent tungsten selection process brings greater interference, resulting in poor stability of the rough selection process of tungsten, difficult to control, and often run through. In order to change the status quo of this production, the mine has been improved in many aspects and achieved certain results, but no significant progress has been made.

After analyzing the ore properties and production status, combined with years of research experience, the idea of ​​replacing the pine oil with high-efficiency new agents was proposed. After the on-site small ore dressing test, the new agent was used to replace the pine oil, the foam viscosity was greatly reduced, and the beneficiation index was significantly improved.

New efficient flotation agent proprietary BK-205, is developed by a constant to both the main foaming agent of the collector, which is based on petrochemical products as raw material, chemical processed of. BK-205 is an oily liquid with a light yellow to light brown color. It is slightly soluble in water and soluble in organic solvents such as ethanol. The product density is 0.84~0.87g/ml. The foaming speed of the medicament is strong, the foaming ability is strong, the brittleness is good, the collecting power is weak, and the retardation is poor. The product has stable performance, wide source of raw materials, low price and almost no toxicity. The product was determined, BK-205 was 5010 mg∕kg body weight for female mice by oral LD 15, and 6810 mg/kg body weight for male mice by oral LD 15 , which was an actual non-toxic grade. At the same time, the product BK-205 is easy to biodegrade compared with the pine oil, which is very beneficial to the environment.

Third, small ore dressing test

According to the ore nature of the mine and the production process at the site, it was determined that the new high-efficiency flotation agent BK-205 was used in the ore dressing comparison test. The test slurry was taken from the concentrated underflow of the thickener after grinding in the production. The process flow used in the test is shown in Figure 1. The flotation agent in the figure is pine oil or BK-205.

The small ore dressing test is divided into two parts: the molybdenum crucible open circuit test and the molybdenum tantalum tungsten open circuit test. The small test was carried out at the Shizhuyuan Mine Laboratory.

(1) Open molybdenum flotation test

The process flow of the molybdenum-bismuth open-circuit flotation test differs from the flow of Figure 1 in that there is no tungsten flotation section. The amount of pine oil is basically the same as that of BK-205 (the number of drops is the same when adding the drug, but the density of the two agents is different, the actual weight is slightly different, and the amount of BK-205 is slightly lower than that of the pine oil). The amount of other drugs is unchanged. The test results are shown in Table 1.

Figure 1 Molybdenum-tantalum tungsten open-circuit flotation process

Table 1 Open molybdenum flotation test results

From the results of Table 1, it can be seen that the two agents exhibited significantly different flotation behaviors. Compared with the pine oil, the new agent BK-205 shows a good selectivity. The grade of molybdenum and tantalum concentrate is multiplied, and the recovery rate of antimony concentrate is also greatly improved. Although the recovery rate of molybdenum is coarse. The concentrate is slightly lower, but the recovery of the concentrate and the medium mine increases the recovery of molybdenum; the loss of molybdenum and rhenium in the tailings is relatively low; and because of the low yield of molybdenum and rhodium concentrate, the tungsten is in the sulfide ore. The loss in the middle is also small, which is beneficial to the recovery of tungsten.

(II) Open-circuit flotation test of molybdenum-tungsten

After the molybdenum rhodium flotation test was carried out, in order to verify the results of the open-loop flotation test of the two kinds of the drug table 2 molybdenum-tungsten tungsten, the tungsten-containing test was carried out in the subsequent tungsten-selective test. The test results are shown in Table 2.

Table 2 Open-circuit flotation test results of molybdenum-tungsten

According to the open circuit test results of molybdenum rhenium tungsten, the results of the molybdenum rhodium flotation exhibited by the two agents are the same as those of the open molybdenum flotation test, and the crude concentrate grade and recovery rate of molybdenum rhenium are improved. The conclusion is consistent and the new agent is highly reproducible. From the selection results of tungsten, the application of the new agent BK-205 is beneficial to the tungsten sorting result, and the loss of tungsten is small. The grade of tungsten coarse concentrate is slightly higher, and the recovery rate of tungsten is also higher. Therefore, the new agent BK-205 is advantageous for tungsten selection.

From the results of the small open circuit test, the new drug BK-205 has high selectivity compared with the pine oil, which is conducive to improving the concentrate grade, which is beneficial to improve the metal recovery rate, and the loss of tungsten in the sulfide ore. Smaller, it is conducive to the subsequent flotation recovery of tungsten.

Fourth, industrial trials

Due to the small test results of the new agent, in order to further verify the small test results obtained by the new agent, the mine was determined to conduct industrial tests at one of the largest concentrators in the mine. The concentrating plant has a designed processing capacity of 1000 rid and an actual processing capacity of 1200 t/d. At present, the processing capacity of the plant has reached 1700 dd.

(1) Production process principle process

The basic situation of the process is: after the ore is graded by grinding, the overflow enters the thickener to concentrate, and the concentrated bottom stream enters the flotation operation. The fineness of the underflow is from 74 μm to 80% to 85%, and the basic monomers of various purposes are dissociated. Before the flotation operation such as molybdenum crucible, adding water glass to suppress other minerals, flotation of molybdenum crucible with molybdenum oil, molybdenum crucible and other floating concentrates to obtain molybdenum concentrate, and separation of tailings by dense desiliconization flotation to obtain eel Mine 1; molybdenum crucible and other floating tailings with ethyl sulphide nitrogen for sulphur and other floats, and other floating tailings into tungsten flotation, and other sulphur concentrates are separated by sulphur and sulphur separation to obtain bismuth concentrate 2 and sulfur concentrate; In the rough selection section, the black and white tungsten mineral is floated at a natural pH value to obtain a tungsten coarse concentrate. After thickening of tungsten coarse concentrate, it is heated to 95 ° C, water glass is added, then dehydrated and dehydrated, and then flotation is selected to obtain scheelite concentrate. After warming and selecting scheelite concentrate and hydrochloric acid leaching desulfurization, the final white is obtained. Tungsten concentrate. After the warm flotation, the tailings are selected by the shaker to obtain the black tungsten concentrate 1; after the shaker tailings are dense, the wolframite is floated by a similar agent to the rough selection of tungsten to obtain the black tungsten concentrate.

(2) Test methods

In the industrial test, when the other process flow and the dosage of the agent are basically the same, the pine oil is replaced only in the floating section such as molybdenum crucible, and the new agent BK-205 is added.

The molybdenum crucible and the like float, the molybdenum crucible separation, the antimony sulfur flotation, and the tungsten rough selection section 24 are continuously performed. Desiliconization flotation, sulphur separation and flotation are carried out according to the amount of ore.

(3) Industrial test results

During the test period, the production data of 26 classes were officially counted. In order to compare the flotation effects of the two agents, we selected a total of 25 production data for the original production process before the test. Production indicators during this time are used as reference for the test indicators. See Tables 3 and 4 for the statistical indicators of the rough selected section of tungsten-molybdenum-bismuth during the test and during the production period.

Table 3 Comparison of tungsten index and previous production index with new drug BK-205

Table 4 Comparison of rough selection index of molybdenum bismuth with new production agent BK-205 and previous production index

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