Coordinated regulation micro-fine particle molybdenite surface and edge combined collecting agent and flotation method thereof

Abstract

The invention provides a flotation method of micro-fine-particle molybdenite, which comprises the following steps: adding water into micro-fine-particle molybdenite raw ore, stirring into ore pulp, and then adjusting the pH value of the ore pulp; firstly adding emulsified composite hydrocarbon oil with a certain concentration for size mixing, then adding AEO-3P or AEO-9P for size mixing, and finally adding a foaming agent for size mixing and then carrying out flotation; and carrying out air inflation flotation to obtain foam concentrate products and tailings. According to the combined collecting agent, the hydrophobicity of surfaces and edges of molybdenite can be regulated and controlled at the same time, the floatability of micro-fine particle molybdenite is remarkably improved, and the compatibility among all agent components is good. The collecting effect of the combined collecting agent is obviously better than that of the single emulsified hydrocarbon oil or anionic surfactant, and the combined collecting agent is small in dosage and low in cost.

Description

Technical Field

[0001] The invention discloses a combined collector for cooperatively regulating fine-grained molybdenite faces and edges and a use method thereof, and relates to the technical field of mineral flotation. Background Art

[0002] As an important strategic reserve metal, molybdenum is widely used in various fields such as aerospace, energy and chemical industry, and medical equipment. At present, 95% of molybdenum is produced from molybdenite. As high-grade and easy-to-select molybdenite resources are gradually exhausted, the phenomenon of poor and fine ore hybridization is becoming more and more serious. It must be finely ground to fully dissociate it and efficiently recover the molybdenite by flotation. Molybdenite is a typical anisotropic layered mineral. During its dissociation process, two crystal faces are formed: non-polar hydrophobic "faces" formed by van der Waals force fracture and polar hydrophilic "edges" formed by covalent bond fracture. Fine-grained molybdenite has a high edge / face ratio, so it has strong hydrophilicity and poor floatability. Kerosene, diesel and other non-polar hydrocarbon oils are widely used in molybdenite flotation as traditional molybdenite collectors. Usually, trace amounts of emulsifiers are added to improve the dispersibility and stability of non-polar hydrocarbon oils, which mainly act on the molybdenite "face" in the form of physical adsorption. The "edges" of fine-grained molybdenite are dominant, and the "surface" area of ​​molybdenite is reduced, making it difficult for hydrocarbon oil collector molecules to act effectively on its "surface", resulting in poor floatability and poor flotation effect. Therefore, the development of an efficient, low-cost, and fine-grained molybdenite combined collector that can selectively adsorb on both the "surface" and "edges" of molybdenite is of great significance for the recovery of fine-grained molybdenite.

[0003] In terms of molybdenite flotation collectors, Chinese patent CN113171879A reported "a flotation collector for low-grade molybdenite and its preparation method". This method uses a composite hydrocarbon oil composed of kerosene, light diesel and o-divinylbenzene, and introduces double-bonded hydrocarbons with a certain polarity to prepare a flotation collector for low-grade molybdenite. This method has complex ingredients and requires a long emulsification time. Chinese patent CN114226071A reported "a molybdenite emulsified collector and its preparation method". The collector is made of diesel, coconut oil, methanol, concentrated sulfuric acid, water and other raw materials in a certain weight fraction, which effectively improves the rough recovery rate of molybdenite. However, the preparation process of this method requires heating, the conditions are relatively harsh, the time is long, and the cost is high, which is not conducive to large-scale production and use. Chinese patent CN117206085A reported "Highly selective molybdenite flotation collector and its preparation method and use", which prepared sodium diisobutyl dithiophosphite and mixed it with aromatic oil to obtain a highly selective molybdenite flotation collector. This study mainly focused on molybdenite particles with a particle size greater than -20μm, but for -20μm fine molybdenite, due to its dominant "edges" and enhanced hydrophobicity, the flotation efficiency needs further exploration. Summary of the invention

[0004] In view of the problems of poor floatability and low recovery rate of fine-particle molybdenite, the purpose of the present invention is to provide a combined collector to improve the flotation of fine-particle molybdenite, and the hydrophobicity of the "face" and "edge" of molybdenite is synergistically regulated by the combined collector, thereby achieving efficient recovery of fine-particle molybdenite.

[0005] The technical solution provided by the present invention is as follows: A collector for synergistically regulating the surface and edge combination of fine-grained molybdenite, which uses an emulsified composite hydrocarbon oil and a phosphate anionic surfactant to achieve the collector effect; The emulsified composite hydrocarbon oil is obtained by mixing kerosene and diesel and then emulsifying with an emulsifier, alkylphenol polyoxyethylene ether APE-9; The phosphate anionic surfactant is AEO-3P or AEO-9P.

[0006] The mixing mass ratio of the kerosene to the diesel is 1:(0.25-2).

[0007] The mass percentage of the emulsifier alkylphenol polyoxyethylene ether APE-9 is 10% to 30% of the total amount of the composite hydrocarbon oil and the emulsifier.

[0008] Another technical solution of the present invention is to provide a flotation method for fine-grained molybdenite, comprising the following steps: (1) Add water to the fine-grained molybdenite ore and stir it into a slurry, and then adjust the pH value of the slurry; (2) First, add a certain concentration of emulsified composite hydrocarbon oil to make a slurry, then add AEO-3P or AEO-9P to make a slurry, and finally add a frother to make a slurry and then flotation; (3) Aeration flotation to obtain foam concentrate products and tailings.

[0009] In step (1), the slurry concentration is 2-10%, and the pH is adjusted to 2-12, and more preferably the pH is adjusted to 2-10. For example, 2, 4, 6, 8, 10, etc., but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0010] The mass concentration of the emulsified composite hydrocarbon oil in step (2) is 10-30 mg / L.

[0011] The emulsified composite hydrocarbon oil is obtained by mixing kerosene and diesel and then emulsifying them with an emulsifier, alkylphenol polyoxyethylene ether APE-9.

[0012] The mixing mass ratio of kerosene to 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.

[0013] In some preferred schemes, the mixing 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.

[0014] The mass concentration of AEO-3P or AEO-9P is 10 mg / L -50 mg / L. For example, 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, 45 mg / L, etc., but it is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0015] The foaming agent is selected from any one of methyl isobutyl carbinol and No. 2 oil; the concentration of the foaming agent is 20-40 mg / L.

[0016] Fatty alcohol polyoxyethylene ether phosphate AEO-3P and AEO-9P both have excellent cleaning, emulsification, dispersion, cleaning, wetting, antistatic and rust prevention properties, good stability, acid resistance, alkali resistance, high temperature resistance, hard water resistance, inorganic salt resistance, good biodegradability, and are widely used in daily chemical industry and are harmless to the environment.

[0017] The inventors found that when applied to the field of mineral processing and flotation technology, fatty alcohol polyoxyethylene ether phosphate AEO-3P and AEO-9P can perform characteristic adsorption on molybdenite, thereby achieving the capture of fine-grained molybdenite and significantly improving the flotation effect of fine-grained molybdenite. In addition, it is non-toxic and environmentally friendly, and has a good capture effect.

[0018] In this solution, 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, and form an extremely stable hydrocarbon oil microemulsion, thereby improving the adsorption of the emulsified composite hydrocarbon oil on the "surface" of molybdenite and improving its "surface" hydrophobicity. Fatty alcohol polyoxyethylene ether phosphate AEO-3P and AEO-9P both have solid-philic phosphate groups, hydrophilic polyoxyethylene ether groups, and hydrophobic hydrocarbon groups. This structure makes it easy for the phosphate groups in the collector molecular structure to chemically react with the molybdenum atoms on the "edges" of fine-grained molybdenite to generate PO-Mo bonds, exposing the hydrophobic groups to the aqueous solution to improve the hydrophobicity on the "edges". The hydrophilic polyoxyethylene ether groups have the ability to reduce the surface tension of water, produce good foaming effects, and improve the floating effect of fine-grained molybdenite.

[0019] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects: (1) The anionic surfactant described in the present invention has good solubility as a collector, strong collecting effect, and a wide pH range. It has been widely used in the chemical industry and is easy to promote on a large scale.

[0020] (2) The combined collector of the present invention can simultaneously regulate the hydrophobicity of the "face" and "edge" of molybdenite, significantly improve the floatability of fine-grained molybdenite, and the compatibility between the various reagent components is good.

[0021] (3) The combined collector provided by the present invention has a significantly stronger capture effect than using emulsified hydrocarbon oil or anionic surfactant alone, and the amount used is small and the cost is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a flow chart of the application steps of the combined collector of the present application in the flotation of fine-grained molybdenite. DETAILED DESCRIPTION

[0023] The following are specific embodiments of the present invention and the accompanying drawings to further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.

[0024] Example 1 Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation, take an appropriate amount of deionized water and add it into 70 mL of the hanging tank flotation machine, stir and adjust the slurry at a speed of 1300 r / min to make the slurry fully dispersed.

[0025] according to Figure 1 The reagent system adds reagents to adjust the pH of the ore pulp to 2, the concentration of the emulsified composite hydrocarbon oil is 10 mg / L (wherein the mass percentage of kerosene:diesel is 4:1, and the mass percentage of the composite hydrocarbon oil:emulsifier is 4:1), the concentration of AEO-3P or AEO-9P is 10 mg / L, and the concentration of MIBC is 20 mg / L. After aeration flotation, foam products and tailings are obtained.

[0026] The foam product and tailings were filtered, dried, and weighed, and the floating rate was calculated. Under the same conditions, only the same amount of emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC were added as comparative example 1. The results are shown in Table 1.

[0027] From the flotation results, it can be seen 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 the combined collector can significantly improve the recovery effect of molybdenite, and the compatibility between the reagent components is good.

[0028] Table 1

[0029] Example 2 Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation, take an appropriate amount of deionized water and add it into 70 mL of the hanging tank flotation machine, stir and adjust the slurry at a speed of 1300 r / min to make the slurry fully dispersed.

[0030] according to Figure 1 The reagent system adds reagents to adjust the pH of the slurry to 4, the concentration of the emulsified composite hydrocarbon oil is 20 mg / L (wherein the mass percentage of kerosene:diesel is 4:1, and the mass percentage of the composite hydrocarbon oil:emulsifier is 3:1), the concentration of AEO-3P or AEO-9P is 25 mg / L, and the concentration of MIBC is 20 mg / L. After aeration flotation, foam products and tailings are obtained.

[0031] The foam product and tailings were filtered, dried, and weighed, and the floating rate was calculated. Under the same conditions, only the same amount of single emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC were added as comparative example 2. The results are shown in Table 2.

[0032] From the flotation results, it can be seen that the flotation rate of the 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 the emulsified mixed hydrocarbon oil and 10.14% higher than that of AEO-3P.

[0033] Table 2

[0034] Example 3 Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation, take an appropriate amount of deionized water and add it into 70 mL of the hanging tank flotation machine, stir and adjust the slurry at a speed of 1300 r / min to make the slurry fully dispersed.

[0035] according to Figure 1 The reagent system adds reagents to adjust the pH of the slurry to 6, the concentration of the emulsified composite hydrocarbon oil is 40 mg / L (wherein the mass percentage of kerosene:diesel is 4:1, and the mass percentage of the composite hydrocarbon oil:emulsifier is 4:1), the concentration of AEO-3P or AEO-9P is 25 mg / L and 30 mg / L respectively, and the concentration of MIBC is 20 mg / L. After aeration flotation, foam products and tailings are obtained.

[0036] The foam product and tailings were filtered, dried, and weighed, and the floating rate was calculated. Under the same conditions, only the same amount of single emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC were added as comparative example 3. The results are shown in Table 3.

[0037] From the flotation results, it can be seen that the capture effect of fine molybdenite in Example 3 is significantly better than that in 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.

[0038] Table 3

[0039] Example 4 Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation, take an appropriate amount of deionized water and add it into 70 mL of the hanging tank flotation machine, stir and adjust the slurry at a speed of 1300 r / min to make the slurry fully dispersed.

[0040] according to Figure 1 The reagent system adds reagents to adjust the pH of the ore pulp to 8, the concentration of the emulsified composite hydrocarbon oil is 40 mg / L (wherein the mass percentage of kerosene:diesel is 1:1, and the mass percentage of the composite hydrocarbon oil:emulsifier is 3:1), the concentration of AEO-3P or AEO-9P is 25 mg / L and 40 mg / L respectively, and the concentration of MIBC is 20 mg / L. After aeration flotation, foam products and tailings are obtained.

[0041] The foam product and tailings were filtered, dried, and weighed, and the floating rate was calculated. Under the same conditions, only the same amount of single emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC were added as comparative example 4. The results are shown in Table 4.

[0042] From the flotation results, it can be seen that the capture effect of fine molybdenite in Example 4 is significantly better than that in 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.

[0043] Table 4

[0044] Example 5 Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation, take an appropriate amount of deionized water and add it into 70 mL of the hanging tank flotation machine, stir and adjust the slurry at a speed of 1300 r / min to make the slurry fully dispersed.

[0045] according to Figure 1The reagent system adds reagents to adjust the pulp pH to 10, the concentration of emulsified composite hydrocarbon oil is 40 mg / L (wherein the mass percentage of kerosene:diesel is 1:1, the mass percentage of composite hydrocarbon oil:emulsifier is 2:1), the concentration of AEO-3P or AEO-9P is 50 mg / L, and the concentration of MIBC is 20 mg / L. After aeration flotation, foam products and tailings are obtained.

[0046] The foam product and tailings were filtered, dried, and weighed, and the floating rate was calculated. Under the same conditions, only the same amount of emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC were added as comparative example 5. The results are shown in Table 5.

[0047] From the flotation results, it can be seen that the capture effect of fine molybdenite in Example 5 is significantly better than that in 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.

[0048] Table 5

[0049] Example 6 Take 2 g of molybdenite single mineral with a particle size of -20 μm for flotation, take an appropriate amount of deionized water and add it into 70 mL of the hanging tank flotation machine, stir and adjust the slurry at a speed of 1300 r / min to make the slurry fully dispersed.

[0050] according to Figure 1 The reagent system adds reagents to adjust the pulp pH to 12, the concentration of emulsified composite hydrocarbon oil is 50 mg / L (wherein the mass percentage of kerosene:diesel is 1:2, the mass percentage of composite hydrocarbon oil:emulsifier is 10:1), the concentration of AEO-3P or AEO-9P is 50 mg / L, and the concentration of MIBC is 20 mg / L. After aeration flotation, foam products and tailings are obtained.

[0051] The foam product and tailings were filtered, dried, and weighed, and the floating rate was calculated. Under the same conditions, only the same amount of single emulsified mixed hydrocarbon oil, AEO-3P / AEO-9P, and MIBC were added as comparative example 6. The results are shown in Table 6.

[0052] Compared with Comparative Example 6, Example 6 can significantly improve the flotation rate of fine molybdenite. Although the collecting ability of the single collector in the comparative example is relatively weak, the collecting ability of the combined collector is significantly enhanced, achieving a better flotation effect.

[0053] Table 6

[0054] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A collector for synergistically regulating fine-grained molybdenite surface and edge combination, characterized in that: The collector effect is achieved by using emulsified composite hydrocarbon oil and phosphate anionic surfactant in combination; The emulsified composite hydrocarbon oil is obtained by mixing kerosene and diesel and then emulsifying with an emulsifier, alkylphenol polyoxyethylene ether APE-9; The phosphate anionic surfactant is AEO-3P or AEO-9P.

2. The synergistically regulated fine-grained molybdenite surface and edge combined collector according to claim 1, characterized in that: The mixing mass ratio of kerosene to diesel is 1:(0.25-2).

3. The synergistically regulated fine-grained molybdenite surface and edge combined collector according to claim 1, characterized in that: The mass percentage of the emulsifier alkylphenol polyoxyethylene ether APE-9 is 10% to 30% of the total amount of the composite hydrocarbon oil and the emulsifier.

4. A flotation method for fine-grained molybdenite, characterized in that: The following steps are involved: (1) Add water to the fine-grained molybdenite ore and stir it into a slurry, and then adjust the pH value of the slurry; (2) First, add a certain concentration of emulsified composite hydrocarbon oil to make a slurry, then add AEO-3P or AEO-9P to make a slurry, and finally add a frother to make a slurry and then flotation; (3) Aeration flotation to obtain foam concentrate products and tailings.

5. The flotation method of fine-grained molybdenite according to claim 4, characterized in that: In step (1), the slurry concentration is 2-10%, and the pH is adjusted to 2-12, more preferably the pH is adjusted to 2-10.

6. The flotation method of fine-grained molybdenite according to claim 4, characterized in that: The mass concentration of the emulsified composite hydrocarbon oil in step (2) is 10-30 mg / L; The emulsified composite hydrocarbon oil is obtained by mixing kerosene and diesel and then emulsifying with an emulsifier alkylphenol polyoxyethylene ether APE-9; The mixing mass ratio of kerosene to 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.

7. The flotation method of fine-grained molybdenite according to claim 6, characterized in that: The mixing 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.

8. The flotation method of fine-grained molybdenite according to claim 4, characterized in that: The mass concentration of AEO-3P or AEO-9P is 10 mg / L -50 mg / L.

9. The flotation method of fine-grained molybdenite according to claim 4, characterized in that: The foaming agent is selected from any one of methyl isobutyl carbinol and No. 2 oil; the concentration of the foaming agent is 20-40 mg / L.

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