Beneficiation method for low-grade superfine silt containing lithium, rubidium and cesium

Abstract

The invention provides a beneficiation method of low-grade superfine silt containing lithium, rubidium and cesium, which comprises the following steps: adding sodium hexametaphosphate and a collecting agent JXL-01 into ore pulp, stirring, and roughing to obtain lepidolite rough concentrate and flotation tailings I; a collecting agent JXL-01 is added into the flotation tailings I for two times of scavenging, the 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 two concentrated middlings are sequentially returned to the upper layer for operation. And the collecting agent JXL-01 is obtained by mixing dodecylamine and sodium alpha-olefin sulfonate according to the mass ratio of 3: 2. According to the method, comprehensive utilization of the lithium-rubidium-cesium-containing superfine silt is achieved, the recovery effect of the lithium-rubidium-cesium-containing superfine silt is effectively improved, and the method is a novel mineral separation method which is stable, efficient, high in adaptability and high in recovery index and is suitable for application and popularization.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing, and in particular relates to a mineral processing method for low-grade ultrafine mud containing lithium, rubidium and cesium. Background Art

[0002] As one of the most important lithium resources, lepidolite holds an irreplaceable strategic position in the new energy industry. With the surge in global demand for lithium resources, lepidolite has become an important raw material for lithium extraction due to its abundant reserves and widespread distribution, especially in hard rock lithium mines. However, my country's lepidolite is characterized by a diverse mineral composition and complex intercalation characteristics. In particular, the intercalation particle size of lepidolite varies, and the ore crushing process easily produces a large number of fine lepidolite particles. These particles have low mass and kinetic energy, making them unable to effectively break through the energy barrier of the foam.

[0003] In order to obtain high-quality lepidolite concentrate, the traditional mineral processing method adopts the desludging flotation process to remove fine mineral particles and reduce the influence of fine mineral mud on the flotation of lepidolite. As a result, a large amount of fine lepidolite is lost with the fine mud. Rubidium and cesium often replace potassium atoms in the lepidolite lattice, which simultaneously causes the loss of rubidium and cesium metals. In addition, some studies adopt the full-mud direct flotation process, which adds large doses of sodium carbonate and sodium hydroxide to scrub the mineral surface to reduce the adsorption cover of fine mud on the mineral surface. However, it still does not effectively solve the problem of flotation recovery of fine lepidolite particles, resulting in the loss of fine lepidolite particles with the tailings, resulting in poor development and utilization of lepidolite and serious loss of lithium resources.

[0004] Ultrafine mud, due to its large specific surface area and high surface energy, is prone to slime capping during flotation, making the selective separation of lepidolite and gangue minerals difficult. Furthermore, traditional anionic collectors (such as sodium dodecyl sulfate) are poorly adapted to fine mud. As anionic surfactants, they can produce excessively viscous foam and excessive size, resulting in low flotation selectivity. The complex interfacial properties of fine mud also exacerbate foam stability issues, further reducing concentrate grade and recovery.

[0005] Therefore, there is an urgent need for a collector that can enhance the efficient separation of low-grade lepidolite and gangue minerals under near-neutral conditions to solve the above problems and realize the comprehensive utilization of lithium-rubidium-cesium fine mud resources. Summary of the Invention

[0006] The purpose of the present invention is to overcome the problems of difficulty in flotation recovery of low-grade lithium-rubidium-cesium ultrafine mud and poor separation effect of lepidolite from gangue minerals such as feldspar and quartz in the prior art, and to provide a beneficiation method for low-grade lithium-rubidium-cesium ultrafine mud with good separation effect, high screening index, good stability and strong adaptability, so as to realize the efficient development and utilization of lithium-rubidium-cesium ultrafine mud resources.

[0007] The present invention is achieved by a beneficiation method of low-grade lithium-rubidium-cesium mica ultrafine mud, comprising the following steps: (1) Sodium hexametaphosphate is added to the slurry; (2) Add collector JXL-01 to the slurry treated in step (1) and stir; (3) subjecting the slurry obtained in step (2) to rough separation of lepidolite to obtain lepidolite coarse concentrate and flotation tailings I; (4) The flotation tailings I obtained in step (3) 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 scavenging the flotation tailings I twice are: adding 100-200 g / t of collector JXL-01 to scavenging I and adding 100-200 g / t of collector JXL-01 to scavenging II; (5) The lepidolite coarse concentrate obtained in step (3) 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 coarse concentrate twice are as follows: 100-200 g / t of sodium hexametaphosphate as a regulating agent is added in beneficiation I, and 100-200 g / t of sodium hexametaphosphate is added in beneficiation II; Preferably, in step (1), the amount of sodium hexametaphosphate used is 400-600 g / t.

[0008] Preferably, in step (2), the amount of the collector JXL-01 is 500-1200 g / t, and the stirring time is 4-6 min.

[0009] Preferably, the particle size of the low-grade lithium-rubidium-cesium-containing ultrafine mud is less than 38 μm.

[0010] Preferably, the collector JXL-01 is obtained by mixing dodecylamine and sodium α-olefin sulfonate in a mass ratio of 3:2.

[0011] The present invention overcomes the shortcomings of the prior art and provides a beneficiation method for low-grade ultrafine mud containing lithium, rubidium and cesium, which has the following technical features: (1) The present invention adopts a combination of anionic and cationic collectors, which produce a synergistic adsorption effect on the surface of lithium rubidium cesium mica. Dodecylamine (R-NH3 + ) is adsorbed by electrostatic action, while sodium α-olefin sulfonate (R-SO3 - ) and Li on the mica surface + 、Al 3+ etc. form "R-SO3 - -M +-mineral surface" bridging model (M is a metal ion) improves the recovery rate of lepidolite particles; gangue minerals such as feldspar and quartz have weak adsorption of anion and cation combination collectors, and the inhibitor sodium hexametaphosphate is used to cover and shield the active sites of gangue minerals, further improving the selectivity of the combination collector.

[0012] (2) The present invention addresses the problem of large foam size and high viscosity of traditional collectors, and cleverly utilizes molecular design screening to improve the flotation index of ultrafine mud containing lithium, rubidium and cesium from the foam state. The dodecyl group of sodium dodecyl sulfonate is a saturated straight chain (C 12 H 25 -SO3 - The molecules are tightly packed, easily forming a rigid monolayer at the gas-liquid interface. This invention introduces steric hindrance and utilizes the curved structure of double bonds to disrupt the tight arrangement of alkyl chains, thereby reducing foam size and viscosity. The anionic surfactant sodium α-olefin sulfonate has a higher CMC value (approximately 11 mM) than sodium dodecyl sulfonate (approximately 8 mM), altering the surface tension of the slurry and delaying micelle formation, thereby reducing foam stability and shortening foam life. The collector JXL-01 used in this invention was developed through molecular design, computational screening, and flotation testing. Its composition and molecular branching structure are not previously disclosed or readily anticipated in the art.

[0013] Compared with the prior art, the advantages of the present invention are: ① The present invention improves the recovery rate of lepidolite in lithium-rubidium-cesium ultrafine mud under neutral conditions through the synergistic adsorption of anionic and cationic combined collectors, and strengthens the separation effect of lepidolite from other minerals.

[0014] ② The present invention improves the flotation foam state by calculating and screening the branched structure of the anion collector, solves the problem of poor separation effect caused by low collection capacity and poor selectivity of the traditional reagent system, improves the sorting efficiency of low-grade lithium, rubidium and cesium ultrafine mud, and improves the comprehensive utilization level of fine mud. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The figure is a process flow chart of the low-grade ultrafine mud containing lithium, rubidium and cesium according to the present invention. DETAILED DESCRIPTION

[0016] 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. Example 1

[0017] 300 g of octadecylamine and 200 g of sodium α-olefin sulfonate 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 or additives were required. After mixing evenly, the collector JXL-01 was obtained. Example 2

[0018] Fine mud is a fine particle product produced after the crushing, grinding, and classification of granite-type lepidolite ore. It contains 0.42% Li₂O, 0.15% Rb₂O, and 0.03% Cs₂O, with a particle size of less than 38 μm. Its primary mineral components are lepidolite, albite, plagioclase, potassium feldspar, and quartz, along with minor amounts of muscovite, sericite, apatite, beryl, and chlorite. Using traditional fine mud flotation technology, the lepidolite concentrate obtained has a Li₂O grade of 2.17% with a recovery rate of 58.36%; a Rb₂O grade of 0.62% with a recovery rate of 54.48%; and a Cs₂O grade of 0.15% with a recovery rate of 68.45%.

[0019] The low-grade lithium-rubidium-cesium ultrafine mud beneficiation method of the present invention is used for separation, and the separation steps are as follows: (1) Add 500g / t of sodium hexametaphosphate to the slurry; (2) Add 900 g / t of collector JXL-01 to the slurry treated in step (1), stir, and slurry for 5 minutes; (3) subjecting the slurry obtained in step (2) to rough separation of lepidolite to obtain lepidolite coarse concentrate and flotation tailings I; (4) The flotation tailings I obtained in step (3) 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 scavenging the flotation tailings I twice are: adding 200g / t of collector JXL-01 to scavenging I and adding 120g / t of collector JXL-01 to scavenging II; (5) The lepidolite concentrate obtained in step (3) is beneficiated twice to obtain lepidolite concentrate and two beneficiated intermediates, and the two beneficiated intermediates are returned to the previous operation in sequence; wherein the process conditions for beneficiating the lepidolite concentrate twice are as follows: sodium hexametaphosphate is added as the adjusting agent in beneficiation I. 160g / t, Concentrated II adds 100g / t of sodium hexametaphosphate; In the lepidolite concentrate obtained in this embodiment, the Li2O grade was 2.51%, the recovery rate was 65.32%, the Rb2O grade was 0.72%, the recovery rate was 60.58%, and the Cs2O grade was 0.19%, the recovery rate was 71.52%. Example 3

[0020] The fine mud is a fine particle product produced after the crushing, grinding, and classification of granite-type lepidolite ore. It contains 0.39% Li₂O, 0.16% Rb₂O, and 0.04% Cs₂O, with a particle size of less than 38 μm. Its main mineral components include lepidolite, quartz, albite, plagioclase, quartz, muscovite, kaolinite, apatite, calcite, chlorite, and topaz. Using traditional fine mud flotation technology, the lepidolite concentrate obtained has a Li₂O grade of 2.07% and a recovery rate of 57.81%; a Rb₂O grade of 0.65% and a recovery rate of 55.27%; and a Cs₂O grade of 0.17% and a recovery rate of 67.84%.

[0021] The low-grade lithium-rubidium-cesium ultrafine mud beneficiation method of the present invention is used for separation, and the separation steps are as follows: (1) Add 500g / t of sodium hexametaphosphate to the slurry; (2) Add 800 g / t of collector JXL-01 to the slurry treated in step (1), stir, and slurry for 6 minutes; (3) subjecting the slurry obtained in step (2) to rough separation of lepidolite to obtain lepidolite coarse concentrate and flotation tailings I; (4) The flotation tailings I obtained in step (3) 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 scavenging the flotation tailings I twice are: adding 180g / t of collector JXL-01 to scavenging I and adding 140g / t of collector JXL-01 to scavenging II; (5) The lepidolite concentrate obtained in step (3) is beneficiated twice to obtain lepidolite concentrate and two beneficiated intermediates, and the two beneficiated intermediates are returned to the previous operation in sequence; wherein the process conditions for beneficiating the lepidolite concentrate twice are as follows: sodium hexametaphosphate is added as the adjusting agent in beneficiation I. 150g / t, Concentrated II adds sodium hexametaphosphate 110g / t; In the lepidolite concentrate obtained in this embodiment, the Li2O grade was 2.47%, the recovery rate was 64.76%, the Rb2O grade was 0.75%, the recovery rate was 61.88%, and the Cs2O grade was 0.21%, the recovery rate was 70.24%. Example 4

[0022] The fine mud is a fine particle product produced after the crushing, grinding, and classification of granite-type lepidolite ore. It contains 0.44% Li₂O, 0.14% Rb₂O, and 0.03% Cs₂O, with a particle size of less than 38 μm. Its main mineral components include lepidolite, potassium feldspar, plagioclase, quartz, sericite, kaolinite, chlorite, topaz, corundum, and fluorite. Using traditional fine mud flotation technology, the lepidolite concentrate obtained has a Li₂O grade of 2.17% and a recovery rate of 59.27%; a Rb₂O grade of 0.63% and a recovery rate of 54.69%; and a Cs₂O grade of 0.15% and a recovery rate of 68.14%.

[0023] The low-grade lithium-rubidium-cesium ultrafine mud beneficiation method of the present invention is used for separation, and the separation steps are as follows: (1) Add 500g / t of sodium hexametaphosphate to the slurry; (2) Add 700 g / t of collector JXL-01 to the slurry treated in step (1), stir, and slurry for 4 minutes; (3) subjecting the slurry obtained in step (2) to rough separation of lepidolite to obtain lepidolite coarse concentrate and flotation tailings I; (4) The flotation tailings I obtained in step (3) 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 scavenging the flotation tailings I twice are: adding 200g / t of collector JXL-01 to scavenging I and adding 120g / t of collector JXL-01 to scavenging II; (5) The lepidolite concentrate obtained in step (3) is beneficiated twice to obtain lepidolite concentrate and two beneficiated intermediates, and the two beneficiated intermediates are returned to the previous operation in sequence; wherein the process conditions for beneficiating the lepidolite concentrate twice are as follows: sodium hexametaphosphate is added as the adjusting agent in beneficiation I. 190g / t, Concentrated II adds sodium hexametaphosphate 140g / t; In the lepidolite concentrate obtained in this embodiment, the Li2O grade was 2.62%, the recovery rate was 67.58%, the Rb2O grade was 0.78%, the recovery rate was 60.34%, and the Cs2O grade was 0.22%, the recovery rate was 70.19%.

[0024] The present invention provides a beneficiation method for low-grade lithium-, rubidium-, and cesium-containing ultrafine mud, belonging to the field of mineral processing technology. The method comprises the steps of stirring and slurry mixing, roughing, concentrating, and scavenging lepidolite. Fine-grained lepidolite is recovered using the anion-cation combined collector JXL-01, achieving comprehensive utilization of the lithium-, rubidium-, and cesium-containing ultrafine mud. The method of the present invention can effectively improve the recovery efficiency of the lithium-, rubidium-, and cesium-containing ultrafine mud. It is a new mineral processing method that is stable, efficient, highly adaptable, and has high recovery indicators, and is suitable for widespread application.

[0025] 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 beneficiation method for low-grade ultrafine mud containing lithium, rubidium and cesium, characterized in that: The following steps are involved: (1) Sodium hexametaphosphate is added to the slurry; (2) Add collector JXL-01 to the slurry treated in step (1) and stir; (3) subjecting the slurry obtained in step (2) to rough separation of lepidolite to obtain lepidolite coarse concentrate and flotation tailings I; (4) The flotation tailings I obtained in step (3) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are sequentially returned to the previous operation layer; The process conditions for the two scavenging of flotation tailings I are as follows: adding collector JXL-01 100-200g / t in scavenging I and adding collector JXL-01 100-200g / t in scavenging II; (5) The lepidolite coarse concentrate obtained in step (3) is beneficiated twice to obtain the lepidolite concentrate and two beneficiated middlings, and the two beneficiated middlings 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 as an adjusting agent in selection I, and adding 100-200 g / t of sodium hexametaphosphate in selection II.

2. The beneficiation method of a low-grade ultrafine mud containing lithium, rubidium and cesium according to claim 1, characterized in that: In step (1), the amount of sodium hexametaphosphate used is 400-600 g / t.

3. The beneficiation method of a low-grade lithium-rubidium-cesium ultrafine mud according to claim 1, characterized in that: In step (2), the amount of the collector JXL-01 is 500 to 1200 g / t, and the stirring time is 4 to 6 minutes.

4. The beneficiation method of a low-grade ultrafine mud containing lithium, rubidium and cesium according to claim 1, characterized in that: The particle size of the low-grade ultrafine mud containing lithium, rubidium and cesium is less than 38 μm.

5. The beneficiation method of low-grade lithium-rubidium-cesium ultrafine mud according to claim 1, characterized in that: The collector JXL-01 is obtained by mixing dodecylamine and sodium α-olefin sulfonate in a mass ratio of 3:2.

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