A composite collector and its application in fluorite flotation

Abstract

The present invention discloses a composite collector and its application in fluorite flotation, belonging to the field of mineral processing technology. The composite collector comprises components such as oleic acid, succinate sulfonate, fatty alcohol polyoxyethylene ether, and sodium hydroxide. When used in low-temperature fluorite flotation, the composite collector can significantly improve the low-temperature recovery rate of fluorite and reduce reagent consumption, thus having important significance for the clean and efficient utilization of strategic mineral resources.

Description

Technical Field

[0001] The present invention relates to a collector, in particular to a fluorite flotation composite collector, and also to the application of the composite collector in fluorite flotation, in particular to the application of the composite collector in fluorite low-temperature flotation, belonging to the field of mineral flotation agent preparation and application. Background Art

[0002] Fluorite is a non-renewable, strategically scarce mineral resource widely used in traditional and strategic emerging industries, including chemicals, metallurgy, defense, healthcare, semiconductors, new energy, and new materials. Its strategic importance is growing. my country boasts abundant fluorite resources. As of 2020, proven reserves of fluorite reached approximately 42 million tons, accounting for approximately 15% of the world's total. However, my country has long led the world in fluorite mining, consumption, and exports. With the increasing depletion of easily beneficiated rich ores and the continued growth of market demand, the supply and demand imbalance of fluorite in my country is becoming increasingly prominent. Therefore, strengthening the efficient recycling and utilization of fluorite resources is an urgent requirement and a key approach to ensuring my country's strategic demand for fluorite resources.

[0003] Flotation is an effective method for recovering fluorite resources, and flotation reagents are a key factor in determining flotation effectiveness. Fatty acid collectors, primarily oleic acid, are the most commonly used collectors in fluorite flotation due to their widespread availability and relatively low price. However, these collectors are not tolerant to low temperatures, resulting in increased reagent usage and reduced fluorite flotation recovery rates in winter (when slurry temperatures fall below 15°C). Therefore, the development of flotation collectors for low-temperature, high-efficiency fluorite recovery is urgently needed to improve the comprehensive utilization of fluorite resources and provide strong support for the development of my country's fluorine chemical industry. Summary of the Invention

[0004] In view of the defects of the existing technology, the first purpose of the present invention is to provide a composite collector, which has good low-temperature resistance and strong selectivity and collection ability for fluorite. It overcomes the defects of the existing technology such as low fluorite recovery efficiency at low temperature and large reagent consumption, and is conducive to the comprehensive utilization of fluorite resources.

[0005] The second object of the present invention is to provide a composite collector for use in fluorite flotation, wherein the composite collector still has high selectivity and collection capacity for fluorite at low temperatures, thereby improving the low-temperature recovery efficiency of fluorite, reducing reagent consumption, and reducing the cost of fluorite beneficiation.

[0006] In order to achieve the above technical purpose, the present invention provides a composite collector comprising oleic acid, succinate sulfonate, fatty alcohol polyoxyethylene ether and sodium hydroxide.

[0007] The collector of the present invention has oleic acid as a main component. The oleic acid is partially saponified with sodium hydroxide to obtain a mixture of oleic acid and sodium oleate. This mixture not only improves the low-temperature resistance of the oleic acid, but also enhances its flotation and collection capacity for fluorite minerals. The introduction of succinate sulfonate can improve the selectivity and collection capacity of the oleic acid collector. The fatty alcohol polyoxyethylene ether has an emulsifying effect and can enhance the low-temperature resistance of the fatty acid collector. In summary, by modifying the oleic acid collector with the components of succinate sulfonate, fatty alcohol polyoxyethylene ether, and sodium hydroxide, and utilizing the synergistic effects of saponification, emulsification, and enhanced collection capacity, the composite collector has good collection capacity and low-temperature resistance.

[0008] As a preferred embodiment, the composite collector comprises the following components by weight: 60-70% oleic acid; 3-6% succinate sulfonate; 5-10% fatty alcohol polyoxyethylene ether; 4-8% sodium hydroxide; and the balance is water. Excessively high or low proportions of succinate sulfonate, fatty alcohol polyoxyethylene ether, and sodium hydroxide in the composite collector can affect the collector's effectiveness in various ways.

[0009] As a preferred embodiment, the oleic acid comprises at least one of soybean oleic acid, rapeseed oleic acid, and rice bran oleic acid, which are conventional oleic acid collectors.

[0010] As a preferred solution, the fatty alcohol polyoxyethylene ether is lauryl alcohol polyoxyethylene ether with an ethylene oxide addition number of not more than 9. The preferred fatty alcohol polyoxyethylene ether has a good emulsifying effect on oleic acid and can enhance the low-temperature resistance of oleic acid.

[0011] As a preferred solution, the succinate sulfonate is sodium lauryl polyoxyethylene ether succinate monoester sulfonate. The preferred succinate sulfonate acts as a cooperative collector for the oleic acid collector, which can improve the selectivity and collection ability of oleic acid for minerals such as fluorite.

[0012] The present invention also provides an application of a fluorite flotation composite collector, which is applied to fluorite flotation.

[0013] As a preferred solution, the flotation is low-temperature flotation, and the flotation temperature is 6-10°C.

[0014] As a preferred solution, the fluorite flotation composite collector is used for the flotation separation of fluorite and gangue minerals; the gangue minerals include at least one of calcium-containing gangue minerals, quartz, and silicate minerals. The calcium-containing gangue minerals include calcite, dolomite, garnet, etc.

[0015] As a preferred solution, the fluorite flotation composite collector is used in combination with water glass and / or ATM inhibitor.

[0016] As a preferred solution, the dosage of the fluorite flotation composite collector is 200-400 g / t.

[0017] The application process of the fluorite flotation composite collector of the present invention in fluorite low-temperature flotation is as follows: when the pulp temperature is 6-10°C and under suitable pulp conditions, the inhibitor and the fluorite flotation composite collector are sequentially added to the fluorite flotation pulp, and flotation is performed after sufficient stirring.

[0018] The composite collector of the present invention comprises 60-70% by mass of industrial oleic acid, 3-6% by mass of succinate sulfonate, 5-10% by mass of fatty alcohol polyoxyethylene ether, 4-8% by mass of sodium hydroxide and the balance of water. The composite collector is prepared by subjecting these components to a simple mixing reaction. The specific preparation process is as follows: sodium hydroxide and water are mixed according to a mass ratio to prepare a sodium hydroxide aqueous solution; industrial oleic acid, succinate sulfonate and fatty alcohol polyoxyethylene ether are mixed according to a mass ratio, heated and continuously stirred, and after the temperature is raised to 90°C, the sodium hydroxide aqueous solution is slowly added and kept at a constant temperature for about 2 hours to prepare the fluorite composite collector.

[0019] Compared with the existing technology, the technical solution of the present invention brings the following beneficial technical effects:

[0020] 1) The fluorite flotation composite collector of the present invention adopts the principles of saponification and surfactant compound assembly to synergistically enhance the surface activity and collection performance of the oleic acid collector, thereby significantly improving the selectivity and low-temperature resistance of the oleic acid collector.

[0021] 2) The fluorite flotation composite collector of the present invention can realize the flotation separation of fluorite at low temperature (below 10°C), and has the advantages of low reagent consumption and high fluorite recovery rate, which is of great significance to the efficient recovery and utilization of strategic mineral resources such as fluorite.

[0022] 3) The fluorite flotation composite collector of the present invention is easy to obtain and has low cost, which is conducive to large-scale promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 These are the results of the flotation test on pure fluorite minerals using soybean oleic acid and composite collectors. DETAILED DESCRIPTION

[0024] The specific embodiments described herein are only used to explain the content of the present invention and further elaborate the objectives, technical solutions and advantages of the present invention, but are not used to limit the present invention.

[0025] The composite collectors in the following specific examples and comparative examples are obtained by the following specific preparation process: sodium hydroxide and water are mixed in a mass ratio to prepare a sodium hydroxide aqueous solution; industrial oleic acid, succinate sulfonate, and fatty alcohol polyoxyethylene ether are mixed in a mass ratio, heated and continuously stirred, and after the temperature is raised to 90° C., the sodium hydroxide aqueous solution is slowly added and kept at a constant temperature for about 2 hours to prepare the composite collector.

[0026] Example 1

[0027] Single mineral flotation:

[0028] The composite collector in this example was prepared using the method described herein, comprising 62% soybean oleic acid, 3% sodium lauryl polyoxyethylene ether succinate sulfonate, 10% lauryl polyoxyethylene ether-9, 5% sodium hydroxide, and 20% water in a mass ratio. Fluorite had a single mineral purity of 99.04% and a particle size of 0.038-0.074 mm. Flotation experiments were conducted in an XFG hanging trough flotation cell at approximately 8°C. 2.000 g of ore sample was weighed, 40 mL of deionized water was added, and the mixture was stirred for 1 minute to obtain a uniform slurry. Hydrochloric acid or sodium hydroxide solution was then added to adjust the pH to 9. After 2 minutes of stirring, the single soybean oleic acid collector or composite collector was added and allowed to react for 3 minutes before flotation to produce concentrate and tailings. Results showed that the composite collector exhibited enhanced fluorite capture, significantly improving the low-temperature flotation recovery rate and reducing reagent usage.

[0029] Example 2

[0030] Flotation separation of single high calcium fluorite ore:

[0031] The composite collector in this embodiment is prepared according to the preparation method of the present invention from 30% rice bran oleic acid, 35% rapeseed oleic acid, 3% sodium lauryl polyoxyethylene ether succinate sulfonate, 8% lauryl polyoxyethylene ether-9, 6% sodium hydroxide, and 18% water in a mass ratio. Fluorite ore contains 30.28% CaF2 and 37.96% CaCO3, with gangue minerals primarily consisting of calcite, quartz, and a small amount of dolomite. The ore is ground to a particle size of approximately -0.074 mm, accounting for approximately 70% of the total particle size. Flotation is performed at an initial slurry pH of 7.48, followed by the addition of a combined depressant of water glass and ATM, and the composite collector prepared in this embodiment. Fluorite concentrate is obtained through a closed-circuit flotation process consisting of a coarse, a scavenger, and a fine, five-process flotation process. When the pulp temperature is about 9°C and the dosage of the composite collector is 400g / t, a fluorite concentrate with a CaF2 content of 97.45% and a recovery rate of 78.83% is obtained.

[0032] Comparative Example 1

[0033] See Example 2 for details, except that: a single fatty acid collector is used, rice bran oleic acid and rapeseed oleic acid are mixed in a mass ratio of 1:1, the dosage is 400 g / t, and under the condition that the slurry temperature is about 9°C, a fluorite concentrate containing 95.81% CaF2 and a recovery rate of 69.73% is obtained.

[0034] Comparative Example 2

[0035] See Example 2 for details, except that lauryl polyoxyethylene ether-9 is omitted. Instead, a composite collector is prepared according to the preparation method of the present invention using a mixture of 30% rice bran oleic acid, 35% rapeseed oil acid, 3% sodium lauryl polyoxyethylene ether succinate sulfonate, 6% sodium hydroxide, and 26% water in a mass ratio. At a slurry temperature of approximately 9°C and a composite collector dosage of 400 g / t, a fluorite concentrate containing 97.72% CaF2 and a recovery rate of 73.31% is obtained.

[0036] Example 3

[0037] Comprehensive recovery of polymetallic associated fluorite resources:

[0038] The composite collector in this example is prepared using the method described in the present invention, comprising 60% rice bran oleic acid, 4% sodium lauryl polyoxyethylene ether succinate monosulfonate, 10% lauryl polyoxyethylene ether-9, 4% sodium hydroxide, and 22% water in a mass ratio. Fluorite is recovered from the flotation tailings of a tungsten-molybdenum polymetallic ore containing approximately 15% CaF2 and 8% CaCO3, with the primary gangue minerals being garnet, calcite, feldspar, and quartz. A one-roughing, one-sweeping, five-fine flotation process is employed, with a slurry temperature of 10°C. The roughing operation uses Na2CO3 to adjust the slurry pH to 10-10.5, and 1000g / t of water glass is added as a silicate gangue mineral depressant. Subsequently, either rice bran oleic acid alone or the composite collector prepared in this example is added to flotate the fluorite, while acidified water glass is used as a depressant in the finer operation. The results show that when the dosage of single rice bran oleic acid is 500g / t, a fluorite concentrate with a CaF2 content of 80.95% and a recovery rate of 67.84% can be obtained; when the dosage of the composite collector is 300g / t, a fluorite concentrate with a CaF2 content of 88.75% and a recovery rate of 75.12% can be obtained. The composite collector shows good low-temperature resistance and better selectivity and collection ability for fluorite than single oleic acid.

[0039] Comparative Example 3

[0040] See Example 3 for details, the difference being that when a single fatty acid collector is used and the amount of rice bran oleic acid is 500 g / t, a fluorite concentrate containing 0.95% CaF2 and a recovery rate of 67.84% is obtained.

[0041] Comparative Example 4

[0042] See Example 3 for details, except that: only oleic acid is saponified, and sodium lauryl polyoxyethylene ether succinate monoester sulfonate and lauryl polyoxyethylene ether-9 are not added. When the dosage of the agent is 400 g / t, a fluorite concentrate containing 1.06% CaF28 and a recovery rate of 68.55% is obtained.

[0043] Comparative Example 5

[0044] See Example 3 for details, except that sodium monosulfosuccinate was omitted. Instead, a composite collector was prepared using a mixture of 60% rice bran oleic acid, 10% lauryl polyoxyethylene ether-9, 4% sodium hydroxide, and 26% water in a mass ratio according to the present invention. When the agent dosage was 300 g / t, a fluorite concentrate containing 85.71% CaF2 and a recovery rate of 74.35% was obtained.

[0045] The above examples are not intended to limit the present invention. Without departing from the principles of the present invention, variations and modifications made by those skilled in the art to the embodiments are within the scope of the present invention. Unless otherwise specified, the various reagents and equipment used in the present invention can be purchased directly or prepared by existing methods.

Claims

1. A composite collector for low-temperature flotation of fluorite, characterized by: Contains the following components by mass percentage: Oleic acid 60~70%; Sulfosuccinate ester 3~6%; Fatty alcohol polyoxyethylene ether 5~10%; Sodium hydroxide 4~8%; The balance is water; The fatty alcohol polyoxyethylene ether is lauryl alcohol polyoxyethylene ether with an ethylene oxide addition number of not more than 9; The succinate sulfonate is sodium lauryl polyoxyethylene ether succinate monoester sulfonate.

2. The composite collector according to claim 1, wherein: The oleic acid includes at least one of soybean oleic acid, rapeseed oleic acid, and rice bran oleic acid.

3. An application of the composite collector according to claim 1 or 2, characterized in that: Applied to fluorite flotation; the flotation is low-temperature flotation, and the flotation temperature is 6-10°C.

4. The use according to claim 3, characterized in that: It is used for flotation separation of fluorite and gangue minerals; the gangue minerals include at least one of calcium-containing gangue minerals, quartz, and silicate minerals.

5. The use according to claim 3, characterized in that: The composite collector is used in combination with water glass and / or an ATM inhibitor.

6. The use according to claim 3, characterized in that: The dosage of the composite collector is 200-400 g / t.

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