Method for recycling high-purity biotite through collecting agent based on rigid bisphenol fluorene skeleton
By using a rigid bisphenol fluorene skeleton collector in combination with a specific flotation process, the problem of poor selectivity of biotite in existing technologies has been solved, achieving efficient recovery of high-purity biotite and simplifying the process flow. This method is suitable for the preparation of high-end electronic materials and functional fillers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHANGCHUN GOLD RES INST
- Filing Date
- 2025-12-30
- Publication Date
- 2026-04-10
AI Technical Summary
Existing collectors have poor selectivity for biotite in minerals and lack the ability to target iron ions occupying specific sites in the octahedral layer of biotite, thus failing to extract high-purity biotite.
Using a rigid bisphenol fluorene framework as the collector, and through the design of a unique V-shaped spatial configuration and sulfur-oxygen dual active sites, the coordination geometry and electron cloud distribution of iron ions in the interlayer of biotite are precisely matched. Combined with a specific flotation process, efficient collection of biotite is achieved in weakly alkaline to neutral media.
It achieves efficient harvesting of biotite with a purity of over 98%, simplifies the process, reduces reagent consumption and wastewater treatment load, and avoids acid etching damage to the layered structure of biotite. It is suitable for the preparation of high-purity biotite for high-end electronic materials and functional fillers.
Smart Images
Figure CN121823602A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of hydrometallurgical technology, specifically to a method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework. Background Technology
[0002] Biotite, as an important member of layered silicate minerals, shows broad application prospects in high-end electronic materials, functional fillers, and insulating composite materials due to its unique insulation, thermal stability, and chemical inertness. However, the efficient recovery and high-purity preparation of biotite remains a prominent challenge in the mineral processing field. Natural biotite often occurs in dense association with gangue minerals such as quartz and feldspar, and its platy crystallization habit easily leads to mud formation and heterogeneous inclusions during the separation process, making it difficult for traditional flotation processes to achieve effective liberation and enrichment of single minerals.
[0003] Existing collector systems mostly rely on cationic collectors such as dodecylamine or xanthate-based thiocyanates. While the former has some collecting ability for silicate minerals, its selectivity is generally poor, especially when processing iron-bearing biotite varieties, where severe micellization tends to lead to increased iron impurities in the concentrate and decreased product whiteness. The latter, due to its limited ability to recognize aluminum / iron active sites on the biotite surface, is difficult to achieve efficient separation from associated minerals. More importantly, conventional reagent molecules lack the ability to target specific iron ions occupying certain sites in the octahedral layer of biotite, causing the concentrate purity to hover around 90-95% for a long time, failing to meet the stringent requirement of ≥98% purity for electronic-grade biotite raw materials. Summary of the Invention
[0004] In view of the technical problems existing in the background art, this application provides a method for recovering high-purity biotite based on a collector with a rigid bisphenol fluorene framework. It aims to solve the problems of poor selectivity of existing collectors for biotite in minerals, lack of directional action on iron ions occupying specific sites in the octahedral layer of biotite, and inability to extract high-purity biotite.
[0005] This application provides a method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework, comprising the following steps: S1. Grind the mineral sample containing biotite to obtain the ground sample; S2. Add water to the ground sample, stir, and prepare a slurry of a preset concentration; S3. Adjust the pH of the slurry, then add a collector and a frother with a rigid bisphenol fluorene framework, stir, and obtain a flotation mixture; S4. Perform flotation on the flotation mixture and collect the floating biotite to obtain high-purity biotite.
[0006] In the technical solution of this application embodiment, a specially structured collector combined with a specific extraction process for biotite from minerals achieves highly efficient collection of biotite from ores, resulting in high-purity biotite. This agent uses a rigid bisphenol fluorene ring as its core framework, replacing the traditional aliphatic long-chain structure to construct a unique V-shaped spatial configuration. The pre-organized cavity formed by phenolic bond bridging in its molecular structure can precisely match the coordination geometry and electron cloud distribution of iron ions in the interlayer domains of biotite, greatly enhancing the coordination binding ability and selectivity for target ions. This recovery process is simple, represents a green transformation, and can achieve highly efficient collection of biotite in weakly alkaline to neutral media, without the need for strong alkali or strong acid conditioning of the slurry environment. This reduces reagent consumption and wastewater treatment load, and avoids acid etching damage to the layered structure of biotite, laying a dual technical and economic foundation for the preparation of high-grade biotite products with a purity of over 98%.
[0007] In some embodiments, in step S3, the structural formula of the collector of the rigid bisphenol fluorene skeleton is as follows: .
[0008] In this embodiment, the harvesting agent uses a rigid bisphenol fluorene ring as its core framework, replacing the traditional aliphatic long-chain structure to construct a unique V-shaped spatial configuration. The pre-organized cavity formed by phenolic bond bridging in its molecular structure can precisely match the coordination geometry and electron cloud distribution of iron ions in the interlayer domain of biotite, greatly enhancing the coordination binding ability and selectivity for target ions. At the same time, the extended π-electron system of the bisphenol fluorene framework and the introduced thioamide group produce a synergistic effect, constructing sulfur-oxygen dual active sites at the molecular level. The sulfur atom preferentially forms a strong covalent bond with Fe(II) / Fe(III) ions in the biotite structure, while the oxygen atom generates electrostatic-coordination dual effects with the structural aluminum through lone pair electrons, achieving comprehensive locking of the key iron active sites in biotite.
[0009] In some embodiments, the mass ratio of the collector of the rigid bisphenol fluorene framework to the mineral sample containing biotite is 0.5~2 kg / t.
[0010] In this embodiment, adding a specific amount of collector enables the collector to fully extract biotite from the mineral sample.
[0011] In some embodiments, during step S3, the pH value is 7-11 during pH adjustment.
[0012] In this embodiment, by adjusting the slurry to weakly alkaline to neutral, the chemical environment of the reagent system is ensured, so that the collector of the rigid bisphenol fluorene skeleton exists in anionic form.
[0013] In some embodiments, in step S3, the foaming agent is MIBC, and the mass ratio of the foaming agent to the mineral sample containing biotite is 50 g / t.
[0014] In this embodiment, by adding a foaming agent, the surface tension of water is reduced, a stable foam layer is formed, and the adhesion and separation of hydrophobic mineral particles and bubbles are promoted.
[0015] In some embodiments, the stirring time in step S3 is 5 minutes.
[0016] In this embodiment, reagents are added and treated for a period of time to allow the reagents to fully react with the minerals, preparing for subsequent flotation.
[0017] In some embodiments, in step S1, the particle size of the ground sample is 95-99% by mass of 200 mesh or less.
[0018] In this embodiment, the target components in the mineral are exposed and fully contacted with the reagent by grinding the mineral sample to a specific fineness.
[0019] In some embodiments, in step S2, the stirring speed is 2000 r / min; the stirring time is 2 min.
[0020] In this embodiment, the slurry is thoroughly mixed and homogeneous by stirring.
[0021] In some embodiments, in step S2, the mass concentration of the slurry is 10-30%.
[0022] In this embodiment, the slurry is adjusted to a specific concentration to facilitate subsequent flotation.
[0023] In some embodiments, step S4 specifically includes the following steps: introducing air into the flotation mixture, skimming off bubbles every 5 seconds, adding water every 30 seconds, and repeating this process until the mineral processing is completed.
[0024] In this embodiment, biotite in the ore is separated through a flotation process.
[0025] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description
[0026] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.
[0027] Figure 1 The structural formula of the collector with the rigid bisphenol fluorene skeleton in Example 1 of this application is shown. Figure 2 This is a scanning electron microscope backscattering image of the biotite concentrate prepared in Example 1 of this application; Figure 3 This is an energy dispersive spectroscopy (EDS) analysis diagram of the biotite concentrate prepared in Example 1 of this application; Figure 4 The images shown are scanning electron microscope backscattering images and surface scanning analysis images of the biotite concentrate prepared in Example 1 of this application. Figure 5 The scanning electron microscope backscattering image and energy dispersive spectroscopy (EDS) analysis of the biotite concentrate prepared in Comparative Example 2 of this application are shown. Figure 6 This is a scanning electron microscope backscattering image of the biotite concentrate prepared in Comparative Example 5 of this application. Detailed Implementation
[0028] The embodiments of the technical solution of this application are described in detail below. These embodiments are only used to more clearly illustrate the technical solution of this application, and are therefore merely examples and should not be used to limit the scope of protection of this application.
[0029] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.
[0030] To address the problems of poor selectivity of existing collectors for biotite in minerals, lack of directional action on iron ions occupying specific sites in the octahedral layer of biotite, and inability to extract high-purity biotite, this application provides a method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework. By designing a collector with a special structure and combining it with a specific process for extracting biotite from minerals, a simple and efficient collection of biotite from ores is achieved, and the obtained biotite has high purity.
[0031] This collector uses a rigid bisphenol fluorene ring as its core framework. By replacing the traditional aliphatic long-chain structure, it constructs a unique V-shaped spatial configuration. The pre-organized cavity formed by phenolic bond bridging in its molecular structure can precisely match the coordination geometry and electron cloud distribution of iron ions in the interlayer domain of biotite, greatly enhancing the coordination binding ability and selectivity for target ions. At the same time, the extended π-electron system of bisphenol fluorene and the thioamide group synergistically construct a "sulfur-oxygen dual active site". In this site, sulfur atoms form strong covalent bonds with iron ions, while oxygen atoms assist in coordinating at sites such as aluminum and magnesium, strongly anchoring to the surface of biotite through a multidentate coordination mode. In addition, this rigid three-dimensional structure also produces a significant steric hindrance effect on the surface of gangue minerals, thus simultaneously achieving the triple functions of precise recognition, synergistic collection, and selective shielding at the molecular level.
[0032] Compared to traditional amine collectors: 1) The collector's molecular configuration is precisely customized. The rigid structure and pre-organized cavity of the bisphenol fluorene framework significantly improve the recognition accuracy of iron sites in biotite, effectively avoiding non-selective adsorption of gangue minerals such as quartz and feldspar; the active sites of the collector synergistically enhance the effect. The design of sulfur-oxygen bifunctional groups breaks through the limitations of single functional groups, and strengthens the specific binding with the iron structure of biotite through a multidentate coordination mode, providing a new solution for the efficient enrichment of iron-containing biotite, and laying a technical and economic foundation for the preparation of high-grade biotite products with a purity of over 98%; 2) The application of this agent significantly simplifies the overall process. Compared with traditional methods, this method, with its inherent high selectivity for biotite and natural inhibition of gangue minerals, significantly reduces or even eliminates the need for large amounts of modifiers required to suppress impurities in traditional processes. It can achieve efficient harvesting of biotite in weakly alkaline to neutral media without the need for strong alkali or strong acid conditioning of the slurry environment, thus reducing reagent consumption and wastewater treatment load, and avoiding acid erosion damage to the layered structure of biotite. This method not only reduces the overall reagent cost, but also simplifies the process configuration and improves the solid-liquid separation efficiency. It is particularly suitable for the efficient and clean recovery and preparation of high-purity (≥98%) biotite products from complex symbiotic minerals, demonstrating significant industrial application value and market promotion prospects.
[0033] This application provides a method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework, comprising the following steps: S1. Grind the mineral sample containing biotite to obtain the ground sample; S2. Add water to the ground sample, stir, and prepare a slurry of a preset concentration; S3. Adjust the pH of the slurry, then add a collector and a frother with a rigid bisphenol fluorene framework, stir, and obtain a flotation mixture; S4. Perform flotation on the flotation mixture and collect the floating biotite to obtain high-purity biotite.
[0034] In the technical solution of this application embodiment, a specially structured collector combined with a specific extraction process for biotite from minerals achieves highly efficient collection of biotite from ores, resulting in high-purity biotite. This agent uses a rigid bisphenol fluorene ring as its core framework, replacing the traditional aliphatic long-chain structure to construct a unique V-shaped spatial configuration. The pre-organized cavity formed by phenolic bond bridging in its molecular structure can precisely match the coordination geometry and electron cloud distribution of iron ions in the interlayer domains of biotite, greatly enhancing the coordination binding ability and selectivity for target ions. This recovery process is simple, represents a green transformation, and can achieve highly efficient collection of biotite in weakly alkaline to neutral media, without the need for strong alkali or strong acid conditioning of the slurry environment. This reduces reagent consumption and wastewater treatment load, and avoids acid etching damage to the layered structure of biotite, laying a dual technical and economic foundation for the preparation of high-grade biotite products with a purity of over 98%.
[0035] Furthermore, in some embodiments, in step S3, the structural formula of the collector with the rigid bisphenol fluorene skeleton is as follows: .
[0036] In the technical solution of this application embodiment, the harvesting agent uses a rigid bisphenol fluorene ring as its core skeleton, and constructs a unique V-shaped spatial configuration by replacing the traditional aliphatic long-chain structure. The pre-organized cavity formed by the phenolic bond bridging in its molecular structure can precisely match the coordination geometry and electron cloud distribution of iron ions in the interlayer domain of biotite, greatly enhancing the coordination binding ability and selectivity for target ions; at the same time, the extended π-electron system of the bisphenol fluorene skeleton and the introduced thioamide group produce a synergistic effect, constructing sulfur-oxygen dual active sites at the molecular level. The sulfur atom preferentially forms a strong covalent bond with Fe(II) / Fe(III) ions in the biotite structure, while the oxygen atom generates electrostatic-coordination dual effects with the structural aluminum through lone pair electrons, achieving all-round locking of the key iron active sites of biotite.
[0037] Furthermore, in some embodiments, the mass ratio of the collector of the rigid bisphenol fluorene framework to the mineral sample containing biotite is 0.5~2 kg / t.
[0038] In the technical solution of this application embodiment, adding a specific amount of collector can enable the collector to fully extract biotite from the mineral sample.
[0039] Furthermore, in some embodiments, in step S3, the pH value during pH adjustment is 7-11.
[0040] In the technical solution of this application embodiment, by adjusting the slurry to weakly alkaline to neutral, the chemical environment of the reagent system is guaranteed, so that the collector of the rigid bisphenol fluorene skeleton exists in anionic form.
[0041] Furthermore, in some embodiments, in step S3, the foaming agent is MIBC, and the mass ratio of the foaming agent to the mineral sample containing biotite is 50 g / t.
[0042] In the technical solution of this application embodiment, by adding a foaming agent, the surface tension of water is reduced, a stable foam layer is formed, and the adhesion and separation of hydrophobic mineral particles and bubbles are promoted.
[0043] Furthermore, in some embodiments, the stirring time in step S3 is 5 minutes.
[0044] In the technical solution of this application embodiment, a reagent is added for a period of time to allow the reagent to fully react with the mineral, in preparation for subsequent flotation.
[0045] Furthermore, in some embodiments, in step S1, the particle size of the ground sample is 95-99% below 200 mesh by mass.
[0046] In the technical solution of this application embodiment, by grinding the mineral sample to a specific fineness, the target component in the mineral is exposed and fully contacts the reagent.
[0047] Furthermore, in some embodiments, in step S2, the stirring speed is 2000 r / min; the stirring time is 2 min.
[0048] In the technical solution of this application embodiment, the slurry is thoroughly and evenly mixed by stirring.
[0049] Furthermore, in some embodiments, in step S2, the mass concentration of the slurry is 10-30%.
[0050] In the technical solution of this application embodiment, the slurry is adjusted to a specific concentration to facilitate subsequent flotation.
[0051] Furthermore, in some embodiments, step S4 specifically includes the following steps: introducing air into the flotation mixture, skimming off bubbles every 5 seconds, adding water every 30 seconds, and repeating this process until the mineral processing is completed.
[0052] In the technical solution of this application embodiment, biotite in ore is separated through a flotation process.
[0053] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.
[0054] Example 1 This embodiment provides a method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework, comprising the following steps: (1) Grind the mineral sample containing biotite to a particle size of less than 200 mesh with a mass ratio of 97% to obtain the ground sample; (2) Put 2 L of biotite-containing slurry (1000 g dry ore) into a flotation machine and stir it; wherein, the impeller speed of the flotation machine is set to 2000 r / min, and the slurry is adjusted for 2 minutes to obtain the slurry; (3) Adjust the pH of the above slurry to 9 and add 1 kg / t 矿 Collector with a rigid bisphenol fluorene skeleton, 50 g / t 矿 The MIBC was stirred for 5 minutes to obtain a flotation mixture; (4) Open the air valve to introduce air, scrape the bubbles every 5 seconds, add water every 30 seconds, repeat until the flotation is completed, and collect the biotite concentrate that floats to the surface; collect the biotite concentrate that floats to the surface at the cumulative flotation time of 2, 4, 6, 8 and 10 minutes respectively, dry the obtained biotite concentrate in an oven at 45℃, weigh it, and calculate the total recovery rate.
[0055] Among them, the relative content of biotite in the mineral sample containing biotite is 23%, and the total recovery rate of biotite is calculated by dividing the total mass of biotite concentrate by the total mass of raw ore containing biotite. The structural formula of the collector with a rigid bisphenol fluorene skeleton is as follows: Figure 1 As shown.
[0056] Figure 2 This is a scanning electron microscope backscattering image of the biotite concentrate prepared in this embodiment. Figure 3 This is an energy dispersive spectroscopy (EDS) analysis result of the biotite concentrate obtained in this embodiment.
[0057] pass Figure 2 As can be seen, the biotite concentrate obtained in this embodiment exhibits a complete and well-developed typical layered scaly structure with clear and complete crystal boundaries and no obvious signs of fragmentation or alteration. This indicates that the flotation process effectively recovers the biotite while maintaining its original crystal morphology. Figure 3 Quantitative analysis using medium-energy spectroscopy (MES) revealed that the main constituent elements of the sample were oxygen (55.10 wt%), silicon (19.89 wt%), iron (8.96 wt%), aluminum (6.59 wt%), and potassium (4.30 wt%). The elemental composition was similar to that of ideal biotite (K(Mg,Fe)3AlSi3O). 10The crystal chemical characteristics of (F, OH)2 are highly consistent, while the content of impurity elements is extremely low, which fully demonstrates that high-quality biotite concentrate with pure chemical composition and complete crystal structure can be obtained by using the rigid bisphenol fluorene skeleton collector described in this invention.
[0058] Figure 4 The images shown are scanning electron microscope backscattering images and surface scanning analysis images of the biotite concentrate prepared in this embodiment.
[0059] Backscattered images revealed that the biotite had a complete sheet-like structure and a smooth surface. The simultaneously acquired elemental distribution maps clearly showed that iron (Fe) and sulfur (S) had highly consistent spatial distribution characteristics on the biotite matrix surface. Their signal regions significantly overlapped and were evenly and continuously distributed. This key phenomenon confirmed that the sulfur atoms of the thioamide group in the collector molecule had a directional and stable chelation effect with the iron ions in the interlayer structure of biotite. This spatial correspondence of elemental distribution not only verified at the microscale that the rigid bisphenol fluorene skeleton collector achieved precise positioning of iron active sites through its pre-organized cavity, but also confirmed the successful implementation of its "sulfur-oxygen dual active site" design concept through the substantial formation of sulfur-iron bonds. Ultimately, a strong hydrophobic collector layer was constructed on the mineral surface, thus ensuring the high selectivity flotation of biotite and the achievement of 98% ultra-high purity at the molecular level.
[0060] Examples 2-3 and Comparative Examples 1-2 Examples 2-3 and Comparative Examples 1-2 respectively provide a method for recovering high-purity biotite based on a collector with a rigid bisphenol fluorene framework. The difference between Example 1 and Example 2 is that the amount of collector with the rigid bisphenol fluorene framework is different, as shown in Table 1. The other steps are roughly the same as in Example 1 and will not be described again here.
[0061] Table 1 shows the amount of collector, recovery rate, and purity of biotite in Examples 1-3 and Comparative Examples 1-2. Based on the data in Table 1, it can be seen that the dosage of the rigid bisphenol fluorene skeleton collector has a significant impact on the biotite separation effect: within a relatively wide dosage range of 0.5~2.0 kg / t, the biotite recovery rate steadily increases with the increase of reagent dosage (from 83% to 92%), and the concentrate purity remains consistently at an excellent level of 98%. This fully demonstrates that the collector can maintain high selectivity of its molecular recognition mechanism even under a wide operating window; however, when the dosage is too low (Comparative Example 1), the biotite surface is not completely covered. The presence of all active sites resulted in a significant decrease in recovery to 68% and a drop in purity to 91%. Notably, when the dosage was too high (Comparative Example 2), although the recovery further increased to 95%, the purity decreased significantly (94%). This indicates that excessive reagent may have triggered non-selective adsorption on some gangue minerals, thus confirming that the collector configuration recognition-co-coordination mechanism can only achieve the optimal balance between recovery and purity at appropriate dosages, providing guidance for the optimization of reagent formulations in industrial applications.
[0062] The scanning electron microscopy backscattering imaging and energy dispersive spectroscopy analysis results of the biotite concentrate sample obtained in Comparative Example 2 are as follows: Figure 5 As shown.
[0063] Depend on Figure 5 It can be observed that the abnormal accumulation of biotite concentrate particles and the decrease in concentrate purity to 94% in Comparative Example 2 are fundamentally caused by the dual effects of "non-selective adsorption" and "mechanical entrainment" resulting from excessive collector dosage. Energy dispersive spectroscopy (EDS) data provides crucial evidence for this: compared to the EDS of the concentrate in Example 1 (98% purity), the aluminum (Al) content in Comparative Example 2 sample abnormally increased to 20.72 wt%, the silicon (Si) content was 20.38 wt%, while the characteristic element iron (Fe) content significantly decreased to 2.74 wt%. This drastic change in elemental composition indicates that a large amount of aluminosilicate gangue minerals (such as feldspar and clay minerals) were mixed into the concentrate. This is because when an excessive amount of collector with a rigid bisphenol fluorene framework is added, the concentration of free reagent molecules in the solution becomes too high, exceeding its ability to specifically adsorb onto the iron active sites of biotite through the "configuration recognition" mechanism. These excess molecules break its inherent high selectivity, and through their thioamide groups, they interact with aluminum ions (Al) exposed on the surface of the gangue minerals. 3+Non-specific coordination with other cations can cause the surfaces of minerals such as feldspar, which should not otherwise float, to become hydrophobic. Simultaneously, excessive reagent can make the foam layer overly stable and viscous, making it easier for biotite flakes to accumulate. This physical environment significantly enhances the mechanical entrainment of fine gangue minerals that have already undergone monomeric dissociation, ultimately causing a large amount of impurities to be scraped off along with the biotite, resulting in a falsely high recovery rate but significantly degraded purity. This result also confirms that this novel collector can only exert its high selectivity advantage of "configuration recognition" at an appropriate dosage.
[0064] Examples 4-5 and Comparative Examples 3-5 Examples 4-5 and Comparative Examples 3-5 respectively provide a method for recovering high-purity biotite based on a collector with a rigid bisphenol fluorene framework. The difference from Example 1 is that the pH value of the slurry is different, as shown in Table 1. The other steps are roughly the same as in Example 1, and will not be repeated here.
[0065] Table 2 shows the pH value, biotite recovery rate, and purity of the slurry in Examples 1, 4-5, and Comparative Examples 3-5. Based on the data in Table 1, it can be seen that the rigid bisphenol fluorene skeleton collector described in this invention maintains excellent separation performance over a wide pH range (pH 7-11), with biotite recovery remaining stable between 85% and 91%, and concentrate purity consistently maintained at 98%. This demonstrates that the agent has good adaptability to pulp pH, and its configuration recognition-co-coordination mechanism is not significantly affected within this range. However, when the system is under strongly acidic conditions (pH=6), both the recovery rate (54%) and purity (63%) show a sharp drop, mainly due to the high concentration of H+. + It will protonate the thioamide groups of the collector molecule, destroying its coordination ability, and may also cause K in the biotite crystal structure. + H + Displacement causes the layered structure to break down and impurity ions to dissolve, both of which lead to the failure of selective adsorption. It is noteworthy that in a strongly alkaline environment (pH ≥ 12), although the recovery rate remains high (91%), the purity shows a downward trend, which is likely due to excess OH-. - It can form hydroxyl complexes with metal ions on the surface of gangue minerals. These complexes can then undergo non-selective adsorption with the collector. At the same time, excessively high alkalinity may also weaken the stereo shielding effect of the V-shaped cavity of the agent. Ultimately, this confirms that neutral to weakly alkaline conditions are the optimal process window for this high-performance collector to exert its molecular recognition advantages and simultaneously achieve high recovery rate and ultra-high purity.
[0066] Backscattered image of biotite concentrate obtained in Comparative Example 5, such as Figure 6 As shown.
[0067] Depend on Figure 6 The observable precipitation of large amounts of iron is fundamentally caused by the irreversible chemical corrosion of the biotite crystal structure by the strongly alkaline environment (pH=13). Under such high pH conditions, the high concentration of OH... - Ions strongly attack the aluminosilicate framework structure of biotite, particularly breaking the Fe-O bonds in the octahedral layer and the Si-O-Al bonds in the tetrahedral layer. This causes structural iron in the crystal lattice to be released and migrate to the mineral surface and fissures. These dissolved iron ions then undergo secondary hydrolysis and precipitation in a strongly alkaline environment, forming iron-containing hydroxyl complexes or oxides such as ferric hydroxide, which appear as bright white iron precipitates in backscattered images. This corrosion process not only destroys the integrity of the platy crystals of biotite but also introduces secondary iron impurities that are difficult to remove through physical sorting. This directly resulted in the concentrate purity in Comparative Example 5 dropping to 92%, and also confirms the crucial importance of controlling the flotation pH within the range of 7-11 for maintaining the structural stability of biotite and achieving high-purity purification.
[0068] Comparative Examples 6-10 Comparative Examples 6-10 provide methods for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework. The difference between these methods and Example 1 is the use of a different collector, as shown in Table 3. The other steps are largely the same as in Example 1 and will not be repeated here.
[0069] Table 3. Types of collectors, recovery rates, and purity of biotite in Examples 1 and Comparative Examples 6-10. As shown in Table 3, the rigid bisphenol fluorene framework collector described in this invention significantly outperforms traditional collectors in terms of biotite recovery (89%) and concentrate purity (98%). This significant difference stems from the unique molecular structure-activity relationship of this novel collector: the V-shaped pre-organized cavity formed by its rigid bisphenol fluorene framework accurately identifies the coordination environment of iron ions in the interlayer of biotite through geometric matching effect. At the same time, the sulfur-oxygen dual active sites constructed by the thioamide group and the framework π-electron system can achieve stable polydentate coordination with Fe(II) / Fe(III). This dual mechanism of configuration recognition and co-coordination not only enhances the specific adsorption intensity on the surface of the target mineral, but also effectively blocks the non-selective adsorption on gangue minerals such as quartz and feldspar through the stereo shielding effect, thereby achieving a breakthrough improvement in high recovery rate and ultra-high purity at the molecular level.
[0070] In summary, this application provides a method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework. By designing a collector with a special structure and combining it with a specific extraction process for biotite from minerals, a simple and efficient method for collecting biotite from ores is achieved, and the obtained biotite has high purity.
[0071] This collector uses a rigid bisphenol fluorene ring as its core framework. By replacing the traditional aliphatic long-chain structure, it constructs a unique V-shaped spatial configuration. The pre-organized cavity formed by phenolic bond bridging in its molecular structure can precisely match the coordination geometry and electron cloud distribution of iron ions in the interlayer domain of biotite, greatly enhancing the coordination binding ability and selectivity for target ions. At the same time, the extended π-electron system of bisphenol fluorene and the thioamide group synergistically construct a "sulfur-oxygen dual active site". In this site, sulfur atoms form strong covalent bonds with iron ions, while oxygen atoms assist in coordinating at sites such as aluminum and magnesium, strongly anchoring to the surface of biotite through a multidentate coordination mode. In addition, this rigid three-dimensional structure also produces a significant steric hindrance effect on the surface of gangue minerals, thus simultaneously achieving the triple functions of precise recognition, synergistic collection, and selective shielding at the molecular level.
[0072] Compared to traditional amine collectors: 1) The collector's molecular configuration is precisely customized. The rigid structure and pre-organized cavity of the bisphenol fluorene framework significantly improve the recognition accuracy of iron sites in biotite, effectively avoiding non-selective adsorption of gangue minerals such as quartz and feldspar; the active sites of the collector synergistically enhance the effect. The design of sulfur-oxygen bifunctional groups breaks through the limitations of single functional groups, and strengthens the specific binding with the iron structure of biotite through a multidentate coordination mode, providing a new solution for the efficient enrichment of iron-containing biotite, and laying a technical and economic foundation for the preparation of high-grade biotite products with a purity of over 98%; 2) The application of this agent significantly simplifies the overall process. Compared with traditional methods, this method, with its inherent high selectivity for biotite and natural inhibition of gangue minerals, significantly reduces or even eliminates the need for large amounts of modifiers required to suppress impurities in traditional processes. It can achieve efficient harvesting of biotite in weakly alkaline to neutral media without the need for strong alkali or strong acid conditioning of the slurry environment, thus reducing reagent consumption and wastewater treatment load, and avoiding acid erosion damage to the layered structure of biotite. This method not only reduces the overall reagent cost, but also simplifies the process configuration and improves the solid-liquid separation efficiency. It is particularly suitable for the efficient and clean recovery and preparation of high-purity (≥98%) biotite products from complex symbiotic minerals, demonstrating significant industrial application value and market promotion prospects.
[0073] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.
Claims
1. A method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework, characterized in that, Includes the following steps: S1. Grind the mineral sample containing biotite to obtain the ground sample; S2. Add water to the ground sample, stir, and prepare a slurry of a preset concentration; S3. Adjust the pH of the slurry, then add a collector and a frother with a rigid bisphenol fluorene framework, stir, and obtain a flotation mixture; S4. Perform flotation on the flotation mixture and collect the floating biotite to obtain high-purity biotite.
2. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S3, the structural formula of the collector with the rigid bisphenol fluorene skeleton is as follows: 。 3. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 2, characterized in that, The collector of the rigid bisphenol fluorene framework has a mass ratio of 0.5~2 kg / t to the mineral sample containing biotite.
4. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S3, the pH value during pH adjustment is 7~11.
5. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S3, the foaming agent is MIBC, and the mass ratio of the foaming agent to the mineral sample containing biotite is 50 g / t.
6. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S3, the stirring time is 5 minutes.
7. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S1, the particle size of the ground sample is 95-99% below 200 mesh by mass.
8. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S2, the stirring speed is 2000 r / min; the stirring time is 2 min.
9. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S2, the mass concentration of the slurry is 10-30%.
10. The method for recovering high-purity biotite using a collector based on a rigid bisphenol fluorene framework according to claim 1, characterized in that, In step S4, the flotation specifically includes the following steps: introducing air into the flotation mixture, skimming off bubbles every 5 seconds, adding water every 30 seconds, and repeating this process until the mineral processing is completed.