Micro-emulsion collecting agent for flotation of high-mud-content and high-oxidation molybdenite and preparation and application of micro-emulsion collecting agent

Abstract

The invention discloses a microemulsion collecting agent for flotation of high-mud-content and high-oxidation molybdenite and preparation and application of the microemulsion collecting agent and belongs to the technical field of mineral processing, kerosene, xanthate or black powder collecting agents, a main emulsifier, a cosurfactant and water are mixed according to a certain proportion and then subjected to ultrasonic emulsification treatment, and the microemulsion collecting agent is obtained. According to the micro-emulsion collecting agent prepared through the method, after one-time roughing and two-time scavenging are conducted, the molybdenum recovery rate is remarkably increased compared with the molybdenum recovery rate when a kerosene collecting agent is singly used, the micro-emulsion collecting agent is simple in preparation method, high in emulsion stability, high in dispersity in ore pulp and free of slime interference, and the separation and recovery problem of high-argillization molybdenite is well solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of mineral processing, and in particular relates to a microemulsion collector for high-silt high-oxidized molybdenite flotation and a preparation and application thereof. BACKGROUND

[0002] Molybdenum, as a strategic rare metal, is mainly derived from molybdenite. Molybdenite has good natural floatability and is traditionally recovered by flotation using non-polar hydrocarbon oil collectors such as kerosene and diesel. However, with the continuous development and utilization of molybdenum resources, the properties of molybdenite ores gradually exhibit the characteristics of "poor, fine and impure", with a smaller "area-to-edge ratio" and increased hydrophilicity, significantly increasing the difficulty of flotation. Traditional hydrocarbon oil collectors have good collecting ability for the hydrophobic "area" of molybdenite, but poor adsorption effect on the hydrophilic "edge", and poor dispersibility in the ore slurry, which is easily affected by the inevitable sludge in the ore slurry, resulting in large reagent dosage, poor recovery index and difficulty in meeting the current production needs.

[0003] In terms of molybdenite flotation collectors, Chinese patent CN118594776A reports "a collector for fine-grained molybdenite and its preparation method and application". The collector used in this patent is a complex hydrocarbon oil collector, which is composed of pyrolysis oil, 1-allyl-3-3-methyl imidazole bis-trifluoromethanesulfonate and kerosene. Although the complex hydrocarbon oil collector has good flotation recovery effect, the preparation process requires a long time and complex operation. Chinese patent CN114226071A reports "a molybdenite emulsified collector and its preparation method". The emulsified collector in this patent is prepared from diesel, coconut oil, methanol, concentrated sulfuric acid, etc. The emulsified collector of this invention has a higher molybdenum recovery rate than the single use of diesel collector in mineral flotation, but its preparation process is complex, costly and harsh, which limits its wide application.

[0004] The use of multiple collectors can improve the collecting power and selectivity of the reagent, and emulsification can reduce the oil-water interfacial tension, form stable emulsions, increase the collision probability with mineral particles, and thus improve the flotation efficiency. Therefore, based on the above background technology, it is urgent to develop a microemulsion complex collector that is efficient, environmentally friendly and simple to prepare, in order to overcome the poor recovery index of existing collectors for high-silt high-oxidized molybdenite. SUMMARY

[0005] The technical problem solved by the present application is to overcome the deficiencies of the prior art, and provide a microemulsion collector for high-mud high-oxidized molybdenum ore flotation and a preparation and application thereof.

[0006] To solve the above technical problems, the basic idea of the technical solution of the present application is:

[0007] A preparation method of a microemulsion collector for strengthening high-mud high-oxidized molybdenum ore flotation, comprising the following steps:

[0008] (1) A certain mass ratio of kerosene, main emulsifier, xanthate or black drug, co-surfactant and water phase (ultra-pure water) is weighed, and then oscillated for 2-3 min, and then mixed by stirring until the solution in the system becomes slightly turbid, and a microemulsion collector is preliminarily formed;

[0009] (2) The microemulsion collector preliminarily obtained in step (1) is further emulsified in an ultrasonic emulsification disperser at room temperature, and a stable microemulsion collector is obtained.

[0010] Preferably, the main emulsifier in step (1) is selected from at least one of the following: sodium dodecyl sulfonate, dioctadecyl dimethyl ammonium chloride, OP-13, sorbitan monostearate (Span 60), sorbitan monooleate (Span 80), polyoxyethylene sorbitan monooleate (Tween 80), and polyoxyethylene sorbitan monolaurate (Tween 20)

[0011] Preferably, the co-surfactant in step (1) is selected from at least one of the following: n-butanol, ethanol, n-pentanol, and n-hexanol.

[0012] Preferably, the xanthate or black drug in step (1) is selected from at least one of the following: ethyl xanthate, butyl xanthate, or butyl ammonium black drug, and No. 25 black drug.

[0013] Preferably, the ultrasonic power in step (2) is 60-200 W, and the ultrasonic time is 20 min.

[0014] After adopting the above technical solution, the present application has the following beneficial effects compared with the prior art.

[0015] The prepared molybdenum flotation collector has simple preparation method, and is prepared on site. After one roughing and two scavenging, the molybdenum recovery rate is significantly improved compared with the single use of kerosene collector. The microemulsion collector is applied to the flotation of high-silt high-oxidized molybdenum, which effectively improves the grade and recovery rate of molybdenum roughing, and is beneficial to the efficient recovery and utilization of molybdenum resources.

[0016] The specific embodiments of the present application will be further described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0017] The accompanying drawings, which are part of the present application, serve to further understand the present application, and the schematic embodiments of the present application and the descriptions thereof serve to explain the present application, but do not constitute improper limitations on the present application. Obviously, the accompanying drawings in the following description are only some embodiments, and other drawings can be obtained by those skilled in the art without creative labor. In the drawings:

[0018] Figure 1 is the particle size distribution of the conventional collector kerosene;

[0019] Figure 2 is the particle size distribution of the microemulsion collector of the present application.

[0020] It should be noted that these drawings and written descriptions are not intended to limit the scope of the concept of the present application in any way, but to illustrate the concept of the present application to those skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present application. The following embodiments are used to illustrate the present application, but not to limit the scope of the present application.

[0022] Case 1

[0023] A microemulsion collector preparation method for strengthening high-silt high-oxidized molybdenum flotation, comprising the following steps:

[0024] (1) Take kerosene, main emulsifier, xanthate or black drug, co-surfactant and ultrapure water according to the mass ratio of 7:4:1:2:7, first shake for 2-3 min, then mix by stirring until the solution in the system becomes slightly turbid, and preliminarily form a microemulsion collector;

[0025] (2) The microemulsion collector obtained in step (1) is placed in an ultrasonic emulsification disperser at room temperature for further emulsification for 20 min, and the ultrasonic power is 60 W, to obtain a stable microemulsion collector;

[0026] Figure 2 The particle size distribution of the microemulsion collector is determined by Zeta measurement. As shown in the figure, the average particle size is 28.21 nm. As shown in the figure, the average particle size of the traditional kerosene is 531.2 nm, which indicates that the particle size of the microemulsion collector is smaller, and its dispersion performance in the ore slurry is better, which can increase the collision probability with molybdenite. Figure 1

[0027] Case 2: Application of a certain high-mud high-oxidized tungsten-molybdenum ore flotation

[0028] A certain tungsten-molybdenum ore in Sanmenxia, Henan Province is selected. The molybdenum grade of the raw ore is about 0.394%, and the grinding fineness of the roughing section is less than 200 mesh, accounting for 80%. The reagent system of the plant is: water glass as depressant, MIBC as frother (dosage is 20 g / t), and kerosene as collector; the reagent system used in this study is: sodium hexametaphosphate as depressant, MIBC as frother, dosage is 2500 g / t and 20 g / t, respectively, and the microemulsion collector prepared with a mass ratio of 7:4:1:2:7 as collector. The flotation test process of "one roughing and two scavenging" is adopted, and the results are shown in Table 1.

[0029] Table 1 is the flotation effect of different collectors

[0030] Flotation conditions Mo grade, % Mo recovery, % Ore grade, % Water glass 2500 g / t, kerosene 200 g / t 1.31 19.69 0.394 Water glass 3500 g / t, kerosene 200 g / t 0.96 39.01 0.394 Water glass 2500 g / t, kerosene 208 g / t 0.68 34.20 0.394 Water glass 2500 g / t, kerosene 800 g / t 1.572 33.18 0.394 Microemulsion collector 400 g / t 1.720 37.63 0.394 Microemulsion collector 800 g / t 2.673 48.25 0.394 Microemulsion collector 1000 g / t 2.671 51.76 0.394 Microemulsion collector 1500 g / t 2.096 56.96 0.394

[0031] It can be seen that after one roughing and two scavenging, a molybdenum concentrate with a grade of 2.671% and a recovery of 51.76% is obtained. Compared with the single kerosene used in the plant, under the same process conditions, the grade and recovery of molybdenum are increased by 1.101% and 15.07%, respectively.

[0032] Case 3: Application of a certain molybdenum ore flotation

[0033] A certain molybdenum ore in Luoyang, Henan Province is selected. The molybdenum grade of the raw ore is 0.137%, and the grinding fineness of the roughing section is less than 200 mesh, accounting for 80%. The roughing section adopts the open-circuit flotation experiment of "one roughing and two scavenging". The microemulsion collector prepared with a mass ratio of 7:4:1:2:7 of kerosene, main emulsifier, xanthate or black drug, auxiliary surfactant and pure water is used as collector, and the dosage of the depressant is increased in turn. The results of the roughing test for flotation of molybdenum ore are shown in Table 2.

[0034] Table 2 is the flotation effect of the microemulsion collector

[0035] Flotation conditions Mo grade, % Mo recovery, % Ore grade, % Inhibitor A 250 g / t, kerosene 800 g / t 1.01 45.02 0.1374 Inhibitor A 250 g / t, microemulsion collector 800 g / t 1.86 53.38 0.1374 Inhibitor A 1000 g / t, microemulsion collector 800 g / t 2.11 49.76 0.1374 Inhibitor A 2500 g / t, microemulsion collector 800 g / t 4.88 45.24 0.1374

[0036] ​The test results show that when the grinding fineness, inhibitor and dosage of the foaming agent are the same, the grade and recovery of the rough concentrate obtained by using the microemulsion collector are significantly higher than those obtained by using the traditional kerosene collector, and the flotation performance can be improved by preparing the microemulsion collector by using the emulsification method.

[0037] Embodiment 4

[0038] The microemulsion collector is prepared by using Span80 and Tween20 with a mass ratio of 1:1 as the main emulsifier, adding kerosene and the main emulsifier in a mass ratio of 6:4, and then adding ultrapure water and performing oscillation and ultrasonic emulsification, and under the premise that other process parameters are not changed, the microemulsion collector is used as the collector, added into the ore slurry, stirred for a period of time, and then the foaming agent is added for flotation and froth scraping operations.

[0039] When kerosene is used as the collector, the grade of the rough molybdenum concentrate obtained by flotation is 3.692%, and the recovery rate is 25.32%, and when the microemulsion collector is used, the grade of the rough molybdenum concentrate is 1.941%, and the recovery rate is 39.57%, which is increased by 14.25 percentage points.

[0040] Embodiment 5

[0041] The microemulsion collector is prepared by using Span80 and Tween20 with a mass ratio of 1:1 as the main emulsifier, adding kerosene and the main emulsifier in a mass ratio of 6:4, and then adding ultrapure water and performing oscillation and ultrasonic emulsification, and under the premise that other process parameters are not changed, the microemulsion collector is used as the collector, added into the ore slurry, stirred for a period of time, and then the foaming agent is added for flotation and froth scraping operations.

[0042] When kerosene is used as the collector, the grade of the rough molybdenum concentrate obtained by flotation is 3.692%, and the recovery rate is 25.32%, and when the microemulsion collector is used, the grade of the rough molybdenum concentrate is 1.538%, and the recovery rate is 49.06%, which is increased by 23.74 percentage points.

[0043] Embodiment 6

[0044] The molybdenite with a purity of 98% is prepared by crushing, selecting and removing impurities, and the microemulsion collector prepared by using kerosene, the main emulsifier, xanthate or black drug, a cosurfactant and pure water in a mass ratio of 7:4:1:2:7 is used in the pure mineral flotation test, and when the dosage of the microemulsion collector is 100, 125 and 150 mg / L, the recovery rate of the molybdenite reaches more than 99%, but when kerosene is used as the collector, the recovery rate of the molybdenite is about 95%, and therefore, the flotation effect of the microemulsion collector of the application is better than that of the traditional kerosene collector in the pure mineral flotation test.

[0045] The above merely describes the preferred embodiments of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed with the preferred embodiments as above, it is not intended to limit the present application, and any skilled person in the art can make some changes or modifications to the above-mentioned technical content with the prompt as equivalent embodiments of equivalent changes without departing from the technical solution of the present application. Any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, which does not depart from the technical solution of the present application, still belongs to the scope of the present application.

Claims

1. A microemulsion collector for enhancing the flotation of high-muddy, high-oxidation molybdenite, characterized in that, It comprises the following components: kerosene, primary emulsifier, xanthate or black powder, co-surfactant, and ultrapure water, wherein the mass ratio of kerosene, primary emulsifier, xanthate or black powder, co-surfactant, and ultrapure water is 7:4:1:2:

7.

2. The microemulsion collector for enhancing the flotation of high-muddy, high-oxidation molybdenite according to claim 1, characterized in that, The primary emulsifier is selected from one or any combination of sodium dodecyl sulfonate, dioctadecyl dimethyl ammonium chloride, OP-13, sorbitan monostearate, and sorbitan monooleate.

3. The microemulsion collector for enhancing the flotation of high-muddy, high-oxidation molybdenite according to claim 1, characterized in that, The co-surfactant is selected from one or any combination of n-butanol, ethanol, n-pentanol, and n-hexanol.

4. The microemulsion collector for enhancing the flotation of high-muddy, high-oxidation molybdenite according to claim 1, characterized in that, The yellow or black powder is selected from one or any combination of ethyl yellow powder, butyl yellow powder, butylammonium black powder, and No. 25 black powder.

5. The method for preparing the microemulsion collector according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Weigh kerosene, main emulsifier, xanthate or black powder, co-surfactant and ultrapure water according to the mass ratio, shake for 2-3 minutes, then stir and mix until the solution in the system becomes slightly turbid, and a microemulsion collector is initially formed. (2) At room temperature, place the microemulsion collector obtained in step (1) into an ultrasonic emulsifier for further emulsification to obtain a stable microemulsion collector.

6. The preparation method according to claim 5, characterized in that, The ultrasonic power of the ultrasonic emulsifier and disperser is 60-200W, and the ultrasonic time is 20min.

7. The application of a microemulsion collector as described in any one of claims 1-4 or a microemulsion collector prepared by the method described in claim 5 or 6 in the flotation of high-muddy, high-oxidation tungsten-molybdenum ore.

8. The application according to claim 7, characterized in that, The dosage of microemulsion collector is 400-1500 g / t.

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