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

Abstract

The invention discloses an asynchronous flotation enrichment method for beryllium-containing minerals in fluorite tailings, and belongs to the technical field of mineral separation. The method comprises the steps that after fluorite tailings are subjected to size mixing, flotation I is conducted on the fluorite tailings through a fatty acid collecting agent under the alkaline condition that the pH is smaller than or equal to 10, and high-fluorine beryllium rough concentrate and tailings I are obtained; the high-fluorine beryllium rough concentrate is subjected to flotation II through a beryllium mineral inhibitor and a fluorite collecting agent, fluorite concentrate and tailings are obtained, and the tailings are beryllium concentrate I; the tailings I are treated with a beryllium mineral collecting agent and a silicate inhibitor at the pH gt; and flotation III is conducted under the alkaline condition of 10, and beryllium concentrate II is obtained. According to the method, the comprehensive recovery rate of BeO in the fluorite tailings reaches 70% or above, the process is short, the cost is low, operation is easy, and efficient comprehensive recovery of beryllium resources in the fluorite tailings is truly achieved.

Description

Technical Field

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

[0002] As an important non-renewable resource, beryllium is of indispensable importance to the country's industrial development and scientific and technological progress. For example, in the field of aerospace, beryllium is used to manufacture lightweight and high-strength structural parts to improve the performance of aircraft. In the nuclear industry, beryllium is used as a neutron moderator and reflector material, which is crucial to the safe operation of nuclear reactors. In addition, metallic beryllium and its compounds are also widely used in the electronics industry, such as in the manufacture of X-ray fluorescent screens, neutron detectors, etc., which plays an important role in improving the performance and quality of electronic products. Summary of the invention

[0004] 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, and meets industrial production requirements.

[0005] 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: 1) After slurrying, the fluorite tailings are firstly subjected to flotation I with 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 a fluorite concentrate and tailings, wherein the tailings are the beryllium concentrate I; 3) The tailings I are subjected to flotation III with a beryllium mineral collector and a silicate inhibitor under alkaline conditions of pH>10 to obtain beryllium concentrate II.

[0006] 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 beneficiation idea of ​​"asynchronous flotation" to divide 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 for preliminary flotation separation under low alkalinity conditions, which 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 stage caused by the "strong pulling and strong pressing" method adopted in the existing technology to first remove fluorite 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.

[0007] As a preferred solution, the beryllium-containing minerals in the fluorite tailings include at least one of chrysoberyl, hydroxysilicate, heliotropy, silicate, beryl, blue stone and taaffeite. The present invention is particularly suitable for fluorite tailings containing a variety of beryllium-containing minerals with different flotation difficulties.

[0008] As a preferred solution, 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), sodium pearl mica, etc. Calcium-containing gangue minerals include fluorite, calcite, etc. Clay minerals include chlorite, lithium chlorite, etc.

[0009] As a preferred solution, the mass content of BeO in the fluorite tailings is ≥0.26%.

[0010] As a preferred solution, the fluorite tailings are slurried to a concentration of 30-55wt.%, and a pH of 8.0-10.0. By adjusting the pH of the slurry in a weakly alkaline environment, under low alkalinity conditions, it is more conducive for the carboxyl functional groups of the fatty acid collector to coordinate with the active sites of the metal calcium ions on the surface of the fluorite to form a hydrophobic precipitate or a double-layer film of the collector. At the same time, sodium carbonate can also make the surface of the mineral particles negatively charged, promoting the dispersion of the slurry. The pH can be adjusted using sodium carbonate as an adjusting agent.

[0011] As a preferred solution, 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. The preferred fatty acid collector is a conventional collector for fluorite flotation, and some beryllium minerals in fluorite tailings are also sensitive to fatty acid collectors. The present invention adopts the fatty acid collector through the strategy of "floating as much as possible" to realize mixed flotation recovery of the part of beryllium minerals with good floatability and high flotation rate with fluorite.

[0012] As a more preferred solution, the flotation I includes 1 roughing, 1 to 3 cleaning and 1 to 2 scavenging. As a more preferred solution, the reagent system of the roughing is: the amount of fatty acid collector added relative to the original ore is 100 to 300 g / t; the reagent system of the scavenging is: the amount of fatty acid collector added relative to the original ore is 50 to 100 g / t; the cleaning is blank cleaning. In the flotation I process of the present invention, no inhibitors need to be added, and the "strong pulling and strong pressure" method is not adopted to preferentially remove calcium-containing gangue minerals such as fluorite and calcite. Instead, the strategy of "floating as much as possible" is adopted, so that some beryllium-containing minerals with good floatability and high flotation rate float up with fluorite, and become a mixed concentrate of fluorite and beryllium, and then further separated. Compared with beryllium-containing minerals and silicate gangue minerals with similar floatability, the surface physical and chemical properties of fluorite and beryllium-containing minerals are quite different, which is easy to be efficiently separated by flotation. Under the optimal flotation reagent system, the mass content of CaF2 in the recovered high-fluorine beryllium rough concentrate is ≥50%.

[0013] As a preferred solution, the beryllium mineral inhibitor is formed by reacting components including sulfuric acid, water glass and starch. Preferred starches include at least one of potato starch, bean starch and cereal starch, such as sweet potato starch, corn starch, potato starch and the like. As a more preferred solution, 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 can etch the surface of beryllium-containing minerals, destroy the Al-O bonds in its lattice structure, promote the chelation and hydrogen bond adsorption of starch hydroxyl groups with aluminum and beryllium active metal particles on the surface of beryllium-containing minerals, and at the same time, sulfuric acid can also promote water glass to form hydrophilic silicate colloids adsorbed on the surface of beryllium-containing minerals, so that they are selectively inhibited.

[0014] As a preferred solution, the fluorite collector includes a fatty acid collector and a cationic collector.

[0015] The cationic collector includes at least one of fatty amines, amides, etheramines and quaternary ammonium salts, such as dodecylamine, coconut amine, polyetheramine, hexadecyltrimethylammonium bromide, etc. The fatty acid collector includes at least one of oleic acid, linoleic acid, linolenic acid, palmitic acid, cyclohexane acid, tall oil, ricinoleic acid, and 731 oxidized paraffin soap. As a more preferred solution, the fluorite collector is composed of a fatty acid collector and a cationic collector in a mass ratio of (1-8):1. The fatty acid collector and the cationic collector are used in combination as an anionic collector and a cationic collector, respectively, which has a significant synergistic effect on the selective capture of fluorite minerals. In particular, the introduction of the cationic collector can enhance the flotation removal of part of the siliceous gangue in the high-fluorine beryllium rough concentrate, and improve the separation efficiency of fluorite and beryllium-containing minerals.

[0016] As a more preferred solution, the flotation II includes 1 roughing, 1-2 fines and 1-2 scavenging. As a more preferred solution, the reagent system of the roughing is: 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 reagent system of the fine is: only beryllium mineral inhibitor is added, following the principle of gradual decrease; the reagent system of the scavenging is: only fluorite collector is added, following the principle of gradual decrease, wherein the mass of beryllium mineral inhibitor is measured according to the mass of starch, and the mass of fluorite collector is measured according to the mass of fatty acid. Based on the similar flotation performance 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 inhibitor composed of sulfuric acid, water glass and starch, etc., which can enhance the hydrophilic modification of the surface of the beryllium-containing mineral. On the other hand, the present invention optimizes the conventional fatty acid collector and improves its selectivity for fluorite by introducing a cationic collector. After the preferred scheme, a fluorite concentrate product and a beryllium concentrate I with a BeO mass content of ≥2.0% can be obtained.

[0017] As a preferred solution, the beryllium mineral collector includes a fatty acid collector and a C5-C8 alkyl hydroxamic acid collector. The alkyl chain contained in the alkyl hydroxamic acid collector can be a straight chain alkyl or a branched alkyl. As a further preferred solution, the mass ratio of the fatty acid collector and the C5-C8 alkyl hydroxamic acid collector is (1-4):1. The functions of the two collectors are complementary, which improves the collection capacity and selectivity. The combination of the two can significantly reduce the critical micelle concentration, strengthen the co-adsorption strength of the collector on the mineral surface, and achieve efficient and synchronous recovery of multiple beryllium-containing minerals. A further preferred fatty acid collector includes at least one of oleic acid, linoleic acid, linolenic acid, palmitic acid, cyclohexane acid, tall oil, ricinoleic acid, and 731 oxidized paraffin soap.

[0018] As a more preferred solution, the silicate inhibitor includes at least one of water glass, sodium sulfide, tartaric acid, and sodium hexametaphosphate.

[0019] As a preferred solution, the flotation III includes 1 roughing, 2-3 fine cleaning and 1-2 scavenging. As a more preferred solution, the reagent system of the roughing is: 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 reagent system of the fine cleaning is: only silicate inhibitor is added, following the principle of gradual decrease; the reagent system of the scavenging is: only beryllium mineral collector is added, following the principle of gradual decrease, wherein the mass of beryllium mineral collector is measured according to the mass of fatty acid. The pH in the flotation III process is further >10 and ≤12.0. Under this high alkalinity condition, it is more conducive to the flotation recovery of difficult-to-float beryllium-containing minerals. At the same time, most of the metal ions exist in the form of hydroxide precipitation under this condition, which effectively avoids the non-selective activation of the inevitable metal ions in the slurry for silicate gangue minerals such as muscovite. By optimizing the flotation collector and controlling the pH conditions, beryllium concentrate product II with a BeO mass content ≥1.0% can be obtained.

[0020] The selected and scavenged middlings of the present invention are sequentially returned to the previous flotation operation.

[0021] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects: (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 properties, and are flotated and enriched separately. This can achieve efficient and comprehensive recovery of a variety of 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%.

[0022] (2) The technical solution of the present invention is aimed at the separation of fluorite and beryllium-containing minerals in high-fluorine beryllium rough 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.

[0023] (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

[0024] Figure 1 It is a process flow chart of the present invention.

[0025] Figure 2This is a mineral composition analysis of a fluorite tailings in Hunan.

[0026] Figure 3 This is the process flow chart of Comparative Example 1.

[0027] Figure 4 This is the process flow chart of Comparative Example 2. DETAILED DESCRIPTION

[0028] 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.

[0029] 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 distribution of element content of the fluorite flotation tailings, among which the content of CaF2 is 12.48% and the content of BeO 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 mainly exist in the form of various beryllium-containing minerals such as chrysoberyl, hydroxysilicate, beryl, blue stone, and a small amount of beryllium is dispersed in sodium pearl mica. The particle size screening results of the samples are shown in Table 1 below. It can be seen from the table that the embedded particle size of beryllium-containing minerals is relatively fine, of which the -0.074 mm particle size accounts for 80.21%, and nearly half of the BeO is distributed in the -0.043 mm particle size, and the BeO grade of this part reaches 0.40%. Overall, the comprehensive recovery of beryllium in the fluorite tailings is relatively difficult.

[0030]

[0031] Example 1 Weigh 1 g of sulfuric acid, 5 g of water glass and 1 g of potato starch respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the beryllium mineral inhibitor aqueous solution.

[0032] Weigh 2 g of sodium oleate and 1 g of dodecylamine respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the fluorite collector aqueous solution.

[0033] Weigh 4 g of sodium oleate and 1 g of octyl hydroxamic acid respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the beryllium mineral collector aqueous solution.

[0034] The fluorite tailings are treated by this process. The specific process flow is as follows: Figure 1 shown.

[0035] After the fluorite tailings were re-pulped, the pulp concentration was 45wt.%. First, the pulp pH was adjusted to 10.0 with sodium carbonate, and sodium oleate was used as a collector at a dosage of 150g / t. After aeration and slurry mixing for 5 minutes, the roughing operation of flotation I was carried out, and the amount of sodium oleate added for scavenging was 50g / t. The product in the tank obtained by roughing and scavenging was tailings I. After two blank selections, a high-fluorine beryllium rough concentrate was obtained, and the mass percentage of CaF2 was 55.89%.

[0036] 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 in scavenging, and add 20g / t of beryllium mineral inhibitor in concentrating. After fluorine and beryllium separation, fluorite concentrate and beryllium concentrate product I are obtained.

[0037] For tailings I, the pH value of the ore pulp is adjusted to 11.0 with sodium carbonate, 400 g / t of beryllium mineral collector is added, and sodium hexametaphosphate is used as a silicate inhibitor at a dosage of 80 g / t. 200 g / t of beryllium mineral collector is added during scavenging. The dosages of sodium hexametaphosphate added in the two concentrating operations are 40 g / t and 20 g / t respectively, to obtain beryllium concentrate product II.

[0038] From the flotation test results in Table 2, it can be seen that by using the technical solution of the present invention, more than 70% of BeO is recovered into the two-stage beryllium concentrate products, truly realizing the resource utilization of beryllium-containing minerals in fluorite tailings. At the same time, from the phase composition analysis of beryllium concentrate product II in Table 3, it can be found that the flotation reagent of the present invention has good selective capture ability for various beryllium-containing minerals such as chrysoberyl, hydroxysilicate, beryl, blue stone, and wollastonite, and can achieve synchronous flotation recovery of various beryllium-containing minerals.

[0039]

[0040]

[0041] Control group 1 The fluorite tailings are treated by conventional flotation method of fluorite first and then beryllium. The specific process flow is as follows: Figure 3 shown.

[0042] Firstly, 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 amount of sodium oleate added in the roughing process is 300g / t, and water glass is used as a depressant at a dosage of 400g / t. The amount of sodium oleate added in the scavenging process is 100g / t, and the amounts of water glass added in the concentrating process are 200g / t and 100g / t respectively. After one roughing, two concentrating processes and one scavenging process, the fluorite concentrate product is obtained.

[0043] After the fluorite flotation tailings were re-slurried with sodium carbonate, sodium oleate was used as a collector for beryllium flotation. The amount of sodium oleate added in the roughing process was 400g / t, and sodium hexametaphosphate was used as a silicate inhibitor at a dosage of 80g / t. The amount of sodium oleate added in the scavenging process was 200g / t. The amounts of sodium hexametaphosphate added in the two concentrating operations were 40g / t and 20g / t, respectively, to obtain a beryllium concentrate product containing 0.751% BeO and a recovery rate of 35.66%.

[0044] 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 is the dosage of reagents large and the cost high, 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 grade lost in the tailings is high and the amount is large, making it difficult to efficiently float and enrich beryllium-containing minerals.

[0045]

[0046] Control group 2 Weigh 4 g of sodium oleate and 1 g of octyl hydroxamic acid respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the beryllium mineral collector aqueous solution.

[0047] The control experiment group 2 is used to illustrate the effect of the pulp pH of flotation III on the enhanced flotation recovery of beryllium minerals with poor floatability, wherein the operation of flotation I is consistent with Example 1. For the tailings I produced by the front-end mixed flotation closed circuit, the open circuit flotation operation of flotation II is carried out, the pulp is adjusted to different pH values ​​with sodium carbonate, 400g / t of beryllium mineral collector and 80g / t of sodium hexametaphosphate inhibitor are added, and 40g / t and 20g / t of sodium hexametaphosphate are added in the selection I and selection II operations, respectively, to obtain beryllium concentrate product II.

[0048] 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 one rough and two fine open-circuit flotation is only 0.9-1.0%, and the recovery rate is less than 30%. In 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 more than 1.2%, and the recovery rate reaches more than 40%, which can achieve efficient enrichment and recovery of beryllium minerals.

[0049]

[0050] Control group 3 Weigh 4 g of sodium oleate and 1 g of octyl hydroxamic acid respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the beryllium mineral collector (NaOL-OHA) aqueous solution.

[0051] Weigh 4 g of sodium oleate and 1 g of sodium dodecyl sulfate respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, react for 10 minutes, and obtain a NaOL-SDS collector aqueous solution.

[0052] 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, react for 10 minutes, and obtain an Al-NaOL collector aqueous solution.

[0053] The control experiment group 3 uses different types of collectors to carry out enhanced flotation of beryllium ore, evaluates the superiority of the flotation performance of the beryllium ore collector of the present invention, and the operation of flotation I is consistent with Example 1. For the tailings I produced by the front-end mixed flotation closed circuit, the open circuit flotation operation of flotation II is carried out, the pH of the slurry is adjusted to 11.0 with sodium carbonate, and the amount of sodium hexametaphosphate inhibitor added is 80g / t. Different types of collectors are used for roughing operations, and the amount of collectors is 400g / t. Sodium hexametaphosphate 40g / t and 20g / t are added in the fine operation, respectively, and beryllium concentrate product II is obtained through one roughing and two fines.

[0054]

[0055] It can be seen from the flotation test results in Table 6 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 fatty acid collector has a high flotation concentrate grade and the alkyl hydroxamic acid collector has a high recovery rate. The beryllium mineral collector assembled by using the two in combination can achieve efficient flotation recovery of beryllium minerals.

[0056] Example 2 Weigh 1 g of sulfuric acid, 4 g of water glass and 1 g of corn starch respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the beryllium mineral inhibitor aqueous solution.

[0057] Weigh 2 g of sodium linoleate and 1 g of polyetheramine respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the fluorite collector aqueous solution.

[0058] Weigh 3 g of sodium oleate and 1 g of heptyl hydroxamic acid respectively, add water to make the total weight of the solution 100 g, stir and mix thoroughly, and react for 10 minutes to obtain the beryllium mineral collector aqueous solution.

[0059] The fluorite tailings were treated by the process method. 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 was 50g / t. The product in the tank obtained by roughing and scavenging 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%.

[0060] Further, 60 g / t of beryllium mineral inhibitor and 30 g / t of combined fluorite collector were added, and after aeration and slurry stirring for 5 minutes, roughing operation of flotation II was carried out, 15 g / t of combined fluorite collector was added in scavenging, and 30 g / t of beryllium mineral inhibitor was added in concentrating. After fluorine and beryllium separation, fluorite concentrate and beryllium concentrate product I were obtained.

[0061] Tailings I was prepared by adjusting the pH of the slurry to 10.5 with sodium carbonate, adding 360 g / t of beryllium mineral collector, using 200 g / t of tartaric acid as a silicate inhibitor, adding 180 g / t of beryllium mineral collector during scavenging, and adding 100 g / t and 50 g / t of tartaric acid in the two concentrating operations respectively to obtain beryllium concentrate product II.

[0062] It can be seen from the flotation test results in Table 7 that the technical solution of the present invention can achieve effective recovery of more than 70% of beryllium resources in fluorite tailings, and produce two parts of beryllium concentrate products with BeO grades of 2.391% and 1.223%. The flotation agent of the present invention has good performance, high flotation efficiency, good adaptability, optimized concentrate product structure, short process flow, simple operation, and low ore dressing cost, which is conducive to further promotion and use.

[0063]

[0064] Control group The fluorite tailings are treated by reverse flotation process. The specific process flow 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 to carry out fluorite flotation. The amount of sodium oleate added in the roughing process is 400g / t, and water glass is used as a depressant at an amount of 800g / t. The amounts of sodium oleate added in the scavenging process are 200g / t and 100g / t respectively, and the amounts of water glass added in the concentrating process are 400g / t and 200g / t respectively. After one roughing, two concentrating and two scavenging processes, the fluorite concentrate product is obtained.

[0065] 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 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 the in-tank tailings, which are the 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 one roughing, one fine and four scavenging operations is the beryllium concentrate.

[0066] 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 not good, 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.

[0067]

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 firstly subjected to flotation I with 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 a fluorite concentrate and tailings, wherein the tailings are the beryllium concentrate I; 3) The tailings I are subjected to flotation III with 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 of beryllium-containing minerals in fluorite tailings according to claim 1, characterized in that: The beryllium-containing minerals in the fluorite tailings include at least one of chrysoberyl, beryllite, heliotropy, beryllite, beryl, blue stone 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 of beryllium-containing minerals in fluorite tailings according to claim 1, characterized in that: The fluorite tailings are slurried to a concentration of 30-55wt.%, and a pH of 8.0-10.

0.

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

5. The asynchronous flotation enrichment method of 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 100-300 g / t; The reagent system for the sweeping selection 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 of beryllium-containing minerals in fluorite tailings according to claim 1, characterized in that: 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 of 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 of beryllium-containing minerals in fluorite tailings according to claim 1, 2, 3, 4, 6 or 7, characterized in that: The 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, following the principle of gradual reduction; The reagent system for the sweeping selection is: only add fluorite collector and follow the principle of gradual reduction.

9. The asynchronous flotation enrichment method of 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 of 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 of the 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 reagent system is: only silicate inhibitor is added, following the principle of gradual reduction; The reagent system for the scavenging is: only add beryllium mineral collector, following the principle of gradual reduction.

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