A combined collector and its application in the flotation of fine molybdenite

Abstract

The present application relates to the technical field of mineral flotation, and particularly relates to a combined collector and application thereof in flotation of micro-fine molybdenite. The combined collector comprises emulsified non-polar hydrocarbon oil and phosphate anionic surfactant. The combined collector is simple to prepare, can simultaneously control the hydrophobicity of the "face" and "edge" of molybdenite, realizes effective flotation of micro-fine molybdenite, especially micro-fine molybdenite with a particle size of-20 mu m, and shows excellent positive synergistic effect in a wide pH range.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral flotation, and relates to a combined collector and application of the combined collector in micro-fine molybdenite flotation, in particular to a combined collector and application of the combined collector in micro-fine molybdenite flotation with a particle size of-20 μm. BACKGROUND

[0002] In the development of national economy, molybdenum is an indispensable strategic reserve metal. Molybdenum not only can maintain high strength and high hardness at high temperature, but also has outstanding heat resistance and corrosion resistance, and is widely used in electronic devices such as electron tubes, transistors and rectifiers. Molybdenite is the main source of molybdenum metal, and more than 90% of molybdenum resources in the world come from molybdenite. Molybdenite has good natural floatability, and flotation is the most effective method for recovering molybdenite. Non-polar hydrocarbon oils such as kerosene, transformer oil and diesel are commonly used as collectors for molybdenite recovery. However, with the rapid decrease of high-grade and easily selected molybdenite ores, the development of low-grade and fine-grained and refractory molybdenite resources is an inevitable trend for future molybdenite resource development. However, this kind of molybdenite has low grade, fine particle size and high impurity content, and usually needs to be finely ground before recovery to fully dissociate it. Molybdenite is a typical anisotropic layered structure mineral, and its "face" has good hydrophobicity, and its "edge" is hydrophilic. With the decrease of particle size, the "edge-to-face ratio" increases rapidly, and the hydrophilic "edge" gradually dominates, resulting in a sharp decrease in hydrophobicity and poor floatability.

[0003] Molybdenite flotation commonly uses kerosene, transformer oil, diesel and other non-polar hydrocarbon oils as collectors. These hydrocarbon oils mainly adsorb on the "face" of molybdenite through hydrophobic force and van der Waals force, and are difficult to adsorb on the "edge". Non-polar hydrocarbon oils have poor dispersibility in water and usually need to be emulsified for use. With the decrease of molybdenite particle size, the "face" area of molybdenite decreases sharply, and the "edge" area increases sharply. The particle size of traditional emulsified kerosene is large, and it is difficult to effectively adhere to the "face" of molybdenite. Moreover, non-polar oil itself is difficult to adsorb on the "edge" of molybdenite, resulting in poor flotation effect of micro-fine molybdenite. Therefore, it is of great significance to develop a combined collector that is efficient, environmentally friendly and can selectively adsorb on the "face" and "edge" of molybdenite for the efficient recovery of micro-fine molybdenite.

[0004] In the aspect of collector for fine molybdenite, the patent document with the publication number CN116809240A reports "a new combined collector for fine molybdenite and its application". The combined collector described in the patent is composed of main collector coconut oil, auxiliary collector palm oil and emulsifier methyl naphthalene. The combined collector has obvious effect on coarse molybdenite (-43 μm accounts for 85%~90%) and is obviously superior to kerosene, and mainly focuses on the regulation of the hydrophobicity of the "face" of molybdenite, but the collecting effect on fine molybdenite (-20 μm) is still unclear. The patent document with the publication number CN117797952A reports "a microemulsion collector for strengthening the flotation of fine molybdenite and a preparation method thereof". The method mixes coal tar-based aromatic hydrocarbon oil, diesel and kerosene to prepare a composite hydrocarbon oil; mixes the main surfactant and the auxiliary surfactant to prepare a composite emulsifier; and then performs strong ultrasonic dispersion on the composite hydrocarbon oil and the composite emulsifier to finally prepare the microemulsion collector. The microemulsion collector has good collecting effect, but the composition of the microemulsion collector is complex, the preparation process is long, the cost is high, and the flotation effect on -20 μm fine molybdenite is not clear. The patent document with the publication number CN115846054A reports "a composite hydrocarbon collector for fine molybdenite flotation and a preparation method thereof". The method mixes toluene and coal tar to obtain an extraction liquid, distills the extraction liquid at 110~115 ℃, condenses the steam by backwater to reuse as an extraction agent, and mixes the residual liquid with a conventional hydrocarbon collector for molybdenite according to a certain mass ratio to obtain the composite hydrocarbon collector. Although the collector can improve the flotation efficiency of fine molybdenite, the preparation method is complicated and time-consuming. In general, the collectors for molybdenite still have problems such as difficult flotation of -20 μm fine molybdenite, low flotation rate or complex preparation method. SUMMARY

[0005] The present application solves the above problems, and provides a combined collector which is simple to prepare, can simultaneously regulate the hydrophobicity of the "face" and "edge" of molybdenite, realizes effective flotation of fine molybdenite, especially -20 μm fine molybdenite, and has high flotation rate, and the application of the combined collector in the flotation of fine molybdenite.

[0006] The technical solution for solving the problem of the present application is to provide a combined collector, which includes emulsified non-polar hydrocarbon oil and phosphate anionic surfactant.

[0007] In the present application, the emulsified non-polar hydrocarbon oil and the phosphate anionic surfactant are used to act on the "face" and "edge" of molybdenite respectively, to synergistically control the hydrophobicity of the "face" and "edge" of molybdenite, so as to realize efficient recovery of fine molybdenite. Specifically, in the emulsified non-polar hydrocarbon oil, the interfacial tension between the oil phase and the water phase is significantly reduced by the emulsifier, which greatly promotes the dispersion of the non-polar hydrocarbon oil in water, forms extremely stable hydrocarbon oil microemulsion, and thus improves the adsorption of the non-polar hydrocarbon oil on the "face" of molybdenite and improves the "face" hydrophobicity. In the phosphate anionic surfactant, the phosphate group selectively chelates with the molybdenum atom on the "edge" of molybdenite to form a P-O-Mo bond and is firmly adsorbed on the "edge". Thus, the emulsified non-polar hydrocarbon oil and the phosphate anionic surfactant synergistically act on the "face" and "edge" to strengthen the flotation recovery of fine molybdenite.

[0008] As a preferred embodiment of the present application, the combined collector is composed of the emulsified non-polar hydrocarbon oil and the phosphate anionic surfactant.

[0009] for phosphate ester anionic surfactants, The phosphate group and the selectivity of the phosphate group are focused on. The optional phosphate anionic surfactant includes alkyl (aryl) phosphate, fatty alcohol (alkyl phenol) polyoxyethylene ether phosphate, alkyl alcohol amide phosphate, imidazoline phosphate, high molecular polyphosphate, silicone phosphate, etc.

[0010] As a preferred embodiment of the present application, the phosphate anionic surfactant is selected from fatty alcohol (alkyl phenol) polyoxyethylene ether phosphate. The phosphate with polyoxyethylene ether chain segment is selected, and the introduction of the polyoxyethylene ether chain segment improves the water solubility and wetting performance of the surfactant, so that it performs more excellent in flotation.

[0011] Further preferably, the phosphate anionic surfactant is selected from at least one of nonylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, trityl phenol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate.

[0012] Still further preferably, the phosphate anionic surfactant is selected from at least one of dodecanol polyoxyethylene ether phosphate and nonylphenol polyoxyethylene ether phosphate.

[0013] Still further preferably, the phosphate anionic surfactant is selected from dodecanol polyoxyethylene ether phosphate or nonylphenol polyoxyethylene ether phosphate.

[0014] for emulsified non-polar hydrocarbon oils, It is prepared by mixing and stirring the non-polar hydrocarbon oil and the emulsifier.

[0015] The non-polar hydrocarbon oils that can be selected include C12-C22 hydrocarbon mixtures, such as kerosene, diesel oil, naphthenic oil, and paraffin oil. Preferably, the non-polar hydrocarbon oil is selected from at least one of kerosene and diesel oil.

[0016] Further preferably, the non-polar hydrocarbon oil is composed of kerosene and diesel oil.

[0017] More preferably, the mass ratio of kerosene to diesel oil is 1:(0.25~4), for example, it can be 1:0.25, 1:0.5, 1:0.75, 1:1, 1:1.25, 1:1.5, 1:1.75, 1:2, 1:2.25, 1:2.5, 1:2.75, 1:3, 1:3.25, 1:3.5, 1:3.75, 1:4; preferably 1:(1~4); preferably 1:(2~4); preferably 1:4.

[0018] The emulsifiers that can be selected include ionic surfactants and / or nonionic surfactants. As a preferred embodiment of the present invention, the emulsifier is a nonionic surfactant.

[0019] More preferably, the emulsifier is selected from at least one of fatty alcohol polyoxyethylene ether and cetearyl alcohol polyoxyethylene ether.

[0020] Further preferably, the emulsifier is a mixture of fatty alcohol polyoxyethylene ether and cetearyl alcohol polyoxyethylene ether.

[0021] More preferably, the mass ratio of the fatty alcohol polyoxyethylene ether to the cetearyl alcohol polyoxyethylene ether is 1:(0.5~2), for example, it can be 1:0.5, 1:1, 1:1.5, 1:2; preferably 1:1.

[0022] As a preferred embodiment of the present invention, the mass ratio of the nonpolar hydrocarbon oil to the emulsifier is (2~10):1, for example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1; preferably (2~6):1; and more preferably 2:1.

[0023] As a preferred embodiment of the present invention, during emulsification, the non-polar hydrocarbon oil and the emulsifier are mixed and stirred with a high-speed shearing machine for 3 to 7 minutes, for example, 3 minutes, 4 minutes, 5 minutes, 6 minutes, or 7 minutes; preferably 4 to 6 minutes; and preferably 5 minutes.

[0024] for a combined collector,As a preferred embodiment of the present invention, the mass ratio of the emulsified nonpolar hydrocarbon oil to the phosphate ester anionic surfactant is 1:(0.1~10), for example, it can be 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10; preferably 1:(0.5~5); preferably 1:1.

[0025] Secondly, another objective of this invention is to provide an application of a combined collector in the flotation of fine-grained molybdenite.

[0026] As a preferred embodiment of the present invention, the fine-grained molybdenite refers to molybdenite with a particle size of -20μm, that is, a particle size not exceeding 20μm.

[0027] As a preferred embodiment of the present invention, when applied to the flotation of fine-grained molybdenite, the amount of the emulsified non-polar hydrocarbon oil is 20~200 mg / L, for example, it can be 20 mg / L, 30 mg / L, 40 mg / L, 50 mg / L, 60 mg / L, 70 mg / L, 80 mg / L, 90 mg / L, 100 mg / L, 110 mg / L, 120 mg / L, 130 mg / L, 140 mg / L, 150 mg / L, 160 mg / L, 170 mg / L, 180 mg / L, 190 mg / L, or 200 mg / L; preferably 30~120 mg / L; preferably 50~100 mg / L; and preferably 50 mg / L. The dosage of the phosphate ester anionic surfactant is 20-200 mg / L, for example, it can be 20 mg / L, 30 mg / L, 40 mg / L, 50 mg / L, 60 mg / L, 70 mg / L, 80 mg / L, 90 mg / L, 100 mg / L, 110 mg / L, 120 mg / L, 130 mg / L, 140 mg / L, 150 mg / L, 160 mg / L, 170 mg / L, 180 mg / L, 190 mg / L, or 200 mg / L; preferably 30-120 mg / L; preferably 50-100 mg / L; and preferably 50 mg / L. The combined collector of this application, after simultaneously controlling the hydrophobicity of both the "face" and "edge," can achieve good flotation results at a relatively low dosage.

[0028] As a preferred embodiment of the present invention, when applied to the flotation of fine-grained molybdenite, the mass ratio of molybdenite to the combined collector is 1000:(3~9), for example, it can be 1000:3, 1000:3.5, 1000:4, 1000:4.5, 1000:5, 1000:5.5, 1000:6, 1000:6.5, 1000:7, 1000:7.5, 1000:8, 1000:8.5, 1000:9; preferably 1000:(3.5~8); preferably 1000:3.5.

[0029] As a preferred embodiment of the present invention, when applied to the flotation of fine-grained molybdenite, the pH of the flotation process is 4 to 10, for example, pH can be 4, 5, 6, 7, 8, 9, or 10; preferably, pH is 6.

[0030] As a preferred embodiment of the present invention, when applied to the flotation of fine-grained molybdenite, the method includes the following steps: first adding the emulsified non-polar hydrocarbon oil to the fine-grained molybdenite pulp, and then adding the phosphate ester anionic surfactant. The emulsified non-polar hydrocarbon oil and the phosphate ester anionic surfactant of this application can be added in one step after mixing, or they can be added separately and in stages; the staged addition method allows the emulsified non-polar hydrocarbon oil and the phosphate ester anionic surfactant to function effectively, resulting in higher flotation efficiency.

[0031] As a preferred embodiment of the present invention, when applied to the flotation of fine-grained molybdenite, the following steps are included:

[0032] S1. Add water to the fine-grained molybdenite ore and stir to form a slurry, then adjust the pH of the slurry;

[0033] S2. First, add emulsified non-polar hydrocarbon oil and adjust the slurry for 3-7 minutes, for example, 3 minutes, 4 minutes, 5 minutes, 6 minutes, or 7 minutes, preferably 5 minutes; then add phosphate ester anionic surfactant and adjust the slurry for 3-7 minutes, for example, 3 minutes, 4 minutes, 5 minutes, 6 minutes, or 7 minutes, preferably 5 minutes; finally, add foaming agent and adjust the slurry for 0.5-1.5 minutes, preferably 1 minute, before flotation.

[0034] S3. Aeration flotation for 1~5 minutes, for example, aeration flotation for 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes, preferably 3 minutes.

[0035] Optional foaming agents include pine oil, alcohols (including methyl isobutyl methanol, methyl pentanol, 2-ethylhexanol, etc.), and ethers (such as 1,1,3-triethoxybutane); as a preferred embodiment of the present invention, the foaming agent is methyl isobutyl methanol (MIBC).

[0036] Further preferably, the amount of foaming agent used is 10~30 mg / L, for example, it can be 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, or 30 mg / L; preferably 20 mg / L.

[0037] The beneficial effects of this invention are:

[0038] 1. This application provides a combined collector and its application in the flotation of fine-grained molybdenite. The combined collector enhances the flotation recovery of fine-grained molybdenite through the synergistic effect of emulsified non-polar hydrocarbon oil and phosphate ester anionic surfactants on both the "surface" and "edge". No other treatment of the components is required besides emulsification, and the preparation is simple. It is particularly suitable for the flotation of fine-grained molybdenite with a particle size of -20μm, and the flotation rate can reach more than 80%. In some embodiments, the flotation rate can reach about 90%.

[0039] 2. The components of the combined collector in this application are low in toxicity, environmentally friendly, and biodegradable, posing minimal harm to humans and animals.

[0040] 3. When the combined collector of this application is applied to the flotation of fine-grained molybdenite, the hydrophobicity of both the "face" and the "edge" is controlled at the same time. Therefore, even a low dosage of the combined collector can significantly improve the flotation rate of fine-grained molybdenite, which has the advantages of low dosage and low cost.

[0041] 4. When the combined collector of this application is applied to the flotation of fine-grained molybdenite, it exhibits excellent positive synergistic effects over a wide pH range, and has the advantages of a wide applicable pH range and strong practicality. Attached Figure Description

[0042] Figure 1 This is a flowchart illustrating the application steps of the combined collector in the flotation of fine-grained molybdenite. Detailed Implementation

[0043] The following are specific embodiments of the present invention, and the technical solution of the present invention will be further described in conjunction with the accompanying drawings. However, the present invention is not limited to these embodiments.

[0044] Examples 1~2, Blank Example 1, and Comparative Examples 1~6

[0045] Example 1

[0046] A combined collector This includes emulsified nonpolar hydrocarbon oils and phosphate ester anionic surfactants.

[0047] Emulsified nonpolar hydrocarbon oil is prepared by the following steps: fatty alcohol polyoxyethylene ether (AEO-5) and cetearyl alcohol polyoxyethylene ether 10 (Pingpingjia O-10) are mixed at a mass ratio of 1:1 to obtain an emulsifier; kerosene and diesel are mixed at a mass ratio of 1:4 to obtain a composite hydrocarbon oil; the emulsifier is then added to the composite hydrocarbon oil, the mass ratio of the composite hydrocarbon oil to the emulsifier is 2:1, and the mixture is stirred for 5 minutes using a high-speed shearing machine to obtain the emulsified nonpolar hydrocarbon oil.

[0048] For anionic surfactants of the phosphate ester type, dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is selected.

[0049] The mass ratio of the emulsified nonpolar hydrocarbon oil to the phosphate ester anionic surfactant is 1:1.

[0050] Use of this combined collector in the flotation of fine particles of molybdenite According to Figure 1 The process shown includes the following steps:

[0051] S1. Take 2 g of pure molybdenite mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation tank. Control the rotation speed of the flotation tank to 1300 r / min and adjust the pulp for 2 min to ensure thorough dispersion. Control the pH of the pulp to 6.

[0052] S2. First, add the above-mentioned emulsified non-polar hydrocarbon oil at a concentration of 50 mg / L and adjust the slurry for 5 minutes; then add DOPO-POSS at a concentration of 50 mg / L and adjust the slurry for 5 minutes; finally, add the frother MIBC at a concentration of 20 mg / L, adjust the slurry for 1 minute, and then proceed with flotation.

[0053] S3. Perform aeration flotation for 3 min to obtain froth product and tailings. Filter, dry, weigh, and calculate the flotation rate of the froth concentrate and tailings respectively.

[0054] Example 2

[0055] This embodiment is basically the same as Example 1, except that the nonylphenol polyoxyethylene ether phosphate (APE-4P) is selected as the anionic surfactant of phosphate ester.

[0056] Blank example 1

[0057] This blank example is basically the same as Example 1, except that the combined collector is not used. Specifically, in step S2, the frother MIBC is added directly at a concentration of 20 mg / L, and flotation is performed after adjusting the slurry for 1 minute.

[0058] Comparative Example 1

[0059] This comparative example is basically the same as Example 1, except that only emulsified non-polar hydrocarbon oil is used as the collector. Specifically, in step S2, the above-mentioned emulsified non-polar hydrocarbon oil with a concentration of 50 mg / L is added and the slurry is adjusted for 5 min; then the foaming agent MIBC with a concentration of 20 mg / L is added, and the slurry is adjusted for 1 min before flotation.

[0060] Comparative Example 2

[0061] This comparative example is basically the same as Example 1, except that only dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is used as the collector. Specifically, in step S2, DOPO-POSS is first added at a concentration of 50 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0062] Comparative Example 3

[0063] This comparative example is basically the same as Example 1, except that only nonylphenol polyoxyethylene ether phosphate (APE-4P) is used as the collector. Specifically, in step S2, APE-4P is first added at a concentration of 50 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0064] Comparative Example 4

[0065] This comparative example is basically the same as Example 1, except that DOPO-POSS is replaced with an equal amount of emulsified non-polar hydrocarbon oil. Specifically, in step S2, emulsified non-polar hydrocarbon oil is first added to a concentration of 50 mg / L and the mixture is prepared for 5 minutes; then, emulsified non-polar hydrocarbon oil is added to a concentration of 100 mg / L and the mixture is prepared for 5 minutes; finally, frother MIBC is added at a concentration of 20 mg / L, and the mixture is prepared for 1 minute before flotation.

[0066] Comparative Example 5

[0067] This comparative example is basically the same as Example 1, except that the emulsified non-polar hydrocarbon oil is replaced with an equal amount of DOPO-POSS. Specifically, in step S2, DOPO-POSS is first added to a concentration of 50 mg / L and the slurry is prepared for 5 minutes; then DOPO-POSS is added to a concentration of 100 mg / L and the slurry is prepared for 5 minutes; finally, the frother MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 minute before flotation.

[0068] Comparative Example 6

[0069] This comparative example is basically the same as Example 1, except that the emulsified non-polar hydrocarbon oil is replaced with an equal amount of APE-4P. Specifically, in step S2, APE-4P is first added to a concentration of 50 mg / L and the slurry is prepared for 5 minutes; then APE-4P is added to a concentration of 100 mg / L and the slurry is prepared for 5 minutes; finally, the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 minute before flotation.

[0070] The buoyancy rates of Examples 1-2, Blank Example 1, and Comparative Examples 1-6 are shown in Table 1 below.

[0071] Table 1.

[0072]

[0073] As shown in Table 1, comparing Examples 1, 2, and 4, it can be seen that, under the same conditions, replacing only part of the emulsified non-polar hydrocarbon oil with DOPO-POSS or APE-4P significantly improved the flotation rate of pure molybdenite with a particle size of -20 μm. Similarly, comparing Examples 1 and 5, and Examples 2 and 6, it can be seen that, under the same conditions, replacing part of DOPO-POSS or APE-4P with emulsified non-polar hydrocarbon oil also significantly improved the flotation rate of pure molybdenite with a particle size of -20 μm. This indicates that when emulsified non-polar hydrocarbon oil and phosphate ester anionic surfactants are used together, they can synergistically enhance the flotation recovery of fine-grained molybdenite at both the surface and the edges, resulting in a synergistic improvement in the flotation rate.

[0074] Examples 3~4, Blank Example 2, and Comparative Examples 7~9

[0075] Example 3

[0076] A combined collector This includes emulsified nonpolar hydrocarbon oils and phosphate ester anionic surfactants.

[0077] Emulsified nonpolar hydrocarbon oil is prepared by the following steps: fatty alcohol polyoxyethylene ether (AEO-5) and cetearyl alcohol polyoxyethylene ether 10 (Pingpingjia O-10) are mixed at a mass ratio of 1:1 to obtain an emulsifier; kerosene and diesel are mixed at a mass ratio of 4:1 to obtain a composite hydrocarbon oil; the emulsifier is then added to the composite hydrocarbon oil, the mass ratio of the composite hydrocarbon oil to the emulsifier is 2:1, and the mixture is stirred for 5 minutes using a high-speed shear machine to obtain the emulsified nonpolar hydrocarbon oil.

[0078] The phosphate ester anionic surfactant selected is dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS).

[0079] The mass ratio of emulsified nonpolar hydrocarbon oil to phosphate ester anionic surfactant is 1:10.

[0080] Use of this combined collector in the flotation of fine particles of molybdenite, According to such Figure 1 The process shown includes the following steps:

[0081] S1. Take 2 g of pure molybdenite mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation tank. Control the rotation speed of the flotation tank to 1300 r / min and adjust the pulp for 2 min to ensure sufficient dispersion. Control the pH of the pulp to 4.

[0082] S2. First, add the above-mentioned emulsified non-polar hydrocarbon oil at a concentration of 20 mg / L and adjust the slurry for 5 min; then add DOPO-POSS at a concentration of 200 mg / L and adjust the slurry for 5 min; finally, add the frother MIBC at a concentration of 20 mg / L, adjust the slurry for 1 min, and then proceed with flotation.

[0083] S3. Perform aeration flotation for 3 min to obtain froth product and tailings. Filter, dry, weigh, and calculate the flotation rate of the froth concentrate and tailings respectively.

[0084] Example 4

[0085] This embodiment is basically the same as Example 3, except that: the anionic surfactant of phosphate ester is nonylphenol polyoxyethylene ether phosphate (APE-4P).

[0086] Blank example 2

[0087] This blank example is basically the same as Example 3, except that the combined collector is not used. Specifically, in step S2, the frother MIBC is added directly at a concentration of 20 mg / L, and flotation is performed after adjusting the slurry for 1 minute.

[0088] Comparative Example 7

[0089] This comparative example is basically the same as Example 3, except that only emulsified non-polar hydrocarbon oil is used as the collector. Specifically, in step S2, the above-mentioned emulsified non-polar hydrocarbon oil with a concentration of 20 mg / L is added and the slurry is adjusted for 5 min; then the foaming agent MIBC with a concentration of 20 mg / L is added, and the slurry is adjusted for 1 min before flotation.

[0090] Comparative Example 8

[0091] This comparative example is basically the same as Example 3, except that only dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is used as the collector. Specifically, in step S2, DOPO-POSS is first added at a concentration of 200 mg / L and the slurry is prepared for 5 minutes; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 minute before flotation.

[0092] Comparative Example 9

[0093] This comparative example is basically the same as Example 3, except that only nonylphenol polyoxyethylene ether phosphate (APE-4P) is used as the collector. Specifically, in step S2, APE-4P is first added at a concentration of 200 mg / L and the slurry is prepared for 5 minutes; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 minute before flotation.

[0094] The buoyancy rates of Examples 3-4, Blank Example 2, and Comparative Examples 7-9 are shown in Table 2 below.

[0095] Table 2.

[0096]

[0097] Examples 5~6, Blank Example 3, and Comparative Examples 10~12

[0098] Example 5

[0099] A combined collector This includes emulsified nonpolar hydrocarbon oils and phosphate ester anionic surfactants.

[0100] Emulsified nonpolar hydrocarbon oil is prepared by the following steps: fatty alcohol polyoxyethylene ether (AEO-5) and cetearyl alcohol polyoxyethylene ether 10 (Pingpingjia O-10) are mixed in a mass ratio of 1:1 to obtain an emulsifier; kerosene and diesel are mixed in a mass ratio of 1:1 to obtain a composite hydrocarbon oil; the emulsifier is then added to the composite hydrocarbon oil, the mass ratio of the composite hydrocarbon oil to the emulsifier is 10:1, and the mixture is stirred for 5 minutes using a high-speed shearing machine to obtain the emulsified nonpolar hydrocarbon oil.

[0101] For anionic surfactants of the phosphate ester type, dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is selected.

[0102] The mass ratio of the emulsified nonpolar hydrocarbon oil to the phosphate ester anionic surfactant is 10:1.

[0103] Use of this combined collector in the flotation of fine particles of molybdenite, According to such Figure 1 The process shown includes the following steps:

[0104] S1. Take 2 g of pure molybdenite mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation tank. Control the rotation speed of the flotation tank to 1300 r / min and adjust the pulp for 2 min to ensure sufficient dispersion. Control the pH of the pulp to 7.

[0105] S2. First, add the above-mentioned emulsified non-polar hydrocarbon oil at a concentration of 200 mg / L and adjust the slurry for 5 min; then add DOPO-POSS at a concentration of 20 mg / L and adjust the slurry for 5 min; finally, add the frother MIBC at a concentration of 20 mg / L, adjust the slurry for 1 min, and then proceed with flotation.

[0106] S3. Perform aeration flotation for 3 min to obtain froth product and tailings. Filter, dry, weigh, and calculate the flotation rate of the froth concentrate and tailings respectively.

[0107] Example 6

[0108] This embodiment is basically the same as embodiment 5, except that: the anionic surfactant of phosphate ester is nonylphenol polyoxyethylene ether phosphate (APE-4P).

[0109] Blank example 3

[0110] This blank example is basically the same as Example 5, except that the combined collector is not used. Specifically, in step S2, the frother MIBC is added directly at a concentration of 20 mg / L, and flotation is performed after adjusting the slurry for 1 minute.

[0111] Comparative Example 10

[0112] This comparative example is basically the same as Example 5, except that only emulsified non-polar hydrocarbon oil is used as the collector. Specifically, in step S2, the above-mentioned emulsified non-polar hydrocarbon oil with a concentration of 200 mg / L is added and the slurry is adjusted for 5 min; then the foaming agent MIBC with a concentration of 20 mg / L is added, and the slurry is adjusted for 1 min before flotation.

[0113] Comparative Example 11

[0114] This comparative example is basically the same as Example 5, except that only dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is used as the collector. Specifically, in step S2, DOPO-POSS is first added at a concentration of 20 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0115] Comparative Example 12

[0116] This comparative example is basically the same as Example 5, except that only nonylphenol polyoxyethylene ether phosphate (APE-4P) is used as the collector. Specifically, in step S2, APE-4P is first added at a concentration of 20 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0117] The buoyancy rates of Examples 5-6, Blank Example 3, and Comparative Examples 10-12 are shown in Table 3 below.

[0118] Table 3.

[0119]

[0120] Examples 7~8, Blank Example 4, and Comparative Examples 13~15

[0121] Example 7

[0122] A combined collector This includes emulsified nonpolar hydrocarbon oils and phosphate ester anionic surfactants.

[0123] Emulsified nonpolar hydrocarbon oil is prepared by the following steps: fatty alcohol polyoxyethylene ether (AEO-5) and cetearyl alcohol polyoxyethylene ether 10 (Pingpingjia O-10) are mixed at a mass ratio of 1:1 to obtain an emulsifier; kerosene and diesel are mixed at a mass ratio of 1:4 to obtain a composite hydrocarbon oil; the emulsifier is then added to the composite hydrocarbon oil, the mass ratio of the composite hydrocarbon oil to the emulsifier is 4:1, and the mixture is stirred for 5 minutes using a high-speed shear machine to obtain the emulsified nonpolar hydrocarbon oil.

[0124] For anionic surfactants of the phosphate ester type, dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is selected.

[0125] The mass ratio of the emulsified nonpolar hydrocarbon oil to the phosphate ester anionic surfactant is 1:1.

[0126] Use of this combined collector in the flotation of fine particles of molybdenite According to Figure 1 The process shown includes the following steps:

[0127] S1. Take 2 g of pure molybdenite mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation tank. Control the rotation speed of the flotation tank to 1300 r / min and adjust the pulp for 2 min to ensure thorough dispersion. Control the pH of the pulp to 10.

[0128] S2. First, add the above-mentioned emulsified non-polar hydrocarbon oil at a concentration of 100 mg / L and adjust the slurry for 5 minutes; then add DOPO-POSS at a concentration of 100 mg / L and adjust the slurry for 5 minutes; finally, add the frother MIBC at a concentration of 20 mg / L, adjust the slurry for 1 minute, and then proceed with flotation.

[0129] S3. Perform aeration flotation for 3 min to obtain froth product and tailings. Filter, dry, weigh, and calculate the flotation rate of the froth concentrate and tailings respectively.

[0130] Example 8

[0131] This embodiment is basically the same as embodiment 7, except that: the anionic surfactant of phosphate ester is nonylphenol polyoxyethylene ether phosphate (APE-4P).

[0132] Blank example 4

[0133] This blank example is basically the same as Example 7, except that the combined collector is not used. Specifically, in step S2, the frother MIBC is added directly at a concentration of 20 mg / L, and flotation is performed after adjusting the slurry for 1 minute.

[0134] Comparative Example 13

[0135] This comparative example is basically the same as Example 7, except that only emulsified non-polar hydrocarbon oil is used as the collector. Specifically, in step S2, the above-mentioned emulsified non-polar hydrocarbon oil with a concentration of 100 mg / L is added and the slurry is adjusted for 5 min; then the foaming agent MIBC with a concentration of 20 mg / L is added, and the slurry is adjusted for 1 min before flotation.

[0136] Comparative Example 14

[0137] This comparative example is basically the same as Example 7, except that only dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is used as the collector. Specifically, in step S2, DOPO-POSS is first added at a concentration of 100 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0138] Comparative Example 15

[0139] This comparative example is basically the same as Example 7, except that only nonylphenol polyoxyethylene ether phosphate (APE-4P) is used as the collector. Specifically, in step S2, APE-4P is first added at a concentration of 100 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0140] Examples 7~8, Blank Example 4, and Comparative Examples 13~15 The upward floating rate is shown in Table 4 below.

[0141] Table 4.

[0142]

[0143] Examples 9~10, Blank Example 5, and Comparative Examples 16~18

[0144] Example 9

[0145] A combined collector This includes emulsified nonpolar hydrocarbon oils and phosphate ester anionic surfactants.

[0146] Emulsified nonpolar hydrocarbon oil is prepared by the following steps: fatty alcohol polyoxyethylene ether (AEO-5) and cetearyl alcohol polyoxyethylene ether 10 (Pingpingjia O-10) are mixed at a mass ratio of 1:1 to obtain an emulsifier; kerosene and diesel are mixed at a mass ratio of 1:2 to obtain a composite hydrocarbon oil; the emulsifier is then added to the composite hydrocarbon oil, the mass ratio of the composite hydrocarbon oil to the emulsifier is 6:1, and the mixture is stirred for 5 minutes using a high-speed shear machine to obtain the emulsified nonpolar hydrocarbon oil.

[0147] The phosphate ester anionic surfactant selected is dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS).

[0148] The mass ratio of the emulsified nonpolar hydrocarbon oil to the phosphate ester anionic surfactant is 1:1.

[0149] Use of this combined collector in the flotation of fine particles of molybdenite According to Figure 1 The process shown includes the following steps:

[0150] S1. Take 2 g of pure molybdenite mineral with a particle size of -20 μm for flotation. Add an appropriate amount of deionized water to a 70 mL hanging flotation tank. Control the rotation speed of the flotation tank to 1300 r / min and adjust the pulp for 2 min to ensure sufficient dispersion. Control the pH of the pulp to 9.

[0151] S2. First, add the above-mentioned emulsified non-polar hydrocarbon oil at a concentration of 50 mg / L and adjust the slurry for 5 minutes; then add DOPO-POSS at a concentration of 50 mg / L and adjust the slurry for 5 minutes; finally, add the frother MIBC at a concentration of 20 mg / L, adjust the slurry for 1 minute, and then proceed with flotation.

[0152] S3. Perform aeration flotation for 3 min to obtain froth product and tailings. Filter, dry, weigh, and calculate the flotation rate of the froth concentrate and tailings respectively.

[0153] Example 10

[0154] This embodiment is basically the same as embodiment 9, except that: the anionic surfactant of phosphate ester is nonylphenol polyoxyethylene ether phosphate (APE-4P).

[0155] Blank example 5

[0156] This blank example is basically the same as Example 9, except that the combined collector is not used. Specifically, in step S2, the frother MIBC is added directly at a concentration of 20 mg / L, and flotation is performed after adjusting the slurry for 1 minute.

[0157] Comparative Example 16

[0158] This comparative example is basically the same as Example 9, except that only emulsified non-polar hydrocarbon oil is used as the collector. Specifically, in step S2, the above-mentioned emulsified non-polar hydrocarbon oil with a concentration of 50 mg / L is added and the slurry is adjusted for 5 min; then the foaming agent MIBC with a concentration of 20 mg / L is added, and the slurry is adjusted for 1 min before flotation.

[0159] Comparative Example 17

[0160] This comparative example is basically the same as Example 9, except that only dodecyl alcohol polyoxyethylene ether phosphate (DOPO-POSS) is used as the collector. Specifically, in step S2, DOPO-POSS is first added at a concentration of 50 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0161] Comparative Example 18

[0162] This comparative example is basically the same as Example 9, except that only nonylphenol polyoxyethylene ether phosphate (APE-4P) is used as the collector. Specifically, in step S2, APE-4P is first added at a concentration of 50 mg / L and the slurry is prepared for 5 min; then the foaming agent MIBC is added at a concentration of 20 mg / L, and the slurry is prepared for 1 min before flotation.

[0163] The buoyancy rates of Examples 9-10, Blank Example 5, and Comparative Examples 16-18 are shown in Table 5 below.

[0164] Table 5.

[0165]

[0166] As shown in Tables 1 to 5, the comparison shows that when the mass ratio of emulsified nonpolar hydrocarbon oil to phosphate ester anionic surfactant is 1:1, and when the emulsified nonpolar hydrocarbon oil and phosphate ester anionic surfactant are only 50 mg / L, the flotation rate can reach a relatively high level. This indicates that by simultaneously controlling the hydrophobicity of the "surface" and "edge", the low dosage of the combined collector can significantly improve the flotation rate of fine-grained molybdenite.

[0167] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A method for floating fine molybdenite, characterized in that: comprising the following steps: adding emulsified non-polar hydrocarbon oil to the fine molybdenite slurry, and then adding phosphate anionic surfactant; the emulsified non-polar hydrocarbon oil improves the hydrophobicity of the "face" of the fine molybdenite, and the phosphate anionic surfactant selectively chelates with molybdenum atoms on the "edge" of the fine molybdenite through phosphate groups to form a P-O-Mo bond and firmly adsorb on the "edge". The phosphate anionic surfactant is selected from at least one of dodecanol polyoxyethylene ether phosphate and nonylphenol polyoxyethylene ether phosphate. The mass ratio of the emulsified non-polar hydrocarbon oil to the phosphate anionic surfactant is 1: (0.1-10). The emulsified non-polar hydrocarbon oil is prepared by mixing and stirring non-polar hydrocarbon oil and emulsifier; the mass ratio of the non-polar hydrocarbon oil to the emulsifier is (2-10):

1.

2. The method of claim 1, wherein: The emulsifier is selected from at least one of fatty alcohol polyoxyethylene ether and cetyl stearyl alcohol polyoxyethylene ether.

3. The method of claim 1, wherein the method is characterized by: The particle size of the fine molybdenite is not more than 20 μm.

4. The method of claim 1, wherein: The amount of the emulsified non-polar hydrocarbon oil is 20-200 mg / L; the amount of the phosphate anionic surfactant is 20-200 mg / L.

5. The method of claim 4, wherein: The pH of the flotation process is 4-10.

6. The method of claim 1, wherein: ​ 7. The method of claim 1, wherein the method is characterized by: ​ 8. The method of claim 1, wherein the method is characterized by: ​

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