Cationic ether amine collecting agent as well as preparation method and application thereof

Abstract

The invention discloses an ether amine cation collecting agent as well as a preparation method and application thereof. The ether amine cation collecting agent is a compound # imgabs0 # ether amine cation collecting agent shown in the following formula, and the solubility of the ether amine cation collecting agent is better than that of amine flotation reagents due to the fact that the ether amine cation collecting agent has hydroxyl. The chelating probability of ether functional groups and lithium is increased, the collecting capacity is improved, the flexibility and hydrophobicity of molecules are improved due to existence of ether bonds, the molecules can be better attached to the surface of lepidolite, and therefore efficient collecting of the lepidolite is achieved.

Description

Technical Field

[0001] The invention relates to a cationic ether amine collector, a preparation method and application thereof. Background Art

[0002] With the rapid growth of global demand for clean energy and high-tech electronic products, the application of lithium is constantly expanding. The lithium contained in lepidolite is a key raw material for the production of lithium-ion batteries, which are core components of electric vehicles, portable electronic devices and renewable energy storage systems. It is of great significance to promote global energy transformation and achieve sustainable development goals.

[0003] In the mining and processing of lithium ore, flotation reagents play a vital role. Suitable flotation reagents can effectively improve the recovery rate and grade of lithium ore and reduce production costs. It can selectively adsorb on the surface of lithium minerals, making them hydrophobic and thus separating them from other minerals.

[0004] By rationally selecting and using amine flotation agents, the flotation efficiency and quality of lithium ore can be greatly improved, providing a strong guarantee for the efficient development and utilization of lithium resources. Summary of the invention

[0005] The main purpose of the present invention is to provide a cationic etheramine collector, a preparation method and application thereof, aiming to provide an etheramine cationic collector.

[0006] To achieve the above object, the present invention provides a method for preparing an etheramine cationic collector, which specifically comprises:

[0007] Take a clean and dry flask, then dissolve compound A in dry THF under N2 atmosphere, stir the solution and cool it to 0°C with an ice bath, then add sodium hydroxide to the stirred mixture, stir for 1h, and then add compound B and stir;

[0008] After the reaction was completed, H2O was added to neutralize it and extracted with ether, the organic layers were combined, dried over MgSO4, filtered and concentrated in vacuo;

[0009] Add MeOH to the concentrate and heat until the suspension is completely dissolved, then purify by column chromatography to obtain compound C;

[0010] After adding compound C to THF, potassium o-phenylenediamine was added and the mixture was heated to 60°C and reacted overnight. After cooling to room temperature, the mixture was diluted with acidic water with pH=3, extracted with ethyl acetate, and the organic layer was combined with MgSO4, dried, filtered, and concentrated in vacuo, and purified by column chromatography to obtain compound E;

[0011] Dissolve compound E in ethanol, slowly add 64w% hydrazine hydrate dropwise while stirring, then heat the mixture to 100°C and stir under reflux overnight;

[0012] The mixture was cooled and concentrated in vacuo, dissolved in chloroform, washed twice with NaOH, washed twice with saline, dried over MgSO4 and concentrated in vacuo to finally obtain compound G;

[0013] Compound G was dissolved in MeOH, 2M HCl solution was added, and then heated, ether was removed by argon flow, methanol was added after ether was evaporated, and the mixture was bubbled with argon, and then Pd / C catalyst was added at room temperature, and the mixture was stirred under H2 gas overnight, and then the mixture was filtered through glass, washed with MeOH, and concentrated in vacuo to obtain the final white solid compound I;

[0014] Wherein, the chemical structure formula of compound A is:

[0015]

[0016] The general chemical structure formula of compound B is:

[0017]

[0018] The general chemical structure formula of compound C is:

[0019]

[0020] The general chemical structure formula of compound E is:

[0021]

[0022] The general chemical structure formula of compound G is:

[0023]

[0024] The general chemical structure formula of compound I is:

[0025]

[0026] in:

[0027] m is any integer from 0 to 9;

[0028] Wherein, n is any integer from 0 to 14.

[0029] In addition, the present invention also provides an etheramine cationic collector, which is a compound having the following chemical structural formula or its chemical isomer or salt:

[0030]

[0031] Wherein, m is any integer from 0 to 9;

[0032] Wherein, n is any integer from 0 to 14.

[0033] In one embodiment, the compound A is And compound B is When the corresponding compound I is

[0034] In one embodiment, the compound A is And compound B is When the corresponding compound I is

[0035] In one embodiment, the compound A is And compound B is When the corresponding compound I is

[0036] In addition, the present invention also provides an application of an etheramine cationic collector in the flotation of lepidolite. The etheramine cationic collector is applied in the flotation process of lepidolite.

[0037] In the technical solution of the present invention, because the etheramine cationic collector has a hydroxyl group, its solubility is better than that of an amine flotation reagent. The ether functional group increases the probability of chelating with lithium and increases the collection capacity. The presence of the ether bond increases the flexibility and hydrophobicity of the molecule, allowing it to better adhere to the surface of lepidolite, thereby achieving efficient collection of lepidolite. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] 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.

[0039] Figure 1 This is a schematic diagram of the concentrate grade and recovery rate of Example 1 of the present invention;

[0040] Figure 2 Schematic diagram of the flotation agent dosage and recovery rate of etheramine and primary amine in Example 2 of the present invention;

[0041] Figure 3 The figure is a schematic diagram of the recovery rate and grade change of the etheramine collector of Example 3 of the present invention at different temperatures.

[0042] 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

[0043] 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.

[0044] 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.

[0045] 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.

[0046] The present invention provides a method for preparing an etheramine cationic collector, comprising:

[0047] Take a clean and dry flask, then, under a N2 atmosphere, dissolve alcohol benzyl ether A (Compound A) in dry THF, stir the solution and cool it to 0°C with an ice bath, add sodium hydroxide to the stirred mixture, after the addition is complete, stir for 1 hour, then add Compound B and stir overnight.

[0048] After the reaction is completed, H2O is added to neutralize and extract with ether, the organic layers are combined, dried over MgSO4, filtered and concentrated in vacuo. MeOH is added to the concentrate and heated until the suspension is completely dissolved. Then, it is purified by column chromatography to obtain compound C.

[0049] After adding compound C (1 eq) to THF, potassium o-phenylenediamine (1.4 eq) was added and the mixture was heated to 60°C and reacted overnight. After cooling to room temperature, the mixture was diluted with acidic water (pH = 3) and extracted with ethyl acetate. The organic layer was combined with MgSO4, dried, filtered, concentrated in vacuo, and purified by column chromatography to obtain compound E.

[0050] Compound E (1 eq) was dissolved in ethanol, and 64 w% (4 eq) of hydrazine hydrate was slowly added dropwise while stirring. The mixture was then heated to 100°C and stirred under reflux overnight.

[0051] The mixture was cooled and concentrated in vacuo, dissolved in chloroform, washed twice with NaOH (1M), washed twice with saline, dried over MgSO4 and concentrated in vacuo. Compound G was finally obtained as an oil.

[0052] G (1 eq) is dissolved in MeOH, 2M HCl solution (1.2 eq) is added, then carefully heated with a heat gun, and ether is removed by a stream of argon gas. After ether is evaporated, methanol is added and the mixture is bubbled with argon. At room temperature, Pd / C catalyst is added and the mixture is stirred overnight under H2 gas. The mixture is then filtered through glass and washed with MeOH. Vacuum concentration obtains final white solid product I.

[0053] In this embodiment, the synthesis route of compound I is as follows:

[0054]

[0055] in,

[0056] m is any integer from 0 to 9;

[0057] n is any integer from 0 to 14.

[0058] Compared with the existing amine flotation reagents, the ether amine collector of the present invention has better solubility than amine flotation reagents due to the hydroxyl group. The ether functional group increases the probability of chelating with lithium and increases the capture capacity. The presence of the ether bond increases the flexibility and hydrophobicity of the molecule, allowing it to better adhere to the surface of lepidolite, thereby achieving efficient capture of lepidolite.

[0059] The molecular structure of etheramine collectors contains functional groups such as ether bonds and amine groups, which can specifically adsorb to specific sites on the surface of lepidolite, thereby achieving selective capture of lepidolite. Amine collectors mainly interact with the mineral surface through electrostatic attraction, and have poor selectivity for different minerals.

[0060] The etheramine collector of the present invention has effective chemical adsorption and physical adsorption on the surface of lepidolite, and the polyetheramine group collector has certain selectivity for lepidolite. The collector has a good collection effect on lepidolite in a wide pH range and is not very sensitive to changes in the pH value of the ore pulp. Compared with traditional amine collectors, the etheramine collector has more stable foam and proper fluidity, and the breakage and merger of the foam are reduced, which is conducive to improving the recovery rate of the flotation process.

[0061] The etheramine cationic collector provided in the present application can be combined with other anionic collectors to obtain a flotation agent, and the lepidolite can be floated by the flotation agent.

[0062] The anionic collector includes one or a mixture of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid, sodium olefin sulfonate, oxidized paraffin soap, tall oil, peroxy fatty acid soap and rosin acid, oleic acid, sodium oleate, cyclohexane acid soap, tall oil, peroxy fatty acid soap, salicylic hydroxamic acid, and benzohydroxamic acid.

[0063] The application of the present invention is explained below through specific embodiments.

[0064] 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 1.03% (that is, the Li2O content in the raw ore is 1.03%).

[0065] Example 1

[0066] 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 1350r / min stirring speed. Do not add any acid or alkali to adjust the pH of the ore pulp. The pH of the ore pulp after grinding is about 6-7. Through acid and alkali adjustment, explore the lithium mica flotation test of etheramine collector at different pH. The grade and recovery rate of Li2O concentrate are shown in Figure 1 .

[0067] Ether amines can achieve the highest yield under weakly acidic conditions, which means that there is no need to add extra acid or base reagents to adjust the pH. As the acidity / alkalinity increases, the Li2O recovery rate and grade decrease, but it is not difficult to observe from the figure that the reduction is very low.

[0068] The collector has a good collection effect on lepidolite in a wide pH range and is not very sensitive to changes in the pH value of the slurry.

[0069] Example 2

[0070] According to the above implementation case, we adjusted the flotation slurry environment to a weak acid environment with a pH of 6.

[0071] Weigh the same weight of lepidolite ore, crush it and pour it into the flotation tank, add etheramine and primary amine collectors respectively, and stir again. According to the experimental process of 1 coarse 2 fine 2 sweep, flotation is carried out under the same time and operation, please refer to Figure 2 .

[0072] from Figure 2From the data, we can see that only 200g / t of etheramine is needed to recover etheramine collector with a yield of more than 90%, while primary amine requires 700g / t. When we are in large-scale production, one ton of raw ore flotation can save us more than 500g of reagent cost, which is a considerable cost saving.

[0073] Example 3

[0074] Weigh an appropriate amount of lithium mica ore sample and adjust the temperature of the water in different flotation tanks by heating and freezing. The temperature in the flotation tank is 5, 10, 15, 20, 25, 30, 35 ℃ , add the etheramine collector of this invention, and compare the Li2O recovery rate and grade change of different etheramine collectors at different temperatures. Please refer to Figure 3 .

[0075] Within the temperature range of 5-25℃, the recovery rate and grade of Li2O increase with the increase of temperature. When the temperature exceeds 25℃, the recovery rate and grade of Li2O decrease slightly, but still meet the standards of subsequent processes. Although etheramine reagents are not sensitive to temperature, temperature changes do affect the activity of the reagents. However, compared with the situation where amine reagents cannot work at temperatures below 20℃, the decrease in the activity of etheramine reagents is not so serious.

[0076] In summary, the etheramine collector prepared in the present invention reduces the breakage and annealing of foam in the flotation test, does not produce large clumps of enriched foam, and has good foam continuity, which is conducive to scraper collection in production.

[0077] It has a good collection effect on lepidolite in a wide range of pH and temperature, and is not very sensitive to changes in pulp pH and temperature. Compared with traditional amine collectors, etheramine collectors are used in smaller quantities, the foam is more stable and has proper fluidity, the foam breakage and merger are reduced, and the recovery rate of the flotation process is improved.

[0078] 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 an etheramine cationic collector, characterized in that: The preparation method of the etheramine cationic collector comprises: Take a clean and dry flask, then dissolve compound A in dry THF under N2 atmosphere, stir the solution and cool it to 0°C with an ice bath, then add sodium hydroxide to the stirred mixture, stir for 1h, and then add compound B and stir; After the reaction was completed, H2O was added to neutralize it and extracted with ether, and the organic layers were combined, dried over MgSO4, filtered and concentrated in vacuo; Add MeOH to the concentrate and heat until the suspension is completely dissolved, then purify by column chromatography to obtain compound C; After adding compound C to THF, potassium o-phenylenediamine was added and the mixture was heated to 60°C and reacted overnight. After cooling to room temperature, the mixture was diluted with acidic water with pH=3, extracted with ethyl acetate, and the organic layer was combined with MgSO4, dried, filtered, and concentrated in vacuo, and purified by column chromatography to obtain compound E; Dissolve compound E in ethanol, slowly add 64w% hydrazine hydrate dropwise while stirring, then heat the mixture to 100°C and stir under reflux overnight; The mixture was cooled and concentrated in vacuo, dissolved in chloroform, washed twice with NaOH, washed twice with saline, dried over MgSO4 and concentrated in vacuo to finally obtain compound G; Compound G was dissolved in MeOH, 2M HCl solution was added, and then heated, ether was removed by argon flow, methanol was added after ether was evaporated, and the mixture was bubbled with argon, and then Pd / C catalyst was added at room temperature, and the mixture was stirred under H2 gas overnight, and then the mixture was filtered through glass, washed with MeOH, and concentrated in vacuo to obtain the final white solid compound I; Wherein, the chemical structure formula of compound A is: The general chemical structure formula of compound B is: The general chemical structure formula of compound C is: The general chemical structure formula of compound E is: The general chemical structure formula of compound G is: The general chemical structure formula of compound I is: in: m is any integer from 0 to 9; Wherein, n is any integer from 0 to 14.

2. An etheramine cationic collector, characterized in that: The etheramine cationic collector is a compound having the following general chemical structure formula or its chemical isomer or salt: Wherein, m is any integer from 0 to 9; Wherein, n is any integer from 0 to 14.

3. The etheramine cationic collector according to claim 2, characterized in that: The compound A is And compound B is When the corresponding compound I is 4. The etheramine cationic collector according to claim 2, characterized in that: The compound A is And compound B is When the corresponding compound I is 5. The etheramine cationic collector according to claim 2, characterized in that: The compound A is And compound B is When the corresponding compound I is 6. Application of an etheramine cationic collector in lepidolite flotation, characterized in that: The etheramine cationic collector as claimed in claim 2 is used in the flotation process of lepidolite.

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