High-selectivity flotation method for micro-fine particle mica containing rubidium, cesium and lithium

Abstract

The invention provides a high-selectivity flotation method for micro-fine particle lepidolite containing rubidium and cesium, which comprises the following steps: levigating raw lepidolite ore, and desliming to obtain a flotation material and slime; adding sodium hexametaphosphate and a collecting agent HT8-01 into the flotation material, stirring, and roughing to obtain lepidolite rough concentrate and flotation tailings I; a collecting agent HT8-01 is added into the flotation tailings I for two times of scavenging, flotation tailings and two scavenging middlings are obtained, and the scavenging middlings are sequentially returned to the upper layer for operation; sodium hexametaphosphate is added into the lepidolite rough concentrate for two times of concentration, lepidolite concentrate and two concentrated middlings are obtained, and the concentrated middlings are sequentially returned to the upper layer for operation; the collecting agent HT8-01 is obtained by mixing octadecylamine and sodium dioctyl sulfosuccinate according to the mass ratio of 5: 3. According to the method, the separation effect of the rubidium-cesium-lithium-containing mica and gangue minerals such as quartz and feldspar is improved, the problems that foam is too stable, the viscosity is too high and the size is too large are solved, and high-selectivity separation of the micro-fine-particle rubidium-cesium-lithium-containing mica is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing, and in particular relates to a highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite. Background Art

[0002] Lithium is a crucial raw material for the new energy industry, and lepidolite is a key raw material for lithium extraction. Rubidium and cesium are rare alkali metals with unique physical and chemical properties. They play an irreplaceable role in high-tech, energy, military, and scientific research, and are hailed as "strategic metals of the 21st century." Lepidolite often coexists closely with minerals such as feldspar and quartz. Their similar chemical composition results in similar surface properties, making flotation separation difficult using traditional fatty acid collector systems. Rubidium and cesium often replace K atoms in the lepidolite lattice, resulting in the simultaneous loss of rubidium and cesium metals. Furthermore, feldspar is susceptible to weathering and alteration, breaking down into clay minerals that are easily crushed. During the crushing process, they are easily sludged. The resulting fine sludge has high surface energy and strong adsorption properties, which can cover mineral particles in the slurry with the fine sludge, reducing the difference in surface properties and increasing the difficulty of flotation separation of lepidolite from gangue.

[0003] The efficient development of low-grade lepidolite containing rubidium and cesium has become a crucial task in ensuring the supply of lithium resources to the market. However, low-grade lepidolite ores typically have higher feldspar content, more severe weathering, and finer particle size, requiring higher grinding fineness. This results in a higher concentration of fine mud in the ore pulp and a higher concentration of metal ions inevitably generated by the weathering process. This further exacerbates the accumulation of fine mud on the mineral surface. Furthermore, the finer particle size of the lepidolite increases the difficulty of flotation recovery. Breakthroughs in flotation technology are key to achieving the comprehensive utilization of low-grade lepidolite containing rubidium and cesium, particularly improvements in flotation collectors and production processes. Currently, lepidolite is often separated and purified under acidic conditions using cationic amine collectors. While these agents have strong collector capacity, they are sensitive to fine mud. Consequently, the flotation process requires the addition of washing and desludging processes, which can easily lead to the loss of fine lepidolite particles in the mud. The highly acidic flotation environment can cause severe corrosion to equipment and pipelines, posing significant safety risks and increasing wastewater treatment costs. In addition, amine collectors have a low freezing point and require heating and the introduction of hydrochloric acid or acetic acid to aid dissolution when taking the medicine. The amount of flotation foam is large, the "tank running" phenomenon is serious, the foam is stable and not easy to break, and the fluidity is poor.

[0004] To this end, for low-grade rubidium-cesium-containing difficult-to-select lithium mica ores, the slurry fluid environment is controlled and the mineral processing reagent system is optimized to solve the problems of fine mud cover adsorption, difficulty in flotation separation of lithium mica and gangue, and difficulty in recovering fine lithium mica. A mineral processing method for low-grade rubidium-cesium lithium mica ores with good stability, excellent separation effect, high screening index and strong adaptability is developed, which is of great significance to improving the utilization level of low-grade rubidium-cesium lithium mica resources and ensuring the healthy development of the lithium battery new energy industry. Summary of the Invention

[0005] The purpose of the present invention is to provide a flotation method for fine-grained rubidium-cesium-containing lepidolite with good stability, excellent separation effect, high screening index and strong adaptability, aiming to solve the problems existing in the existing fine-grained rubidium-cesium-containing lepidolite beneficiation technology, such as the difficulty in flotation separation of lepidolite and gangue, and the difficulty in recovering the fine-grained rubidium-cesium-containing lepidolite.

[0006] The present invention is achieved by a highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite, comprising the following steps:

[0007] (1) Grinding the raw lepidolite ore;

[0008] (2) desludging the lepidolite slurry obtained in step (1) to obtain flotation material and ore slime;

[0009] (3) adding sodium hexametaphosphate to the flotation material obtained in step (2) to promote dispersion;

[0010] (4) adding the collector HT8-01 to the slurry after stirring in step (3) and stirring;

[0011] (5) roughing the slurry stirred in step (4) to obtain lepidolite concentrate and flotation tailings I;

[0012] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are sequentially returned to the previous layer; wherein the process conditions for the flotation tailings scavenging twice are: adding 100-200 g / t of collector HT8-01 to scavenging I and adding 100-200 g / t of collector HT8-01 to scavenging II;

[0013] (7) The lepidolite crude concentrate obtained in step (5) is beneficiated twice to obtain a lepidolite concentrate and two beneficiated intermediates, and the two beneficiated intermediates are sequentially returned to the previous operation; wherein the process conditions for beneficiating the lepidolite crude concentrate twice are: adding 100-200 g / t of sodium hexametaphosphate in beneficiation I and adding 100-200 g / t of sodium hexametaphosphate in beneficiation II;

[0014] Preferably, in step (1), the grinding fineness is -0.074 mm and the content is 70-85%, and the mass concentration of the ore pulp obtained after grinding is 28-40%;

[0015] Preferably, in step (3), the amount of sodium hexametaphosphate used is 400-600 g / t.

[0016] Preferably, in step (4), the amount of the collector HT8-01 is 500-800 g / t, and the stirring time is 3-5 min.

[0017] Preferably, the collector HT8-01 is obtained by mixing octadecylamine and sodium dioctyl sulfosuccinate in a mass ratio of 5:3 and stirring uniformly.

[0018] The present invention overcomes the deficiencies of the prior art and provides a highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite, which has the following technical features:

[0019] (1) The present invention cleverly utilizes the anisotropy of fine-grained lepidolite crystals containing rubidium and cesium, and uses the anionic collector sodium dioctyl sulfonated succinate to react with the active metal atoms exposed after fine grinding, thereby strengthening the charge compensation effect on the lepidolite surface, further promoting the electrostatic adsorption of the cationic collector octadecylamine, forming a synergistic adsorption layer, and improving the flotation recovery rate; utilizing the amphiphilic solid group (-SO3 - and -COO - ) to strengthen the chelation between the collector and the surface of lepidolite, thereby improving the collection capacity of the agent; by utilizing the difference in active sites between the surfaces of lepidolite and gangue minerals such as feldspar and the sulfonic acid groups, the separation effect of lepidolite is further enhanced.

[0020] (2) The present invention adopts sodium dioctyl sulfonate as an anionic surfactant, which solves the problem of low flotation selectivity caused by excessive foam stability, high viscosity and large size of traditional fine-grained rubidium-cesium lithium mica collectors. The specific mode of action is to use the octyl side chain structure of sodium dioctyl sulfonate to replace the linear straight chain to form a low-elasticity liquid film, accelerate the merging of small bubbles into large bubbles and their rupture, and reduce the foam size; the steric hindrance of the side chain octyl destroys the close arrangement of molecules at the gas-liquid interface, reduces the van der Waals force interaction in the liquid film, and thus reduces the foam viscosity; the collector HT8-01 used in the present invention is obtained through molecular structure design and a large number of flotation tests. Its reagent components and proportions have not been disclosed and are not easy to be imagined in the field of this technology.

[0021] Compared with the prior art, the advantages of the present invention are:

[0022] ① The present invention solves the problem of low selectivity of fine-grained lepidolite containing rubidium and cesium, improves the quality of lepidolite concentrate, and simultaneously improves the recovery rate of lepidolite.

[0023] ② The present invention solves the problems of excessive foam, excessive viscosity and excessive size in traditional pharmaceutical systems, and improves the sorting efficiency of lepidolite. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The present invention is a flow chart of the steps of the highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0026] Example 1

[0027] 500 g of octadecylamine and 300 g of sodium dioctyl sulfosuccinate were mixed and prepared. The mixing process was carried out at room temperature and pressure. A beaker was used as a container and a linkage stirrer was used for stirring (stirring time was 30 min). No other auxiliary facilities and additives were required. After mixing evenly, the collector HT8-01 was obtained.

[0028] Example 2

[0029] The selected ore is a granite-type lepidolite ore with a raw ore content of 0.45% Li₂O, 0.19% Rb₂O, and 0.04% Cs₂O. The ore's primary mineral components are lepidolite, albite, plagioclase, quartz, muscovite, biotite, kaolinite, apatite, beryl, and illite. The lepidolite is fine-grained and exhibits a high degree of weathering and alteration. Using a traditional lepidolite flotation process, the lepidolite concentrate obtained has a Li₂O grade of 2.35% with a recovery rate of 77.84%; a Rb₂O grade of 0.72% with a recovery rate of 75.44%; and a Cs₂O grade of 0.21% with a recovery rate of 76.25%.

[0030] The highly selective flotation method of the present invention for separating fine particles of rubidium-cesium lepidolite is used, and the separation steps are as follows:

[0031] (1) Grind the raw lepidolite ore to a grinding fineness of -0.074 mm and a content of 83%. The ore pulp mass concentration after grinding is 34%;

[0032] (2) desludging the lepidolite slurry obtained in step (1) to obtain flotation material and ore slime;

[0033] (3) adding 400 g / t of sodium hexametaphosphate to the flotation material obtained in step (2) to promote dispersion;

[0034] (4) The slurry after stirring in step (3) was added with a collector HT8-01 500g / t, stirred, and stirred for 5min;

[0035] (5) roughing the slurry stirred in step (4) to obtain lepidolite concentrate and flotation tailings I;

[0036] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are sequentially returned to the previous layer; wherein the process conditions for the two scavenging of the flotation tailings are: adding 200g / t of collector HT8-01 to scavenging I and adding 100g / t of collector HT8-01 to scavenging II;

[0037] (7) The lepidolite crude concentrate obtained in step (5) is beneficiated twice to obtain a lepidolite concentrate and two beneficiated intermediates, and the two beneficiated intermediates are sequentially returned to the previous operation; wherein the process conditions for beneficiating the lepidolite crude concentrate twice are: adding 200 g / t of sodium hexametaphosphate to beneficiation I and adding 100 g / t of sodium hexametaphosphate to beneficiation II;

[0038] In the lepidolite concentrate obtained in this embodiment, the Li2O grade was 2.67% and the recovery rate was 81.79%; the Rb2O grade was 0.93% and the recovery rate was 80.21%; and the Cs2O grade was 0.28% and the recovery rate was 80.37%.

[0039] Example 3

[0040] The selected ore contains 0.41% Li₂O, 0.21% Rb₂O, and 0.05% Cs₂O. The ore's main mineral components include lepidolite, potassium feldspar, plagioclase, petalite, quartz, biotite, kaolinite, chlorite, montmorillonite, topaz, fluorite, and garnet. The ore occurs primarily in massive structures, with lepidolite and feldspar distributed as aggregates and finely embedded. Albite and sericite are severely weathered and altered, with clay minerals replacing the ore margins, resulting in a high degree of muddiing. Using conventional lepidolite flotation technology, the lepidolite concentrate obtained has a Li₂O grade of 2.32% with a recovery rate of 78.02%; a Rb₂O grade of 0.71% with a recovery rate of 74.72%; and a Cs₂O grade of 0.20% with a recovery rate of 76.87%.

[0041] The highly selective flotation method of the present invention for separating fine particles of rubidium-cesium lepidolite is used, and the separation steps are as follows:

[0042] (1) Grind the raw lepidolite ore to a grinding fineness of -0.074 mm and a content of 81%. The ore pulp mass concentration after grinding is 31%;

[0043] (2) desludging the lepidolite slurry obtained in step (1) to obtain flotation material and ore slime;

[0044] (3) adding 500 g / t of sodium hexametaphosphate to the flotation material obtained in step (2) to promote dispersion;

[0045] (4) The slurry after stirring in step (3) was added with a collector HT8-01 700g / t, stirred, and stirred for 4min;

[0046] (5) roughing the slurry stirred in step (4) to obtain lepidolite concentrate and flotation tailings I;

[0047] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are sequentially returned to the previous layer; wherein the process conditions for the flotation tailings scavenging twice are: adding 150g / t of collector HT8-01 to scavenging I and adding 100g / t of collector HT8-01 to scavenging II;

[0048] (7) The lepidolite crude concentrate obtained in step (5) is beneficiated twice to obtain a lepidolite concentrate and two beneficiated intermediates, and the two beneficiated intermediates are sequentially returned to the previous operation; wherein the process conditions for beneficiating the lepidolite crude concentrate twice are: 150 g / t of sodium hexametaphosphate is added in beneficiation I, and 100 g / t of sodium hexametaphosphate is added in beneficiation II;

[0049] In the lepidolite concentrate obtained in this embodiment, the Li2O grade was 2.61% and the recovery rate was 81.29%; the Rb2O grade was 0.89% and the recovery rate was 80.52%; and the Cs2O grade was 0.27% and the recovery rate was 80.62%.

[0050] Example 4

[0051] The selected ore contained 0.46% Li₂O, 0.22% Rb₂O, and 0.04% Cs₂O. The ore's primary mineral components include lepidolite, potassium feldspar, plagioclase, pyroxene, quartz, muscovite, sericite, kaolinite, chlorite, topaz, and fluorite. The lepidolite and feldspar are distributed as aggregates with fine-grained dispersal. The ore is highly weathered and heavily argillized, with a significant presence of yellow clay minerals, primarily weathering products of the primary ore body. Using a traditional lepidolite flotation process, the lepidolite concentrate obtained had a Li₂O grade of 2.35% with a recovery rate of 77.63%; a Rb₂O grade of 0.74% with a recovery rate of 74.29%; and a Cs₂O grade of 0.19% with a recovery rate of 76.41%.

[0052] The highly selective flotation method of the present invention for separating fine particles of rubidium-cesium lepidolite is used, and the separation steps are as follows:

[0053] (1) Grind the raw lepidolite ore to a grinding fineness of -0.074 mm and a content of 84%. The ore pulp mass concentration after grinding is 32%;

[0054] (2) desludging the lepidolite slurry obtained in step (1) to obtain flotation material and ore slime;

[0055] (3) adding 600 g / t of sodium hexametaphosphate to the flotation material obtained in step (2) to promote dispersion;

[0056] (4) The slurry after stirring in step (3) was added with a collector HT8-01 800g / t, stirred, and stirred for 5min;

[0057] (5) roughing the slurry stirred in step (4) to obtain lepidolite concentrate and flotation tailings I;

[0058] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are sequentially returned to the previous layer; wherein the process conditions for the two scavenging of the flotation tailings are: adding 200g / t of collector HT8-01 to scavenging I and adding 150g / t of collector HT8-01 to scavenging II;

[0059] (7) The lepidolite crude concentrate obtained in step (5) is beneficiated twice to obtain a lepidolite concentrate and two beneficiated middlings, and the two beneficiated middlings are sequentially returned to the previous operation; wherein the process conditions for beneficiating the lepidolite crude concentrate twice are: adding 200 g / t of sodium hexametaphosphate in beneficiation I and adding 150 g / t of sodium hexametaphosphate in beneficiation II;

[0060] In the lepidolite concentrate obtained in this embodiment, the Li2O grade was 2.71% and the recovery rate was 81.04%; the Rb2O grade was 0.83% and the recovery rate was 79.89%; and the Cs2O grade was 0.29% and the recovery rate was 81.28%.

[0061] The present invention provides a beneficiation method for low-grade lepidolite containing rubidium and cesium, belonging to the field of mineral processing technology. The method comprises the following steps: grinding the raw ore, stirring and slurrying, and flotation. The flotation process improves the separation of lepidolite from gangue minerals such as quartz and feldspar through the selective adsorption of the collector HT8-01 on the lepidolite surface. It also effectively solves the problems of excessive foam stability, excessive viscosity, and excessive size, achieving highly selective separation of fine-grained lepidolite containing rubidium and cesium. The present invention is a new mineral processing method with excellent stability, excellent separation effect, high separation index, and strong adaptability, and is suitable for promotion and application.

[0062] In the above embodiments, matters not described in detail in this specification are well known to those skilled in the art. The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A highly selective flotation method for fine particles of rubidium-cesium-containing lepidolite, characterized in that: The following steps are involved: (1) Grinding the raw lepidolite ore; (2) desludging the lepidolite slurry obtained in step (1) to obtain flotation material and ore slime; (3) adding sodium hexametaphosphate to the flotation material obtained in step (2) to promote dispersion; (4) adding the collector HT8-01 to the slurry after stirring in step (3) and stirring; (5) roughing the slurry stirred in step (4) to obtain lepidolite concentrate and flotation tailings I; (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are returned to the previous operation in sequence; The process conditions for the two scavenging of flotation tailings are as follows: adding 100-200g / t of collector HT8-01 in scavenging I and 100-200g / t of collector HT8-01 in scavenging II; (7) The lepidolite coarse concentrate obtained in step (5) is beneficiated twice to obtain the lepidolite concentrate and two beneficiated intermediates, and the two beneficiated intermediates are returned to the previous operation in sequence; The process conditions for the two-time selection of lepidolite coarse concentrate are as follows: adding 100-200 g / t of sodium hexametaphosphate in selection I and adding 100-200 g / t of sodium hexametaphosphate in selection II.

2. A highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite according to claim 1, characterized in that: In step (1), the grinding fineness is -0.074 mm and the content is 70-85%, and the mass concentration of the ore pulp obtained after grinding is 28-40%.

3. A highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite according to claim 1, characterized in that: In step (3), the amount of sodium hexametaphosphate used is 400-600 g / t.

4. A highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite according to claim 1, characterized in that: In step (4), the amount of the collector HT8-01 is 500-800 g / t, and the stirring time is 3-5 min.

5. A highly selective flotation method for fine-grained rubidium-cesium-containing lepidolite according to claim 1, characterized in that: The collector HT8-01 is obtained by mixing octadecylamine and sodium dioctyl sulfosuccinate in a mass ratio of 5:3 and stirring the mixture evenly.

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