Lepidolite collecting agent and preparation method and application thereof

Abstract

The invention discloses a lepidolite collecting agent and a preparation method and application thereof, and belongs to the technical field of lepidolite flotation. The lepidolite collecting agent is prepared from 10-20 parts of coconut oil amine, 10-40 parts of ethylene glycol, 5-20 parts of hydrochloric acid, 3-5 parts of an emulsifier, 1-10 parts of alkali and 22-51 parts of soybean oil. The lepidolite collecting agent is good in universality and has a good collecting effect on refractory mica ore; and when lepidolite flotation is carried out under a low-temperature condition, relatively high lithium oxide grade and recovery rate can also be obtained. According to the lepidolite collecting agent, by optimizing the formula, the optimal collecting effect of ore pulp can be achieved under the neutral condition, and multiple times of desliming are not needed. The preparation process of the lepidolite collecting agent is simple, the collecting effect is good, and the lepidolite collecting agent has very important practical value.

Description

Technical Field

[0001] The invention relates to the technical field of lepidolite flotation, and in particular to a lepidolite collector and a preparation method and application thereof. Background Art

[0002] Lithium is an important strategic key metal, which is widely used in energy storage, batteries, ceramics, lubricants, glass, metallurgy and other industries. At present, the main sources of domestic lithium resources are salt lake lithium and ore lithium. Ore lithium mainly includes spodumene, lithium mica, lithium feldspar, iron lithium mica, lithium white mica, phosphate lithium aluminum stone, etc. The global lithium mica resources are mainly distributed in China, Zimbabwe, Australia, Canada, Brazil, Argentina and other countries. Domestic lithium mica resources are mainly distributed in Yichun, Jiangxi and Chenzhou, Hunan. Among them, the lithium mica reserves (equivalent to lithium oxide) in Yichun, Jiangxi are about 2.58 million tons, which is equivalent to about 6.36 million tons of lithium carbonate equivalent. Chenzhou is also mica lithium, mainly distributed in Linwu County, Yizhang County, and Guiyang County. According to preliminary exploration, the potential lithium oxide reserves in Linwu County are more than 5 million tons.

[0003] Most of the lithium mica ores are fine-grained and interwoven, and lithium mica is mainly intergrown with gangue minerals such as quartz and feldspar. Lithium mica is a silicate mineral, and after monomer dissociation, the ore mainly presents a flaky or scaly structure. As the most widely used and most efficient mineral processing technology at this stage, flotation is widely used in lithium mica purification and recovery operations. It mainly uses flotation agents to change the hydrophilicity and hydrophobicity of the mineral surface, thereby changing the floatability of the mineral. Therefore, the research and development and adjustment of flotation agents play a pivotal role in the optimization of lithium mica flotation process, and the research on collectors is the most important. At present, lithium mica collectors mainly include amine cationic collectors (primary amines, secondary amines, quaternary ammonium salts, ether amines and gemini amines) and combined collectors that mix amines and anionic collectors in a certain proportion. "CN 114160313 B A flotation collector for lithium mica and its application" discloses a flotation collector for lithium mica. The mass proportion of the anionic collector component of HQ-Li is about 4 times the mass proportion of the cationic collector component. The effect of the anionic collector is mainly to expand the effective pulp pH range for flotation separation of lithium mica and quartz / feldspar to pH = 2.0-7.5, but the acidity is still strong, and the equipment used still has a high risk of corrosion. "CN 116967017A A flotation collector for low-grade lithium mica and its preparation method and application" provides a collector. When used for flotation of low-grade lithium mica, the pulp pH is 8-10, but the pulp still needs to be settled and desludged. At the same time, due to the high cost of mineral transportation, many companies choose to flotation directly at the mineral production site. In Xinjiang, my country or Africa, where production has increased in recent years, many mineral flotation sites are set up in the open air or in factories without heating equipment, resulting in the flotation efficiency in autumn, winter and spring when the temperature is low, which is affected by the reduced performance of the flotation agent. Therefore, it is of practical significance for lithium ore flotation to prepare an efficient lithium mica collector with mild working pH conditions, good low-temperature flotation effect, good flotation effect on low-grade ores, and easy to use without sedimentation and desludging. Summary of the invention

[0004] In view of the above-mentioned prior art, the purpose of the present invention is to provide a lepidolite collector and a preparation method and application thereof.

[0005] To achieve the above object, the present invention adopts the following technical solution:

[0006] The first aspect of the present invention provides a lepidolite collector, which is prepared from the following raw materials in parts by weight: 10-20 parts of coconut amine, 10-40 parts of ethylene glycol, 5-20 parts of hydrochloric acid, 3-5 parts of emulsifier, 1-10 parts of alkali, and 22-51 parts of soybean oil;

[0007] The emulsifier is at least one of sorbitan oleate, N-dodecyl pyrrolidone and sodium fatty acid methyl ester sulfonate;

[0008] The base is triethanolamine.

[0009] Furthermore, in the emulsifier, the mass ratio of sorbitan oleate, N-dodecyl pyrrolidone and sodium fatty acid methyl ester sulfonate is (0.5-5): (0.5-5): (0.5-5).

[0010] The second aspect of the present invention provides a method for preparing the lepidolite collector, comprising the following steps:

[0011] Coconut amine is dispersed in soybean oil and ethylene glycol, and then hydrochloric acid is added to react; after the reaction is completed, an emulsifier and a base are added, and the mixture is stirred evenly to obtain a lepidolite collector.

[0012] The third aspect of the present invention provides the use of the lepidolite collector in mineral flotation.

[0013] Further, the following steps are included:

[0014] The lithium ore is crushed, ground and water is added to form a pulp; a lithium mica collector is added to the pulp, and a flotation process of a roughing selection, a scavenging selection and a concentrating selection is carried out in sequence to obtain the desired ore sample.

[0015] Further, the operation of a roughing operation is to add 200-400g / t of soda ash, stir for 5-10 minutes, then add 100-500g / t of sodium hexametaphosphate, and continue to stir for 3-10 minutes; after adding 200-800g / t of collector, stir for 3-10 minutes, aerate and scrape for 1-10 minutes to obtain roughing;

[0016] The scavenging operation is to add 100-200g / t of collector, stir for 3-10 minutes, aerate and scrape for 1-10 minutes to obtain scavenging;

[0017] The primary concentration operation is to combine the roughing concentration and the scavenging concentration, stir for 3-10 minutes, aerate and scrape for 1-10 minutes to obtain the concentrated ore.

[0018] Furthermore, the pH value of flotation is 5-9.

[0019] Beneficial effects of the present invention:

[0020] (1) When the lepidolite collector of the present invention is used for flotation of refractory mica ore, a higher lithium oxide grade and recovery rate can be obtained. The lepidolite collector of the present invention can be used for low-grade lepidolite ore from different sources in China and Africa, which, on the one hand, broadens the source of raw materials and, on the other hand, saves the use cost of enterprises, without the need to specifically prepare corresponding collectors for different ore samples.

[0021] (2) The present invention aims at the fact that most collectors have harsh use conditions and need to be used within the pH range of 2-3, and that metal equipment and pipelines in the concentrator are easily corroded. By optimizing the formula of the collector, the slurry can achieve the best collection effect under neutral conditions.

[0022] (3) The present invention aims at the fact that the climate conditions in the source areas of lithium mica minerals vary greatly, and the local collectors in the mines need to be used in scenarios with different temperatures. The collector of the present invention can be used under low temperature conditions (5°C) to room temperature conditions (25°C to 40°C), and has good low temperature resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a flow chart of the one roughing, one sweeping and one fine flotation scheme. DETAILED DESCRIPTION

[0024] It should be noted that the following detailed descriptions are illustrative and are intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present application belongs.

[0025] In order to enable those skilled in the art to more clearly understand the technical solution of the present application, the technical solution of the present application will be described in detail below in conjunction with specific embodiments.

[0026] The test materials used in the examples of the present invention that are not specifically described are all conventional test materials in the art and can be purchased through commercial channels. The CAS number of coconut amine used in the present invention is 61788-46-3, the CAS number of sorbitan oleate used is 1338-43-8, the CAS number of sodium methyl sulfonate is 93348-22-2, the CAS number of triethanolamine is 102-71-6, and the CAS number of N-dodecyl pyrrolidone is 2687-96-9.

[0027] Embodiment 1:

[0028] The preparation process of lepidolite collector is as follows:

[0029] At room temperature, 20 parts of coconut amine were dispersed in 44 parts of soybean oil and 10 parts of ethylene glycol by weight, and then 16 parts of hydrochloric acid (content 37%) were added to react. After the reaction was completed, 5 parts of emulsifier and 5 parts of alkali were added and stirred evenly to obtain a lepidolite collector.

[0030] In the emulsifier used, the mass proportions of sorbitan oleate, N-dodecyl pyrrolidone and sodium fatty acid methyl ester sulfonate are 3 parts, 1 part and 1 part respectively.

[0031] The base used was triethanolamine.

[0032] Embodiment 2:

[0033] The preparation process of lepidolite collector is as follows:

[0034] At room temperature, 20 parts of coconut amine were dispersed in 44 parts of soybean oil and 10 parts of ethylene glycol by weight, and then 16 parts of hydrochloric acid (content 37%) were added to react. After the reaction was completed, 5 parts of emulsifier and 5 parts of alkali were added and stirred evenly to obtain a lepidolite collector.

[0035] In the emulsifier used, the weight proportions of sorbitan oleate, N-dodecyl pyrrolidone and sodium fatty acid methyl ester sulfonate are 1 part, 3 parts and 1 part respectively.

[0036] The base used was triethanolamine.

[0037] Embodiment 3:

[0038] The preparation process of lepidolite collector is as follows:

[0039] At room temperature, 20 parts of coconut amine were dispersed in 44 parts of soybean oil and 10 parts of ethylene glycol by weight, and then 16 parts of hydrochloric acid (content 37%) were added to react. After the reaction was completed, 5 parts of emulsifier and 5 parts of alkali were added and stirred evenly to obtain a lepidolite collector.

[0040] In the emulsifier used, the weight proportions of sorbitan oleate, N-dodecyl pyrrolidone and sodium fatty acid methyl ester sulfonate are 1 part, 1 part and 3 parts respectively.

[0041] The base used was triethanolamine.

[0042] Comparative Example 1:

[0043] The preparation process of lepidolite collector is as follows:

[0044] At room temperature, 20 parts of coconut amine were dispersed in 44 parts of soybean oil and 10 parts of ethylene glycol by weight, and then 16 parts of hydrochloric acid (content 37%) were added to react. After the reaction was completed, 5 parts of emulsifier and 5 parts of alkali were added and stirred evenly to obtain a lepidolite collector.

[0045] The emulsifier used was sorbitan oleate.

[0046] The base used was triethanolamine.

[0047] Comparative Example 2:

[0048] The preparation process of lepidolite collector is as follows:

[0049] At room temperature, 20 parts of coconut amine were dispersed in 44 parts of soybean oil and 10 parts of ethylene glycol by weight, and then 16 parts of hydrochloric acid (content 37%) were added to react. After the reaction was completed, 5 parts of emulsifier and 5 parts of alkali were added and stirred evenly to obtain a lepidolite collector.

[0050] The emulsifier used is sodium fatty acid methyl ester sulfonate.

[0051] The base used was triethanolamine.

[0052] Comparative Example 3:

[0053] The preparation process of lepidolite collector is as follows:

[0054] At room temperature, 20 parts of coconut amine were dispersed in 44 parts of soybean oil and 10 parts of ethylene glycol by weight, and then 16 parts of hydrochloric acid (content 37%) were added to react. After the reaction was completed, 5 parts of emulsifier and 5 parts of alkali were added and stirred evenly to obtain a lepidolite collector.

[0055] The emulsifier used was N-dodecylpyrrolidone.

[0056] The base used was triethanolamine.

[0057] Test Example 1:

[0058] This example uses Xinjiang lithium mica mine, Li 2 O grade is 1.24%, and the lepidolite flake crystals are obvious through polarizing microscope observation. The laboratory rod mill grinding adopts the "one coarse one sweep one fine flotation scheme", and the lepidolite collector prepared according to the method of Example 3 is selected. The experimental temperature is 20°C, and the rod mill grinds the ore to 65% weight ratio. The mineral can pass through the 200 mesh sieve and first enters the flotation of mica. The foam is dense and solid, the mica concentrate grade is 5.46%, the lepidolite recovery rate is 87.16%, the tailing product foam is false white, and the test grade achieves double zero. Through observation and analysis of the data in Table 1, the ore sample has achieved effective separation and enrichment of lepidolite through flotation experiments.

[0059] The steps of the "one roughing, one sweeping, one fine flotation scheme" are as follows:

[0060] The first roughing operation is to add 300g / t of soda ash, stir for 7 minutes, then add 220g / t of sodium hexametaphosphate, and continue stirring for 5 minutes; after adding 500g / t of collector, stir for 5 minutes, aerate and scrape for 3 minutes to obtain roughing;

[0061] The operation of one scavenging is to add 150g / t collector, stir for 5 minutes, aerate and scrape for 3 minutes to obtain scavenging;

[0062] The primary concentration operation is to combine the roughing concentration and the scavenging concentration, stir for 5 minutes, aerate and scrape for 3 minutes to obtain the concentrated ore.

[0063] Among them, yield = weight of minerals after flotation / total weight of minerals*100%, lithium oxide grade = mass of lithium oxide in the product / product mass*100%, lithium oxide occupancy rate = weight of lithium oxide in minerals after flotation / total weight of lithium oxide in minerals*100%.

[0064] Table 1 Flotation results of African lithium mica ore

[0065]

[0066] The lepidolite collectors prepared by Comparative Examples 1 to 3 and Examples 1 to 2 were used to replace the lepidolite collector prepared by the method of Example 3 used in this test example, respectively. The results are shown in Table 2.

[0067] Table 2 Flotation results of different collectors

[0068]

[0069] It can be seen from Table 2 in combination with Table 1 that after flotation, the lepidolite collectors used in Examples 1 to 3 achieved further optimization of the formulation performance, with improvements in both lithium oxide grade and lithium oxide occupancy.

[0070] Test Example 2:

[0071] This example uses the Chenzhou lepidolite mine, Li 2 O grade is 0.97%, and the lepidolite flake crystals are obvious through polarizing microscope observation. The laboratory rod mill grinding adopts the "one coarse one sweep one fine flotation scheme" of test example 1, and the lepidolite collector prepared according to the method of embodiment 3 is selected. The experimental temperature is 20°C, and the rod mill grinds the ore to 65% weight ratio. The mineral can pass through the 200 mesh sieve and first enters the flotation of mica. The foam is dense and solid, the mica concentrate grade is 4.61%, the lepidolite recovery rate is 70.93%, the tailing product foam is false white, and the test grade achieves double zero. Through observation and analysis of the data in Table 3, the ore sample has achieved effective separation and enrichment of lepidolite through flotation experiments.

[0072] Table 3 Flotation results of Chenzhou lepidolite ore

[0073]

[0074] Test Example 3:

[0075] This example uses the Ganzhou lithium mica mine. 2 O grade is 0.4%, and the lepidolite flake crystals are obvious through polarizing microscope observation. Laboratory rod mill grinding, using the "one coarse one sweep one fine flotation scheme" of test example 1, the lepidolite collector prepared according to the method of Example 3 is selected, the experimental temperature is 20 ° C, the rod mill grinds the ore to 65% weight ratio, the mineral can pass through the 200 mesh sieve and first enters the flotation of mica, the foam is dense and solid, the mica concentrate grade is 1.82%, the lepidolite recovery rate is 73.91%, the tailing product foam is false white, and the test grade achieves double zero. Through observation and analysis of the data in Table 4, the ore sample has achieved effective separation and enrichment of lepidolite through flotation experiments.

[0076] Table 4 Flotation results of Ganzhou lepidolite ore

[0077]

[0078] Test example 4:

[0079] The African lithium mica mine is used in this example. 2 O grade is 0.51%, and the lepidolite flake crystals are obvious through polarizing microscope observation. Laboratory rod mill grinding, using the "one coarse one sweep one fine flotation scheme" of test example 1, the lepidolite collector prepared according to the method of Example 3 is selected, the experimental temperature is 40℃, 20℃, 10℃ and 5℃, the rod mill grinds the ore to 65% weight ratio, the mineral can pass through the 200 mesh sieve and first enter the flotation of mica, the foam is dense and solid, the sweep product foam is white, and the test grade achieves double zero. The content of lepidolite minerals in the tailings was observed through a polarizing microscope, proving that the ore sample has achieved effective separation and enrichment of lepidolite through the flotation experiment, and the results are shown in Table 5.

[0080] Table 5 Flotation treatment of lithium mica ore at different temperatures

[0081]

[0082]

[0083] As can be seen from Table 5, the collector of the present invention can be used under low temperature conditions (5°C) to room temperature conditions (25°C to 40°C), and has good low temperature resistance.

[0084] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A lepidolite collector, characterized in that: The lepidolite collector is prepared from the following raw materials in parts by weight: 10-20 parts of coconut amine, 10-40 parts of ethylene glycol, 5-20 parts of hydrochloric acid, 3-5 parts of emulsifier, 1-10 parts of alkali, and 22-51 parts of soybean oil; The emulsifier is at least one of sorbitan oleate, N-dodecyl pyrrolidone and sodium fatty acid methyl ester sulfonate; The base is triethanolamine.

2. The lepidolite collector according to claim 1, characterized in that In the emulsifier, the mass ratio of sorbitan oleate, N-dodecyl pyrrolidone and sodium fatty acid methyl ester sulfonate is (0.5-5): (0.5-5): (0.5-5).

3. The preparation method of the lepidolite collector according to any one of claims 1 to 2, characterized in that: The steps include: Coconut amine is dispersed in soybean oil and ethylene glycol, and then hydrochloric acid is added to react; after the reaction is completed, an emulsifier and a base are added, and the mixture is stirred evenly to obtain a lepidolite collector.

4. Application of the lepidolite collector according to any one of claims 1 to 2 in mineral flotation.

5. The use of the lepidolite collector in mineral flotation according to claim 4, characterized in that: The steps include: The lithium ore is crushed, ground and water is added to form a pulp; a lithium mica collector is added to the pulp, and a flotation process of a roughing selection, a scavenging selection and a concentrating selection is carried out in sequence to obtain the desired ore sample.

6. The use of the lepidolite collector in mineral flotation according to claim 5, characterized in that: The first roughing operation is to add 200-400g / t of alkali, stir for 5-10 minutes, then add 100-500g / t of sodium hexametaphosphate, and continue to stir for 3-10 minutes; after adding 200-800g / t of collector, stir for 3-10 minutes, aerate and scrape for 1-10 minutes to obtain roughing; The scavenging operation is to add 100-200g / t of collector, stir for 3-10 minutes, aerate and scrape for 1-10 minutes to obtain scavenging; The primary concentration operation is to combine the roughing concentration and the scavenging concentration, stir for 3-10 minutes, aerate and scrape for 1-10 minutes to obtain the concentrated ore.

7. The use of the lepidolite collector in mineral flotation according to claim 6, characterized in that: The pH value for flotation is 5-9.

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