Ether amine for flotation of lepidolite, preparation method and application thereof

Abstract

The invention discloses ether amine of flotation lepidolite, the ether amine of the flotation lepidolite has the following structure: # imgabs0 #. The invention further discloses a preparation method of the ether amine of the flotation lepidolite and application of the ether amine in lepidolite flotation. The solubility is better than that of an amine flotation reagent. Therefore, higher activity and selectivity are achieved in the aspect of target mineral collection, and the concentrate grade and the recovery rate of the lithium ore can be remarkably improved.

Description

Technical Field

[0001] The invention relates to an ether amine for floating lepidolite, a preparation method and application thereof. Background Art

[0002] Lepidolite flotation plays a vital role in today's resource development and new energy industry. As the global demand for clean energy is growing explosively, lithium, as a key raw material for lithium-ion batteries, has a strategic significance that is self-evident.

[0003] As one of the important sources of lithium resources, flotation technology has become the core means to unlock the economic value of lepidolite. Through flotation, lepidolite can be effectively separated from the complex ore mineral system, greatly improving the enrichment and recovery rate of lithium resources, and providing high-quality raw materials for subsequent lithium extraction and refining. Only high-quality lithium concentrate can meet the growing demand for lithium in battery manufacturing, new energy vehicles and other fields, and promote the sustainable and rapid development of related industries.

[0004] These important uses of lithium make the importance of lithium ore self-evident. Lithium ore is the main source of lithium resources, and its utilization efficiency is directly related to the supply of lithium.

[0005] The development of lithium ore flotation reagents, as an important step in mineral processing, affects all subsequent operations.

[0006] From the perspective of comprehensive resource utilization, the advancement of lithium mica flotation technology can drive the optimization and upgrading of the entire lithium mica ore dressing process, reduce resource waste, reduce potential negative impacts on the environment, and achieve a delicate balance between promoting efficient resource utilization and ecological environmental protection. It lays a solid foundation for building a green, low-carbon, sustainable future energy and material supply system, and is an indispensable key link in the journey of achieving efficient development of lithium resources and the vigorous development of the new energy industry.

[0007] Amine collectors can undergo effective chemical adsorption on the surface of lepidolite, making its surface hydrophobic, thereby achieving better collection effects and improving the flotation recovery rate of lepidolite.

[0008] Amine collectors have relatively good selectivity for lepidolite and can be preferentially adsorbed on the surface of lepidolite, but less adsorbed on other gangue minerals, which helps to improve the grade of lepidolite concentrate.

[0009] Amine collectors can be used under different pulp pH conditions, especially under strong acidic pulp conditions. Amine collectors usually have better performance and can adapt to the flotation of various types of lithium mica ores.

[0010] In addition to the collecting function, amine collectors also have a certain foaming ability, which can produce an appropriate amount of stable foam during the flotation process, which is beneficial to the flotation separation of lithium mica minerals, reducing the need for additional foaming agents and reducing costs. However, amine collectors are sensitive to ore mud and temperature, so there is an urgent need to develop new collectors. Summary of the invention

[0011] The main purpose of the present invention is to provide an ether amine for flotation of lepidolite, a preparation method and application thereof, aiming to solve the above technical problems.

[0012] To achieve the above object, the present invention provides a method for preparing etheramine for flotation of lepidolite, which specifically comprises:

[0013] In a vacuum glove box, take a clean and dry reactor, and drop reactant A and ethanol in turn at a molar ratio of 1:3;

[0014] After adding the raw materials, the reactor was first rotated in the glove box for 30 minutes, then ammonia water and calcium oxide were added, and then rotated for 30 minutes before being placed in an oil bath for heating;

[0015] The gas replacement process is completed through the branch port of the reactor and the gas cylinder; and the reactor is placed in a heated and rotating oil bath pot to react overnight;

[0016] After the reaction is completed, wait for the reactor to cool to room temperature, open the reactor, and add water;

[0017] Pour the reaction solution after adding water into a separatory funnel, shake and let stand to separate the layers, then extract with ether and take the upper oil phase; repeat three times, collect the oil phase in a large beaker, and the halogen group in reactant A can be converted into an amino group;

[0018] Repeat the above operation to convert another halogen group of reactant A into an amino group to form compound C;

[0019] Wherein, the chemical structure formula of compound A is:

[0020]

[0021] The general chemical structure formula of compound C is:

[0022]

[0023] in:

[0024] R1 and R2 are one of methyl, ethyl, propyl, butyl, olefins or benzene rings.

[0025] In addition, the present invention also provides an etheramine for flotation of lepidolite, wherein the etheramine C for flotation of lepidolite is a compound having the following general chemical structure formula or its chemical isomer or salt thereof:

[0026]

[0027] in:

[0028] R1 and R2 are one of methyl, ethyl, propyl, butyl, olefins or benzene rings.

[0029] In one embodiment, the compound A1 is When the corresponding compound C1 is

[0030] In one embodiment, the compound A2 is When the corresponding compound C2 is

[0031] In one embodiment, the compound A3 is When the corresponding compound C3 is

[0032] In addition, the present invention also provides an application of the etheramine for floating lepidolite in the flotation of lepidolite. The etheramine for floating lepidolite is applied in the flotation process of lepidolite.

[0033] In the technical solution of the present invention, compared with the existing amine flotation reagents, the ether amine collector of the present invention has better solubility than the amine flotation reagents due to the difference in molecular structure and hydrogen bonding. Therefore, it has higher activity and selectivity in collecting target minerals, and can significantly improve the concentrate grade and recovery rate of lithium ore.

[0034] The molecular structure of etheramine collectors contains functional groups such as ether bonds and amine groups. These functional groups can specifically adsorb to specific sites on the surface of lepidolite, thereby achieving selective capture of lepidolite. BRIEF DESCRIPTION OF THE DRAWINGS In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work. Figure 1 A line graph showing the effect of pH on the flotation of lepidolite according to an embodiment of the present invention; Figure 2 A bar graph showing the effect of inhibitor types on taste according to an embodiment of the present invention; Figure 3This is a line graph showing the effect of dosage of the drug on the recovery rate according to an embodiment of the present invention. The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] In addition, in the present invention, descriptions such as "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0037] Furthermore, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that they can be implemented by ordinary technicians in the field. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0038] The present invention provides a method for preparing etheramine for flotation lepidolite, comprising:

[0039] In a vacuum glove box, take a clean and dry reactor, and drop reactant A and ethanol in turn at a molar ratio of 1:3;

[0040] After adding the raw materials, the reactor was first rotated in the glove box for 30 minutes, then ammonia water and calcium oxide were added, and then rotated for 30 minutes before being placed in an oil bath for heating;

[0041] The gas replacement process is completed through the branch port of the reactor and the gas cylinder; and the reactor is placed in a heated and rotating oil bath pot to react overnight;

[0042] After the reaction is completed, wait for the reactor to cool to room temperature, open the reactor, and add water;

[0043] Pour the reaction solution after adding water into a separatory funnel, shake and let stand to separate the layers, then extract with ether and take the upper oil phase; repeat three times, collect the oil phase in a large beaker, and the halogen group in reactant A can be converted into an amino group;

[0044] Repeat the above operation to convert another halogen group of reactant A into an amino group to form compound C;

[0045] Wherein, the chemical structure formula of compound A is:

[0046]

[0047] The general chemical structure formula of compound C is:

[0048]

[0049] In this embodiment, the synthesis path of compound C is as follows:

[0050]

[0051]

[0052] In an optional embodiment, R1 and R2 in compound C are one of methyl, ethyl, propyl, butyl, olefins or benzene rings.

[0053] Exemplarily, the compound A1 is When the corresponding compound C1 is

[0054] The compound A2 is When the corresponding compound C2 is

[0055] The compound A3 is When the corresponding compound C3 is

[0056] Compared with the existing amine flotation reagents, the etheramine collector of the present invention has better solubility than amine flotation reagents due to the difference in molecular structure and hydrogen bonding. The molecular structure of the etheramine collector contains functional groups such as ether bonds and amine groups, which can be specifically adsorbed to specific sites on the surface of lepidolite, thereby achieving selective capture of lepidolite.

[0057] The present application is explained below through specific embodiments.

[0058] The raw ore sample this time comes from the lithium mica ore sample in Yichun City, Jiangxi Province. According to the ICP test of Jiuling Research Institute, the Li2O grade of the raw ore is 0.83 (that is, the Li2O content in the raw ore is 0.83%).

[0059] Example

[0060] Weigh a certain weight of lithium mica ore, crush it and pour it into the flotation tank. Stir it evenly for 5-20 minutes at room temperature and a stirring speed of 1200r / min. Add an adjuster to adjust the pH of the slurry to explore the effect of pH on the flotation of lithium mica. Figure 1 shown.

[0061] Ether amines can achieve the best recovery rate in a weak acid environment, while when the pH of dodecylamine is less than 3, the negative charge on the surface of lepidolite enhances its adsorption of the cationic collector dodecylamine, resulting in a higher recovery rate.

[0062] However, in actual production, in a strong acid environment, production equipment is easily corroded and the maintenance cost is too high. However, ether amine can achieve the recovery rate of dodecylamine in a weak acid environment as in a strong acid environment.

[0063] According to the above embodiment, the flotation pulp environment is adjusted to a weak acid environment with a pH of 6.

[0064] The same weight of lepidolite ore was weighed, crushed and poured into the flotation tank, different inhibitors were added and stirred again, and finally the etheramine collector prepared by the present invention was added, and flotation was carried out under the same time and operation according to the experimental process of one coarse, one fine and one sweep.

[0065] from Figure 2 The data show that the combination of sodium hexametaphosphate and etheramine collector has better effect. This is because sodium hexametaphosphate can keep the mineral particles in the slurry in a good dispersed state and avoid agglomeration between the mineral particles. The etheramine collector can fully combine with the mineral particles, and the separation effect of lithium mica and gangue minerals is better.

[0066] An appropriate amount of lepidolite sample was weighed and added to two flotation cells for uniform stirring. Then, sodium hexametaphosphate was added to adjust the pH value of the slurry to 6. Etheramine collector was added to one flotation cell and dodecylamine collector was added to the other flotation cell. The Li2O recovery rate and grade change brought about by different doses of collectors were compared.

[0067] like Figure 3 As shown in the figure, at low dosage, the recovery rate of etheramine can reach more than 85%, while the recovery rate of dodecylamine is only 55%. As the dosage of collector increases, the Li2O recovery rate of etheramine gradually decreases, while the Li2O recovery of dodecylamine first increases and then decreases. This means that only less etheramine collector is needed to achieve good returns, which can reduce the use of reagents and environmental pressure.

[0068] The etheramine collector prepared by the invention has better foam fluidity in a flotation test, is not easy to accumulate, is easy to break, and has moderate foam volume and foam height.

[0069] In summary, the etheramine lepidolite flotation agent for flotation of lepidolite of the present invention has high selectivity, strong collecting ability, good foam fluidity and low required dosage.

[0070] In addition, the etheramine for flotation of lepidolite provided by the present invention is the above-mentioned compound C, and the chemical formula of compound C is as follows:

[0071]

[0072] in:

[0073] R1 and R2 are one of methyl, ethyl, propyl, butyl, olefins or benzene rings.

[0074] In summary, the etheramine for flotation of lepidolite provided by the present invention can greatly increase the collection effect when applied to the flotation of lepidolite, and the flotation process is more stable and efficient, which can improve the recovery rate of metallic lithium in the flotation of lepidolite. Combined with the use of inhibitors, the flotation lithium recovery rate can reach 87.9%, and the Li2O grade of the concentrate can reach 4.18.

[0075] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification and drawings under the concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for preparing etheramine for flotation lepidolite, characterized in that: The method for preparing etheramine for flotation lepidolite comprises: In a vacuum glove box, take a clean and dry reactor, and drop reactant A and ethanol in turn at a molar ratio of 1:3; After adding the raw materials, the reactor was first rotated in the glove box for 30 minutes, then ammonia water and calcium oxide were added, and then rotated for 30 minutes before being placed in an oil bath for heating; The gas replacement process is completed through the branch port of the reactor and the gas cylinder; and the reactor is placed in a heated and rotating oil bath pot to react overnight; After the reaction is completed, wait for the reactor to cool to room temperature, open the reactor, and add water; Pour the reaction solution after adding water into a separatory funnel, shake and let stand to separate the layers, then extract with ether and take the upper oil phase; repeat three times, collect the oil phase in a large beaker, and the halogen group in reactant A can be converted into an amino group; Repeat the above operation to convert another halogen group of reactant A into an amino group to form compound C; Wherein, the chemical structure formula of compound A is: The general chemical structure formula of compound C is: in: R1 and R2 are one of methyl, ethyl, propyl, butyl, olefins or benzene rings.

2. An etheramine for flotation of lepidolite, characterized in that: The etheramine C for flotation of lepidolite is a compound having the following general chemical structure formula or its chemical isomer or salt thereof: in: R1 and R2 are one of methyl, ethyl, propyl, butyl, olefins or benzene rings.

3. The etheramine for flotation of lepidolite according to claim 2, characterized in that: The compound A1 is When the corresponding compound C1 is 4. The etheramine for flotation of lepidolite according to claim 2, characterized in that: The compound A2 is When the corresponding compound C2 is 5. The etheramine for flotation of lepidolite according to claim 2, characterized in that: The compound A3 is When the corresponding compound C3 is 6. An application of an etheramine for flotation of lepidolite in flotation of lepidolite, characterized in that: The etheramine for flotation of lepidolite as claimed in any one of claims 2 to 4 is used in the flotation process of lepidolite.

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