Micro-fine particle molybdenite combined collecting agent and application method thereof

Abstract

The invention provides emulsified kerosene, the emulsified kerosene comprises an emulsifier and kerosene, and the emulsifier is selected from C10-16 alcohol alkoxylate and / or polyethylene glycol 600 monooleate. The mass percent of the emulsifier is 10%-35% of the kerosene; and when the emulsifier is the C10-16 alcohol alkoxylate and the polyethylene glycol 600 monooleate, the mass ratio of the C10-16 alcohol alkoxylate to the polyethylene glycol 600 monooleate is (0.3-3): 1. According to the combined collecting agent, hydrophobicity of the surface and the edge of molybdenite can be cooperatively regulated and controlled, the flotation performance of micro-fine particle molybdenite is remarkably improved, and meanwhile good compatibility is shown among all agent components. The combined collecting agent provided by the invention is obviously superior to the single emulsified kerosene or nonionic surfactant in collecting effect, and has lower dosage and cost.

Description

Technical Field

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

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

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

[0004] Kerosene is a traditional collector in the flotation process of molybdenite. It mainly acts on the surface of molybdenite in the form of physical adsorption. Due to its non-polar characteristics, it is not easily soluble in water, making it difficult to disperse evenly in the slurry. When the dosage of the agent is large, it is easy to defoam, resulting in a shallow foam layer, and it usually needs to be emulsified for use. In the grinding process, the coarser-grained molybdenite is mainly broken along the cleavage plane. At this time, the surface area of ​​the molybdenite is more than the edge. In addition to being broken along the cleavage plane, the fine-grained molybdenite is also broken along the fracture surface, and the edge area increases sharply. Therefore, the edge of molybdenite less than 20 μm is dominant. The traditional emulsified kerosene has a large particle size and is difficult to adsorb on the edge of fine-grained molybdenite. Therefore, the development of a highly efficient, environmentally friendly combined collector that can selectively adsorb on the surface and edge of molybdenite at the same time is of great significance for achieving efficient recovery of fine-grained molybdenite.

[0005] In terms of molybdenite flotation collectors, Chinese patent CN118594776A reports "a collector for fine-grained molybdenite, its preparation method and application". The collector described in the patent is a composite hydrocarbon oil collector, the components of which include pyrolysis oil, 1-allyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt and kerosene. Although the collector is better than kerosene, the preparation process takes a long time and is mainly suitable for coarser-sized molybdenite (-38 μm accounts for 90%). The collection effect on finer-sized molybdenite (-20 μm) needs further study. Chinese patent CN117797952A reported "a microemulsion collector for flotation enhancement of fine-grained molybdenite and its preparation method", which is a method of mixing coal tar-based aromatic hydrocarbon oil, diesel and kerosene in a mass ratio to obtain a composite hydrocarbon oil, mixing the main surfactant and the auxiliary surfactant in proportion to obtain a composite emulsifier, and then ultrasonically enhancing the dispersion of the composite hydrocarbon oil and the composite emulsifier to obtain a microemulsion collector. The microemulsion collector has a good flotation rate for molybdenite, but the composition is complex and the preparation process is lengthy, which is not conducive to its promotion and use in the flotation of -20 μm fine-grained molybdenite. Summary of the invention

[0006] In view of the problems of poor flotation performance and low recovery rate of fine-particle molybdenite, the present invention aims to provide a combined collector to optimize the flotation process of fine-particle molybdenite. The combined collector is used to synergistically regulate the hydrophobicity of the molybdenite faces and edges, thereby achieving efficient recovery of fine-particle molybdenite.

[0007] The technical solution of the present invention is as follows: The first object of the present invention is to provide an emulsified kerosene, which comprises an emulsifier and kerosene, wherein the emulsifier is selected from C10-16 alcohol alkoxylate (NEP-10) and / or polyethylene glycol 600 monooleate (PEG600MO).

[0008] 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.

[0009] The mass percentage of the emulsifier is 10% to 35% of the kerosene.

[0010] In the preparation method of the emulsified kerosene, an emulsifier is added to kerosene, and the emulsified kerosene is obtained by high-speed shearing and stirring.

[0011] The high-speed shear stirring refers to shear stirring at 2000-3000 r / min for 3-5 min.

[0012] High-speed shear stirring generates high shear force, and the combination of emulsifier NEP-10 or PEG600MO can significantly reduce the oil-water interfacial tension. In the molecular structure of emulsifiers 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 emulsifiers can effectively reduce the interfacial tension between kerosene and water, and form a stable water-in-oil emulsion under the action of high shear force. The emulsifier molecules are oriented on the surface of the oil droplets, and the emulsion particle size is smaller and the distribution is more uniform, which significantly increases the contact area and collision frequency between kerosene and the surface of fine molybdenite, improves the adsorption performance of kerosene on the surface of fine molybdenite, and enhances its hydrophobicity.

[0013] Another object of the present invention is to provide a combined collector of fine-grained molybdenite, wherein the collector comprises the emulsified kerosene.

[0014] In some embodiments, the collector further comprises a nonionic surfactant, and the nonionic surfactant is selected from octadecylamine polyoxyethylene ether AC-1815 and / or AC-1820.

[0015] Octadecaamine polyoxyethylene ether AC-1815 and AC-1820 both contain amine groups, hydrophilic polyoxyethylene ether groups and hydrophobic hydrocarbon groups. This molecular structure enables the collector molecules to preferentially adsorb on the edges of fine-grained molybdenite, thereby exposing the hydrophobic groups to the aqueous solution and improving the hydrophobicity of the edges. In addition, 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.

[0016] Another object of the present invention is to provide an application of a combined collector for fine-grained molybdenite in reagent flotation of fine-grained molybdenite, wherein the fine-grained molybdenite is molybdenite with a particle size less than 20 μm.

[0017] The edges of molybdenite with a particle size less than 20 μm are dominant, and the traditional emulsified kerosene has a large particle size and is difficult to adsorb on the edges of fine molybdenite. Therefore, an application of high efficiency, environmental protection, and the ability to selectively adsorb on the surface and edge of molybdenite at the same time and realize the flotation of fine molybdenite with a particle size less than 20 μm is developed.

[0018] Another object of the present invention is to provide a flotation method for fine-grained molybdenite, comprising the following steps: (1) mixing and stirring fine-grained molybdenite ore with water to prepare a slurry, and then adjusting the pH value of the slurry; (2) First, add a certain concentration of emulsified kerosene to mix the slurry for 1-5 minutes, then add a certain concentration of AC-1815 or AC-1820 to mix the slurry for 1-5 minutes, and finally add a frother to mix the slurry for 0.5-1 minute before flotation; (3) Aeration flotation for 1-3 min to obtain foam concentrate products and tailings.

[0019] In a preferred solution, during the flotation process, the pH range of the slurry is 2-10, and the mass concentration of the emulsified kerosene is 5-50 mg / L.

[0020] The mass concentration of the nonionic surfactant is 0-50 mg / L, more preferably 10-50 mg / L.

[0021] In a preferred embodiment, when the collector is used in the ore pulp, a foaming agent is selected from any one of methyl isobutyl carbinol and No. 2 oil, and the mass concentration of the foaming agent is 0-30 mg / L.

[0022] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects: (1) The combined collector provided by the present invention has a simple formula, high stability, environmental protection, good biodegradability, and the raw materials are low-priced and easy to obtain.

[0023] (2) The nonionic surfactant involved in the present invention has excellent solubility, significant collection effect and a wide applicable pH range as a collector. It has been widely used in the chemical industry and is easy to achieve large-scale promotion.

[0024] (3) The combined collector provided by the present invention can synergistically regulate the hydrophobicity of the surface and edge of molybdenite, significantly improve the flotation performance of fine-grained molybdenite, and at the same time, the various reagent components show good compatibility.

[0025] (4) The combined collector provided by the present invention is significantly better than the emulsified kerosene or non-ionic surfactant used alone in terms of collection effect, and has lower dosage and cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] 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.

[0027] Figure 2 This is a SEM-EDX scan of the edge after being treated with emulsified kerosene and octadecylamine polyoxyethylene ether AC-1815 in Example 1.

[0028] FIG. 3 is a SEM-EDX scan of the substrate after being treated with emulsified kerosene and octadecylamine polyoxyethylene ether AC-1815 in Example 1. DETAILED DESCRIPTION

[0029] 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.

[0030] C 10-16 Alcohol block polyether (NEP-10) was purchased from Zhonghe Chemical Co., Ltd. It is a new type of environmentally friendly non-ionic surfactant that is easily dispersed and soluble in water. Polyethylene glycol 600 monooleate (PEG600MO) was purchased from Aladdin Reagent Company.

[0031] Example 1 Weigh 2g of molybdenite with a particle size of -20 μm for flotation, add an appropriate amount of ultrapure water into a 70 ml flotation cell, set the speed to 1300 r / min, stir and slurry to make the slurry fully dispersed. Figure 1 The reagent system adds reagents to adjust the pH of the slurry to 2, the concentration of emulsified kerosene is 10 mg / L (wherein the mass percentage of kerosene: emulsifier is 10:1, and the mass percentage of NEP-10: PEG600MO is 3:1), the concentration of AC-1815 or AC-1820 is 15 mg / L, and the concentration of MIBC is 20 mg / L. Concentrate and tailings are obtained after aeration flotation. 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, and MIBC are added as comparative example 1. The results are shown in Table 1.

[0032] According to the flotation test results, the floating rate of fine molybdenite in Example 1 is significantly higher than that in Comparative Example 1. Taking the combination of "emulsified kerosene + AC-1815 + MIBC" as an example, its floating rate is increased by 24.26% compared with the use of emulsified kerosene alone, and by 13.86% compared with the use of AC-1815 alone. Figure 2 , 3 As shown, this combination of collectors can significantly improve the recovery efficiency of molybdenite, and the components of each agent show good compatibility. SEM-EDX results show that the surface is mainly adsorbed by emulsified kerosene, accompanied by a small amount of octadecylamine polyoxyethylene ether adsorption; the edge is mainly adsorbed by octadecylamine polyoxyethylene ether.

[0033] Table 1

[0034] Example 2 Weigh 2g of molybdenite with a particle size of -20 μm for flotation, add an appropriate amount of ultrapure water into a 70 ml flotation cell, set the speed to 1300 r / min, stir and slurry to make the slurry fully dispersed. Figure 1The reagent system adds reagents to adjust the pH of the slurry to 4, the concentration of emulsified kerosene is 50 mg / L (wherein the mass percentage of kerosene: emulsifier is 5:1, and 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. Concentrate and tailings are obtained after aeration flotation. 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, and MIBC are added as comparative example 2. The results are shown in Table 2.

[0035] The test results show that the performance of the combined collector in the flotation process is significantly better than that of a single agent.

[0036] Table 2

[0037] Example 3 Weigh 2g of molybdenite with a particle size of -20 μm for flotation, add an appropriate amount of ultrapure water into a 70 ml flotation cell, set the speed to 1300 r / min, stir and slurry to make the slurry fully dispersed. Figure 1 The reagent system adds reagents to adjust the pH of the slurry to 6, the concentration of emulsified kerosene is 30 mg / L (wherein the mass percentage of kerosene: emulsifier is 4:1, and the mass percentage of NEP-10: PEG600MO is 2:1), the concentration of AC-1815 or AC-1820 is 50 mg / L, and the concentration of MIBC is 20 mg / L. Concentrate and tailings are obtained after aeration flotation. 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, and MIBC are added as comparative example 3. The results are shown in Table 3.

[0038] According to the flotation results, the capture effect of fine molybdenite in Example 3 is significantly better than that in Comparative Example 3. Example 3 shows a more superior flotation performance at a lower dosage than Comparative Example 3 at a higher dosage.

[0039] Table 3

[0040] Example 4 Weigh 2g of molybdenite with a particle size of -20 μm for flotation, add an appropriate amount of ultrapure water into a 70 ml flotation cell, set the speed to 1300 r / min, stir and slurry to make the slurry fully dispersed. Figure 1The reagent system adds reagents to adjust the pH of the slurry to 8, the concentration of emulsified kerosene is 50 mg / L (wherein the mass percentage of kerosene: emulsifier is 10:3, and the mass percentage of NEP-10: PEG600MO is 1:1), the concentration of AC-1815 or AC-1820 is 40 mg / L, and the concentration of MIBC is 20 mg / L. Concentrate and tailings are obtained after aeration flotation. 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, and MIBC are added as comparative example 4. The results are shown in Table 4.

[0041] The flotation results show that Example 4 has a stronger ability to capture fine molybdenite than Comparative Example 4. Taking "emulsified kerosene + AC-1815 + MIBC" as an example, its flotation rate is 6.93% higher than that of emulsified kerosene and 17.04% higher than that of AC-1815.

[0042] Table 4

[0043] Example 5 Weigh 2g of molybdenite with a particle size of -20 μm for flotation, add an appropriate amount of ultrapure water into a 70 ml flotation cell, set the speed to 1300 r / min, stir and slurry to make the slurry fully dispersed. Figure 1 The reagent system adds reagents to adjust the pH of the slurry to 10, the concentration of emulsified kerosene is 40 mg / L (wherein the mass percentage of kerosene: emulsifier is 20:7, and the mass percentage of NEP-10: PEG600MO is 1:2), the concentration of AC-1815 or AC-1820 is 50 mg / L, and the concentration of MIBC is 20 mg / L. Concentrate and tailings are obtained after aeration flotation. 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, and MIBC are added as comparative example 5. The results are shown in Table 5.

[0044] The flotation test data show that Example 5 significantly improves the flotation rate of fine-grained molybdenite compared to Comparative Example 5. Although the collection efficiency of a single collector in the comparative example is relatively weak, the combined collector significantly enhances the collection capacity, thereby achieving a more excellent flotation effect.

[0045] Table 5

[0046] 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. An emulsified kerosene, characterized in that: The emulsified kerosene comprises an emulsifier and kerosene, wherein the emulsifier is selected from C10-16 alcohol alkoxylate and / or polyethylene glycol 600 monooleate.

2. The emulsified kerosene according to claim 1, characterized in that The mass percentage of emulsifier is 10%~35% of 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 emulsified kerosene according to claim 2, characterized in that: The emulsifier is added to kerosene and stirred with high-speed shearing to obtain emulsified kerosene.

4. The emulsified kerosene according to claim 3, characterized in that: High-speed shear stirring refers to shear stirring at 2000-3000r / min for 3-5 min.

5. A micro-fine molybdenite combined collector, characterized in that: The collector comprises the emulsified kerosene according to any one of claims 1 to 4.

6. The fine-grained molybdenite combined collector according to claim 5, characterized in that: The collector also includes a nonionic surfactant, which is selected from octadecylamine polyoxyethylene ether AC-1815 and / or AC-1820.

7. Use of the fine-grained molybdenite combined collector according to claim 5 or 6 in reagent flotation of fine-grained molybdenite, wherein the fine-grained molybdenite is molybdenite with a particle size less than 20 μm.

8. The use according to claim 7, characterized in that: The micro-fine molybdenite combined collector is used for selectively adsorbing on the surface and edge of molybdenite and realizing the flotation of micro-fine molybdenite with a particle size less than 20 μm.

9. A flotation method for fine-grained molybdenite, characterized in that: The following steps are included (1) mixing and stirring fine-grained molybdenite ore with water to prepare a slurry; (2) First, add a certain concentration of emulsified kerosene to adjust the slurry, then add a certain concentration of non-ionic surfactant to adjust the slurry, and finally add a frother to adjust the slurry before flotation; (3) Aeration flotation to obtain foam concentrate products and tailings.

10. The flotation method of fine-grained molybdenite according to claim 9, characterized in that: In step (1), the pH is adjusted to 2-10; The mass concentration of the emulsified kerosene in step (2) is 5-50 mg / L; the mass concentration of the nonionic surfactant is 0-50 mg / L; 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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