A fine particle molybdenite combined collector and its application method

Abstract

The present application provides emulsified kerosene, which comprises an emulsifier and kerosene, the emulsifier being selected from C10-16 alcohol alkoxylate and / or polyethylene glycol 600 monooleate. The mass percentage of the emulsifier is 10% to 35% of the kerosene; when the emulsifier is C10-16 alcohol alkoxylate and polyethylene glycol 600 monooleate, the mass ratio of C10-16 alcohol alkoxylate to polyethylene glycol 600 monooleate is 0.3-3:1. The combined collector provided by the present application can synergistically regulate the hydrophobicity of the surface and edge of molybdenite, significantly improve the flotation performance of fine-grained molybdenite, and meanwhile, good compatibility is shown between the components of the collector. The combined collector provided by the present application is significantly superior to emulsified kerosene or non-ionic surfactant used alone in terms of collecting effect, and has lower dosage and cost.

Description

TECHNICAL FIELD

[0001] The application discloses a combined collector for fine molybdenite and an application method thereof, and relates to the field of mineral flotation reagents. BACKGROUND

[0002] Molybdenum, as a transition metal element in the fifth period of the periodic table, is widely used in national defense, aerospace, energy and chemical industry, and electronic and electric power industries due to its excellent thermal and electrical conductivity, outstanding mechanical properties, and unique advantages of maintaining high strength and high hardness in high-temperature environments. Molybdenite is the main mineral of molybdenum metal, and has extremely high industrial value. With the exhaustion of high-grade molybdenite resources, the exploitation of fine-grained and low-grade molybdenite is crucial to meet the huge market demand. The ore needs to be finely ground to separate molybdenite from gangue, and then flotation is performed. Molybdenite is a typical layered structure mineral with obvious anisotropy, and has both hydrophilic and hydrophobic surface properties.

[0003] The hydrophilic edge is formed by the breakage of Mo-S covalent bonds, and the hydrophobic surface is formed by the breakage of S-Mo-S interlayer van der Waals forces. As the particle size of molybdenite decreases, the edge / surface ratio increases, resulting in a decrease in the hydrophobicity of molybdenite and a sharp decrease in floatability.

[0004] Kerosene, as a traditional collector in the flotation process of molybdenite, mainly acts on the surface of molybdenite in the form of physical adsorption. Due to its non-polar characteristics, it is difficult to dissolve in water, making it difficult to disperse uniformly in the ore slurry. When the dosage of the reagent is large, it is easy to defoam, resulting in a shallow and thin foam layer, and usually needs to be emulsified for use. During the grinding process, the coarse molybdenite mainly breaks along the cleavage plane, at this time the surface area of molybdenite is greater than the edge, while the fine molybdenite breaks along the cleavage plane and the fracture plane, and the edge area increases sharply. Therefore, the edge of molybdenite less than 20 μm dominates, and the traditional emulsified kerosene is difficult to adsorb on the edge of fine molybdenite due to its large particle size. Therefore, it is of great significance to develop a combined collector that is efficient, environmentally friendly, and can selectively adsorb on the surface and edge of molybdenite for the efficient recovery of fine molybdenite.

[0005] In terms of molybdenite flotation collector, Chinese patent CN118594776A reports "a collector for fine-grained molybdenite and its preparation method and application", the collector described in the patent is a complex hydrocarbon oil collector, the composition includes pyrolysis oil, 1-allyl-3-methyl imidazole bis-trifluoromethyl sulfonimide salt and kerosene, although the effect of the collector is better than kerosene, the preparation process requires a long time, and it is mainly suitable for molybdenite with relatively coarse particle size (-38 μm accounts for 90%), the collector effect for molybdenite with finer particle size (-20 μm) needs further study. Chinese patent CN117797952A reports "a microemulsion collector for strengthening molybdenite flotation and its preparation method", the method mixes coal tar-based aromatic hydrocarbon oil, diesel and kerosene according to the mass ratio to prepare a composite hydrocarbon oil, mixes the main surfactant and the auxiliary surfactant according to the proportion to prepare a composite emulsifier, and then ultrasonically strengthens the dispersion of the composite hydrocarbon oil and the composite emulsifier to prepare the microemulsion collector. The microemulsion collector has good molybdenite floating rate, but the composition is complex, the preparation process is long, and it is not conducive to popularization and use in -20 μm fine-grained molybdenite flotation. SUMMARY

[0006] In view of the problems of poor flotation performance and low recovery rate of fine-grained molybdenite, the present application aims to provide a combined collector to optimize the flotation process of fine-grained molybdenite, and to realize efficient recovery of fine-grained molybdenite by synergistically regulating the hydrophobicity of the faces and edges of molybdenite through the combined collector.

[0007] The technical scheme of the present application is as follows:

[0008] The first object of the present application is to provide an emulsified kerosene, which comprises an emulsifier and kerosene, and the emulsifier is selected from C10-16 alcohol alkoxylate (NEP-10) and / or polyethylene glycol 600 monooleate (PEG600MO).

[0009] When the emulsifier is C10-16 alcohol alkoxylate (NEP-10) and polyethylene glycol 600 monooleate (PEG600MO), the mass ratio of C10-16 alcohol alkoxylate (NEP-10) and polyethylene glycol 600 monooleate (PEG600MO) is 0.3-3:1.

[0010] The mass percentage of the emulsifier is 10%-35% of the kerosene.

[0011] In the preparation method of the emulsified kerosene, the emulsifier is added to the kerosene, and the emulsified kerosene is obtained by high-speed shearing stirring.

[0012] The high-speed shearing stirring refers to shearing stirring at 2000-3000 r / min for 3-5 min.

[0013] High shear stirring generates high shear force, combined with the use of emulsifier NEP-10 or PEG600MO can significantly reduce the oil-water interfacial tension. In the molecular structure of emulsifier NEP-10 and PEG600MO, the hydrophobic alkyl chain enhances the affinity with the oil phase, and the hydrophilic polyoxyethylene ether group enhances the affinity with the water phase, both of which can effectively reduce the interfacial tension between kerosene and water, and form stable oil-in-water emulsion under the action of high shear force, the emulsifier molecules are oriented on the surface of oil droplets, the emulsion particle size is smaller, the distribution is more uniform, thereby significantly increasing the contact area and collision times of kerosene on the surface of fine-grained molybdenite, improving the adsorption performance of kerosene on the surface of fine-grained molybdenite, and enhancing the hydrophobic performance.

[0014] Another object of the present application is to provide a fine-grained molybdenite combined collector, which comprises the emulsified kerosene.

[0015] In some embodiments, the collector further comprises a non-ionic surfactant selected from octadecylamine polyoxyethylene ether AC-1815 and / or AC-1820.

[0016] Both octadecylamine polyoxyethylene ether AC-1815 and AC-1820 contain amine groups, hydrophilic polyoxyethylene ether groups and hydrophobic hydrocarbon groups, such molecular structure enables the collector molecules to preferentially adsorb on the edge of fine-grained molybdenite, thereby exposing the hydrophobic group to the aqueous solution, improving the hydrophobicity of the edge. In addition, the hydrophilic polyoxyethylene ether group has the property of reducing the water surface tension, producing good foaming effect, and improving the floating effect of fine-grained molybdenite.

[0017] Another object of the present application is to provide the application of the fine-grained molybdenite combined collector in the flotation of fine-grained molybdenite, which is less than 20 μm molybdenite.

[0018] The edge of molybdenite less than 20 μm is dominant, and the traditional emulsified kerosene has a large particle size and is difficult to adsorb on the edge of fine-grained molybdenite, therefore, a kind of efficient, environmentally friendly, and capable of selectively adsorbing on the surface and edge of molybdenite and realizing the flotation of fine-grained molybdenite less than 20 μm is developed.

[0019] Another object of the present application is to provide a flotation method of fine-grained molybdenite, comprising the following steps:

[0020] (1) mixing and stirring the fine-grained molybdenite ore with water to prepare a slurry, and then adjusting the pH value of the slurry;

[0021] (2) first add a certain concentration of emulsified kerosene for 1-5 min, then add a certain concentration of AC-1815 or AC-1820 for 1-5 min, finally add a foaming agent for 0.5-1 min before flotation;

[0022] (3) aerated flotation for 1-3 min to obtain a foam concentrate product and tailings.

[0023] In a preferred embodiment, the pH of the slurry during the flotation process is in the range of 2-10, and the mass concentration of the emulsified kerosene is 5-50 mg / L.

[0024] The mass concentration of the non-ionic surfactant is 0-50 mg / L, and is further preferably 10-50 mg / L.

[0025] In a preferred embodiment, when the collector is used in the slurry, the foaming agent is selected from any one of methyl isobutyl carbinol or No. 2 oil, and the mass concentration of the foaming agent is 0-30 mg / L.

[0026] Compared with the prior art, the technical scheme of the present application has the following beneficial technical effects:

[0027] (1) The combination collector provided by the present application has a simple formula, high stability, environmental protection, good biodegradability, and low prices and easy availability of raw materials.

[0028] (2) The non-ionic surfactant involved in the present application has excellent solubility, significant collecting effect, and a wide applicable pH range, and has been widely used in the chemical industry and is easy to implement large-scale promotion.

[0029] (3) The combination collector provided by the present application can synergistically regulate the hydrophobicity of the surface and edge of molybdenite, significantly improving the flotation performance of fine and micro-fine molybdenite, and showing good compatibility between the components of the medicament.

[0030] (4) The combination collector provided by the present application is significantly superior to emulsified kerosene or non-ionic surfactants in terms of collecting effect, and has a low dosage and cost. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is the application steps flow chart of the combination collector in the flotation of fine and micro-fine molybdenite.

[0032] Figure 2 is the SEM-EDX scanning diagram of the edge after being treated by emulsified kerosene and octadecylamine polyoxyethylene ether AC-1815 in Example 1.

[0033] Figure 3 is a SEM-EDX scanning diagram of the surface of the molybdenite treated with emulsified kerosene and octadecylamine polyoxyethylene ether AC-1815 in Example 1. DETAILED DESCRIPTION

[0034] The following is a specific embodiment of the present application and further describes the technical solutions of the present application in conjunction with the drawings, but the present application is not limited to these embodiments.

[0035] C 10-16 The alcohol block polyether (NEP-10) is purchased from Zhonghe Chemical Co., Ltd. and is a new type of environmentally friendly non-ionic surfactant, which is easy to disperse and dissolve in water. The polyethylene glycol 600 monooleate (PEG600MO) is purchased from Aldrich Reagent Company.

[0036] Example 1

[0037] 2 g of molybdenite with a particle size of -20 μm was weighed for flotation, and an appropriate amount of ultrapure water was added to a 70 ml flotation tank, and the rotation speed was set to 1300 r / min. The slurry was stirred and mixed to fully disperse the slurry. According to the Figure 1 The medicament was added according to the medicament system, the pH of the slurry was adjusted to 2, the concentration of the emulsified kerosene was 10 mg / L (the mass percentage of kerosene: emulsifier was 10:1, the mass percentage of NEP-10: PEG600MO was 3:1), the concentration of AC-1815 or AC-1820 was 15 mg / L, and the concentration of MIBC was 20 mg / L. After flotation, the concentrate and tailings were obtained. The concentrate and tailings were filtered, dried, weighed, and the flotation rate was calculated. Under the same conditions, only the same amount of single emulsified kerosene, AC-1815 / AC-1820, MIBC was added as Comparative Example 1. The results are shown in Table 1.

[0038] According to the flotation test results, the flotation rate of the fine-grained molybdenite in Example 1 was significantly higher than that of Comparative Example 1. Taking the combination of "emulsified kerosene + AC-1815 + MIBC" as an example, the flotation rate was increased by 24.26% compared with the use of emulsified kerosene alone, and by 13.86% compared with the use of AC-1815 alone. As shown in Figure 2 、 3 Table 1, it is shown that the combination of collectors can significantly improve the recovery efficiency of molybdenite, and the components of the medicaments show good compatibility. The SEM-EDX results show that the main adsorption on the surface is emulsified kerosene, accompanied by a small amount of octadecylamine polyoxyethylene ether; the main adsorption on the edge is octadecylamine polyoxyethylene ether.

[0039] Table 1

[0040]

[0041] Example 2

[0042] Take 2 g of molybdenum ore with particle size of -20 μm for flotation, add appropriate amount of ultrapure water in a 70 ml flotation cell, set the rotation speed to 1300 r / min, stir the slurry to make the slurry fully dispersed. According to the dosage system, add reagents to adjust the pH of the slurry to 4, the concentration of emulsified kerosene is 50 mg / L (the mass percentage of kerosene: emulsifier is 5:1, the mass percentage of NEP-10: PEG600MO is 1:3), the concentration of AC-1815 or AC-1820 is 30 mg / L, and the concentration of MIBC is 20 mg / L. After air flotation, the concentrate and tailings are obtained. The concentrate and tailings are filtered, dried and weighed respectively, and the flotation rate is calculated. Under the same conditions, only the same amount of single emulsified kerosene, AC-1815 / AC-1820, MIBC is added as Comparative Example 2. The results are shown in Table 2. Figure 1

[0043] From the test results, it can be seen that the performance of the combined collector in the flotation process is obviously better than that of the single reagent.

[0044] Table 2

[0045]

[0046] Example 3

[0047] Take 2 g of molybdenum ore with particle size of -20 μm for flotation, add appropriate amount of ultrapure water in a 70 ml flotation cell, set the rotation speed to 1300 r / min, stir the slurry to make the slurry fully dispersed. According to the dosage system, add reagents to adjust the pH of the slurry to 4, the concentration of emulsified kerosene is 50 mg / L (the mass percentage of kerosene: emulsifier is 5:1, the mass percentage of NEP-10: PEG600MO is 1:3), the concentration of AC-1815 or AC-1820 is 30 mg / L, and the concentration of MIBC is 20 mg / L. After air flotation, the concentrate and tailings are obtained. The concentrate and tailings are filtered, dried and weighed respectively, and the flotation rate is calculated. Under the same conditions, only the same amount of single emulsified kerosene, AC-1815 / AC-1820, MIBC is added as Comparative Example 2. The results are shown in Table 2. Figure 1

[0048] According to the flotation results, the collecting effect of Example 3 on fine molybdenum ore is significantly better than that of Comparative Example 3. Example 3 exhibits more superior flotation performance than Comparative Example 3 at a higher dosage.

[0049] Table 3

[0050]

[0051] ​​Example 4

[0052] Weigh 2g of molybdenite with a particle size of -20 μm for flotation. Add an appropriate amount of ultrapure water to a 70 ml flotation cell. Set the rotation speed to 1300 r / min and stir to adjust the slurry, ensuring thorough dispersion. Figure 1 The reagent formulation described above involves adding reagents to adjust the pulp pH to 8, setting the concentration of emulsified kerosene to 50 mg / L (kerosene:emulsifier mass percentage 10:3, NEP-10:PEG600MO mass percentage 1:1), the concentration of AC-1815 or AC-1820 to 40 mg / L, and the concentration of MIBC to 20 mg / L. After aeration flotation, concentrate and tailings are obtained. The concentrate and tailings are filtered, dried, and weighed separately, and the flotation rate is calculated. Under the same conditions, only the same amount of single emulsified kerosene, AC-1815 / AC-1820, and MIBC are added as Comparative Example 4. The results are shown in Table 4.

[0053] Flotation results showed that Example 4 had a stronger collecting capacity for fine-grained molybdenite than Comparative Example 4. Taking "emulsified kerosene + AC-1815 + MIBC" as an example, its flotation rate was 6.93% higher than that of emulsified kerosene and 17.04% higher than that of AC-1815.

[0054] Table 4

[0055]

[0056] Example 5

[0057] Weigh 2g of molybdenite with a particle size of -20 μm for flotation. Add an appropriate amount of ultrapure water to a 70 ml flotation cell. Set the rotation speed to 1300 r / min and stir to adjust the slurry, ensuring thorough dispersion. Figure 1 The reagent formulation described above involves adding reagents to adjust the pulp pH to 10, setting the concentration of emulsified kerosene to 40 mg / L (kerosene:emulsifier mass percentage 20:7, NEP-10:PEG600MO mass percentage 1:2), the concentration of AC-1815 or AC-1820 to 50 mg / L, and the concentration of MIBC to 20 mg / L. After aeration flotation, concentrate and tailings are obtained. The concentrate and tailings are filtered, dried, and weighed separately, and the flotation rate is calculated. Under the same conditions, only the same amount of single emulsified kerosene, AC-1815 / AC-1820, and MIBC are added as Comparative Example 5. The results are shown in Table 5.

[0058] Flotation test data showed that, compared with Comparative Example 5, Example 5 significantly improved the flotation rate of fine-grained molybdenite. Although the single collector in the Comparative Example had weaker collecting efficiency, the combined collector significantly enhanced the collecting capacity, thus achieving a superior flotation effect.

[0059] Table 5

[0060]

[0061] The above description is merely that of the preferred embodiments of the application and is not intended to limit the application thereto as modifications, equivalents and improvements, which are apparent to those skilled in the art, are intended to be encompassed by the following claims.

Claims

1. A fine particle molybdenite combined collector characterized by, The collector comprises emulsified kerosene, non-ionic surfactant; The emulsified kerosene comprises emulsifier and kerosene, and the emulsifier is selected from C10-16 alcohol alkoxylate and / or polyethylene glycol 600 monooleate; The non-ionic surfactant is selected from octadecylamine polyoxyethylene ether AC-1815 and / or AC-1820.

2. The microfine molybdenite combination collector according to claim 1, characterized in that, The mass percentage of the emulsifier is 10%-35% of the kerosene; When the emulsifier is C10-16 alcohol alkoxylate and polyethylene glycol 600 monooleate, the mass ratio of C10-16 alcohol alkoxylate to polyethylene glycol 600 monooleate is 0.3-3:

1.

3. The microfine molybdenite combination collector according to claim 2, characterized in that, The emulsifier is added to the kerosene, and the emulsified kerosene is obtained by high-speed shearing stirring.

4. The microfine molybdenite combination collector according to claim 3, characterized in that, The high-speed shearing stirring refers to shearing stirring at 2000-3000 r / min for 3-5 min.

5. The application of the fine molybdenite combined collector in the medicament flotation of fine molybdenite, wherein the fine molybdenite is less than 20 μm molybdenite.

6. Use according to claim 5, characterized in that, The fine molybdenite combined collector is used for the flotation of fine molybdenite less than 20 μm by selective adsorption on the surface and edge of the molybdenite.

7. A method for the flotation of fine molybdenite particles using the combined collector of any one of claims 1 to 4, characterized in that, The method comprises the following steps: (1) mixing and stirring the fine molybdenite raw ore with water to prepare ore slurry; (2) adding a certain concentration of emulsified kerosene for slurry preparation, then adding a certain concentration of non-ionic surfactant for slurry preparation, and finally adding a foaming agent for slurry preparation before flotation; (3) air flotation to obtain froth concentrate product and tailings.

8. The method for the flotation of fine molybdenite particles according to claim 7, characterized by, The pH in step (1) is adjusted to 2-10; In step (2), the mass concentration of the emulsified kerosene is 5-50 mg / L; the mass concentration of the non-ionic surfactant is 0-50 mg / L; and the foaming agent is selected from any one of methyl isobutyl carbinol or No. 2 oil, and the mass concentration of the foaming agent is 0-30 mg / L.

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