Asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings

Abstract

The present invention discloses an asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings, belonging to the field of mineral processing technology. The method involves flotating the fluorite tailings, after slurrying, using a fatty acid collector under alkaline conditions of pH ≤ 10, to obtain a high-fluorine beryllium concentrate and tailings I. The high-fluorine beryllium concentrate is then flotated using a beryllium mineral depressant and a fluorite collector, to obtain a fluorite concentrate and tailings, which is the beryllium concentrate I. The tailings I is then flotated using a beryllium mineral depressant and a silicate depressant under alkaline conditions of pH > 10, to obtain a beryllium concentrate II. This method achieves a comprehensive recovery rate of BeO from fluorite tailings exceeding 70%, and features a short process, low cost, and simple operation, effectively achieving the efficient and comprehensive recovery of beryllium resources from fluorite tailings.

Description

Technical Field

[0001] The invention relates to a beryllium-containing mineral beneficiation method, in particular to an asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings, and belongs to the technical field of mineral processing. Background Art

[0002] As a key non-renewable resource, beryllium is indispensable to a country's industrial development and scientific and technological progress. For example, in aerospace, beryllium is used to manufacture lightweight, high-strength structural components, enhancing aircraft performance. In the nuclear industry, beryllium serves as a neutron moderator and reflector material, crucial for the safe operation of nuclear reactors. Furthermore, metallic beryllium and its compounds are widely used in the electronics industry, such as in the manufacture of X-ray screens and neutron detectors, playing a vital role in improving the performance and quality of electronic products. Summary of the Invention

[0003] In view of the difficulty in comprehensive resource recovery of beryllium-containing minerals in fluorite flotation tailings in the prior art, the beryllium concentrate obtained by re-flotation enrichment of fluorite flotation tailings has low grade and low recovery rate, and the selectivity of conventional reverse flotation is poor, resulting in serious waste of beryllium resources. The purpose of the present invention is to provide an asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings. The method adopts the "asynchronous flotation" mineral processing idea, divides two types of beryllium-containing minerals with good floatability and poor floatability in fluorite tailings into two parts, and efficiently floats and enriches them under different conditions, thereby realizing efficient flotation enrichment and comprehensive recovery of multiple beryllium-containing minerals in fluorite tailings. The method has a short process flow, low energy consumption, and low cost, meeting industrial production requirements.

[0004] In order to achieve the above technical objectives, the present invention provides an asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings, the method comprising the following steps:

[0005] 1) After slurrying, the fluorite tailings are first subjected to flotation I using a fatty acid collector under alkaline conditions of pH ≤ 10 to obtain high-fluorine beryllium rough concentrate and tailings I;

[0006] 2) flotation II of the high-fluorine beryllium rough concentrate using a beryllium mineral depressant and a fluorite collector to obtain fluorite concentrate and tailings, wherein the tailings are beryllium concentrate I;

[0007] 3) The tailings I are subjected to flotation III using a beryllium mineral collector and a silicate inhibitor under alkaline conditions of pH>10 to obtain beryllium concentrate II.

[0008] The technical solution of the present invention is based on the mineral composition and distribution characteristics of fluorite tailings. The key lies in adopting the "asynchronous flotation" beneficiation idea to separate the beryllium minerals with selectivity in the fluorite tailings into two parts and enrich them separately, which greatly improves the comprehensive recovery rate of beryllium and truly realizes the efficient resource utilization of beryllium-containing minerals in fluorite tailings. More specifically, a conventional fatty acid collector is first used to carry out preliminary flotation separation under low alkalinity conditions. It mainly floats beryllium-containing minerals with good floatability and high flotation rate mixed with fluorite to obtain high-fluorine beryllium rough concentrate, and the high-fluorine beryllium rough concentrate is removed from fluorite by reverse flotation to obtain a beryllium concentrate product. The tailings separated by preliminary flotation mainly contain beryllium-containing minerals with poor floatability, and further adopt efficient beryllium mineral collectors and silicate inhibitors to achieve selective separation and enhanced flotation recovery of beryllium-containing minerals with poor floatability under high alkalinity conditions to obtain a beryllium concentrate product. This method not only avoids the problems of large amount of water glass consumption and low efficiency of subsequent beryllium selection caused by the "strong pulling and strong pressing" method used in the existing technology to remove fluorite first and then select beryllium, but also greatly improves the comprehensive recovery rate of beryllium and truly realizes the efficient resource utilization of beryllium-containing minerals in fluorite tailings.

[0009] As a preferred embodiment, the beryllium-containing mineral in the fluorite tailings includes at least one of chrysoberyl, ferromanganese, heliotropite, ferromanganese, beryl, beryl, and taaffeite. The present invention is particularly suitable for fluorite tailings containing multiple beryllium-containing minerals of varying flotation difficulty.

[0010] As a preferred embodiment, the gangue minerals in the fluorite tailings include at least one of silicate gangue minerals, calcium-containing gangue minerals, and clay minerals. Silicate gangue minerals include muscovite (sericite) and sodium pearl mica. Calcium-containing gangue minerals include fluorite and calcite. Clay minerals include chlorite and lithophile.

[0011] As a preferred solution, the mass content of BeO in the fluorite tailings is ≥0.26%.

[0012] As a preferred solution, the fluorite tailings are slurried to a concentration of 30-55 wt.% and a pH of 8.0-10.0. Adjusting the slurry pH to a weakly alkaline environment facilitates the coordination of the carboxyl functional groups of the fatty acid collector with the active sites of the metal calcium ions on the fluorite surface, forming a hydrophobic precipitate or a double-layer collector film. Sodium carbonate can also negatively charge the surface of the mineral particles, promoting slurry dispersion. Sodium carbonate can be used as the pH adjuster.

[0013] As a preferred embodiment, the fatty acid collector includes at least one of oleic acid, linoleic acid, linolenic acid, palmitic acid, naphthenic acid, tall oil, ricinoleic acid, and 731 oxidized paraffin soap. Preferred fatty acid collectors are conventional collectors used in fluorite flotation, and some beryllium minerals in fluorite tailings are also relatively sensitive to fatty acid collectors. The present invention utilizes a fatty acid collector to achieve mixed flotation recovery of the highly floatable and high-floatation-rate beryllium minerals with the fluorite through a "float as much as possible" strategy.

[0014] As a preferred option, flotation I includes one roughing round, one to three cleaning rounds, and one to two scavenging rounds. As a preferred option, the roughing round uses a fatty acid collector at a rate of 100-300 g / t relative to the raw ore; the scavenging round uses a fatty acid collector at a rate of 50-100 g / t relative to the raw ore; and the cleaning round is a blank cleaning round. The flotation I process of the present invention does not require the addition of any inhibitors, and does not employ a "strong pull and strong pressure" approach to preferentially remove calcium-containing gangue minerals such as fluorite and calcite. Instead, it adopts a "float as much as possible" strategy, allowing some beryllium-containing minerals with good floatability and high flotation rates to float along with the fluorite, forming a mixed concentrate of fluorite and beryllium, which is then further separated. Compared to beryllium-containing minerals and silicate gangue minerals, which have similar floatability, the surface physical and chemical properties of fluorite and beryllium-containing minerals differ significantly, making them easier to efficiently separate by flotation. Under the optimal flotation reagent system, the mass content of CaF2 in the recovered high-fluorine beryllium rough concentrate is ≥50%.

[0015] As a preferred embodiment, the beryllium mineral inhibitor is formed by reacting components including sulfuric acid, water glass, and starch. Preferred starches include at least one of tuber starch, bean starch, and cereal starch, specifically sweet potato starch, corn starch, and potato starch. As a more preferred embodiment, the beryllium mineral inhibitor is formed by reacting sulfuric acid, water glass, and starch in a mass ratio of (1-4):(1-10):1. Sulfuric acid etches the surface of beryllium-containing minerals, destroying Al-O bonds in their lattice structure and promoting chelation and hydrogen bonding between starch hydroxyl groups and active aluminum and beryllium metal particles on the beryllium mineral surface. Furthermore, sulfuric acid promotes the formation of hydrophilic silicate colloids by water glass, which adsorbs on the beryllium mineral surface, thereby selectively inhibiting the beryllium mineral.

[0016] As a preferred solution, the fluorite collector includes a fatty acid collector and a cationic collector.

[0017] The cationic collector includes at least one of a fatty amine, an amide, an etheramine, and a quaternary ammonium salt, such as laurylamine, coconut amine, polyetheramine, and cetyltrimethylammonium bromide. The fatty acid collector includes at least one of oleic acid, linoleic acid, linolenic acid, palmitic acid, naphthenic acid, tall oil, ricinoleic acid, and 731 oxidized paraffin soap. As a preferred embodiment, the fluorite collector comprises a fatty acid collector and a cationic collector in a mass ratio of (1-8):1. The combination of the fatty acid collector and the cationic collector, acting as an anionic collector and a cationic collector, respectively, exhibits a significant synergistic effect on the selective capture of fluorite minerals. In particular, the introduction of the cationic collector enhances the flotation removal of siliceous gangue from high-fluorine beryllium crude concentrate, improving the separation efficiency of fluorite and beryllium-containing minerals.

[0018] As a preferred embodiment, flotation II includes one roughing operation, one to two cleaning operations, and one to two scavenging operations. As a preferred embodiment, the roughing agent system is as follows: the beryllium mineral depressant is added in an amount of 40-80 g / t relative to the original ore, and the fluorite collector is added in an amount of 30-60 g / t relative to the original ore; the cleaning agent system is: only the beryllium mineral depressant is added, following a step-by-step decreasing principle; the scavenging agent system is: only the fluorite collector is added, following a step-by-step decreasing principle, wherein the mass of the beryllium mineral depressant is measured according to the mass of starch, and the mass of the fluorite collector is measured according to the mass of fatty acids. Based on the similar flotation properties of fluorite minerals and beryllium-containing minerals in high-fluorine beryllium rough concentrate, on the one hand, the present invention uses a special beryllium mineral depressant composed of sulfuric acid, water glass and starch, which can enhance the hydrophilic modification of the surface of the beryllium-containing mineral. On the other hand, the present invention optimizes conventional fatty acid collectors and improves their selectivity for fluorite by introducing cationic collectors. Through the preferred scheme, fluorite concentrate products and beryllium concentrate I with a BeO mass content of ≥2.0% can be obtained.

[0019] As a preferred embodiment, the beryllium mineral collector comprises a fatty acid collector and a C5-C8 alkyl hydroxamic acid collector. The alkyl chain contained in the alkyl hydroxamic acid collector can be either linear or branched. As a further preferred embodiment, the mass ratio of the fatty acid collector to the C5-C8 alkyl hydroxamic acid collector is (1-4):1. The two collectors complement each other, improving capture capacity and selectivity. Their combined use significantly reduces the critical micelle concentration and enhances the co-adsorption strength of the collectors on the mineral surface, enabling efficient and simultaneous recovery of multiple beryllium-containing minerals. Further preferred fatty acid collectors include at least one of oleic acid, linoleic acid, linolenic acid, palmitic acid, naphthenic acid, tall oil, ricinoleic acid, and 731 oxidized paraffin soap.

[0020] As a more preferred solution, the silicate inhibitor includes at least one of water glass, sodium sulfide, tartaric acid, and sodium hexametaphosphate.

[0021] As a preferred embodiment, flotation III includes one roughing operation, two to three cleaning operations, and one to two scavenging operations. As a more preferred embodiment, the roughing agent system includes a beryllium collector at a rate of 300-600 g / t and a silicate inhibitor at a rate of 40-200 g / t relative to the raw ore; the cleaning agent system includes the addition of only silicate inhibitors, following a step-by-step reduction principle; and the scavenging agent system includes the addition of only beryllium collectors, following a step-by-step reduction principle, where the mass of beryllium collector is measured by the mass of fatty acids. During flotation III, the pH is further maintained at a pH >10 and ≤12.0. These high alkalinity conditions are more conducive to the flotation recovery of difficult-to-float beryllium-containing minerals. Furthermore, most metal ions are precipitated as hydroxides under these conditions, effectively preventing the non-selective activation of silicate gangue minerals such as muscovite by metal ions in the slurry. By optimizing the flotation collector and controlling the pH conditions, beryllium concentrate product II with a BeO mass content ≥1.0% can be obtained.

[0022] The middlings from the concentration and scavenging of the present invention are returned to the previous flotation operation in sequence.

[0023] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects:

[0024] (1) The technical solution of the present invention applies the beneficiation concept of "asynchronous flotation" to the flotation recovery of beryllium-containing minerals in fluorite tailings. The beryllium resources with selectivity in fluorite tailings are divided into two parts according to the difference in flotation ability and are flotated and enriched separately. This can achieve efficient and comprehensive recovery of various beryllium-containing minerals, optimize the concentrate product structure and make it more reasonable, and achieve a comprehensive recovery rate of BeO of more than 70%.

[0025] (2) The technical solution of the present invention is aimed at the separation of fluorite and beryllium-containing minerals in high-fluorine beryllium crude concentrate and the recovery of beryllium-containing minerals with poor flotation properties. Different flotation conditions and reagent systems are used respectively to achieve the flotation enrichment of various beryllium-containing minerals with different floatabilities and different flotation rates. The process is simple and efficient, providing high-quality and qualified beryllium concentrate raw materials for subsequent beryllium smelting.

[0026] (3) The technical solution of the present invention has a short process, low cost and simple operation, and has important guiding significance for the efficient development and utilization of co-existing beryllium ore resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a process flow chart of the present invention.

[0028] Figure 2 This is a mineral composition analysis of a fluorite tailings in Hunan.

[0029] Figure 3 This is a process flow chart of Comparative Example 1.

[0030] Figure 4 This is the process flow chart of Comparative Example 2. DETAILED DESCRIPTION

[0031] The following examples are provided to further illustrate the present invention in detail, but are not intended to limit the scope of protection of the claims of the present invention.

[0032] Taking a fluorite tailing in Hunan as the research object, this paper explores the comprehensive recovery method of beryllium-containing minerals in fluorite tailings. The following is the element content distribution of the fluorite flotation tailings, among which the CaF2 content is 12.48% and the BeO content is 0.33%. Its main mineral phases are fluorite, quartz, sodium pearl mica, muscovite, calcite, chlorite and feldspar (such as Figure 2 Beryllium-containing minerals primarily occur in the form of various minerals, including chrysoberyl, hydroxyl beryllite, beryl, and bluestone. A small amount of beryllium is also dispersed within sodium pearl mica. The particle size analysis results of the samples are shown in Table 1 below. As can be seen, the beryllium-containing minerals are embedded in fine-grained particles, with the -0.074 mm size accounting for 80.21%. Nearly half of the BeO is distributed in the -0.043 mm size fraction, with a BeO grade of 0.40%. Overall, comprehensive recovery of beryllium from this fluorite tailings presents significant challenges.

[0033]

[0034] Example 1

[0035] 1 g of sulfuric acid, 5 g of water glass and 1 g of potato starch were weighed respectively, water was added until the total weight of the solution was 100 g, the mixture was thoroughly stirred and mixed, and the mixture was reacted for 10 minutes to obtain the beryllium mineral inhibitor aqueous solution.

[0036] 2 g of sodium oleate and 1 g of dodecylamine were weighed respectively, and water was added to make the total weight of the solution 100 g. The mixture was stirred and mixed thoroughly, and reacted for 10 minutes to obtain the fluorite collector aqueous solution.

[0037] 4 g of sodium oleate and 1 g of octylhydroxamic acid were weighed respectively, and water was added to make the total weight of the solution 100 g. The mixture was stirred and mixed thoroughly, and reacted for 10 minutes to obtain the beryllium mineral collector aqueous solution.

[0038] The fluorite tailings are treated by this process. The specific process flow is as follows: Figure 1 shown.

[0039] After the fluorite tailings are re-pulped, the pulp concentration is 45wt.%. First, the pulp pH is adjusted to 10.0 with sodium carbonate, and sodium oleate is used as a collector at a dosage of 150g / t. After aeration and slurry mixing for 5 minutes, the roughing operation of flotation I is carried out, and the amount of sodium oleate added for scavenging is 50g / t. The product in the tank obtained by roughing and scavenging is tailings I. After two blank selections, high-fluorine beryllium rough concentrate is obtained, and the mass percentage of CaF2 is 55.89%.

[0040] Further add 40g / t of beryllium mineral inhibitor and 40g / t of combined fluorite collector, aerate and stir for 5 minutes, and then carry out roughing operation of flotation II, add 20g / t of combined fluorite collector for scavenging, and add 20g / t of beryllium mineral inhibitor for concentrating. After fluorine and beryllium separation, fluorite concentrate and beryllium concentrate product I are obtained.

[0041] For tailings I, the pH value of the slurry was adjusted to 11.0 with sodium carbonate, 400 g / t of beryllium mineral collector was added, and sodium hexametaphosphate was used as a silicate inhibitor at a dosage of 80 g / t. 200 g / t of beryllium mineral collector was added during scavenging. The dosages of sodium hexametaphosphate added in the two concentrating operations were 40 g / t and 20 g / t, respectively, to obtain beryllium concentrate product II.

[0042] The flotation test results in Table 2 demonstrate that, utilizing the technical solution of the present invention, over 70% of BeO was recovered in the two-stage beryllium concentrate product, truly realizing the resourceful utilization of beryllium-containing minerals in fluorite tailings. Furthermore, the phase composition analysis of beryllium concentrate product II in Table 3 demonstrates that the flotation reagent of the present invention exhibits excellent selective capture capabilities for a variety of beryllium-containing minerals, including chrysoberyl, ferromanganese, beryl, sillite, and wollastonite, enabling the simultaneous flotation recovery of multiple beryllium-containing minerals.

[0043]

[0044]

[0045] Control experimental group 1

[0046] The fluorite tailings are treated by conventional flotation method of fluorite first and then beryllium separation. The specific process flow is as follows: Figure 3 shown.

[0047] First, the pH value of the pulp is adjusted to 10.0 with sodium carbonate, and conventional sodium oleate is used as a collector to carry out preferential flotation of fluorite. The dosage of sodium oleate in roughing is 300g / t, and water glass is used as a depressant with a dosage of 400g / t. The dosage of sodium oleate added in scavenging is 100g / t, and the dosage of water glass added in concentrating is 200g / t and 100g / t respectively. Fluorite concentrate product is obtained through one roughing, two finishing and one scavenging.

[0048] After the fluorite flotation tailings were re-slurried with sodium carbonate, sodium oleate was used as a collector for beryllium flotation. The dosage of sodium oleate in the roughing process was 400g / t, and sodium hexametaphosphate was added as a silicate inhibitor at a dosage of 80g / t. The dosage of sodium oleate added in the scavenging process was 200g / t. The dosages of sodium hexametaphosphate added in the two cleaning processes were 40g / t and 20g / t, respectively. A beryllium concentrate product with a BeO content of 0.751% and a recovery rate of 35.66% was obtained.

[0049] From the flotation test results in Table 4, it can be seen that the effect of using the "strong pulling and strong pressing" method to preferentially float fluorite and then concentrate on flotation to recover beryllium minerals is not ideal. Not only does it require a large amount of reagents and high costs, but more than 30% of beryllium is lost in the front-end fluorite flotation process. The grade of beryllium concentrate is only 0.751%, and the recovery rate is less than 40%. It also shows that a large amount of water glass at the front end will have an adverse effect on the beryllium selection at the back end. The flotation efficiency of a single fatty acid as a collector is not high, and the "tailing" phenomenon is serious. The beryllium lost in the tailings is high in grade and large in amount, making it difficult to efficiently flotation and enrich beryllium-containing minerals.

[0050]

[0051] Control experimental group 2

[0052] 4 g of sodium oleate and 1 g of octylhydroxamic acid were weighed respectively, and water was added to make the total weight of the solution 100 g. The mixture was stirred and mixed thoroughly, and reacted for 10 minutes to obtain the beryllium mineral collector aqueous solution.

[0053] Control Experiment Group 2 was used to illustrate the effect of the slurry pH during Flotation III on the enhanced flotation recovery of poorly floatable beryllium ore. The operation of Flotation I was consistent with that of Example 1. Open-circuit flotation of Flotation II was performed on tailings I, produced by the front-end mixed flotation closed-circuit process. The slurry was adjusted to different pH values ​​using sodium carbonate, and 400 g / t of a beryllium collector and 80 g / t of sodium hexametaphosphate inhibitor were added. Sodium hexametaphosphate was added at 40 g / t and 20 g / t in Concentration I and Concentration II, respectively, to produce beryllium concentrate Product II.

[0054] From the flotation test results in Table 5, it can be seen that the effect of flotation III under alkaline conditions of pH ≤ 10 is not ideal. The BeO grade of the beryllium concentrate obtained by open-circuit flotation of one coarse and two fine processes is only 0.9-1.0%, and the recovery rate is less than 30%. However, within the preferred pH range of the present invention, the flotation performance of the beryllium mineral collector is good, and the quality of the beryllium concentrate is high. Under alkaline conditions of pH > 10, the flotation efficiency is greatly improved, the BeO grade of the beryllium concentrate is increased to above 1.2%, and the recovery rate reaches above 40%, achieving efficient enrichment and recovery of beryllium minerals.

[0055]

[0056] Control experimental group 3

[0057] 4 g of sodium oleate and 1 g of octylhydroxamic acid were weighed respectively, and water was added to make the total weight of the solution 100 g. The mixture was thoroughly stirred and mixed, and the mixture was reacted for 10 minutes to obtain the beryllium mineral collector (NaOL-OHA) aqueous solution.

[0058] Weigh 4 g of sodium oleate and 1 g of sodium lauryl sulfate respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain a NaOL-SDS collector aqueous solution.

[0059] Weigh 4 g of sodium oleate and 1 g of aluminum sulfate respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain an Al-NaOL collector aqueous solution.

[0060] Control Experiment Group 3 used different types of collectors to perform enhanced flotation of beryllium ore to evaluate the superior flotation performance of the beryllium ore collector of the present invention. The operation of Flotation I was consistent with that of Example 1. For tailings I produced by the front-end mixed flotation closed-circuit flotation, open-circuit flotation II was performed. The slurry pH was adjusted to 11.0 with sodium carbonate, and a sodium hexametaphosphate inhibitor was added at a dosage of 80 g / t. Different types of collectors were used for roughing operations, with the collector dosage of 400 g / t. Sodium hexametaphosphate was added at 40 g / t and 20 g / t, respectively, for fine finishing operations. Beryllium concentrate product II was obtained through one roughing and two fine finishing operations.

[0061]

[0062] From the flotation test results in Table 6, it can be seen that the conventional combined collector has a certain collection ability for beryllium minerals, but the flotation concentrate grade and recovery rate are not as good as the beryllium mineral collector of the present invention. At the same time, it can be seen that the flotation concentrate grade of the fatty acid collector is high, and the recovery rate of the alkyl hydroxamic acid collector is high. The beryllium mineral collector assembled by using the two can achieve efficient flotation recovery of beryllium minerals.

[0063] Example 2

[0064] 1 g of sulfuric acid, 4 g of water glass and 1 g of corn starch were weighed respectively, and water was added to make the total weight of the solution 100 g. The mixture was thoroughly stirred and mixed, and the mixture was reacted for 10 minutes to obtain the beryllium mineral inhibitor aqueous solution.

[0065] 2 g of sodium linoleate and 1 g of polyetheramine were weighed respectively, water was added to make the total weight of the solution 100 g, the mixture was fully stirred and mixed, and the mixture was reacted for 10 minutes to obtain the fluorite collector aqueous solution.

[0066] 3 g of sodium oleate and 1 g of heptylhydroxamic acid were weighed respectively, and water was added to make the total weight of the solution 100 g. The mixture was stirred and mixed thoroughly, and reacted for 10 minutes to obtain the beryllium mineral collector aqueous solution.

[0067] The fluorite tailings were treated by this process. After re-slurrying, the slurry concentration of the fluorite tailings was 45wt.%. First, the slurry pH was adjusted to 9.5 with sodium carbonate. Sodium linoleate was used as a collector in an amount of 100g / t. After aeration and slurrying and stirring for 5 minutes, the roughing operation of flotation I was carried out. The amount of sodium linoleate added in the scavenging operation was 50g / t. The product in the tank obtained by the roughing and scavenging operation was tailings I. The roughing foam product was subjected to two blank selections to obtain a high-fluorine beryllium rough concentrate. The mass percentage of CaF2 in the rough concentrate was 51.25%.

[0068] Further add 60g / t of beryllium mineral inhibitor and 30g / t of combined fluorite collector, aerate and stir for 5 minutes, and then carry out roughing operation of flotation II, add 15g / t of combined fluorite collector for scavenging, and add 30g / t of beryllium mineral inhibitor for concentrating. After fluorine and beryllium separation, fluorite concentrate and beryllium concentrate product I are obtained.

[0069] The pH value of tailings I was adjusted to 10.5 with sodium carbonate, 360 g / t of beryllium mineral collector was added, 200 g / t of tartaric acid was used as silicate inhibitor, 180 g / t of beryllium mineral collector was added during scavenging, and 100 g / t and 50 g / t of tartaric acid were added during the two concentrating operations respectively to obtain beryllium concentrate product II.

[0070] The flotation test results in Table 7 demonstrate that the technical solution of the present invention can effectively recover over 70% of the beryllium resources in fluorite tailings, producing two beryllium concentrate products with BeO grades of 2.391% and 1.223%. The flotation reagent of the present invention offers excellent performance, high flotation efficiency, and adaptability, resulting in an optimized concentrate product structure. Furthermore, the process is short, simple to operate, and has low beneficiation costs, making it promising for further widespread use.

[0071]

[0072] Control experimental group

[0073] The fluorite tailings are treated by reverse flotation process. The specific process is as follows: Figure 4 As shown. First, the pH of the pulp is adjusted to 10.0 with sodium carbonate, and conventional sodium oleate is used as a collector for fluorite flotation. The amount of sodium oleate added in the roughing process is 400g / t, and water glass is used as a depressant at a dosage of 800g / t. The amounts of sodium oleate added in the scavenging process are 200g / t and 100g / t, respectively. The amounts of water glass added in the concentrating process are 400g / t and 200g / t, respectively. Fluorite concentrate is obtained through one roughing, two finishing, and two scavenging processes.

[0074] The fluorite flotation tailings are further reverse floated to remove mica silicate gangue minerals. Dodecylamine is used as a collector and water glass is used as a depressant for reverse flotation desiliconization. The amount of water glass added in the roughing process is 400g / t, the amount of dodecylamine added in the fine process is 160g / t, and the amount of water glass added in the fine process is 200g / t. The roughing tailings are further scavenged four times to obtain in-tank tailings, which are beryllium concentrate products. The amounts of dodecylamine added in the scavenging process are 120g / t, 80g / t, 40g / t and 20g / t respectively. The in-tank product obtained after four scavenging operations, namely, roughing, fine and beryllium concentrate.

[0075] From the flotation test results in Table 8, it can be seen that the reverse flotation efficiency is not high, the selective separation effect of beryllium is poor, the concentrate indicators are not ideal, and the process flow is long and the comprehensive recovery rate is not high, making it difficult to achieve effective recovery of beryllium resources.

[0076]

Claims

1. An asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings, characterized in that: The following steps are involved: 1) After slurrying, the fluorite tailings are first subjected to flotation I using a fatty acid collector under alkaline conditions of pH ≤ 10 to obtain high-fluorine beryllium rough concentrate and tailings I; 2) flotation II of the high-fluorine beryllium rough concentrate using a beryllium mineral depressant and a fluorite collector to obtain fluorite concentrate and tailings, wherein the tailings are beryllium concentrate I; 3) The tailings I are subjected to flotation III using a beryllium mineral collector and a silicate inhibitor under alkaline conditions of pH>10 to obtain beryllium concentrate II.

2. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 1, wherein: The beryllium-containing minerals in the fluorite tailings include at least one of chrysoberyl, hydroxysilicate, heliotropite, silicate, beryl, bluestone and taaffeite; and / or, The gangue minerals in the fluorite tailings include at least one of silicate gangue minerals, calcium-containing gangue minerals and clay minerals; and / or, The mass content of BeO in the fluorite tailings is ≥0.26%.

3. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 1, wherein: The fluorite tailings are slurried to a concentration of 30-55 wt.%, and a pH of 8.0-10.

0.

4. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 1, wherein: The fatty acid collector includes at least one of oleic acid, linoleic acid, linolenic acid, palmitic acid, naphthenic acid, tall oil, ricinoleic acid, and 731 oxidized paraffin soap.

5. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to any one of claims 1 to 4, characterized in that: The flotation I includes 1 roughing, 1 to 3 cleaning and 1 to 2 scavenging; The reagent system for roughing is as follows: the amount of fatty acid collector added relative to the original ore is 100-300g / t; The reagent system for the scavenging is as follows: the amount of fatty acid collector added relative to the original ore is 50-100 g / t; The selection is a blank selection.

6. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 1, wherein: The beryllium mineral inhibitor is formed by reacting components including sulfuric acid, water glass and starch; The fluorite collector includes a fatty acid collector and a cationic collector.

7. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 6, characterized in that: The beryllium mineral inhibitor is formed by reacting sulfuric acid, water glass and starch in a mass ratio of (1-4): (1-10): 1; The fluorite collector is composed of a fatty acid collector and a cationic collector in a mass ratio of (1-8):

1.

8. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 1, 2, 3, 4, 6 or 7, characterized in that: Said flotation II includes 1 roughing, 1-2 cleaning and 1-2 scavenging; The reagent system for roughing is as follows: the amount of beryllium mineral inhibitor added relative to the original ore is 40-80 g / t, and the amount of fluorite collector added relative to the original ore is 30-60 g / t; The selected reagent system is: only add beryllium mineral inhibitor, follow the principle of gradual reduction; The reagent system for the sweeping selection is: only adding fluorite collector, following the principle of gradual decrease.

9. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 1, characterized in that: The beryllium mineral collector includes a fatty acid collector and a C5-C8 alkyl hydroxamic acid collector; The silicate inhibitor includes at least one of water glass, sodium sulfide, tartaric acid, and sodium hexametaphosphate.

10. The asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings according to claim 1, 2, 3, 4, 6, 7 or 9, characterized in that: The flotation III includes 1 roughing, 2-3 cleaning and 1-2 scavenging; The reagent system for roughing is as follows: the amount of beryllium mineral collector added relative to the original ore is 300-600 g / t, and the amount of silicate inhibitor added relative to the original ore is 40-200 g / t; The selected agent system is: only silicate inhibitor is added, following the principle of gradual reduction; The reagent system for the sweeping selection is: only beryllium mineral collector is added, and the principle of gradual decrease is followed.

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