Preparation method and application of micro-fine particle molybdenum ore flotation collecting agent

Abstract

The invention discloses a preparation method and application of a micro-fine particle molybdenum ore flotation collecting agent, and belongs to the technical field of ore dressing separation. The micro-fine particle molybdenum ore flotation collecting agent is a liquid organic collecting agent obtained by compounding kerosene, a glycine solution and an emulsifier which are used as raw materials and performing high-shear emulsification. Compared with a conventional hydrocarbon oil collecting agent, the collecting agent has an efficient recycling effect on micro-fine particle molybdenum ore. The defects that a conventional hydrocarbon oil collecting agent is poor in dispersing effect and the collecting performance is reduced due to the fact that the hydrophobicity of oil-in-water type emulsion is reduced are overcome, and the collecting agent has the advantages of being easy to prepare, low in raw material cost, environmentally friendly and the like. The invention provides an efficient and low-consumption new method for efficient comprehensive recovery of the micro-fine particle molybdenum ore.

Description

Technical Field

[0001] This invention relates to the field of metal ore beneficiation technology, and in particular to a method for preparing a flotation collector for fine-grained molybdenum ore and its application. Background Technology

[0002] Molybdenum is a crucial metallic element and an irreplaceable strategic mineral resource, often referred to as the "energy metal." Molybdenum resources mainly exist in the forms of molybdenum disulfide, molybdenum compounds, metallic molybdenum, and their alloys. It has irreplaceable application value in 22 key sectors of the national economy, including iron and steel metallurgy (accounting for over 80% of global molybdenum consumption), aerospace, nuclear energy equipment, electronic devices, chemical catalysis, and biomedicine. However, as global molybdenum resource development enters the stage of deep mining and utilization of low-grade associated minerals, the proportion of "poor, complex, and fine-grained" difficult-to-process molybdenum ores has exceeded 65%. These ores require further fine grinding to achieve the liberation of molybdenum minerals. However, the fine grinding process increases the surface energy and lattice defects of molybdenite, significantly enhancing surface hydration and reducing the adsorption stability of traditional hydrocarbon oil collectors at the solid-liquid interface. Hydrocarbon oil collectors are good collectors for molybdenite, but because hydrocarbon oils are weakly polar and practically insoluble in water, their dispersion in water is poor. During flotation, they are dispersed into small droplets by mechanical stirring before entering the pulp. This oil-water dispersion system is unstable, resulting in poor collection. The purpose of emulsifying hydrocarbon oils is to ensure they are fully dispersed in the pulp, maintain the stability of the oil-water system, and increase the probability of collisions between hydrocarbon oil droplets and mineral particles, thereby significantly improving flotation efficiency. Emulsifiers generally contain two different polar groups: a polar hydrophilic group and a non-polar lipophilic group. Emulsifiers do not readily approach water molecules but can combine with oil molecules. The emulsifier is oriented on the surfaces of the oil and water phases, reducing the surface tension of the hydrocarbon oil liquid dispersed in the pulp. This allows the hydrocarbon oil to be dispersed more stably in the other liquid as smaller droplets, forming a stable emulsion and thus improving beneficiation efficiency. However, the hydrophilicity of the surface of smaller droplets of hydrocarbon oil is enhanced by the hydrophilic groups of the emulsifier. In conventional dispersion systems (water), the collecting performance of the emulsified hydrocarbon oil collector will be weakened, which will affect the efficiency of mineral processing. Summary of the Invention

[0003] The purpose of this invention is to overcome the problems of insufficient dispersibility and low collection efficiency of kerosene collectors, and to develop a method for preparing a fine-particle molybdenum ore flotation collector and its application.

[0004] A method for preparing a flotation collector for fine-grained molybdenum ore includes the following steps:

[0005] Weigh 1 part of glycine granules by mass and dissolve them in 20 parts of water. After complete dissolution, add 1-5 parts of kerosene and 0.2 parts of emulsifier. After sonication, continue to add water to a certain volume. Use a high-speed shear disperser to physically shear the mixed solution for 2-10 minutes to obtain a milky white kerosene and glycine compound collector.

[0006] Furthermore, when kerosene and glycine are compounded, an emulsifier of 5%-20% by weight of kerosene is added.

[0007] Furthermore, the emulsifier is Triton 100, Span 80, or Tween 80.

[0008] Furthermore, the solution is emulsified using a high-speed shear mixer for 2-10 minutes.

[0009] Furthermore, the mass ratio of kerosene to glycine is 2-5.

[0010] Furthermore, the concentration of the kerosene and glycine compound collector is less than 420 g / L.

[0011] An application of a kerosene and glycine compound collector prepared using the aforementioned method for preparing fine-particle molybdenum ore flotation collector includes the following steps:

[0012] After crushing and fine grinding, the blocky molybdenum ore is added to the flotation cell. First, an appropriate amount of water is added for stirring and slurry preparation. Then, dilute hydrochloric acid or sodium hydroxide solution is added to adjust the pH of the slurry. Subsequently, the compound collector and the frother methyl isobutyl methanol are added in sequence at 3-minute intervals. Finally, the flotation is carried out by aeration. After skimming the foam, frothy products and bottom products are obtained. The frothy product is molybdenum concentrate, and the bottom product is tailings.

[0013] Furthermore, the pulp concentration during flotation is 2-30%, and the proportion of ore samples with a particle size of -15μm is greater than 50%.

[0014] Furthermore, the dosage of this collector is 50-100g / t.

[0015] Furthermore, the pulp pH during flotation is 4-11.

[0016] The fine-particle molybdenum ore flotation collector mentioned in this invention features good stability, small emulsion particle size, and excellent collection performance for fine-particle molybdenite. During emulsification, the emulsifier utilizes its lipophilic groups to interact with micron-sized kerosene droplets, forming a robust film on their surface to prevent droplet aggregation and maintain a uniform emulsion. The hydrophilic groups of the emulsifier enhance the hydrophilicity of the droplet surface, thus weakening the collection performance of emulsified kerosene in conventional dispersion systems (water). Glycine, one of the simplest amino acids, is ionizable in water and possesses strong hydrophilicity, but it is a nonpolar molecule and a hydrophobic amino acid. Using a glycine solution as a dispersion system can synergistically enhance the hydrophobicity of the droplet surface, thereby improving the collection effect of the droplets on fine-particle molybdenite. Therefore, the use of kerosene combined with glycine enhances the dispersibility of kerosene, strengthens its direct interaction with fine molybdenite particles, and simultaneously enhances the hydrophobicity of the microdroplet surface, thus strengthening its collection effect on fine molybdenite particles. This invention overcomes the shortcomings of conventional hydrocarbon oil collectors, such as poor dispersion and decreased collection performance due to reduced hydrophobicity in oil-in-water emulsions, thereby enhancing the recovery capacity of emulsified kerosene microdroplet collectors for fine molybdenum particles. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] The preparation method of a flotation collector for fine-grained molybdenum ore according to the present invention includes the following steps:

[0019] Weigh 1 part of glycine granules by mass and dissolve them in 20 parts of water. After complete dissolution, add 1-5 parts of kerosene and 0.2 parts of emulsifier. After sonication, continue to add water to a certain volume. Use a high-speed shear disperser to physically shear the mixed solution for 2-10 minutes to obtain a milky white kerosene and glycine compound collector.

[0020] Furthermore, when kerosene and glycine are compounded, an emulsifier of 5%-20% by weight of kerosene is added.

[0021] Furthermore, the emulsifier is Triton 100, Span 80, or Tween 80.

[0022] Furthermore, the solution is emulsified using a high-speed shear mixer for 2-10 minutes.

[0023] Furthermore, the mass ratio of kerosene to glycine is 2-5.

[0024] Furthermore, the concentration of the kerosene and glycine compound collector is less than 420 g / L.

[0025] An application of a kerosene and glycine compound collector prepared using the aforementioned method for preparing fine-particle molybdenum ore flotation collector includes the following steps:

[0026] After crushing and fine grinding, the blocky molybdenum ore is added to the flotation cell. First, an appropriate amount of water is added for stirring and slurry preparation. Then, dilute hydrochloric acid or sodium hydroxide solution is added to adjust the pH of the slurry. Subsequently, the compound collector and the frother methyl isobutyl methanol are added in sequence at 3-minute intervals. Finally, the flotation is carried out by aeration. After skimming the foam, frothy products and bottom products are obtained. The frothy product is molybdenum concentrate, and the bottom product is tailings.

[0027] Furthermore, the pulp concentration during flotation is 2-30%, and the proportion of ore samples with a particle size of -15μm is greater than 50%.

[0028] Furthermore, the dosage of this collector is 50-100g / t.

[0029] Furthermore, the pulp pH during flotation is 4-11.

[0030] Example 1

[0031] The preparation of a flotation collector for fine-grained molybdenum ore includes the following steps:

[0032] (1) Weigh 0.667g of glycine granules and add them to a 100mL beaker. Add about 13mL of water to dissolve the glycine and obtain a glycine solution.

[0033] (2) Weigh 1.333g of kerosene and add it dropwise to the glycine solution, while simultaneously adding 0.1333g of Tween 80 to obtain a heterogeneous solution of glycine, kerosene and Tween 80.

[0034] (3) The mixed solution was brought to a final volume of 100 mL and transferred to a 250 mL conical flask for high-speed shear dispersion. The shear speed was 14000 rpm. After shearing for 5 min, a milky white kerosene and glycine compound collector was obtained.

[0035] Example 2

[0036] This embodiment is an application example of the aforementioned fine-particle molybdenum ore flotation collector.

[0037] 2g of molybdenite sample with a particle size of -15μm was weighed into a flotation cell, and water was added to prepare a 4% slurry. After stirring for 3 minutes to ensure complete dispersion of the minerals, dilute hydrochloric acid or sodium hydroxide solution was added to adjust the pH of the slurry to 9. Then, a collector composed of 10mg / L kerosene and glycine was added, and stirring was continued for 3 minutes. Then, 1mg / L frother methyl isobutyl methanol was added, and stirring was continued for 3 minutes. Aeration was then started, and after skimming the foam for 2 minutes, the concentrate product was obtained. The recovery rate of molybdenite reached 97.96%.

[0038] Example 3

[0039] This embodiment is an application example of the aforementioned fine-particle molybdenum ore flotation collector.

[0040] 1g of a mixed sample of molybdenite and quartz with a particle size of -15μm was weighed into a flotation cell. Water was added to prepare a 4% slurry. After stirring for 3 minutes to ensure complete dispersion of the minerals, dilute hydrochloric acid or sodium hydroxide solution was added to adjust the pH of the slurry to 9. Then, 10mg / L of kerosene and glycine were added as a collector. After stirring for another 3 minutes, 1mg / L of frother methyl isobutyl methanol was added. After stirring for another 3 minutes, aeration was started. After skimming the bubbles for 2 minutes, the concentrate product was obtained. The Mo grade and recovery rate in the concentrate reached 42.81% and 98.66%, respectively.

[0041] Example 4

[0042] This embodiment is an application example of the aforementioned fine-particle molybdenum ore flotation collector.

[0043] 360g (dry weight) of molybdenum rough concentrate was weighed and added to a 1.5L flotation cell. Water was added to prepare a 25% slurry. The -15μm particle content in the molybdenum rough concentrate reached approximately 65%, and the Mo grade was approximately 4%. After the slurry was thoroughly stirred, dilute hydrochloric acid or sodium hydroxide solution was first added to adjust the pH of the slurry to 9. Then, 1000g / t water glass was added as a dispersant, 160g / t kerosene and glycine combined collector, and 30g / t frother methyl isobutyl methanol were added sequentially at 3-minute intervals. After that, aeration was started, and a 10-minute skimming operation was performed to obtain the concentrate product. The Mo grade and recovery rate in the concentrate reached 10.03% and 95.51%, respectively.

[0044] Comparative Example 1

[0045] This comparative example demonstrates the flotation of fine-grained molybdenite without the addition of a collector.

[0046] 2g of molybdenite sample with a particle size of -15μm was weighed into a flotation cell, and water was added to prepare a 4% slurry. After stirring for 3 minutes to completely disperse the minerals, dilute hydrochloric acid or sodium hydroxide solution was added to adjust the pH of the slurry. Then, 1mg / L of frother methyl isobutyl methanol was added, and stirring was continued for 3 minutes before aeration was started. After skimming the bubbles for 2 minutes, the concentrate product was obtained. The recovery rate of molybdenite was only 70.23%.

[0047] Comparative Example 2

[0048] This comparative example demonstrates the flotation of fine-grained molybdenite with the addition of kerosene collector.

[0049] 2g of molybdenite sample with a particle size of -15μm was weighed into a flotation cell, and water was added to prepare a 4% slurry. After stirring for 3 minutes to ensure complete dispersion of the minerals, dilute hydrochloric acid or sodium hydroxide solution was added to adjust the pH of the slurry. Then, 10mg / L emulsified kerosene collector was added, and stirring was continued for 3 minutes. Then, 1mg / L frother methyl isobutyl methanol was added, and stirring was continued for 3 minutes. Aeration was then started, and after skimming the foam for 2 minutes, the concentrate product was obtained. The recovery rate of molybdenite was only 83.16%.

[0050] Comparative Example 3

[0051] This comparative example demonstrates the flotation of fine-grained molybdenite without the addition of a collector.

[0052] 1g of a mixed sample of molybdenite and quartz with a particle size of -15μm was weighed into a flotation cell. Water was added to prepare a 4% slurry. After stirring for 3 minutes to ensure complete dispersion of the minerals, dilute hydrochloric acid or sodium hydroxide solution was added to adjust the pH of the slurry to 9. Then, 1mg / L of frother methyl isobutyl methanol was added. After stirring for another 3 minutes, aeration was started. After skimming the bubbles for 2 minutes, the concentrate product was obtained. The Mo grade and recovery rate in the concentrate were only 34.71% and 76.14%, respectively.

[0053] Comparative Example 4

[0054] This comparative example demonstrates the flotation of fine-grained molybdenite with the addition of kerosene collector.

[0055] 1g of a mixed sample of molybdenite and quartz with a particle size of -15μm was weighed into a flotation cell. Water was added to prepare a 4% slurry. After stirring for 3 minutes to ensure complete dispersion of the minerals, dilute hydrochloric acid or sodium hydroxide solution was added to adjust the pH of the slurry to 9. Then, 10mg / L emulsified kerosene collector was added, and stirring was continued for 3 minutes. Next, 1mg / L frother methyl isobutyl methanol was added, and stirring was continued for 3 minutes. Aeration was then started, and after skimming the foam for 2 minutes, the concentrate product was obtained. The Mo grade and recovery rate in the concentrate reached 37.31% and 85.99%, respectively.

[0056] Comparative Example 5

[0057] This comparative example demonstrates the flotation of fine-grained molybdenite without the addition of a collector.

[0058] 360g (dry weight) of molybdenum rough concentrate was weighed and added to a 1.5L flotation cell. Water was added to prepare a 25% slurry. The -15μm particle content in the molybdenum rough concentrate reached approximately 65%, and the Mo grade was approximately 4%. After the slurry was thoroughly stirred, dilute hydrochloric acid or sodium hydroxide solution was first added to adjust the pH of the slurry to 9. Then, 1000g / t water glass was added as a dispersant, and 30g / t frother methyl isobutyl methanol was added sequentially at 3-minute intervals. After that, aeration was started, and a 10-minute skimming operation was performed to obtain the concentrate product. The Mo grade and recovery rate in the concentrate reached 6.68% and 73.46%, respectively.

[0059] Comparative Example 6

[0060] This comparative example demonstrates the flotation of fine-grained molybdenite with the addition of kerosene collector.

[0061] 360g (dry weight) of molybdenum rough concentrate was weighed and added to a 1.5L flotation cell. Water was added to prepare a 25% slurry. The -15μm particle content in the molybdenum rough concentrate reached approximately 65%, and the Mo grade was approximately 4%. After the slurry was thoroughly stirred, dilute hydrochloric acid or sodium hydroxide solution was first added to adjust the pH of the slurry to 9. Then, 1000g / t water glass as a dispersant, 160g / t emulsified kerosene collector, and 30g / t frother methyl isobutyl methanol were added to the slurry sequentially at 3-minute intervals. After that, aeration was started, and a 10-minute skimming operation was performed to obtain the concentrate product. The Mo grade and recovery rate in the concentrate reached 8.40% and 86.71%, respectively.

[0062] The flotation collector for fine-particle molybdenum ore in this invention is a liquid organic collector obtained by compounding and high-shear emulsification of kerosene, glycine solution, and emulsifier. Compared with conventional hydrocarbon oil collectors, the collector of this invention has a more efficient recovery effect on fine-particle molybdenum ore. This invention also overcomes the shortcomings of conventional hydrocarbon oil collectors, such as poor dispersion and decreased collection performance due to reduced hydrophobicity of oil-in-water emulsions. It has advantages such as simple preparation, low raw material cost, and environmental friendliness. This invention provides a new, efficient, and low-consumption method for the comprehensive recovery of fine-particle molybdenum ore.

[0063] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a flotation collector for fine-grained molybdenum ore, characterized in that, Includes the following steps: Weigh 1 part of glycine granules by mass and dissolve them in 20 parts of water. After complete dissolution, add 1-5 parts of kerosene and 0.2 parts of emulsifier. After sonication, continue to add water to make up the volume. Use a high-speed shear disperser to physically shear the mixed solution for 2-10 minutes to obtain a milky white kerosene and glycine compound collector.

2. The preparation of the flotation collector for fine-grained molybdenum ore according to claim 1, characterized in that: When kerosene and glycine are compounded, an emulsifier of 5%-20% of the weight of kerosene is added.

3. The preparation of the flotation collector for fine-grained molybdenum ore according to claim 2, characterized in that: The emulsifier is Triton 100, Span 80, or Tween 80.

4. The preparation of the flotation collector for fine-grained molybdenum ore according to claim 1, characterized in that: Emulsify the solution using a high-speed shear mixer for 2-10 minutes.

5. The preparation of the flotation collector for fine-grained molybdenum ore according to claim 1, characterized in that: The mass ratio of kerosene to glycine is 2-5.

6. The preparation method of the flotation collector for fine-grained molybdenum ore is characterized by: At 25 degrees Celsius, the concentration of the kerosene and glycine compound collector is less than 420 g / L.

7. An application of a kerosene and glycine compound collector prepared using the method for preparing the fine-particle molybdenum ore flotation collector according to claim 1, characterized in that, Includes the following steps: After crushing and fine grinding, the blocky molybdenum ore is added to the flotation cell. First, an appropriate amount of water is added for stirring and slurry preparation. Then, dilute hydrochloric acid or sodium hydroxide solution is added to adjust the pH of the slurry. Subsequently, the compound collector and the frother methyl isobutyl methanol are added in sequence at 3-minute intervals. Finally, the flotation is carried out by aeration. After skimming the foam, frothy products and bottom products are obtained. The frothy product is molybdenum concentrate, and the bottom product is tailings.

8. The application of the fine-grained molybdenite flotation collector according to claim 7, characterized in that: During flotation, the pulp concentration is 2-30%, and the proportion of ore samples with a particle size of -15μm is greater than 50%.

9. The application of the fine-grained molybdenite flotation collector according to claim 7, characterized in that: The dosage of this collector is 50-100g / t.

10. The application of the fine-grained molybdenite flotation collector according to claim 7, characterized in that: The pH of the pulp during flotation is 4-11.