Amine cation collecting agent, preparation method and flotation agent

Abstract

The invention discloses an amine cation collecting agent, a preparation method, a flotation agent and a lepidolite flotation method.The flotation agent comprises 20-35 parts of the amine cation collecting agent, 5-8 parts of an anion hydroximic acid collecting agent, 10-20 parts of an organic solvent and 5-20 parts of deionized water. And the lithium ore is mixed with the anion collecting agent to form the mixed collecting agent, and the concentrate grade and the recovery rate of the lithium ore can be remarkably improved through the mixed collecting agent.

Description

Technical Field

[0001] The invention relates to an amine cationic collector, a preparation method and a flotation agent. Background Art

[0002] Lithium plays a pivotal role in today's world. In the energy field, lithium is the core element of lithium-ion batteries, providing powerful power support for electric vehicles, mobile electronic devices, etc., and promoting the global transition to clean energy.

[0003] In the industrial field, lithium is widely used in metallurgy, glass and ceramics and other industries to improve product performance and quality.

[0004] Lithium is also indispensable in the medical field, playing a unique role in drug synthesis and medical equipment.

[0005] 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.

[0006] The development of lithium ore flotation reagents, as an important step in mineral processing, affects all subsequent operations.

[0007] High-efficiency flotation reagents can accurately separate lithium ore from impurity minerals, improve the recovery rate and grade of lithium ore, and reduce production costs. Currently, cationic collectors used in lithium ore flotation include: dodecylamine, tetradecylamine, octadecylamine, N-dodecyl-1,3-propylenediamine, etc., which have very good collection capabilities. Amine cationic collectors are still limited to the above-mentioned common amine reagents, and no new amine reagents have been developed. Summary of the invention

[0008] The main purpose of the present invention is to provide an amine cationic collector, a preparation method and a flotation agent, aiming to solve the above technical problems.

[0009] To achieve the above object, the present invention provides an amine cationic collector which is a compound having the following chemical structural formula or its chemical isomer or salt thereof:

[0010]

[0011] in:

[0012] R1 and R2 are both alkanes, alkenes, alkynes, benzene rings and their derivatives.

[0013] In addition, the present invention also provides a method for preparing an amine cationic collector, the method comprising:

[0014] Reactant A and trimethylamine were dripped into a clean and dry reactor in a molar ratio of 1:8, and finally 500 mL of ultra-dry acetonitrile was added;

[0015] After adding the raw materials, the reactor is connected to a vacuum pump and a nitrogen cylinder, and the air in the reactor is exhausted by bubbling for 10-30 minutes to fill the reactor with nitrogen;

[0016] Then, tighten the interface connecting the reactor to the air, and place the reactor in a heated and rotating water bath for 18 h;

[0017] After the reaction is completed, wait for the reactor to cool to room temperature, open the reactor, add water, pour the reaction solution with water into a separatory funnel and shake it. After standing and separating the layers, take the upper oil phase. After repeating three times, use a large beaker to collect the oil phase.

[0018] Prepare 3M dilute hydrochloric acid, pour the dilute hydrochloric acid into the collected oil phase, stir at high speed for 5 hours, and finally obtain product C;

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

[0020]

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

[0022]

[0023] in:

[0024] R1 and R2 are both alkanes, alkenes, alkynes, benzene rings and their derivatives.

[0025] In one embodiment, R1 and R2 are methyl, ethyl, propyl, butyl, pentane, etc. or a benzene ring.

[0026] In addition, the present invention also provides a flotation agent, which comprises 30 to 55 parts of the amine cationic collector as claimed in claim 1, 20 to 35 parts of anionic fatty acid / salt collector, 5 to 8 parts of anionic hydroxamic acid collector, 10 to 20 parts of organic solvent, and 5 to 20 parts of deionized water.

[0027] In one embodiment, the sulfonic acid comprises at least one 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 acid hydroxamic acid, and benzoic acid hydroxamic acid.

[0028] In the technical solution of the present invention, an organic synthesis method is adopted to design and synthesize a new amine cationic reagent for lithium mica flotation, and the reagent is mixed with an anionic collector to form a mixed collector. The mixed collector can significantly improve the concentrate grade and recovery rate of lithium ore. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] 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.

[0030] Figure 1 A schematic flow chart of a lepidolite flotation method according to an embodiment of the present invention;

[0031] Figure 2 This is a table of concentrate grade and lithium recovery rate after flotation with anion and cation mixed collectors at low temperature.

[0032] 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

[0033] 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.

[0034] 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.

[0035] 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.

[0036] The invention provides an amine cationic collector.

[0037] like Figure 1 As shown, the amine cationic collector provided in the embodiment of the present invention is a compound having the following chemical structural formula or its chemical isomer or salt thereof:

[0038]

[0039] The specific steps of the synthesis are as follows: in a vacuum glove box, take a clean and dry reactor, drop reactant A and trimethylamine in sequence at a molar ratio of 1:8, and finally add 500 mL of ultra-dry acetonitrile.

[0040] After adding the raw materials, the reactor is connected to a vacuum pump and a nitrogen cylinder, and the air in the reactor is expelled by bubbling for 10-30 minutes to fill the reactor with nitrogen.

[0041] Then, the interface between the reactor and the air was tightened, and the reactor was placed in a heated and rotating water bath for 18 h.

[0042] 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 it up and down a few times, let it stand for stratification, and take the upper oil phase. After repeating three times, use a large beaker to collect the oil phase.

[0043] Prepare 3M dilute hydrochloric acid, pour the dilute hydrochloric acid into the collected oil phase, stir at high speed for 5 hours, and finally obtain the desired product C.

[0044] The purified product C is used in the configuration of anion-cation mixed collector for lithium mica flotation.

[0045] Specifically, the synthetic route of product C is as follows:

[0046]

[0047] Further, when compound A is as follows:

[0048]

[0049] The product C generated by the above synthetic route is as follows:

[0050] Further, when compound A is as follows:

[0051]

[0052] The product C generated by the above synthetic route is as follows:

[0053] Further, when compound A is as follows:

[0054]

[0055] The product C generated by the above synthetic route is as follows:

[0056]

[0057] In the above example:

[0058] R1 and R2 are alkanes, alkenes, alkynes, benzene rings and their derivatives, specifically methyl, ethyl, propyl, butyl, pentane, etc. or benzene rings.

[0059] Furthermore, the present invention provides a flotation agent, which includes 30 to 55 parts of amine cationic collectors (product C), 20 to 35 parts of anionic fatty acid / salt collectors, 5 to 8 parts of anionic hydroxamic acid collectors, 10 to 20 parts of organic solvents, and 5 to 20 parts of deionized water.

[0060] Although the ammonium salt of the present application has a large molecular weight, it still has good solubility. The structure has an ester group with strong hydrophobic groups and a metal chelate group, which can chelate with the surface metal of lithium mica and quickly float to the water surface driven by bubbles. The ester group can improve the stability and dispersibility of the agent and can be repeated many times. The ester group can also adjust the foam properties, change the surface tension and liquid film stability of the foam, so that the foam can better carry mineral particles to float.

[0061] The present application expands the types of cationic amine collectors and successfully inserts ester groups into amine collectors.

[0062] Optionally, 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] In the above embodiments, different components of different types of compounds proposed can be freely combined and are not limited here.

[0064] The flotation agent provided in this application has high selectivity for lithium mica, strong collection ability, moderate viscosity, low temperature resistance, fragile foam and moderate foam volume. It can improve the recovery rate of metallic lithium in lithium mica flotation. Combined with the use of inhibitors, the flotation lithium recovery rate can reach 85.4%, and the Li2O grade of the concentrate can reach 3.48

[0065] The present application is described below through specific embodiments.

[0066] The following flotation comparison is carried out using an anionic and cation mixed collector, an anionic collector constituting an anionic and cation mixed collector, a cationic collector constituting an anionic and cation mixed collector, and a lithium mica collector that has been developed by Jiangxi Jiuling. For further explanation, see Implementation Case 1.

[0067] 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 0.58 (that is, the Li2O content in the raw ore is 0.58%).

[0068] Example 1

[0069] Weigh a certain weight of lepidolite ore respectively, pour it into four flotation tanks after crushing, stir evenly for 5-20 minutes at room temperature and a stirring speed of 1200r / min, add a combined inhibitor, and stir again. Finally, add the anion-cation mixed collector prepared by the present invention, the cationic collector constituting the anion-cation mixed collector, the cationic collector constituting the anion-cation mixed collector, and the developed and applied lepidolite collector, and perform flotation under the same time and operation according to the experimental process of one coarse, one fine, and one sweep.

[0070] Finally, we collected the lithium mica concentrate, dried it in an oven overnight, collected and mixed it, and sent it to test the concentrate grade (i.e. the mass fraction of lithium compounds in the concentrate) and calculate the lithium recovery rate (i.e. the percentage of lithium compounds obtained in the concentrate to the lithium compounds in the original ore). The results are shown in the table below.

[0071]

[0072]

[0073] Table 1 Concentrate grade and lithium recovery rate of different collectors

[0074] As can be seen from Table 1, the anion-cation mixed collector prepared by the present invention is higher than the other three collectors in terms of both concentrate grade and lithium recovery rate. The anion collector alone has good selectivity, but weak collection ability. The cation collector alone has good lithium recovery rate, but poor selectivity and low grade. The flotation performance of the anion-cation mixed collector prepared by the present invention is also improved compared with the lithium mica collector that has been used in production on the market.

[0075] Example 2

[0076] The anion-cation mixed collector prepared by the invention can maintain a good collecting effect even at low temperatures.

[0077] Weigh a certain weight of lepidolite ore respectively, pour it into the flotation tank after crushing, stir it at low temperature for 5-20 minutes, add the inhibitor, and stir it again. Finally, add the anion-cation mixed collector prepared by the present invention, and flotation is carried out under the same time and operation according to the experimental process of one coarse, one fine, and one sweep.

[0078] from Figure 2 It can be seen from the data that at extremely low temperatures, the concentrate grade and lithium yield both slightly decreased, but at 5°C, there was still a concentrate grade of 3.20 and a lithium recovery rate of 81.7%. As the temperature rises, the concentrate grade and lithium yield both increase. This is because the activity of amine compounds is easily affected by temperature, which also reflects the importance of the amine compounds prepared by the present invention in the mixed collector.

[0079] Example 3

[0080] Weigh an appropriate amount of lithium mica ore sample, add it into a flotation tank and stir it evenly, then add the amine compound, dodecylamine, tetradecylamine, octadecylamine, etc. prepared by the present invention to prepare an anion-cation mixed collector. Add the same dose of collector, stir it for a certain period of time, and then ventilate to generate bubbles.

[0081] During the scraping process of bubbles, the bubbles will be mixed with water, ore mud and other impurities, so the amount and height of the bubbles will have a great impact on the concentrate grade and lithium recovery rate. After the bubbles containing the amine compound collector prepared by the present invention are scraped and collected, the foam can be eliminated within 2 minutes, while the bubbles containing dodecylamine and tetradecylamine collectors will still remain after 15 minutes.

[0082] The dodecylamine and tetradecylamine collectors also scrape more concentrate water samples than the amine compound collector prepared by the present invention, which increases the energy loss in the drying process.

[0083] The foam of the mixed collector composed of amine compounds prepared by the invention is easy to break, and the foam amount and foam height are moderate.

[0084] In summary, the flotation reagent containing the novel amine cationic collector of lepidolite has good selectivity, strong collecting ability, easy-to-break foam and moderate amount.

[0085] 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. An amine cationic collector, characterized in that: The amine cationic collector is a compound having the following general chemical structure or its chemical isomer or salt: in: R1 and R2 are both alkanes, alkenes, alkynes, benzene rings and their derivatives.

2. A method for preparing an amine cationic collector, characterized in that: The preparation method of the amine cationic collector comprises: Reactant A and trimethylamine were dripped into a clean and dry reactor in a molar ratio of 1:8, and finally 500 mL of ultra-dry acetonitrile was added; After adding the raw materials, the reactor is connected to a vacuum pump and a nitrogen cylinder, and the air in the reactor is exhausted by bubbling for 10-30 minutes to fill the reactor with nitrogen; Then, tighten the interface connecting the reactor to the air, and place the reactor in a heated and rotating water bath for 18 h; After the reaction is completed, wait for the reactor to cool to room temperature, open the reactor, add water, pour the reaction solution with water into a separatory funnel and shake it. After standing and separating the layers, take the upper oil phase. After repeating three times, use a large beaker to collect the oil phase. Prepare 3M dilute hydrochloric acid, pour the dilute hydrochloric acid into the collected oil phase, stir at high speed for 5 hours, and finally obtain product C; Wherein, the chemical structure formula of the compound A is: The general chemical structure formula of the product C is: in: R1 and R2 are both alkanes, alkenes, alkynes, benzene rings and their derivatives.

3. The method for preparing an amine cationic collector according to claim 2, characterized in that: The R1 and R2 are methyl, ethyl, propyl, butyl, pentane or a benzene ring.

4. A flotation agent, characterized in that: The flotation agent comprises 30-55 parts of the amine cationic collector as claimed in claim 1, 20-35 parts of anionic fatty acid / salt collector, 5-18 parts of anionic hydroxamic acid collector, 10-20 parts of organic solvent, and 5-20 parts of deionized water.

5. The flotation agent according to claim 4, characterized in that The sulfonic acids include 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 at least one of rosin acid, oleic acid, sodium oleate, cyclohexane acid soap, tall oil, peroxy fatty acid soap, salicylic hydroxamic acid, and benzohydroxamic acid.

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