A combined collector for synergistically regulating the surface of fine molybdenite particles and edges and a flotation method thereof

Abstract

The present application provides a kind of molybdenite flotation method of micro fine particle, and the molybdenite ore of micro fine particle is stirred into ore slurry by adding water, and then the pH of ore slurry is adjusted;First, a certain concentration of emulsified composite hydrocarbon oil is added to adjust the pulp, then AEO-3P or AEO-9P is added to adjust the pulp, and finally a foaming agent is added to adjust the pulp, and then flotation is carried out;Air flotation is carried out to obtain froth concentrate product and tailings.The present application can simultaneously control the hydrophobicity of molybdenite "face" and "edge" in the combined collector, significantly improve the floatability of micro fine particle molybdenite, and the compatibility between each component of the reagent is good.The combined collector provided by the present application has a significantly stronger collecting effect than the emulsified hydrocarbon oil or anionic surfactant used alone, has a small amount and a low cost.

Description

TECHNICAL FIELD

[0001] The application discloses a combined collector for synergistically regulating the surface and edge of fine molybdenite and a use method thereof, and relates to the technical field of mineral flotation. BACKGROUND

[0002] Molybdenum is an important strategic reserve metal and is widely used in various fields such as aerospace, energy and chemical industry, and medical devices. At present, 95% of molybdenum is produced from molybdenite. As high-grade and easily selected molybdenite resources are gradually consumed, the ore is increasingly poor and miscellaneous, and must be finely ground to fully dissociate and then recovered by flotation. Molybdenite is a typical anisotropic layered mineral, and two crystal faces are formed during its dissociation: non-polar hydrophobic "surface" formed by van der Waals force rupture and polar hydrophilic "edge" formed by covalent bond rupture. Fine molybdenite has high edge / surface ratio, strong hydrophilicity and poor floatability. Non-polar hydrocarbons such as kerosene and diesel are widely used as traditional molybdenite collectors in molybdenite flotation, and a small amount of emulsifier is usually added to improve the dispersibility and stability of non-polar hydrocarbons. The collector mainly acts on the "surface" of molybdenite in the form of physical adsorption. The "edge" of fine molybdenite dominates, and the "surface" area of molybdenite is reduced, making it difficult for the hydrocarbon collector molecules to effectively act on the "surface" of molybdenite, resulting in poor floatability and poor flotation effect. Therefore, it is of great significance to develop an efficient, low-cost and combined collector for fine molybdenite that can selectively adsorb on the "surface" and "edge" of molybdenite at the same time.

[0003] In the aspect of molybdenite flotation collectors, Chinese patent CN113171879A reports a "flotation collector for low-grade molybdenite and a preparation method thereof", which uses a composite hydrocarbon oil composed of kerosene, light diesel oil and o-divinylbenzene to prepare a flotation collector for low-grade molybdenite. The method has complex components and requires a long emulsification time. Chinese patent CN114226071A reports a "molybdenite emulsified collector and a preparation method thereof", which is prepared from diesel oil, coconut oil, methanol, concentrated sulfuric acid, water and other raw materials according to a certain weight fraction, effectively improving the recovery rate of molybdenite roughing. However, the preparation process requires heating, harsh conditions, a long time and high cost, which is not conducive to large-scale production and use. Chinese patent CN117206085A reports a "high-selectivity molybdenite flotation collector, a preparation method and use thereof", which prepares diisobutyl sodium dithiophosphinate, mixes it with aromatic hydrocarbon oil to obtain a high-selectivity molybdenite flotation collector. The study mainly focuses on molybdenite particles with a particle size greater than-20 μm, but for fine molybdenite with a particle size of-20 μm, the "edge" dominates, the hydrophobicity is enhanced, and the flotation efficiency needs to be further explored. SUMMARY

[0004] In view of the poor floatability and low recovery rate of micro-fine molybdenite, the purpose of the present application is to provide a combined collector to improve the flotation of micro-fine molybdenite, and to realize the efficient recovery of micro-fine molybdenite by synergistically regulating the hydrophobicity of the "face" and "edge" of molybdenite through the combined collector.

[0005] The technical solution provided by the present application is as follows:

[0006] A combined collector for synergistically regulating the face and edge of micro-fine molybdenite, which realizes the effect of the collector by using emulsified composite hydrocarbon oil and phosphate anionic surfactant in combination;

[0007] The emulsified composite hydrocarbon oil is obtained by emulsifying kerosene and diesel oil with an emulsifier alkylphenol polyoxyethylene ether APE-9 after mixing;

[0008] The phosphate anionic surfactant is AEO-3P or AEO-9P.

[0009] The mass ratio of kerosene to diesel oil is 1:(0.25-2).

[0010] The mass percentage of the emulsifier alkylphenol polyoxyethylene ether APE-9 is 10%-30% of the total amount of composite hydrocarbon oil and emulsifier.

[0011] Another technical solution of the present application is to provide a flotation method for micro-fine molybdenite, which comprises the following steps:

[0012] (1) The micro-fine molybdenite ore is stirred into a slurry with water, and the pH of the slurry is adjusted;

[0013] (2) A certain concentration of emulsified composite hydrocarbon oil is first added to adjust the slurry, then AEO-3P or AEO-9P is added to adjust the slurry, and finally a frother is added to adjust the slurry before flotation;

[0014] (3) Air flotation to obtain froth concentrate product and tailings.

[0015] In step (1), the concentration of the slurry is 2-10%, and the pH is adjusted to 2-12, and further preferably to 2-10. For example, 2, 4, 6, 8, 10, etc., but not limited to the listed values, other values not listed within this range are also applicable.

[0016] In step (2), the mass concentration of the emulsified composite hydrocarbon oil is 10-30 mg / L.

[0017] The emulsified composite hydrocarbon oil is obtained by emulsifying kerosene and diesel oil with an emulsifier alkylphenol polyoxyethylene ether APE-9 after mixing.

[0018] The mass ratio of kerosene and diesel is 1: (0.25-2); the mass percentage of the emulsifier alkylphenol polyoxyethylene ether APE-9 is 10%-30% of the total amount of the composite hydrocarbon oil and the emulsifier.

[0019] In some preferred schemes, the mass ratio of kerosene and diesel is 4:1; the mass percentage of the emulsifier alkylphenol polyoxyethylene ether APE-9 is 25% of the total amount of the composite hydrocarbon oil and the emulsifier.

[0020] The mass concentration of AEO-3P or AEO-9P is 10 mg / L-50 mg / L.

[0021] The foaming agent is selected from any one of methyl isobutyl carbinol or No. 2 oil; the concentration of the foaming agent is 20-40 mg / L.

[0022] The fatty alcohol polyoxyethylene ether phosphate AEO-3P and AEO-9P have excellent dirt removal, emulsification, dispersion, cleaning, wetting, antistatic and antirust properties, and good stability, acid resistance, alkali resistance, high temperature resistance, hard water resistance, inorganic salt resistance, biodegradability, and are widely used in daily chemical industry without harm to the environment.

[0023] The inventors find that, when applied in the field of mineral processing and flotation, the fatty alcohol polyoxyethylene ether phosphate AEO-3P and AEO-9P can be adsorbed on molybdenite, thereby realizing the collection of fine-grained molybdenite and significantly improving the flotation effect of fine-grained molybdenite, and the fatty alcohol polyoxyethylene ether phosphate AEO-3P and AEO-9P are non-toxic and environmentally friendly and have good collection effect.

[0024] In the scheme, APE-9 can significantly reduce the interfacial tension between the oil phase and the water phase, greatly promote the dispersion of the composite hydrocarbon oil in water, form extremely stable hydrocarbon oil microemulsion, and thus improve the adsorption of the emulsified composite hydrocarbon oil on the "surface" of molybdenite and improve the hydrophobicity of the "surface".

[0025] Compared with the prior art, the technical scheme of the present application has the following beneficial technical effects:

[0026] (1) The anionic surfactant described in this invention has good solubility, strong collection effect, and wide pH range as a collector. It has been widely used in the chemical industry and is easy to promote on a large scale.

[0027] (2) The combined collector described in this invention can simultaneously regulate the hydrophobicity of the "face" and "edge" of molybdenite, significantly improve the floatability of fine-grained molybdenite, and the components of the agent have good compatibility.

[0028] (3) The combined collector provided by the present invention has a significantly stronger collecting effect than the use of emulsified hydrocarbon oil or anionic surfactant alone, and requires less dosage and has a lower cost. Attached Figure Description

[0029] Figure 1 This is a flowchart illustrating the application steps of the combined collector in the flotation of fine-grained molybdenite. Detailed Implementation

[0030] The following are specific embodiments of the present invention, which are described in conjunction with the accompanying drawings to further illustrate the technical solutions of the present invention. However, the present invention is not limited to these embodiments.

[0031] Example 1

[0032] Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation cell and stir at 1300 r / min to adjust the slurry and ensure that the slurry is fully dispersed.

[0033] according to Figure 1 The reagent formulation includes the addition of reagents to adjust the slurry pH to 2, the concentration of emulsified complex hydrocarbon oil to 10 mg / L (where the mass percentage of kerosene to diesel is 4:1 and the mass percentage of complex hydrocarbon oil to emulsifier is 4:1), the concentration of AEO-3P or AEO-9P to 10 mg / L, and the concentration of MIBC to 20 mg / L. After aeration flotation, froth products and tailings are obtained.

[0034] The foam product and tailings were filtered, dried, and weighed separately, and the buoyancy rate was calculated. For comparison, only one type of emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC were added in the same amount under the same conditions. The results are shown in Table 1.

[0035] The flotation results show that the flotation rate of fine-grained molybdenite in Example 1 is significantly better than that in Comparative Example 1. Taking "emulsified mixed hydrocarbon oil + AEO-3P + MIBC" as an example, its flotation rate is 30.74% higher than that of emulsified mixed hydrocarbon oil and 26.21% higher than that of AEO-3P, indicating that this combination collector can significantly improve the recovery effect of molybdenite, and that the components of the reagents have good compatibility.

[0036] Table 1

[0037]

[0038] Example 2

[0039] Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation cell and stir at 1300 r / min to adjust the slurry and ensure that the slurry is fully dispersed.

[0040] according to Figure 1 The reagent formulation includes the addition of reagents to adjust the pulp pH to 4, the concentration of emulsified complex hydrocarbon oil to 20 mg / L (where the mass percentage of kerosene to diesel is 4:1 and the mass percentage of complex hydrocarbon oil to emulsifier is 3:1), the concentration of AEO-3P or AEO-9P to 25 mg / L, and the concentration of MIBC to 20 mg / L. After aeration flotation, froth products and tailings are obtained.

[0041] The foam product and tailings were filtered, dried, and weighed separately, and the buoyancy rate was calculated. Comparative Example 2 included the addition of the same amounts of single emulsified mixed hydrocarbon oils, AEO-3P / AEO-9P, and MIBC under identical conditions. The results are shown in Table 2.

[0042] The flotation results show that the flotation rate of fine-grained molybdenite in Example 2 is significantly better than that in Comparative Example 2. Taking "emulsified mixed hydrocarbon oil + AEO-3P + MIBC" as an example, its flotation rate is 21.33% higher than that of emulsified mixed hydrocarbon oil and 10.14% higher than that of AEO-3P.

[0043] Table 2

[0044]

[0045] Example 3

[0046] Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation cell and stir at 1300 r / min to adjust the slurry and ensure that the slurry is fully dispersed.

[0047] according to Figure 1 The reagent formulation described above involves adding reagents to adjust the pulp pH to 6, setting the concentration of the emulsified complex hydrocarbon oil to 40 mg / L (where the mass percentage of kerosene to diesel is 4:1 and the mass percentage of complex hydrocarbon oil to emulsifier is 4:1), the concentrations of AEO-3P and AEO-9P to 25 mg / L and 30 mg / L respectively, and the concentration of MIBC to 20 mg / L. After aeration flotation, froth products and tailings are obtained.

[0048] The foam product and tailings were filtered, dried, and weighed separately, and the buoyancy rate was calculated. Comparative Example 3 included only one emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC, added in the same amounts under the same conditions. The results are shown in Table 3.

[0049] The flotation results show that Example 3 has a significantly better collection effect on fine-grained molybdenite than Comparative Example 3. Taking "emulsified mixed hydrocarbon oil + AEO-3P + MIBC" as an example, its flotation rate is 14.91% higher than that of emulsified mixed hydrocarbon oil and 23.13% higher than that of AEO-3P.

[0050] Table 3

[0051]

[0052] Example 4

[0053] Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation cell and stir at 1300 r / min to adjust the slurry and ensure that the slurry is fully dispersed.

[0054] according to Figure 1 The reagent formulation described above involves adding reagents to adjust the slurry pH to 8, setting the concentration of the emulsified complex hydrocarbon oil to 40 mg / L (where the mass percentage of kerosene to diesel is 1:1 and the mass percentage of complex hydrocarbon oil to emulsifier is 3:1), the concentrations of AEO-3P and AEO-9P to 25 mg / L and 40 mg / L respectively, and the concentration of MIBC to 20 mg / L. After aeration flotation, froth products and tailings are obtained.

[0055] The foam product and tailings were filtered, dried, and weighed separately, and the buoyancy rate was calculated. Comparative Example 4 included only one emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC, with the same dosage added under identical conditions. The results are shown in Table 4.

[0056] The flotation results show that Example 4 has a significantly better collection effect on fine-grained molybdenite than Comparative Example 4. Taking "emulsified mixed hydrocarbon oil + AEO-9P + MIBC" as an example, its flotation rate is 12.17% higher than that of emulsified mixed hydrocarbon oil and 29.6% higher than that of AEO-9P.

[0057] Table 4

[0058]

[0059] Example 5

[0060] Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation cell and stir at 1300 r / min to adjust the slurry and ensure that the slurry is fully dispersed.

[0061] according to Figure 1 The reagent formulation includes the addition of reagents to adjust the pulp pH to 10, the concentration of emulsified complex hydrocarbon oil to 40 mg / L (where the mass percentage of kerosene to diesel is 1:1 and the mass percentage of complex hydrocarbon oil to emulsifier is 2:1), the concentration of AEO-3P or AEO-9P to 50 mg / L, and the concentration of MIBC to 20 mg / L. After aeration flotation, froth products and tailings are obtained.

[0062] The foam product and tailings were filtered, dried, and weighed separately, and the buoyancy rate was calculated. Comparative Example 5 included only one emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC, with the same dosage added under identical conditions. The results are shown in Table 5.

[0063] The flotation results show that Example 5 has a significantly better collection effect on fine-grained molybdenite than Comparative Example 5. Taking "emulsified mixed hydrocarbon oil + AEO-9P + MIBC" as an example, its flotation rate is 22.14% higher than that of emulsified mixed hydrocarbon oil and 23.39% higher than that of AEO-9P.

[0064] Table 5

[0065]

[0066] Example 6

[0067] Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation cell and stir at 1300 r / min to adjust the slurry and ensure that the slurry is fully dispersed.

[0068] according to Figure 1 The reagent formulation includes the addition of reagents to adjust the pulp pH to 12, the concentration of emulsified complex hydrocarbon oil to 50 mg / L (where the mass percentage of kerosene to diesel is 1:2 and the mass percentage of complex hydrocarbon oil to emulsifier is 10:1), the concentration of AEO-3P or AEO-9P to 50 mg / L, and the concentration of MIBC to 20 mg / L. After aeration flotation, froth products and tailings are obtained.

[0069] The foam product and tailings were filtered, dried, and weighed separately, and the buoyancy rate was calculated. Comparative Example 6 included only one emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC, with the same dosage added under identical conditions. The results are shown in Table 6.

[0070] Compared with Comparative Example 6, Example 6 can significantly improve the floating rate of the fine molybdenite particles. Although the collecting ability of the single collector in the comparative example is weak, the collecting ability of the combined collector is obviously enhanced, and a good flotation effect is achieved.

[0071] Table 6

[0072]

[0073] The above description is merely preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A synergistic conditioning collector for fine molybdenite faces and edges, characterized in that, The emulsified composite hydrocarbon oil and phosphate anionic surfactant are included. The emulsified composite hydrocarbon oil is obtained by mixing kerosene and diesel oil and then using emulsifier alkyl phenol polyoxyethylene ether APE-9 for emulsification. The phosphate anionic surfactant is AEO-3P or AEO-9P.

2. The synergistic conditioning micro-finely ground molybdenite face and edge combined collector agent according to claim 1, characterized in that, The mass ratio of kerosene to diesel oil is 1: (0.25-2).

3. The synergistic conditioning micro-finely ground molybdenite face and edge combined collector reagent of claim 1, wherein, The mass percentage of emulsifier alkyl phenol polyoxyethylene ether APE-9 in the total amount of composite hydrocarbon oil and emulsifier is 10%-30%.

4. A method for the flotation of fine molybdenite particles, characterized in that, The method comprises the following steps: (1) stirring the fine-grained molybdenite ore with water to form an ore slurry, and adjusting the pH of the ore slurry; (2) adding a certain concentration of emulsified composite hydrocarbon oil to adjust the slurry, then adding AEO-3P or AEO-9P to adjust the slurry, and finally adding a foaming agent to adjust the slurry and then performing flotation; the emulsified composite hydrocarbon oil is obtained by mixing kerosene and diesel oil and then using emulsifier alkyl phenol polyoxyethylene ether APE-9 for emulsification; (3) air flotation to obtain a foamed concentrate product and tailings.

5. The method for the flotation of fine molybdenite particles according to claim 4, characterized by, The concentration of the ore slurry in step (1) is 2-10%, and the pH is adjusted to 2-12.

6. The method for the flotation of fine molybdenite particles according to claim 5, characterized by, The pH in step (1) is adjusted to 2-10.

7. The method for the flotation of fine molybdenite particles according to claim 4, characterized by, The mass concentration of the emulsified composite hydrocarbon oil in step (2) is 10-30 mg / L. The mass ratio of kerosene to diesel oil is 1: (0.25-2), and the mass percentage of emulsifier alkyl phenol polyoxyethylene ether APE-9 in the total amount of composite hydrocarbon oil and emulsifier is 10%-30%.

8. The method for the flotation of fine molybdenite particles according to claim 7, characterized by, The mass ratio of kerosene to diesel oil is 4:1, and the mass percentage of emulsifier alkyl phenol polyoxyethylene ether APE-9 in the total amount of composite hydrocarbon oil and emulsifier is 25%.

9. The method for the flotation of fine molybdenite particles according to claim 4, characterized by, The mass concentration of AEO-3P or AEO-9P is 10 mg / L-50 mg / L.

10. The method for the flotation of fine molybdenite particles according to claim 4, characterized by, The foaming agent is selected from any one of methyl isobutyl carbinol or No. 2 oil, and the concentration of the foaming agent is 20-40 mg / L.

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