Application of poly (ethylene polyamine) as copper molybdenum mineral flotation copper inhibitor and method

Abstract

The invention provides application of poly (ethylene polyamine) as a copper molybdenum mineral flotation copper inhibitor and a method, and belongs to the technical field of mineral flotation. According to the method, the poly (ethylene polyamine) can inhibit copper minerals and float molybdenum minerals in the flotation process of the copper-molybdenum minerals, can form compounds with high hydrophilic power on the surfaces of the copper minerals, but does not react with the molybdenum minerals, so that selection of the copper minerals is inhibited. Besides, when the poly (ethylene polyamine) is used as the copper molybdenum mineral flotation copper inhibitor, the odor is low, the dosage is small and is equivalent to one tenth of that of sodium sulfide or sodium hydrosulfide, medicament accumulation caused by long-term use is avoided, and the environment-friendly treatment cost can be reduced. And the poly (ethylene polyamine) agent is simple and easy to obtain, relatively stable in chemical property, easy to dissolve in water, convenient to prepare, capable of being stored for a long time and small in danger coefficient.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral flotation, in particular to application and method of polyethylene polyamine as copper inhibitor for copper-molybdenum mineral flotation. BACKGROUND

[0002] Copper and molybdenum are a pair of closely associated elements, and molybdenum is associated with copper in almost all copper minerals. Most molybdenum is also recovered through copper, so copper-molybdenum separation is extremely important in the production process of copper-molybdenum metals. At present, there is no reagent that can have significant selectivity for copper and molybdenum respectively, and it is necessary to inhibit one side while selecting the other side.

[0003] At present, there are mainly three methods for the flotation separation of copper-molybdenum minerals: one is to inhibit copper minerals, first select molybdenum minerals and then select copper minerals, the second is to inhibit molybdenum minerals, first select copper minerals and then select molybdenum minerals, and the third is to first mix copper-molybdenum minerals, then inhibit copper minerals, select molybdenum minerals, and separate copper and molybdenum into copper concentrate and molybdenum concentrate respectively. The first two methods have the same shortcoming, that is, the inhibited copper and molybdenum, when being floated again, have the problem of drug removal, and the recovery rate is greatly reduced. The third method recovers molybdenum while selecting copper, and becomes copper-molybdenum concentrate, with high recovery rate. Although the first process of the third method is simple, the subsequent copper-molybdenum separation is difficult. The main problem is that there is no good inhibitor for inhibiting copper.

[0004] The most commonly used copper flotation inhibitor at present is sodium sulfide and / or sodium hydrosulfide. This reagent is easy to produce sulfide when used, has a bad smell, and has a very poor working environment. In addition, when sodium sulfide and sodium hydrosulfide are used as copper flotation inhibitors, the consumption is large and the effect is not good, and often 8-9 stages of separation are needed to achieve the expected effect. After being used for many times, sulfide will accumulate in the solution, which seriously affects the subsequent production effect, and the solution must be treated regularly to open the circuit, which increases the environmental protection cost of the enterprise. SUMMARY

[0005] Therefore, the present application aims to provide application and method of polyethylene polyamine as copper inhibitor for copper-molybdenum mineral flotation. The present application uses polyethylene polyamine as copper inhibitor for copper-molybdenum mineral flotation, and has high copper removal rate.

[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions: The present application provides application of polyethylene polyamine as copper inhibitor for copper-molybdenum mineral flotation, and the polyethylene polyamine includes one or more of tetraethylene pentamine, triethylene tetramine and diethylene triamine.

[0007] Preferably, the mass content of amino nitrogen in the polyethylene polyamine is 15-25%.

[0008] Preferably, the mass ratio of the polyethylene polyamine to copper-molybdenum minerals is 100-200g:1t.

[0009] The application provides a flotation method of copper-molybdenum minerals, which comprises the following steps: The copper-molybdenum minerals are mixed with water, a dispersing agent, a collecting agent and a copper flotation inhibitor to perform rough selection, so as to obtain rough selection concentrate; The rough selection concentrate is subjected to fine selection, so as to obtain molybdenum concentrate; The copper flotation inhibitor is the polyethylene polyamine.

[0010] Preferably, the dispersing agent comprises sodium silicate; and the mass ratio of the dispersing agent to the copper-molybdenum minerals is 1-3 kg:1 t. The collecting agent comprises kerosene; and the mass ratio of the collecting agent to the copper-molybdenum minerals is 5-15 g:1 t.

[0011] Preferably, the mass ratio of the polyethylene polyamine to the copper-molybdenum minerals is 100-200 g:1 t.

[0012] Preferably, after the copper-molybdenum minerals are mixed with water, a dispersing agent, a collecting agent and a copper flotation inhibitor, the pH value of the obtained mixed solution is adjusted to 5-7.

[0013] Preferably, the liquid-solid ratio of the rough selection is 1-5:1, and the time is 3-8 min.

[0014] Preferably, the liquid-solid ratio of the fine selection is 5-15:1, and the time is 2-6 min. The number of times of the fine selection is 1-6.

[0015] Preferably, the copper content in the copper-molybdenum minerals is 17-22%, and the molybdenum content is 1-4%. The particle size of the copper-molybdenum minerals is 100-200 mesh.

[0016] The application provides application of polyethylene polyamine as a copper flotation inhibitor for copper-molybdenum minerals, wherein the components of the polyethylene polyamine comprise one or more of tetraethylenepentamine, triethylenetetramine and diethylenetriamine. In the application, the polyethylene polyamine can inhibit the copper minerals and float the molybdenum minerals in the flotation process of the copper-molybdenum minerals. The polyethylene polyamine can form a stable amine and copper complex which is easily soluble in water on the surface of the copper minerals, but does not react with the molybdenum minerals, so as to inhibit the selection of the copper minerals. In addition, when the polyethylene polyamine is used as the copper flotation inhibitor for the copper-molybdenum minerals, the polyethylene polyamine has low odor and small dosage, which is equivalent to one tenth of the dosage of sodium sulfide or sodium hydrosulfide, and does not cause accumulation of the reagent due to long-term use, thereby reducing the environmental protection treatment cost. In addition, the polyethylene polyamine reagent is simple to obtain, has stable chemical properties, is easily soluble in water, is convenient to prepare, can be stored for a long time and has small danger coefficient.

[0017] The application provides a flotation method of copper-molybdenum minerals, comprising the following steps: mixing copper-molybdenum minerals with water, a dispersing agent, a collecting agent and a flotation copper inhibitor, performing rough separation to obtain rough separation concentrate; performing cleaning separation on the rough separation concentrate to obtain molybdenum concentrate; the flotation copper inhibitor is the polyethylene polyamine.

[0018] Further, the flotation method provided by the application has a short process, and only 5-6 stages of separation are needed to achieve the expected effect. DETAILED DESCRIPTION

[0019] The application provides application of polyethylene polyamine as a flotation copper inhibitor of copper-molybdenum minerals, and the components of the polyethylene polyamine include one or more of tetraethylenepentamine (H2N(CH2NH)3CH2CH2NH2), triethylenetetramine (H2N(CH2CH2NH)2CH2CH2NH2) and diethylenetriamine (H2NCH2NHCH2CH2NH2).

[0020] In the application, the mass content of amino nitrogen in the polyethylene polyamine is preferably 15-25%, and more preferably 20%.

[0021] In the application, the polyethylene polyamine is a dark viscous liquid and is easily soluble in water. In a solution with a pH value of 5-6, the polyethylene polyamine can form a very stable water-soluble complex with copper.

[0022] In the application, the mass ratio of the polyethylene polyamine to the copper-molybdenum minerals is preferably 100-200 g:1 t, and more preferably 150 g:1 t.

[0023] The application provides a flotation method of copper-molybdenum minerals, comprising the following steps: mixing copper-molybdenum minerals with water, a dispersing agent, a collecting agent and a flotation copper inhibitor, performing rough separation to obtain rough separation concentrate; performing cleaning separation on the rough separation concentrate to obtain molybdenum concentrate; the flotation copper inhibitor is the polyethylene polyamine.

[0024] In the application, the copper-molybdenum minerals are preferably copper-molybdenum concentrate; in the application, the copper content in the copper-molybdenum minerals is preferably 17-22%, and more preferably 18-20%, and the molybdenum content is preferably 1-4%, and more preferably 2-3%. In the application, the particle size of the copper-molybdenum minerals is preferably 150-200 mesh.

[0025] In the application, the dispersing agent preferably includes sodium silicate; the mass ratio of the dispersing agent to the copper-molybdenum minerals is preferably 1-3 kg:1 t, and more preferably 2 kg:1 t.

[0026] In the present application, the collector preferably comprises kerosene; the mass ratio of the collector to the copper-molybdenum mineral is preferably 5-15 g: 1 t, and more preferably 10 g: 1 t. In the present application, the kerosene also serves as a frother.

[0027] In the present application, the mass ratio of the polyethylene polyamine to the copper-molybdenum mineral is preferably 100-200 g: 1 t, and more preferably 150 g: 1 t. In the present application, the mixing is preferably performed under stirring, and the stirring time is preferably 0.5-2 h, and more preferably 1 h.

[0028] In the present application, after the copper-molybdenum mineral is mixed with water, a dispersant, a collector and a copper flotation inhibitor, the pH value of the obtained mixture is adjusted to 5-7. The present application does not have special requirements for the reagent used for adjusting the pH value, and an acidic or basic reagent known in the art can be used.

[0029] In the present application, the liquid-solid ratio of the roughing is preferably 1-5: 1, more preferably 2-4: 1, and further preferably 3: 1, and the time is preferably 3-8 min, and more preferably 5 min. In the present application, in the process of the roughing, the target mineral molybdenum mineral floats on water due to hydrophobicity, and is scraped out from the liquid surface by a scraper, and the non-target mineral copper mineral remains in the slurry due to hydrophilicity, and is discharged from the tank bottom.

[0030] In the present application, the liquid-solid ratio of the cleaning is preferably 5-15: 1, more preferably 8-12: 1, and further preferably 10: 1, and the time of a single cleaning is preferably 2-6 min, and more preferably 4 min; and the number of cleanings is preferably 1-6 times, and more preferably 2-5 times.

[0031] The application of the polyethylene polyamine as a copper-molybdenum mineral copper flotation inhibitor and the method provided by the present application will be described in detail below with reference to the examples, but they should not be understood as limiting the scope of protection of the present application.

[0032] Example 1 A copper-molybdenum concentrate (containing 18.26% of copper and 2.59% of molybdenum) was taken, the liquid-solid ratio was controlled to be 3: 1, and 2 kg / t of sodium silicate, 10 g / t of kerosene and 100 g / t of polyethylene polyamine (specifically triethylene tetramine, the content of amino nitrogen was 20%) were added based on the mass of the copper-molybdenum concentrate, stirring was performed for 1 hour, and then roughing was performed, the roughing time was 5 minutes, and a roughing concentrate was obtained. The roughing concentrate was directly cleaned, the liquid-solid ratio of the cleaning was 10: 1, and the time was 4 minutes.

[0033] Example 2 Compared with Example 1, the addition amount of the polyethylene polyamine was 150 g / t, and the rest of the operations were the same.

[0034] Example 3 Compared with Example 1, the polyethylene polyamine is added in an amount of 200 g / t, and the rest of the operations are the same.

[0035] Comparative Example 1 Compared with Example 1, the polyethylene polyamine is replaced by sodium sulfide, which is added in an amount of 2 kg / t, and the rest of the operations are the same.

[0036] The flotation results obtained in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0037] Table 1 Flotation results obtained in Examples 1-3 and Comparative Example 1

[0038] It can be seen that when the polyethylene polyamine is added in an amount of 150 g / t, which is equivalent to 7.5% of the amount of sodium sulfide, the primary concentrate yield is much lower than that of sodium sulfide, and the molybdenum content and copper removal rate are much higher than those of sodium sulfide as the depressant.

[0039] Example 4 On the basis of Example 2, six cleanings are carried out, and the conditions of each cleaning remain unchanged. The flotation results obtained are shown in Table 2.

[0040] Table 2 Results of six cleanings in Example 4

[0041] As can be seen from Table 2, after six cleanings, the molybdenum content of the molybdenum concentrate obtained using polyethylene polyamine is much higher than that of sodium sulfide, and the molybdenum recovery rate is also higher than that of sodium sulfide.

[0042] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the technical field, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. The application of polyethylene polyamine as a copper depressant in the flotation of copper-molybdenum minerals, characterized in that, The polyethylene polyamine includes one or more of tetraethylenepentamine, triethylenetetramine, and diethylenetriamine.

2. The application according to claim 1, characterized in that, The amino nitrogen content in the polyethylene polyamine is 15-25% by mass.

3. The application according to claim 1 or 2, characterized in that, The mass ratio of the polyethylene polyamine to the copper-molybdenum mineral is 100~200g:1t.

4. A flotation method for copper-molybdenum minerals, characterized in that, Includes the following steps: The copper-molybdenum minerals are mixed with water, dispersant, collector and flotation copper inhibitor, and roughing is carried out to obtain roughing concentrate; The roughing concentrate is further refined to obtain molybdenum concentrate; The flotation copper inhibitor is the polyethylene polyamine used in any one of claims 1 to 3.

5. The method according to claim 4, characterized in that, The dispersant includes sodium silicate; the mass ratio of the dispersant to copper-molybdenum mineral is 1-3 kg: 1 t. The collector includes kerosene; the mass ratio of the collector to copper-molybdenum minerals is 5-15 g: 1 t.

6. The method according to claim 4, characterized in that, The mass ratio of the polyethylene polyamine to the copper-molybdenum mineral is 100~200g:1t.

7. The method according to claim 4, characterized in that, The copper-molybdenum minerals are mixed with water, dispersant, collector and flotation copper inhibitor, and the pH of the resulting mixture is adjusted to 5-7.

8. The method according to claim 4 or 7, characterized in that, The liquid-to-solid ratio for the coarse selection is 1-5:1, and the time is 3-8 minutes.

9. The method according to claim 4 or 7, characterized in that, The selected liquid-to-solid ratio is 5~15:1, and the time is 2~6 minutes; The number of selections is 1 to 6.

10. The method according to claim 4, characterized in that, The copper-molybdenum mineral contains 17-22% copper and 1-4% molybdenum. The copper-molybdenum mineral has a grain size of 100-200 mesh.

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