Collector for desilication of clay-type lithium ore by reverse flotation, and preparation method and use thereof

Abstract

The present application relates to a kind of clay type lithium ore reverse flotation desilication collector and its preparation method and purposes, the clay type lithium ore reverse flotation desilication collector includes by weight parts: quaternary ammonium salt 70-75 parts, imidazole 10-15 parts, surfactant 2-5 parts, tributyl phosphate 3-5 parts and thickening agent 3-5 parts.The collector provided by the present application has the advantages of good solubility and strong collecting performance, and can realize the separation of aluminosilicate minerals and lithium-containing minerals;At the same time, the collector does not need to be saponified, sulfidation reaction, which is beneficial to energy saving and emission reduction and cost reduction and efficiency improvement, and has strong market promotion value.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of mineral processing, in particular to a collector for desilication of clay-type lithium ore by reverse flotation and a preparation method and use thereof. BACKGROUND

[0002] At present, with the rapid development of the lithium battery industry, the demand for lithium resources is rapidly increasing, and the development of lithium resources is continuously increasing. Lithium mineral resources are mainly spodumene, and the characteristics of this type of ore are high grade. At present, there are relatively mature flotation processes on the market, but part of the lithium resources are embedded in clay minerals, mainly in lithium chlorite, which exists in pegmatite aluminosilicate minerals. This type of mineral, lithium resources are evenly distributed in the ore, the main characteristics are high viscosity of the ore pulp, low grade, low Al / Si ratio, etc. Using the traditional bauxite flotation scheme, most of the diaspore in the ore can be effectively floated, and the grade of lithium concentrate can be effectively improved. However, in order to further improve the grade, the ore needs to be treated by reverse flotation desilication.

[0003] At present, the flotation desilication collector for clay-type lithium ore mainly uses one or several of dodecylamine, hexadecylamine, octadecylamine, polyether amine, piperidine amine and mixed amine as the collector.

[0004] CN112474063A discloses a high-efficiency collector for collecting siliceous ore, the main component of which is any one of carbon chain length 8-18 alkyl halogen ion (F, Cl, Br, I) type monquaternary ammonium salt, or two or more of them; the secondary component includes sodium oleate, dodecylamine, hydrochloric acid, polyether amine, ether amine, sodium dodecyl sulfonate, sodium dodecyl sulfate, diesel oil, tributyl phosphate, and water. The main and secondary components of the collector are matched according to the treated ore and solid waste (iron ore, phosphate ore, fluorite, barite, phosphogypsum, etc.), so as to realize the purpose of floating the siliceous minerals in the ore from the flotation froth. The collector does not require high temperature and high pressure in preparation, has a wide pH range, can greatly simplify the reagent process, and save reagent cost; compared with existing siliceous mineral collectors, the collector has strong pH adaptability, good selectivity for collecting siliceous minerals, is not affected by sludge, and the flotation froth is not sticky, easy to dissipate and settle.

[0005] CN111389596A discloses a collector for magnesite flotation desilication and aluminum removal and a preparation method thereof, which realizes aluminum removal while achieving desilication of magnesite ore in reverse flotation. The collector of the scheme takes dodecylamine as the main collector, lauryl amide as the auxiliary collector, and terpineol as the foaming agent, and takes paraffin oil and glacial acetic acid as the adjusting agent. The preparation method of the collector is as follows: first, dissolve dodecylamine in glacial acetic acid, then add paraffin oil and terpineol as auxiliary collectors, and finally add lauryl amide to improve the association ability of the collector and aluminum-containing minerals, thereby obtaining the collector for magnesite flotation desilication and aluminum removal. The collector has strong electrostatic adsorption force on silicate minerals and strong adsorption capacity on aluminum-containing minerals. While achieving good desilication effect in reverse flotation, excellent aluminum removal effect can be obtained. The collector of the present application has an aluminum content of 0.35% in the raw ore and an aluminum content of 0.07% in the concentrate after reverse flotation. The collector of the present application is simple to prepare and has excellent application effect in magnesite flotation desilication and aluminum removal.

[0006] Although the existing amine collector can have a certain separation effect on silicate minerals under acidic conditions, the collector can produce electrostatic adsorption with silicate minerals only under the condition that the pH is adjusted to 2-3, which consumes a large amount of acid, and the treatment of flotation wastewater is troublesome. In addition, the collector has weak collecting ability, large amount of bubbles and poor separation effect. To solve this problem, a collector with good selectivity, small amount of bubbles and strong collecting ability needs to be developed, which can separate silicate minerals in a wide pH range. SUMMARY

[0007] In view of the problems in the prior art, the present application aims to provide a collector for reverse flotation desilication of clay-type lithium ore and a preparation method and use thereof, so as to solve the problems of poor collecting effect, poor selectivity and insufficient amount of bubbles of the collector for reverse flotation desilication of clay-type lithium ore.

[0008] To achieve this purpose, the present application adopts the following technical solutions:

[0009] In a first aspect, the present application provides a collector for reverse flotation desilication of clay-type lithium ore, which comprises, by weight: 70-75 parts of quaternary ammonium salt, 10-15 parts of imidazole, 2-5 parts of surfactant, 3-5 parts of tributyl phosphate and 3-5 parts of thickening agent.

[0010] The collector provided by the present application has the advantages of good solubility and strong collecting performance, can realize the separation of aluminosilicate minerals and lithium-containing minerals, does not need to be saponified or sulfided, is conducive to energy saving and emission reduction, and has strong market promotion value.

[0011] In the present application, the quaternary ammonium salt in the collector for reverse flotation desilication of clay-type lithium ore is 70-75 parts by weight, for example, it can be 70 parts, 70.2 parts, 70.4 parts, 70.6 parts, 70.8 parts, 71 parts, 71.2 parts, 71.4 parts, 71.6 parts, 71.8 parts, 72 parts, 72.2 parts, 72.4 parts, 72.6 parts, 72.8 parts, 73 parts, 73.2 parts, 73.4 parts, 73.6 parts, 73.8 parts, 74 parts, 74.2 parts, 74.4 parts, 74.6 parts, 74.8 parts or 75 parts, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0012] In the present application, the imidazole in the collector for reverse flotation desilication of clay-type lithium ore is 10-15 parts by mass percentage, for example, it can be 10 parts, 10.2 parts, 10.4 parts, 10.6 parts, 10.8 parts, 11 parts, 11.2 parts, 11.4 parts, 11.6 parts, 11.8 parts, 12 parts, 12.2 parts, 12.4 parts, 12.6 parts, 12.8 parts, 13 parts, 13.2 parts, 13.4 parts, 13.6 parts, 13.8 parts, 14 parts, 14.2 parts, 14.4 parts, 14.6 parts, 14.8 parts or 15 parts, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0013] In the present application, the surfactant in the collector for reverse flotation desilication of clay-type lithium ore is 2-5 parts by mass percentage, for example, it can be 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7 parts, 4.8 parts, 4.9 parts or 5 parts, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0014] In the present application, the tributyl phosphate in the collector for reverse flotation desilication of clay-type lithium ore is 3-5 parts by mass percentage, for example, it can be 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7 parts, 4.8 parts, 4.9 parts or 5 parts, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0015] In the present application, the thickening agent in the collector for reverse flotation desilication of clay-type lithium ore is 3-5 parts by weight, for example, it can be 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7 parts, 4.8 parts, 4.9 parts or 5 parts, etc., but not limited to the listed values, other unlisted values within this range are also applicable.

[0016] As a preferred technical solution of the present application, the quaternary ammonium salt comprises dodecyl trimethyl ammonium chloride and / or dodecyl trimethyl ammonium bromide.

[0017] As a preferred technical solution of the present application, the surfactant comprises sodium dodecyl sulfonate and / or sodium dodecyl sulfate.

[0018] In the present application, the specific quaternary ammonium salt, imidazole and surfactant are used in combination, which can enhance the selectivity to silicate minerals in a wide pH range, optimize the dispersion effect of the ore pulp, reduce the viscosity of the ore pulp, and thus improve the flotation and collection effect of silicon in clay-type lithium ore. Further, by cooperating with tributyl phosphate, the formation of foam in the flotation process can be optimized, which is conducive to the formation of foam with good flotation characteristics to realize the collection of silicon-containing minerals.

[0019] As a preferred technical solution of the present application, the surfactant is sodium dodecyl sulfonate and sodium dodecyl sulfate with a mass ratio of 1:(1-3), for example, it can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8 or 1:3, etc., but not limited to the listed values, other unlisted values within this range are also applicable.

[0020] As a preferred technical solution of the present application, the thickening agent comprises carboxymethyl cellulose.

[0021] In the present application, a certain amount of thickening agent is introduced into the collector to adjust the performance of the collector, so that the collector can better realize its collection effect. Specifically, the carboxymethyl and hydroxyl groups in the molecule form hydrogen bonds with water molecules, so that the water molecules form a network structure between the molecules, which can inhibit diaspore and thus improve the collection effect and make the components in the collector mix uniformly.

[0022] In a second aspect, the present application provides a preparation method of the collector for reverse flotation desilication of clay-type lithium ore as described in the first aspect, the preparation method comprises:

[0023] The mixed solution of quaternary ammonium salt and imidazole is mixed with the surfactant solution for the first time, then the tributyl phosphate is added for the second mixing, and then the thickening agent is added for the third mixing to obtain the collector for desilication of clay type lithium ore by reverse flotation.

[0024] In the present application, the third mixing is stirred to 25-30 DEG C, for example, it can be 25 DEG C, 25.5 DEG C, 26 DEG C, 26.5 DEG C, 27 DEG C, 27.5 DEG C, 28 DEG C, 28.5 DEG C, 29 DEG C, 29.5 DEG C or 30 DEG C, but not limited to the listed values, other values not listed in the range are also applicable.

[0025] In the present application, the mixed solution of quaternary ammonium salt and imidazole is obtained by first heating mixing quaternary ammonium salt, imidazole and water, and the water is added in an amount of 0.2-0.3 times the mass of the raw materials, for example, it can be 0.2 times, 0.21 times, 0.22 times, 0.23 times, 0.24 times, 0.25 times, 0.26 times, 0.27 times, 0.28 times, 0.29 times or 0.3 times, but not limited to the listed values, other values not listed in the range are also applicable.

[0026] In the present application, the mass of the raw materials corresponding to the amount of water added during preparation refers to the total mass of quaternary ammonium salt, imidazole, surfactant, tributyl phosphate and thickening agent according to the formula.

[0027] In the present application, the first heating mixing is carried out at a temperature of 75-80 DEG C, for example, it can be 75 DEG C, 75.5 DEG C, 76 DEG C, 76.5 DEG C, 77 DEG C, 77.5 DEG C, 78 DEG C, 78.5 DEG C, 79 DEG C, 79.5 DEG C or 80 DEG C, but not limited to the listed values, other values not listed in the range are also applicable.

[0028] In the present application, the first heating mixing is carried out for a time of 15-20 min, for example, it can be 15 min, 15.5 min, 16 min, 16.5 min, 17 min, 17.5 min, 18 min, 18.5 min, 19 min, 19.5 min or 20 min, but not limited to the listed values, other values not listed in the range are also applicable.

[0029] In the present application, the surfactant solution is obtained by second heating mixing surfactant and water, and the water is added in an amount of 0.4-0.5 times the mass of the raw materials, for example, it can be 0.4 times, 0.41 times, 0.42 times, 0.43 times, 0.44 times, 0.45 times, 0.46 times, 0.47 times, 0.48 times, 0.49 times or 0.5 times, but not limited to the listed values, other values not listed in the range are also applicable.

[0030] In the present application, the temperature of the second heating mixing is 80-95℃, for example, it can be 80℃, 81℃, 82℃, 83℃, 84℃, 85℃, 86℃, 87℃, 88℃, 89℃, 90℃, 91℃, 92℃, 93℃, 94℃ or 95℃, etc., but not limited to the listed values, other values in the range are also applicable.

[0031] In the present application, the time of the second heating mixing is 25-30min, for example, it can be 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min, etc., but not limited to the listed values, other values in the range are also applicable.

[0032] As a preferred technical solution of the present application, the temperature of the first mixing is 80-85℃, for example, it can be 80℃, 80.5℃, 81℃, 81.5℃, 82℃, 82.5℃, 83℃, 83.5℃, 84℃, 84.5℃ or 85℃, etc., but not limited to the listed values, other values in the range are also applicable.

[0033] Preferably, the time of the first mixing is 5-15min, for example, it can be 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min, 10min, 10.5min, 11min, 11.5min, 12min, 12.5min, 13min, 13.5min, 14min, 14.5min or 15min, etc., but not limited to the listed values, other values in the range are also applicable.

[0034] Preferably, the temperature of the second mixing is 60-65℃, for example, it can be 60℃, 60.5℃, 61℃, 61.5℃, 62℃, 62.5℃, 63℃, 63.5℃, 64℃, 64.5℃ or 65℃, etc., but not limited to the listed values, other values in the range are also applicable.

[0035] Preferably, the time of the second mixing is 5-10min, for example, it can be 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10min, etc., but not limited to the listed values, other values in the range are also applicable.

[0036] As a preferred technical solution of the present application, the temperature of the third mixing is 100-110℃, for example, it can be 100℃, 101℃, 102℃, 103℃, 104℃, 105℃, 106℃, 107℃, 108℃, 109℃ or 110℃, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0037] Preferably, the time of the third mixing is 10-15min, for example, it can be 10min, 10.5min, 11min, 11.5min, 12min, 12.5min, 13min, 13.5min, 14min, 14.5min or 15min, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0038] In a third aspect, the present application provides a use of the collector for reverse flotation desilication of clay-type lithium ore, the use comprising using the collector for reverse flotation desilication of clay-type lithium ore to perform reverse flotation desilication on the clay-type lithium ore.

[0039] As a preferred technical solution of the present application, the reverse flotation desilication specifically comprises: mixing and grinding the clay-type lithium ore with a pulp concentration of 60-62wt% and the carbonate to obtain a pulp, and adding an adjusting agent, an activator and the collector for reverse flotation desilication of clay-type lithium ore to the pulp for roughing.

[0040] In the present application, the mass percentage of -200 mesh solid particles in the pulp for flotation accounts for 95-98% of all solid particles, for example, it can be 95%, 95.5%, 96%, 96.5%, 97%, 97.5% or 98%, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0041] Preferably, the amount of the carbonate added is 480-520g / t, for example, it can be 480g / t, 490g / t, 500g / t, 510g / t or 520g / t, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0042] Preferably, the pulp concentration of the pulp is 20-22wt%, for example, it can be 20wt%, 20.5wt%, 21wt%, 21.5wt% or 22wt%, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0043] Preferably, the pH value of the pulp after adding the adjusting agent is controlled to be 3-12, for example, it can be 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, etc., but not limited to the listed values, other values not listed in this range are also applicable.

[0044] Preferably, the amount of the activator added is 200-220 g / t, for example, it can be 200 g / t, 205 g / t, 210 g / t, 215 g / t or 220 g / t, etc., but is not limited to the listed values, and other unlisted values within the range are also applicable.

[0045] Preferably, the amount of the collector for reverse flotation desilication of the clay-type lithium ore is 800-850 g / t, for example, it can be 800 g / t, 810 g / t, 820 g / t, 830 g / t, 840 g / t or 850 g / t, etc., but is not limited to the listed values, and other unlisted values within the range are also applicable.

[0046] In the present application, wt% refers to mass concentration.

[0047] In the present application, g / t refers to adding a certain number of grams of reagent per t of ore, wherein the ore can be clay-type lithium ore, or other mineral materials containing clay-type lithium ore, such as tailings, such as hydrometallurgical leaching residue, etc.

[0048] In the present application, the activator used in the flotation process can be a sodium salt, such as sodium chloride, etc.

[0049] Compared with the prior art, the present application has the following beneficial effects:

[0050] The collector provided by the present application improves the use range of the collector by configuring the complex collector and utilizing the coordination effect between the quaternary ammonium salt and the imidazole, and enhances the selectivity of the collector by cooperating with the surfactant, so as to achieve efficient collection of silicon in the clay-type lithium ore and efficient flotation separation of lithium and silicon in the clay-type lithium ore. Further, by cooperating with the tributyl phosphate, the amount of foam in the use process of the collector is reduced. DETAILED DESCRIPTION

[0051] To better illustrate the present application and facilitate understanding of the technical solutions of the present application, the following are typical but non-limiting embodiments of the present application:

[0052] The following examples were carried out on the test ore sample after flotation desilication of the clay-type lithium ore in a certain place, and the main mineral content in the ore is shown in Table 1 below:

[0053] Table 1

[0054] Mineral Diaspore Kaolinite Mica Hematite Anatase Lepidolite Content (%) 25 55 6 5 5 4

[0055] The Al2O3 content in the raw ore is 19.25%, the SiO2 content is 67.35%, the Fe2O3 content is 6.65%, the Li2O grade is 0.62%, and the ore aluminum-silicon ratio is 0.286. There are more kaolinite in the ore sample, the target mineral particle size is relatively fine, and it is embedded in weathered aluminosilicate minerals, and has similar phase properties to silicate minerals, so it is difficult to separate them by traditional reagents.

[0056] Example 1

[0057] The embodiment provides a collector for reverse flotation desilication of clay-type lithium ore, which comprises the following:

[0058] The collector comprises, by weight parts, quaternary ammonium salt (dodecyltrimethylammonium chloride) 70 parts, imidazole 15 parts, surfactant (sodium dodecyl sulfonate and sodium dodecyl sulfate) 5 parts, tributyl phosphate 5 parts, and thickening agent (carboxymethyl cellulose) 5 parts.

[0059] S1, adding sodium dodecyl sulfonate and sodium dodecyl sulfate with a mass ratio of 1:2 into water according to the above proportion, the water addition amount is 0.45 times the mass of the raw material, heating to 85°C and stirring for 27 min to prepare a surfactant solution;

[0060] S2, mixing the quaternary ammonium salt and imidazole weighed according to the formula, adding UP water, the water addition amount is 0.25 times the mass of the raw material, and heating and stirring at 77°C for 18 min;

[0061] S3, adding the surfactant prepared in S1 to the mixture dissolved in step S2 according to the above proportion, and heating and stirring at 82°C for 10 min;

[0062] S4, adding the weighed tributyl phosphate solution to the mixed solution in step S3 according to the above proportion, and heating and stirring at 63°C for 7 min;

[0063] S5, adding the weighed thickening agent to the mixed solution in step S4 according to the above proportion, slowly adding, heating and stirring at 105°C for 12 min to make it fully dissolved. After heating, continue to stir to room temperature 25°C. The clay-type lithium ore flotation desilication collector is obtained.

[0064] The obtained clay-type lithium ore reverse flotation desilication collector is used for reverse flotation of the aforementioned clay-type lithium ore sample, and the floating mineral is silicate mineral, and the ore pulp is lithium concentrate. The flotation process is as follows: mixing and grinding the clay-type lithium ore with a pulp concentration of 60wt% and carbonate to obtain an ore pulp, the mass ratio of-200 mesh solid particles in the ore pulp is 95%, adding the adjusting agent, the activator and the collector for reverse flotation desilication of the clay-type lithium ore for roughing;

[0065] The amount of the carbonate added in the flotation process is 500 g / t; the pulp concentration of the ore pulp is 20 wt%; the pH value of the ore pulp after adding the adjusting agent is controlled at 11; the amount of the activator added is 200 g / t; and the amount of the collector for the reverse flotation desilication of the clay-type lithium ore is 800 g / t.

[0066] Table 2 below is the flotation result index obtained in the present embodiment.

[0067] Table 2

[0068]

[0069] Example 2

[0070] The present embodiment provides a collector for the reverse flotation desilication of the clay-type lithium ore, which comprises the following:

[0071] The collector comprises, by weight: quaternary ammonium salt (dodecyl trimethyl ammonium chloride) 70 parts, imidazole 15 parts, surfactant (sodium dodecyl sulfonate and sodium dodecyl sulfate) 5 parts, tributyl phosphate 5 parts, and thickening agent (carboxymethyl cellulose) 5 parts.

[0072] S1. Add sodium dodecyl sulfonate and sodium dodecyl sulfate in a mass ratio of 1:2 into water according to the above proportions, the amount of water added is 0.45 times the mass of the raw materials, heat to 85°C and stir for 27 min to prepare a surfactant solution;

[0073] S2. Mix the quaternary ammonium salt and imidazole weighed according to the formula, add UP water, the amount of water added is 0.25 times the mass of the raw materials, and heat and stir at 77°C for 18 min;

[0074] S3. Add the surfactant prepared in step S1 to the mixture dissolved in step S2 according to the above proportions, heat and stir at 82°C for 10 min;

[0075] S4. Add the tributyl phosphate solution weighed according to the above proportions to the mixed solution in step S3, heat and stir at 63°C for 7 min;

[0076] S5. Add the thickening agent weighed according to the above proportions to the mixed solution in step S4, add slowly, heat and stir at 105°C for 12 min to fully dissolve. After heating, continue to stir until the room temperature is 25°C. Thus, the collector for the flotation desilication of the clay-type lithium ore is obtained.

[0077] The obtained clay type lithium ore reverse flotation desilication collector is used for reverse flotation of the clay type lithium ore sample, and the floated mineral is silicate mineral, and the pulp is lithium concentrate. The flotation process is as follows: the clay type lithium ore with a pulp concentration of 60wt% and carbonate are mixed and ground to obtain a pulp, the mass fraction of-200 mesh solid particles in the pulp is 98%, and the adjusting agent, the activator and the clay type lithium ore reverse flotation desilication collector are added to the pulp for roughing.

[0078] In the flotation process, the addition amount of the 10% dilute sulfuric acid is 1000g / t; the pulp concentration of the pulp is 20wt%; the pH value of the pulp after adding the adjusting agent is controlled to be 3; the addition amount of the activator is 200g / t; and the addition amount of the clay type lithium ore reverse flotation desilication collector is 800g / t.

[0079] Table 3 below is the flotation result index obtained in this embodiment.

[0080] Table 3

[0081]

[0082]

[0083] Example 3

[0084] The embodiment provides a clay type lithium ore reverse flotation desilication collector, which comprises the following:

[0085] The collector comprises, by weight: quaternary ammonium salt (dodecyl trimethyl ammonium bromide) 75 parts, imidazole 10 parts, surfactant (sodium dodecyl sulfonate and sodium dodecyl sulfate) 5 parts, tributyl phosphate 5 parts and thickening agent (carboxymethyl cellulose) 5 parts.

[0086] S1, sodium dodecyl sulfonate and sodium dodecyl sulfate are configured according to a mass ratio of 1:2, UP water is added, the water addition amount is 0.4 times the mass of the raw material, and stirring is performed at 80°C for 30min to configure a surfactant solution;

[0087] S2, the weighed quaternary ammonium salt and imidazole in step S1 are mixed, UP water is added, the water addition amount is 0.2 times the mass of the raw material, and heating is performed at 75°C for 20min;

[0088] S3, the surfactant prepared in S1 is added to the mixed solution in step S2 according to the above proportion, and stirring is performed at 80°C for 15min;

[0089] S4, the weighed tributyl phosphate solution is added to the mixed solution in step S3 according to the above proportion, and stirring is performed at 60°C for 10min;

[0090] S5, add the weighed thickening agent to the mixed solution in step S4 according to the above ratio, and stir at 110°C for 10 min. After heating is completed, continue to stir until room temperature 25°C. The clay type lithium ore flotation desilication collector is obtained.

[0091] The obtained clay type lithium ore reverse flotation desilication collector is used for reverse flotation of the aforementioned clay type lithium ore sample. The floated mineral is silicate mineral, and the pulp is lithium concentrate. The flotation process is as follows: the clay type lithium ore and carbonate with a pulp concentration of 62wt% are mixed and ground to obtain a pulp. The mass fraction of-200 mesh solid particles in the pulp is 96%. An adjusting agent, an activator, and the clay type lithium ore reverse flotation desilication collector are added to the pulp for roughing.

[0092] In the flotation process, the addition amount of the carbonate is 480g / t; the pulp concentration of the pulp is 22wt%; the pH value of the pulp after adding the adjusting agent is controlled to be 12; the addition amount of the activator is 220g / t; and the addition amount of the clay type lithium ore reverse flotation desilication collector is 850g / t.

[0093] The following Table 4 shows the flotation result index obtained in this embodiment.

[0094] Table 4

[0095]

[0096] Example 4

[0097] The embodiment provides a clay type lithium ore reverse flotation desilication collector, which comprises the following:

[0098] The collector comprises, by weight parts: quaternary ammonium salt (mass ratio of dodecyltrimethylammonium chloride:dodecyltrimethylammonium bromide is 1:1) 75 parts, imidazole 15 parts, surfactant (sodium dodecyl sulfonate and sodium dodecyl sulfate) 2 parts, tributyl phosphate 3 parts, and thickening agent (carboxymethyl cellulose) 5 parts.

[0099] S1, sodium dodecyl sulfonate and sodium dodecyl sulfate are mixed according to a mass ratio of 1:2.2, and then UP water is added. The amount of water added is 0.5 times the mass of the raw material. Stir at 95°C for 25 min to prepare a surfactant solution;

[0100] S2, mix the weighed quaternary ammonium salt (mass ratio of dodecylammonium chloride and dodecylammonium bromide is 1:1) and imidazole, and then add UP water. The amount of water added is 0.3 times the mass of the raw material. Heat at 80°C for 15 min;

[0101] S3, add the surfactant prepared in S1 to the mixture dissolved in S2 according to the above proportion, and stir at 85°C for 5 min;

[0102] S4, add the weighed TBP solution to the mixed solution in S4 according to the above proportion, and stir at 65°C for 5 min;

[0103] S5, add the weighed thickening agent to the mixed solution in S4 according to the above proportion, and stir at 100°C for 15 min. After heating, continue to stir until the temperature reaches room temperature 30°C. Thus, the clay type lithium ore flotation desilication collector is obtained.

[0104] The obtained clay type lithium ore reverse flotation desilication collector is used for reverse flotation of the aforementioned clay type lithium ore sample. The floated mineral is silicate mineral, and the pulp is lithium concentrate. The flotation process is as follows: the clay type lithium ore and carbonate with a pulp concentration of 61wt% are mixed and ground to obtain a pulp. The mass fraction of-200 mesh solid particles in the pulp is 97%. The adjusting agent, activator and the clay type lithium ore reverse flotation desilication collector are added to the pulp for roughing.

[0105] In the flotation process, the addition amount of the carbonate is 520g / t; the pulp concentration of the pulp is 21wt%; the pH value of the pulp after adding the adjusting agent is controlled at 11.5; the addition amount of the activator is 200g / t; and the addition amount of the clay type lithium ore reverse flotation desilication collector is 800g / t.

[0106] Table 5 below is the flotation result index obtained in this embodiment.

[0107] Table 5

[0108]

[0109]

[0110] Comparative Example 1

[0111] The difference between this embodiment and Example 1 is that the collector does not configure a thickening agent, i.e. carboxymethyl cellulose. Table 6 below is the flotation result index obtained in this embodiment.

[0112] Table 6

[0113]

[0114] Comparative Example 2

[0115] The difference between this embodiment and Example 2 is that the collector does not configure a thickening agent, i.e. carboxymethyl cellulose. Table 7 below is the flotation result index obtained in this embodiment.

[0116] Table 7

[0117]

[0118]

[0119] Comparative Example 3

[0120] The difference from Example 1 is only that no imidazole is added in the preparation process of the collector. The following Table 8 is the flotation result index obtained in this example.

[0121] Table 8

[0122]

[0123] Comparative Example 4

[0124] The difference from Example 1 is only that the imidazole is replaced by an equal amount of phenylalanine. The following Table 9 is the flotation result index obtained in this example.

[0125] Table 9

[0126]

[0127]

[0128] Comparative Example 5

[0129] The difference from Example 1 is only that the dodecyl trimethyl ammonium chloride is replaced by an equal amount of dodecyl ammonium chloride. The following Table 10 is the flotation result index obtained in this example.

[0130] Table 10

[0131]

[0132] Comparative Example 6

[0133] The difference from Example 1 is only that no tributyl phosphate is added. The following Table 11 is the flotation result index obtained in this example.

[0134] Table 11 Comparative Example 7

[0135]

[0136]

[0137] Compared with the results of the examples and the comparative examples, it can be seen that: compared with example 1, comparative example 1 and comparative example 2 do not add the thickening agent carboxymethyl cellulose, and the collecting effect of the collector is obviously reduced; comparative example 3 does not add imidazole, and the collector cannot produce obvious sorting tendency on aluminosilicate, thereby resulting in poor flotation index; comparative example 4 uses amino acid to replace imidazole, and cannot produce obvious sorting tendency on aluminosilicate, thereby resulting in poor flotation index; comparative example 5 uses dodecyl ammonium chloride to replace dodecyl trimethyl ammonium chloride, and cannot produce obvious sorting on aluminosilicate, thereby resulting in poor flotation index. In comparative example 6, tributyl phosphate is not added for complex collection, and cannot produce obvious sorting tendency on aluminosilicate, thereby resulting in poor flotation index.

[0138] It can be seen from the results of the above examples that the collector provided by the present application has good solubility and strong collecting performance, can realize the sorting of aluminosilicate minerals such as kaolinite and lithium-containing minerals in a wide pH range, and the collector does not need to be saponified and sulfidized, which is beneficial to energy saving, emission reduction and cost reduction and efficiency increase, and has strong market promotion value.

[0139] It is declared that the detailed structural features of the present application are illustrated by the above examples, but the present application is not limited to the above detailed structural features, that is, it does not mean that the present application must rely on the above detailed structural features to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of the components selected by the present application, addition of auxiliary components, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

[0140] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, and these simple modifications all belong to the protection scope of the present application.

[0141] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combination manners.

[0142] In addition, various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the idea of the present application, and it should also be considered as disclosed content of the present application.

Claims

1. A collector for reverse flotation desilication of clay-type lithium ore, characterized in that, The collector for reverse flotation desilication of clay-type lithium ore comprises, by weight: 70-75 parts of quaternary ammonium salt, 10-15 parts of imidazole, 2-5 parts of surfactant, 3-5 parts of tributyl phosphate and 3-5 parts of thickener. The quaternary ammonium salt includes dodecyltrimethylammonium chloride and / or dodecyltrimethylammonium bromide; The surfactant includes sodium dodecyl sulfonate and / or sodium dodecyl sulfate.

2. The collector for reverse flotation desilication of clay-type lithium ore as described in claim 1, characterized in that, The surfactant is sodium dodecyl sulfonate and sodium dodecyl sulfate, and the mass ratio of sodium dodecyl sulfonate to sodium dodecyl sulfate is 1:(1-3).

3. The collector for reverse flotation desilication of clay-type lithium ore as described in claim 1, characterized in that, The thickener includes carboxymethyl cellulose.

4. A method for preparing a collector for reverse flotation desilication of clay-type lithium ore as described in any one of claims 1-3, characterized in that, The preparation method includes: A first mixing of a quaternary ammonium salt and imidazole solution with a surfactant solution is performed, followed by a second mixing with the addition of tributyl phosphate, and then a third mixing with the addition of a thickener, to obtain a collector for desilication of clay-type lithium ore by reverse flotation.

5. The preparation method according to claim 4, characterized in that, The temperature of the first mixture is 80-85℃.

6. The preparation method according to claim 4, characterized in that, The first mixing time is 5-15 minutes.

7. The preparation method according to claim 4, characterized in that, The temperature of the second mixture is 60-65℃.

8. The preparation method according to claim 4, characterized in that, The second mixing time is 5-10 minutes.

9. The preparation method according to claim 4, characterized in that, The temperature of the third mixture is 100-110℃.

10. The preparation method according to claim 4, characterized in that, The third mixing time is 10-15 minutes.

11. The use of a collector for reverse flotation desilication of clay-type lithium ore as described in any one of claims 1-3, characterized in that, The application includes using the collector for reverse flotation desilication of clay-type lithium ore to perform reverse flotation desilication on clay-type lithium ore.

12. The use as described in claim 11, characterized in that, The reverse flotation desilication specifically includes: mixing and grinding clay-type lithium ore and carbonate with a slurry concentration of 60-62wt% to obtain a slurry, and adding a modifier, activator and collector for reverse flotation desilication of the clay-type lithium ore to the slurry for roughing.

13. The use as described in claim 12, characterized in that, The amount of carbonate added is 480-520 g / t.

14. The use as described in claim 12, characterized in that, The slurry concentration is 20-22 wt%.

15. The use as described in claim 12, characterized in that, The pH value of the slurry is controlled to be 3-12 after the addition of the adjuster.

16. The use as described in claim 12, characterized in that, The amount of activator added is 200-220 g / t.

17. The use as described in claim 12, characterized in that, The amount of collector added for reverse flotation desilication of clay-type lithium ore is 800-850 g / t.

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