A fluorite low-temperature collector and its preparation method

Abstract

The present invention discloses a fluorite low-temperature collector and a preparation method thereof. The raw materials include sodium oleate, sodium rosinate, a peregal surfactant, and a carboxylic acid copolymer, and the weight proportions of the raw materials are as follows: 65-82 parts of sodium oleate, 10-20 parts of sodium rosinate, 3-5 parts of a peregal surfactant, and 5-10 parts of the carboxylic acid copolymer. The collector provided by the present invention still has good dispersibility and foaming ability under low-temperature environments, can overcome the shortcomings of fatty acid-based agents in poor low-temperature collection ability, enhance the collection of fine particles, ensure the concentrate grade of fluorite, improve the recovery rate of fluorite under low-temperature environments, and has strong ore adaptability.

Description

Technical Field

[0001] The present invention belongs to the field of fluorite flotation, and in particular relates to a fluorite collector, especially a fluorite low-temperature collector and a preparation method thereof. Background Art

[0002] Fluorite (CaF2) is a common mineral found in nature and the primary source of industrial fluorine, often found in association with other minerals. Fluorite concentrate is often used as a flux in steelmaking to remove impurities. It can also be used to produce glass and enamel. Various lenses made from fluorite are in huge demand in the optical field. Furthermore, chip manufacturing, aerospace, healthcare, air conditioning, and refrigeration all require large quantities of fluorite concentrate as a basic raw material. Fluorite ore is primarily recovered by flotation. Fatty acid collectors, the most common fluorite collectors, possess strong collection and foaming abilities. However, at low temperatures, the solubility and dispersibility of fatty acid collectors decrease, leading to a decrease in fluorite recovery and an increase in collector usage. This results in a loss of fluorite resources and damage to the economic benefits of the enterprise.

[0003] To address the problem of insufficient low-temperature collection performance of fatty acid collectors, relevant researchers have proposed many improvement measures. For example, the fluorite collector and its preparation method disclosed in Chinese patent CN114054213B can improve the recovery rate of fluorite in low-temperature environments to a certain extent, but the slurry temperature it is suitable for is 10-20°C. In the winter, the slurry temperature in the main fluorite producing areas in northern my country is often below 10°C. In addition, the preparation process of this fluorite collector involves complex chemical reactions, which are dangerous and polluting. Therefore, this method has certain limitations. Chinese patents CN113441285, CN104056726 and CN102764700 also have a limited applicable temperature range and involve complex chemical reactions and chemical reagents. Although the low-temperature fluorite collector disclosed in Chinese patent CN1071382888 is simple to prepare, its lower temperature limit of application is not low enough. China CN113102112 discloses an oxide mineral capture agent, a preparation method thereof, and an application thereof. Although the agent has good performance and strong low-temperature adaptability, some of the raw materials are expensive and have limited sources, which restricts its large-scale application. Summary of the Invention

[0004] The purpose of the present invention is to provide a fluorite low-temperature collector and a preparation method thereof, so as to solve the problem that fatty acid collectors have poor fluorite collection performance under low-temperature conditions.

[0005] To achieve the above objectives, the present invention provides the following technical solutions:

[0006] According to one aspect of the present invention, the present invention provides a fluorite low-temperature collector, the main raw materials of which include sodium oleate, sodium rosinate, a peregal surfactant and a carboxylic acid copolymer, and the weight proportions of the raw materials are as follows: 65 to 82 parts of sodium oleate, 10 to 20 parts of sodium rosinate, 3 to 5 parts of a peregal surfactant, and 5 to 10 parts of a carboxylic acid copolymer.

[0007] The structural formula of the sodium oleate is shown in Formula I:

[0008]

[0009] The structural formula of the sodium rosinate is shown in Formula II:

[0010]

[0011] Preferably, the peregal surfactant is a nonionic surfactant that is easily soluble in water, stable in hard water, acid or alkali, and has good emulsification, solubilization, dispersion and foaming abilities. The general structural formula of the peregal surfactant is RO(CH2CH2O) n CH2CH2OH, wherein R is a hydrocarbon chain containing 12 to 18 carbon atoms, and n = 15 to 16.

[0012] More preferably, R is a hydrocarbon chain containing 16 to 18 carbon atoms. A longer hydrophobic chain can improve the hydrophobicity of the fluorite surface and increase the recovery rate of fluorite.

[0013] Preferably, the carboxylic acid copolymer is one of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, maleic acid-acrylic acid copolymer and carboxylic acid-sulfonic acid-acrylate copolymer.

[0014] According to another aspect of the present invention, the present invention provides a method for preparing a fluorite low-temperature collector, comprising the following steps:

[0015] 1) dissolving sodium oleate in water to prepare a sodium oleate solution with a mass concentration of 5% to 10%;

[0016] 2) sequentially adding sodium rosinate, a peregal surfactant, and a carboxylic acid copolymer to the sodium oleate solution of step 1) to obtain a mixture;

[0017] 3) The mixture obtained in step 2) is sheared and stirred for 5 to 10 minutes to mix uniformly to obtain a fluorite low-temperature collector.

[0018] Preferably, in step 1), sodium oleate is dissolved in hot water at 50-65° C. to prepare a sodium oleate solution with a mass concentration of 5%-10%.

[0019] More preferably, in step 1), sodium oleate is dissolved in 50° C. hot water to prepare a sodium oleate solution with a mass concentration of 5%. A low concentration facilitates the dissolution and dispersion of sodium oleate.

[0020] Preferably, in step 2), sodium rosinate, a peregal surfactant and a carboxylic acid copolymer are added to the sodium oleate solution in sequence at intervals of 5 minutes.

[0021] The present invention will be further explained below:

[0022] The collector of the present invention has a good collection effect on fluorite in a low temperature environment of not less than 5°C, ensuring the recovery rate of fluorite while also improving the grade of fluorite concentrate to a certain extent and reducing the amount of collector used. The main principle of the present invention is:

[0023] 1. Sodium rosinate has a fluorite collecting effect. Sodium rosinate has a cyclic hydrocarbon structure. According to the hydrophile-lipophile balance theory, when both hydrophilic groups are carboxyl groups, the hydrocarbon chains in sodium rosinate are less hydrophobic than those in sodium oleate. Therefore, sodium rosinate has better water solubility and dispersibility. Furthermore, the cyclic hydrocarbon structure in sodium rosinate has a larger cross-section and intersperses between sodium oleate molecules. This prevents more sodium oleate from adsorbing together due to intermolecular forces between hydrocarbon chains at low temperatures, further improving the dispersibility of the collector.

[0024] 2. Peregal surfactants are stable, with good resistance to hard water, acids, and alkalis. They can improve the low-temperature solubility, dispersibility, and foaming ability of sodium oleate. They also work synergistically with sodium rosinate to further enhance the capture efficiency of sodium oleate at low temperatures. Peregal is a common chemical product, with readily available raw materials and a reasonable price.

[0025] 3. As macromolecular substances, carboxylic acid copolymers have a certain flocculation effect on fine-grained fluorite, which helps to capture micro-fine fluorite. At the same time, they also have good hydrophilicity and can selectively adsorb on the surface of gangue minerals such as calcite, ensuring the quality of the final fluorite concentrate.

[0026] The low-temperature fluorite collector of the present invention has the following advantages:

[0027] ① The collector of the present invention is prepared by compounding sodium oleate, sodium rosinate, a peregal surfactant and a carboxylic acid copolymer. Sodium oleate, sodium rosinate, a peregal surfactant and a carboxylic acid copolymer are all common chemical products on the market. The raw materials are easily available, the cost is low, the collector is environmentally friendly, and the collector is easily degradable, thus having great market promotion value.

[0028] ② Sodium rosinate and pyrocatechol surfactant promote the low-temperature capture ability of sodium oleate through different synergistic mechanisms, and the synergistic effect of the two produces a 1+1>2 effect.

[0029] ③ Compared with general fatty acid collectors, the collector provided by the present invention has greatly improved low-temperature collection performance, can greatly improve the recovery rate of fluorite ore, reduce the amount of collector used, and ensure the quality of the concentrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a flow chart of the application of the fluorite low-temperature collector of the present invention in the flotation of fluorite ore. DETAILED DESCRIPTION

[0031] Example 1

[0032] The weight ratio of the raw materials of the fluorite low-temperature collector in this embodiment is as follows: 82 parts of sodium oleate, 10 parts of sodium rosinate, 3 parts of peregal surfactant (R is a hydrocarbon chain containing 18 carbon atoms, n = 15 to 16), and 5 parts of carboxylic acid-sulfonic acid-acrylate copolymer.

[0033] The preparation of the fluorite low-temperature collector in this embodiment is as follows: ① Sodium oleate is prepared into a 5% solution using 50°C hot water in a stirring barrel; ② Sodium rosin acid, a peregal-type surfactant, and a carboxylic acid copolymer are added to the sodium oleate solution at intervals of 5 minutes; ③ The mixture is sheared and stirred for 10 minutes using an emulsifying shearing machine to mix uniformly, thereby completing the preparation of the fluorite low-temperature collector.

[0034] Comparison of the effects of the fluorite collector in this embodiment and the fluorite collector in the prior art:

[0035] The fluorite low temperature collector prepared in this embodiment and the prior art fluorite collector were respectively applied to the flotation of fluorite ore CaF2 with a feed sample content of 40.23%. Figure 1 The flotation process shown is as follows: the adjusting agent is sodium carbonate, the depressant is water glass, and the comparison results of the use effects are shown in Table 1.

[0036] Table 1 Flotation results

[0037]

[0038]

[0039] It can be seen from the comparison results that in a low-temperature slurry at 8°C, the fluorite concentrate obtained by using the collector in Example 1 is about 9% higher than that of sodium oleate, the grade of fluorite concentrate is still maintained at more than 97%, and the amount of collector is reduced. Adding a single sodium rosinate or peregrine can improve the collection capacity of sodium oleate to a certain extent, but the strong foaming ability of peregrine causes a decrease in fluorite concentrate. Sodium rosinate can improve the dispersibility of sodium oleate, but its own collection capacity is limited, resulting in a fluorite recovery rate that is still not high enough. The combination of the two produces a positive synergistic effect, which ensures the quality of fluorite while improving the low-temperature fluorite recovery rate.

[0040] Example 2

[0041] The weight ratio of the raw materials of the fluorite low-temperature collector in this embodiment is: 65 parts of sodium oleate, 20 parts of sodium rosinate, 7 parts of peregal surfactant (R is a hydrocarbon chain with 12 carbon atoms, n = 15-16), and 8 parts of maleic acid-acrylic acid copolymer.

[0042] The preparation of the fluorite low-temperature collector in this embodiment is as follows: ① Sodium oleate is prepared into a 10% solution in a stirring bucket using 65°C hot water; ② Sodium rosin acid, a peregal-type surfactant, and a carboxylic acid copolymer are added to the sodium oleate solution at intervals of 5 minutes; ③ The mixture is sheared and stirred for 10 minutes using an emulsifying shearing machine to mix uniformly, thereby completing the preparation of the fluorite low-temperature collector.

[0043] Comparison of the effects of the fluorite collector in this embodiment and the fluorite collector in the prior art:

[0044] The fluorite low temperature collector prepared in this embodiment and the prior art fluorite collector were respectively applied to the flotation of fluorite ore CaF2 with a feed sample content of 22.36%, see Figure 1 The flotation process shown is as follows: the adjusting agent is sodium carbonate, the inhibitor is acidified water glass, and the comparison results of the use effects are shown in Table 2.

[0045] Table 2 Flotation results

[0046]

[0047]

[0048] Comparative results show that, in a low-temperature slurry at 5°C, the fluorite concentrate obtained using the collector of Example 2 is approximately 7% higher than that obtained with sodium oleate, while maintaining higher fluorite concentrate quality and reducing the collector dosage by 200g / t. Peregal and sodium rosinate also exhibit a positive synergistic effect. Compared to Example 1 without the copolymer, the grade and recovery rate are further improved. The copolymer facilitates the recovery of fine-grained fluorite and has a certain inhibitory effect on gangue minerals.

[0049] Example 3

[0050] The fluorite low-temperature collector of this embodiment has the following weight ratios of the raw materials: 75 parts of sodium oleate, 10 parts of sodium rosinate, 5 parts of peregal surfactant (R is a hydrocarbon chain with 12 carbon atoms, n = 15-16), and 10 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.

[0051] Preparation of the fluorite low-temperature collector in this embodiment: ① Sodium oleate was prepared into a 5% solution in a stirring bucket using 60°C hot water; ② Sodium rosin acid, a peregal-type surfactant, and a carboxylic acid copolymer were added to the sodium oleate solution at intervals of 5 minutes; ③ The mixture was sheared and stirred for 10 minutes using an emulsifying shearing machine to mix uniformly, thereby completing the preparation of the low-temperature fluorite collector.

[0052] Comparison of the effects of the fluorite collector in this embodiment and the fluorite collector in the prior art:

[0053] The fluorite low temperature collector prepared in this embodiment and the prior art fluorite collector were respectively applied to the flotation of fluorite ore CaF2 with a feed sample content of 25.36%, see Figure 1 The flotation process shown is as follows: the adjusting agent is sodium carbonate, the inhibitor is acidified water glass, and the comparison results of the use effects are shown in Table 3.

[0054] Table 3 Flotation results

[0055]

[0056]

[0057] The comparison results show that, in a low-temperature slurry at 7°C, the collector of Example 3 yields at least 4% more fluorite concentrate than conventional fluorite collectors, while maintaining a high quality. Oxidized paraffin soap, due to its long hydrocarbon chain fatty acids, has the worst low-temperature performance. Tall oil, due to its rosinic acid content, has better foaming power and relatively strong collecting ability, but produces slightly lower fluorite concentrate quality.

Claims

1. A fluorite low-temperature collector, characterized in that: The raw materials include sodium oleate, sodium rosinate, a peregal surfactant and a carboxylic acid copolymer, and the weight proportions of the raw materials are as follows: 65-82 parts of sodium oleate, 10-20 parts of sodium rosinate, 3-5 parts of a peregal surfactant and 5-10 parts of the carboxylic acid copolymer.

2. The fluorite low-temperature collector according to claim 1, characterized in that The peregal surfactant is a nonionic surfactant.

3. The fluorite low-temperature collector according to claim 2, characterized in that The general structural formula of the PEREGAL surfactant is RO(CH2CH2O) n CH2CH2OH, wherein R is a hydrocarbon chain containing 12 to 18 carbon atoms, and n = 15 to 16.

4. The fluorite low-temperature collector according to claim 3, characterized in that The R is a hydrocarbon chain containing 16 to 18 carbon atoms.

5. The fluorite low-temperature collector according to claim 1, characterized in that The carboxylic acid copolymer is one of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, maleic acid-acrylic acid copolymer and carboxylic acid-sulfonic acid-acrylate copolymer.

6. A method for preparing the fluorite low-temperature collector according to any one of claims 1 to 5, comprising the following steps: 1) dissolving sodium oleate in water to prepare a sodium oleate solution with a mass concentration of 5% to 10%; 2) sequentially adding sodium rosinate, a peregal surfactant, and a carboxylic acid copolymer to the sodium oleate solution of step 1) to obtain a mixture; 3) The mixture obtained in step 2) is sheared and stirred for 5 to 10 minutes to mix uniformly to obtain a fluorite low-temperature collector.

7. The preparation method according to claim 6, characterized in that In the step 1), sodium oleate is dissolved in hot water at 50-65° C. to prepare a sodium oleate solution with a mass concentration of 5%-10%.

8. The preparation method according to claim 7, characterized in that In the step 1), sodium oleate is dissolved in 50° C. hot water to prepare a sodium oleate solution with a mass concentration of 5%.

9. The preparation method according to claim 6, characterized in that: In the step 2), sodium rosinate, a peregal surfactant and a carboxylic acid copolymer are sequentially added to the sodium oleate solution at intervals of 5 minutes.

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