Combined flotation reagent and beneficiation method for fluorite associated beryllium ore

Abstract

The invention discloses a combined flotation reagent for fluorite associated beryllium ore and a beneficiation method, and belongs to the technical field of beneficiation. The flotation reagent comprises a beryllium mineral collecting agent and a regulator; the beryllium mineral collecting agent is formed by assembling metal ions with the valence higher than bivalent, C5-C9 alkyl hydroximic acid and fatty acid in a coordination mode. The adjusting agent comprises organic phosphonic acid, alkylol amine and sodium sulfide, the beryllium mineral collecting agent is a ternary coordination colloid collecting agent and can achieve targeted adsorption and synchronous flotation recovery of multiple beryllium-containing minerals, and the adjusting agent has a high-selectivity inhibition effect on gangue minerals such as calcium-containing minerals and silicate minerals; the combined flotation reagent is small in dosage, low in cost, short in beneficiation process, easy to operate and high in applicability, and the comprehensive recovery rate of the fluorite associated beryllium ore can be remarkably increased.

Description

Technical Field

[0001] The invention relates to a flotation reagent, in particular to a combined flotation reagent for fluorite-associated beryllium ore, and also to a beneficiation method for fluorite-associated beryllium ore, belonging to the technical field of beneficiation. Background Art

[0002] Beryllium, as one of the rarest metal mineral resources, is an important metal element in national industrial production and economic development. Due to its light weight and high strength, it has become an indispensable raw material in high-tech fields such as aerospace and nuclear industry.

[0003] At present, domestic beryllium ore dressing technology is still in its infancy, and most of the research focuses on the easily selected beryl resources, while the dressing technology of other key beryllium ore resources such as chrysoberyl, hydroxysilicate, and taaffeite is almost blank. For example, Hunan Province has rich beryllium ore resources such as chrysoberyl, and most of them are associated with fluorite, such as the Xianghualing mining area in Chenzhou and the Jiepailing mining area in Yizhang. This part of the beryllium resources has not been effectively recovered and developed, and most of them are lost in the tailings and wasted. In addition, beryllium is a typical lithophile element, and its relationship with silicon is the closest in nature. Currently known beryllium minerals with industrial mining value are basically aluminates, silicates or aluminosilicates, and have similar physical and chemical properties to gangue minerals such as quartz and mica. Conventional inhibitors such as water glass, sodium fluorosilicate, and sodium hexametaphosphate are difficult to achieve selective separation of the two, and beryllium minerals are easily "crushed" into the tailings. At the same time, in the conventional flotation system of anionic collectors such as fatty acids, fluorite with better floatability tends to float up with the foam and enter the concentrate product more easily. Due to the shortcomings of the current beryllium smelting technology, the fluorine enriched in the beryllium concentrate may have an adverse effect on the back-end beryllium smelting. In the conventional sulfuric acid method for beryllium extraction, stable fluorine-aluminum complexes are easily formed, which hinders the crystallization of ammonium aluminum sulfate during the evaporation and crystallization process of aluminum removal, and seriously reduces the aluminum removal efficiency.

[0004] Therefore, developing new and efficient flotation agents to achieve comprehensive recovery of this part of fluorite-associated beryllium ore will help enhance my country's competitiveness in the global beryllium industry and has important strategic significance for ensuring the sustainable development of my country's beryllium resources. Summary of the invention

[0005] In view of the defects of the prior art, the first object of the present invention is to provide a combined flotation reagent for fluorite-associated beryllium ore, which comprises a beryllium mineral collector with both selectivity and high collection capacity, which can achieve targeted adsorption and synchronous recovery of various beryllium minerals, and also comprises a regulator with highly selective inhibitory effect on calcium-containing gangue minerals and silicate gangue minerals. The combination of the two can achieve highly selective separation and preliminary pre-enrichment of beryllium minerals.

[0006] The second object of the present invention is to provide a beneficiation method for fluorite-associated beryllium ore. The method can achieve efficient flotation separation of fluorite-associated beryllium ore based on a special combination of flotation agents, and the flotation process is simple to operate, has good flotation indicators and good applicability, which is conducive to providing high-quality beryllium concentrate raw materials for subsequent further smelting / smelting combined with synergistic extraction of beryllium elements.

[0007] In order to achieve the above technical objectives, the present invention provides a combined flotation reagent for fluorite-associated beryllium ore, which includes a beryllium mineral collector and a regulator; the beryllium mineral collector is assembled by coordination of divalent or higher metal ions, C5~C9 alkyl hydroxamic acids and fatty acids; the regulator includes organic phosphonic acid, alcohol amine and sodium sulfide.

[0008] The combined flotation reagent of the present invention comprises a beryllium mineral collector with high selectivity and strong capture ability for beryllium minerals and an adjuster with selective inhibition of calcium-containing gangue minerals and silicate gangue minerals. The beryllium mineral collector is assembled by coordination of alkyl hydroxamic acid and fatty acid with high-valent metal ions, and is a complex aggregate with one or more three-dimensional spatial topological structures formed by metal ions as nodes and organic ligands as assembled in a regular manner. It has both the capture ability of fatty acids and the selectivity of hydroxamic acid, and uses metal bases as polar groups to make it have good selectivity for fluorite, thereby achieving targeted recovery of various fluorite-associated beryllium minerals. The adjuster mainly includes organic phosphonic acid, alcohol amine and sodium sulfide. Sodium sulfide can inhibit the adsorption of the collector on the surface of gangue minerals through competitive adsorption, and can also be used as an inhibitor of gangue minerals such as muscovite and an activator of beryllium minerals such as beryl. The phosphate group contained in the organic phosphonic acid can react with the calcium particles rich on the surface of calcium-containing gangue minerals to generate precipitation and adsorb on the surface of the mineral. Alkylamine is an organic small molecule containing both amino and hydroxyl groups at the end. The hydroxyl group has strong hydrophilicity. On the one hand, the amino group can act on the surface of silicate gangue minerals such as mica with negative charge on the surface through electrostatic force. On the other hand, the hydroxyl group can also enhance the hydrophilic activity of the surface of calcium-containing gangue minerals through chemical adsorption. Therefore, the adjuster can achieve surface modification of calcium-containing gangue minerals and silicate gangue minerals through multiple physical and chemical adsorption effects, and inhibit their flotation. In summary, the combination of beryllium mineral collectors and adjusters can achieve efficient selective separation and preliminary pre-enrichment of beryllium minerals.

[0009] As a preferred solution, the divalent or higher metal ions include Mg 2+ 、Zn 2+ , Fe 2+ , Pb 2+ , Fe 3+ 、Al 3+At least one of them. As a preferred embodiment, the fatty acid includes at least one of oleic acid, linoleic acid, lauric acid, linolenic acid, palmitic acid, ricinoleic acid, and oxidized paraffin soap. As a more preferred embodiment, the beryllium mineral collector is assembled by coordination of divalent or higher metal ions, C5~C9 alkyl hydroxamic acid and fatty acid in a molar ratio of (1~10): (1~20): 1. By changing the types and ratios of divalent or higher metal ions, fatty acids and alkyl hydroxamic acid, the microstructure of the beryllium mineral collector molecules can be effectively regulated, thereby improving its flotation performance. The divalent or higher metal ions are further preferably Mg 2+ , Pb 2+ or Fe 3+ . When the ratio of divalent or higher metal ions is high, the beryllium mineral collector is more likely to exert an electrostatic induction effect, while when the ratio of divalent or higher metal ions is low, the beryllium mineral collector is more likely to undergo chemical adsorption. Therefore, divalent or higher metal ions, C5~C9 alkyl hydroxamic acid and fatty acid are further preferably assembled in a molar ratio of (1~5): (5~20): 1. At this time, the assembled beryllium mineral collector exhibits better flotation performance for a variety of beryllium minerals. The beryllium mineral collector of the present invention is an aggregate of a variety of hydrophobic complexes with high-valent metal ions as polar groups, which gives full play to the respective characteristics of high-valent metal ions, hydroxamic acid and fatty acids. Compared with traditional oxidized ore collectors that use highly electronegative atoms such as N, O, S, and P as polar groups to interact with active particles of metal ions on the surface of minerals, it exhibits better selectivity and stronger capture ability.

[0010] As a preferred embodiment, the organic phosphonic acid includes at least one of ATMP (aminotrimethylenephosphonic acid), EDTMP (ethylenediaminetetramethylenephosphonic acid), HEDP (hydroxyethylidene diphosphonic acid), HPAA (2-hydroxyphosphonoacetic acid) or PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid). The preferred organic phosphonic acid can react with the Ca on the fluorite {111} and calcite {104} surfaces through the O in the terminal phosphate group. 2+ The coordination reaction produces strong adsorption with a high adsorption density, which can enhance the hydrophilicity of the surface of calcium-containing gangue minerals and hinder the adsorption of collectors.

[0011] As a preferred solution, the alcoholamine includes at least one of TEA (triethanolamine), MDEA (N-methyldiethanolamine), NH213 (2-amino-1,3-propanediol) or NH312 (3-amino-1,2-propanediol). The most important factor affecting the flotation enrichment of beryllium minerals is silicate gangue minerals such as quartz and mica, which have a low zero point of charge and show a relatively negative charge in a wide pH range. Since the terminal amino group of the alcoholamine is positively charged, it can act on the mica surface as a cation or ion / molecular association through electrostatic force, hydrogen bond, etc., and the other end hydroxyl group is highly hydrophilic. At the same time, the small molecule alcoholamine has a short carbon chain and will not have an adverse effect on the foam state during the flotation process, thus achieving effective selective inhibition of silicate gangue minerals to a certain extent.

[0012] As a preferred solution, the adjusting agent is composed of organic phosphonic acid, alcohol amine and sodium sulfide in a mass ratio of 1: (1-5): (1-20). The specific ratio of the adjusting agent can be flexibly selected and adjusted according to the properties and composition characteristics of the specific gangue mineral to achieve the best inhibition effect. Among them, sodium sulfide can make S in the slurry 2- / HS - Electrostatic adsorption occurs on the local positively charged area on the surface of silicate gangue minerals such as mica, causing the surface potential to increase negatively. It can also be adsorbed on some of its crystal faces and shield its exposed unsaturated Al-O bonds, which hinders the adsorption of collectors on the surface of silicate gangue minerals. At the same time, sodium sulfide can also be used as an effective activator for certain beryllium minerals such as beryl and hydroxyl silicate. The phosphate group of organic phosphonic acid can react with the abundant calcium particles on the surface of calcium-containing gangue minerals to form precipitation and adsorb on the surface of calcium-containing minerals. Alcoholamine is an organic small molecule with both amino and hydroxyl groups at the end. The amino group can act on the surface of silicate gangue minerals such as mica with negative charge on the surface through electrostatic force, and the hydroxyl group can also enhance the hydrophilic activity of the surface of calcium-containing gangue minerals through chemical adsorption. In summary, the use of organic phosphonic acid, alcoholamine and sodium sulfide in appropriate proportions can simultaneously perform multiple physical and chemical actions on various gangue minerals such as calcium-containing minerals and silicate minerals to reduce the floatability of these gangue minerals.

[0013] The present invention also provides a beneficiation method for fluorite-associated beryllium ore, which comprises the following steps: firstly crushing, grinding and slurrying the fluorite-associated beryllium ore, recovering the fluorite concentrate by fluorite flotation, slurrying the obtained fluorite tailings, and then flotating the beryllium ore using the combined flotation agent to obtain the beryllium concentrate.

[0014] As a preferred solution, the beryllium mineral contained in the fluorite-associated beryllium ore is at least one of chrysoberyl, beryllite, taaffeite, beryl and bluestone. The mass percentage of BeO in the fluorite-associated beryllium ore is greater than 0.10%, and the gangue mineral composition is mainly silicate gangue such as muscovite and quartz and calcium-containing gangue such as calcite.

[0015] As a preferred solution, the pH of the fluorite tailings is adjusted to 9.0-11.5, and the concentration is adjusted to 40-50wt.%. Adjusting the fluorite tailings to the preferred pH range is more conducive to exerting the "bridging" effect of hydroxyl groups and reducing the reaction energy barrier, and strengthening the adsorption of the beryllium mineral collector on the surface of the beryllium mineral. The mass content of CaF2 in the fluorite tailings is ≤15%, and the mass percentage content of the particle size of -200 mesh is greater than 70%, so as to ensure the full monomer dissociation of the target beryllium mineral.

[0016] As a preferred solution, the beryllium ore flotation includes one roughing selection, one or more scavenging selections and two or more concentrating selections.

[0017] As a more preferred solution, the reagent system for roughing is: the dosage of the combined adjusting agent is 500-2000 g / t, and the dosage of the beryllium mineral collector is 200-600 g / t; the reagent system for fine selection is: the dosage of the combined adjusting agent is 100-500 g / t; the reagent system for scavenging is: only the beryllium mineral collector is used, and the principle of gradual decrease is followed; wherein the mass of the combined adjusting agent is measured according to the mass of sodium sulfide, and the mass of the beryllium mineral collector is measured according to the mass of fatty acids. Under the preferred reagent system, a low-grade beryllium concentrate product with a BeO mass content of ≥1.2% and a recovery rate of not less than 65% can be obtained.

[0018] The C5-C9 alkyl hydroxamic acid involved in the present invention can be a straight-chain alkyl group or a branched alkyl group. The length of the alkyl chain mainly affects its hydrophobicity.

[0019] The fluorite flotation involved in the present invention is a common technology in the art, with conventional fatty acid as a collector, water glass as a depressant, and sodium carbonate as a regulator.

[0020] Compared with the prior art, the technical solution of the present invention has the following beneficial effects: The combined flotation reagent for fluorite-type beryllium ore provided by the present invention comprises a ternary coordination colloidal collector formed by assembling divalent or higher metal ions, hydroxamic acid and fatty acid ligands at a flotation interface. The novel collector has good collecting performance for various beryllium minerals, has better reaction activity for active particles such as aluminum and silicon on the surface of the beryllium mineral, and can significantly improve the flotation efficiency of fluorite-associated beryllium ore. At the same time, the combined regulator comprising organic phosphonic acid, alcohol amine and sodium sulfide can selectively act on the surface of gangue minerals through hydrogen bonding, electrostatic force and chemical adsorption, and strengthen the efficient inhibition and flotation separation efficiency of calcium-containing gangue and silicate gangue minerals. The two are used in combination to finally obtain a beryllium concentrate product with a BeO mass content of ≥1.2% and a recovery rate of more than 65%, which is helpful to provide a relatively high-quality raw material for subsequent smelting / metallurgy combined synergistic extraction of beryllium.

[0021] The ore dressing method of the present invention is simple to operate, has strong applicability, low labor intensity, and low reagent cost, and is conducive to further promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a flotation process flow chart of Example 1.

[0023] Figure 2 This is the X-ray diffraction pattern of a beryllium-containing fluorite mine in Hunan.

[0024] Figure 3 2 is a flotation flow chart of Example 2 and Comparative Example 2. DETAILED DESCRIPTION

[0025] The following examples are provided to further illustrate the contents of the present invention in detail, but are not intended to limit the scope of protection of the claims of the present invention.

[0026] The beryllium-containing fluorite ore used in the following examples was taken from a place in Chenzhou, Hunan Province. Its main components are fluorite, muscovite, sericite, sodium pearl mica and calcite (see below). Figure 2 ). The results of chemical multi-element analysis show that the main chemical components of the beryllium-containing fluorite ore are CaF2, Al2O3, SiO2, and CaCO3, with contents of 39.35%, 17.46%, 21.45%, and 13.78%, respectively (see Table 1 below).

[0027] The BeO grade of the beryllium fluorite mine is 0.11%. The main beryllium-containing mineral is chrysoberyl, and it also contains a small amount of hydroxysilicate beryllite and blue stone, which has high recovery value and potential.

[0028]

[0029] Example 1 Under stirring conditions, 0.125 mol of sodium oleate and 0.25 mol of lead nitrate were added in sequence to 1 L of 1.0 mol / L octyl hydroxamic acid solution, and the mixture was reacted for 3 minutes to obtain the beryllium mineral collector.

[0030] Under stirring conditions, ATMP (aminotrimethylenephosphonic acid), MDEA (N-methyldiethanolamine) and sodium sulfide are prepared into a mixed reagent in a mass ratio of 1:2:10, and water is added to dilute the mixed reagent to 5% of the total mass of the solution, and the mixture is fully stirred to obtain the combined adjusting agent.

[0031] Use Figure 2 The fluorite removal-beryllium selection process shown in the figure specifically includes the following steps: The raw ore is crushed and ground in sequence, and the mass percentage of the -200 mesh particle size is greater than 70% to ensure sufficient monomer dissociation of the target mineral.

[0032] Fluorite flotation was carried out with fatty acid as collector, water glass as depressant and sodium carbonate as adjuster, specifically: adjust the pulp pH to 10.0-10.5 with sodium carbonate, add 1500g / t water glass and 800g / t oleic acid in sequence, aerate and stir for 5 minutes before roughing fluorite; further add 400g / t oleic acid for scavenging fluorite; add 1000g / t, 500g / t water glass and 250g / t acidified water glass (sulfuric acid and water glass are mixed in a mass ratio of 3:2) as depressants for fluorite concentration; the concentrate and scavenging ore are returned in sequence. After one roughing, three fines and two scavenging, metallurgical grade fluorite concentrate and fluorite tailings are obtained.

[0033] The front-end flotation removal of fluorite is a common technology in this field. The mass content of CaF2 in the fluorite tailings is 11.69%, the mass content of BeO is 0.21%, and the mass percentage of -200 mesh particle size is 84.39%.

[0034] The combined flotation reagent of the present invention is further used to recover beryllium minerals in fluorite tailings, specifically: the amount of combined adjusting agent added relative to fluorite flotation tailings is 1200 g / t, the amount of beryllium mineral collector added is 400 g / t, and after aeration and slurry mixing for 5 minutes, beryllium roughing operation is carried out, and the pH value of the slurry is stabilized at 10.0-11.0 during the roughing process; the reagent system of scavenging follows the principle of gradual decrease, and 200 g / t and 100 g / t of beryllium mineral collector are added to scavenging I and scavenging II respectively; 200 g / t and 100 g / t of combined adjusting agent are added to concentrating I and concentrating II respectively, and the middlings are returned in sequence, and beryllium concentrate products and tailings are obtained through one roughing, two concentrating and two scavenging operations. It can be seen from Table 2 that the flotation reagent of the present invention can effectively realize the flotation recovery of the fluorite-associated beryllium ore, and a pre-enriched beryllium concentrate product with a BeO mass content of 1.501% is obtained, and the recovery rate reaches 71.24%.

[0035]

[0036] Comparative Example 1 The following three beryllium mineral collectors were synthesized for comparison with Example 1: Under stirring conditions, 0.25 mol of lead nitrate was added to 1 L of 1.0 mol / L sodium oleate solution and reacted for 3 minutes to obtain a Pb-NaOL binary complex collector.

[0037] Under stirring conditions, 0.25 mol of lead nitrate was added to 1 L of 1.0 mol / L sodium dodecyl sulfate solution and reacted for 3 minutes to obtain a Pb-SDS binary complex collector.

[0038] Under stirring conditions, 0.25 mol of lead nitrate was added to 1 L of 1.0 mol / L benzohydroxamic acid solution and reacted for 3 minutes to obtain a Pb-BHA binary complex collector.

[0039] Comparative Example 1 is used for comparison with Example 1, wherein the processes of crushing, grinding, and fluorite removal are all consistent with those of Example 1, with the only difference being the type of beryllium mineral collector, specifically: sodium carbonate is used to adjust the pH of the fluorite tailings slurry to 9.5-10.0, 1200 g / t of a combined adjuster (consistent with Example 1) is added, and a binary complex formed by assembling conventional sodium oleate, sodium dodecyl sulfate or benzohydroxamic acid with lead ions is used as a beryllium mineral collector, with amounts of 400 g / t, 200 g / t, and 1000 g / t, respectively. After aeration and slurry mixing for 5 minutes, beryllium roughing operation is performed; the reagent system for scavenging follows the principle of decreasing step by step, and 200 g / t and 100 g / t of a combined adjuster are added to Concentrated I and Concentrated II respectively, and the middlings are returned in sequence, and beryllium concentrate products and tailings are obtained through one roughing, two fines, and two scavenging operations.

[0040] From the flotation test results of Table 3, it can be seen that the conventional binary complex formed by sodium oleate, sodium dodecyl sulfate or benzohydroxamic acid and lead ion assembly as beryllium mineral collector is not suitable for the system to select beryllium. Compared with the chelating collector benzohydroxamic acid, the alkyl acid collector sodium oleate and sodium dodecyl sulfate can show a certain collection ability, which can make beryllium oxide enriched to a certain extent in the concentrate, but the overall recovery rate is not high and the flotation index is not ideal. Among them, sodium oleate has the best effect, but the CaF2 content in the concentrate is high, which may have an adverse effect on subsequent beryllium smelting. This also shows that fatty acids may be potential beryllium mineral collectors, but it is easier to make fluorite float first. Overall, the ternary coordination colloid collector of the present invention has a better flotation index, can promote the comprehensive recovery of high-calcium fluorite associated beryllium resources, and is conducive to further promotion and application.

[0041]

[0042] Example 2 Under stirring conditions, 0.05 mol of sodium oleate and 0.125 mol of ferric chloride were added in sequence to 1 L of 1.0 mol / L nonylhydroxamic acid solution, and the mixture was reacted for 3 minutes to obtain the beryllium mineral collector.

[0043] Under stirring conditions, EDTMP (ethylenediaminetetramethylenephosphonic acid), MDEA (N-methyldiethanolamine) and sodium sulfide are prepared into a mixed reagent in a mass ratio of 1:5:10, and water is added to dilute the mixed reagent to 5% of the total mass of the solution, and the mixture is fully stirred to obtain the combined adjuster.

[0044] The flotation reagent of the present invention is used to treat the fluorite flotation tailings at the production site of the concentrator. The process flow is as follows: Figure 3 As shown in the figure, the specific method steps are: using sodium carbonate to adjust the pulp pH of fluorite flotation tailings to 9.5-10.0, adding 1000g / t of combined adjusting agent, adding 400g / t of beryllium mineral collector (relative to the feed), aerating and slurry mixing for 5 minutes, and then performing beryllium roughing operation; the reagent system of scavenging follows the principle of gradual reduction, and 200g / t of beryllium mineral collector is added in scavenging; 400g / t, 200g / t and 100g / t of combined adjusting agent are added in selection I, selection II and selection III respectively. After a flotation open circuit operation of one roughing, three fines and one scavenging, beryllium concentrate K, scavenging concentrate SK, tailings X and medium ore products M1, M2 and M3 are obtained.

[0045] The process mineralogical analysis of the fluorite tailings in this example shows that the mass content of CaF2 in the sample is 11.24%, the mass content of BeO is 0.32%, the mass percentage of the -200 mesh particle size is 90.22%, and the main gangue minerals are mica silicate gangue minerals, accounting for more than 60%.

[0046] It can be seen from the open circuit flotation results in Table 4 that the flotation reagent of the present invention can achieve effective enrichment of beryllium minerals, the mass content of beryllium oxide in the concentrate is 1.56%, the beryllium loss in the tailings is less than 20%, the flotation efficiency is high, the index is good, and the CaF2 mass content in the final concentrate is less than 10%, which can also explain that the combined depressant of the present invention has better selectivity for calcium-containing gangue minerals and can effectively control the F element content in the concentrate.

[0047]

[0048] Comparative Example 2 Comparative Example 2 is used for comparison with Example 2. The specific flotation process is consistent with Example 2. The ternary complex formed by assembling iron ions, nonyl hydroxamic acid and sodium oleate is used as a beryllium mineral collector. The only difference is that the combined regulator is different from Example 2. Sodium sulfide is used in combination with a conventional inhibitor. The amount of sodium sulfide is the same as that of Example 2. Typical water glass (SBL), sodium fluorosilicate (SSF), sodium hexametaphosphate (SHMP), tartaric acid (TA), citric acid (CA) or carboxymethyl cellulose (CMC) are used as inhibitors of gangue minerals. Specifically, the amount of combined regulator added relative to the feed during the roughing process is 200g / t, and the concentration I, concentration II and concentration III are gradually reduced, and 100g / t, 50g / t and 25g / t are added in sequence. The foam product obtained after three concentrations is the beryllium concentrate. The specific flotation test results are shown in Table 5 below.

[0049] As can be seen from the table, with the increase in the number of beneficiation passes, fluorite is significantly enriched in the foam product, even overshadowing the floating trend of beryllium ore. The CaF2 mass content in the beryllium concentrate obtained by using a combined adjuster consisting of sodium sulfide and conventional inhibitors reaches more than 25%, resulting in an excessive F element content in the concentrate, which may have an adverse effect on subsequent beryllium smelting, and the grade and recovery rate of beryllium oxide in the concentrate are not as good as those in Example 2.

[0050]

Claims

1. A combined flotation reagent for fluorite-associated beryllium ore, characterized in that: Includes beryllium mineral collectors and conditioners; The beryllium mineral collector is assembled by coordination of divalent or higher metal ions, C5-C9 alkyl hydroxamic acid and fatty acid; The regulator includes organic phosphonic acid, alcohol amine and sodium sulfide.

2. The combined flotation reagent for fluorite-associated beryllium ore according to claim 1, characterized in that: The divalent or higher metal ions include Mg 2+ 、Zn 2+ , Fe 2+ , Pb 2+ , Fe 3+ 、Al 3+ At least one of the following; The fatty acid comprises at least one of oleic acid, linoleic acid, lauric acid, linolenic acid, palmitic acid, ricinoleic acid and oxidized paraffin soap.

3. The combined flotation reagent for fluorite-associated beryllium ore according to claim 1 or 2, characterized in that: The beryllium mineral collector is assembled by coordination of divalent or higher metal ions, C5-C9 alkyl hydroxamic acid and fatty acid in a molar ratio of (1-10): (1-20):

1.

4. The combined flotation reagent for fluorite-associated beryllium ore according to claim 1, characterized in that: The organic phosphonic acid includes at least one of aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hydroxyethylidene diphosphonic acid, 2-hydroxyphosphonoacetic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid; The alcohol amine includes at least one of triethanolamine, N-methyldiethanolamine, 2-amino-1,3-propylene glycol, and 3-amino-1,2-propylene glycol.

5. The combined flotation reagent for fluorite-associated beryllium ore according to claim 1 or 4, characterized in that: The adjusting agent is composed of organic phosphonic acid, alcohol amine and sodium sulfide in a mass ratio of 1: (1-5): (1-20).

6. A method for beneficiating fluorite-associated beryllium ore, characterized in that: After crushing, grinding and slurrying of fluorite associated beryllium ore, fluorite concentrate is firstly recovered by fluorite flotation, and the obtained fluorite tailings are slurried and then beryllium ore is floated using the combined flotation reagent described in any one of claims 1 to 5 to obtain beryllium concentrate.

7. The beneficiation method of fluorite-associated beryllium ore according to claim 6, characterized in that: The beryllium mineral contained in the fluorite-associated beryllium ore is at least one of chrysoberyl, beryllite, taaffeite, beryl and bluestone.

8. The beneficiation method of a fluorite-associated beryllium ore according to claim 6 or 7, characterized in that: The pH of the fluorite tailings is adjusted to 9.0-11.5, and the concentration is adjusted to 40-50 wt.%.

9. The beneficiation method of fluorite-associated beryllium ore according to claim 6 or 7, characterized in that: The beryllium ore flotation includes one roughing selection, one or more scavenging selections and two or more concentrating selections.

10. The beneficiation method of fluorite-associated beryllium ore according to claim 9, characterized in that: The reagent system of the roughing selection is: the dosage of the adjusting agent is 500-2000 g / t, and the dosage of the beryllium mineral collector is 200-600 g / t; The selected pharmaceutical system is as follows: the dosage of the adjusting agent is 100-500 g / t; The reagent system of the sweeping selection is: only beryllium mineral collector is used, and the principle of gradual reduction is followed; The mass of the adjusting agent is measured according to the mass of sodium sulfide, and the mass of the beryllium mineral collector is measured according to the mass of the fatty acid.

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