Flotation reagent for improving separation efficiency of indium tin antimony ore and preparation method thereof

Abstract

The invention relates to the technical field of mineral processing, in particular to a flotation reagent for improving the separation efficiency of indium tin antimony ores and a preparation method of the flotation reagent, the flotation reagent comprises an activating agent, a collecting agent, an inhibitor, a foaming agent, a pH adjusting agent and an auxiliary agent, the collecting agent is a mixed solution of N, N-diethyldithiocarbamate, N-phenylacetylhydroxamic acid (NPHA) and sodium carbonate, and the inhibitor is a compound complex of sodium hexametaphosphate and water glass. According to the method, diethyl ((2-hydroxyethoxy) methyl) phosphonic acid ester (DEHEMP) serves as an activating agent, a mixed solution prepared from N, N-diethyldithiocarbamate, N-phenylacetylhydroxamic acid (NPHA) and sodium carbonate according to a certain proportion serves as a collecting agent, and a compound complex of sodium hexametaphosphate and water glass serves as an inhibitor. The effect of improving the flotation process efficiency is achieved, waste of metal resources can be effectively avoided, the production cost is reduced, and the production benefit is improved.

Description

Technical Field

[0001] The invention relates to the technical field of mineral processing, and in particular to a flotation agent for improving the separation efficiency of indium tin antimony ore and a preparation method thereof. Background Art

[0002] Indium tin antimony ore has always been a difficult point in the field of mineral processing due to its complex mineral composition and fine-grained distribution characteristics. At present, the industrial separation of this type of polymetallic sulfide ore mainly relies on flotation technology. Commonly used flotation reagents include traditional sulfur-based collectors such as xanthate and black medicine, as well as inhibitors such as water glass.

[0003] However, these agents can sort some metal minerals to a certain extent, but the recovery effect of elements such as indium, tin and antimony is not ideal. In particular, as a scattered element, indium often exists in the ore in the form of fine particles, which is difficult to effectively capture with traditional agents. In addition, the inhibitory effect of existing inhibitors on gangue minerals is limited, and it is impossible to effectively reduce the floating of impurities, which affects the quality of the concentrate. In terms of activators, commonly used inorganic activators such as copper sulfate have limited activation effects on some minerals, the interactions between agents are complex, and the formulation optimization is difficult, making it difficult to meet the sorting requirements of complex ores. These problems seriously restrict the efficient recovery of indium, tin and antimony ores.

[0004] Therefore, there is a need for an efficient and environmentally friendly flotation agent that can improve the separation efficiency of indium tin antimony ore. Summary of the invention

[0005] The main purpose of the present invention is to provide a flotation agent for improving the separation efficiency of indium tin antimony ore and a preparation method thereof, aiming to solve the problem of low efficiency of existing indium tin antimony ore separation efficiency.

[0006] To achieve the above object, the present invention proposes a flotation agent for improving the separation efficiency of indium tin antimony ore. The flotation agent includes an activator, a collector, an inhibitor, a frother, a pH regulator and an auxiliary agent, including the following raw materials in parts by weight:

[0007] Activator: diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) 5-15 wt%, water 95-85 wt%;

[0008] Collector: 8-12 wt% of ethylthiocyanate, 18-22 wt% of N-phenylacetoisoxamic acid (NPHA), 25-35 wt% of sodium carbonate, and 31-49 wt% of water;

[0009] Inhibitor: sodium hexametaphosphate 25-35wt%, water glass solution 43-53wt%, water 32-12wt%;

[0010] Foaming agent: methyl isobutyl carbinol 4-7wt%, water 96-93wt%;

[0011] pH regulator: sodium carbonate 5-20wt%, water 80-95wt%;

[0012] Auxiliary agent: sodium sulfide nonahydrate 8-12wt%, 88-92wt%.

[0013] Furthermore, the flotation reagent includes the following raw materials by mass fraction:

[0014] Activator: diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) 5-15 wt%, water 95-85 wt%;

[0015] Collector: 8-12 wt% of ethylthiocyanate, 18-22 wt% of N-phenylacetoisoxamic acid (NPHA), 25-35 wt% of sodium carbonate, and 31-49 wt% of water;

[0016] Inhibitor: sodium hexametaphosphate 30wt%, water glass solution 50wt%, water 20wt%;

[0017] Foaming agent: methyl isobutyl carbinol 5wt%, water 95wt%;

[0018] pH adjuster: sodium carbonate 10wt%, water 90wt%;

[0019] Auxiliary agent: sodium sulfide nonahydrate 10wt%, 90wt%.

[0020] Furthermore, the water glass solution is a Na2SiO3 solution with a solid content of 30%.

[0021] Furthermore, the solute in the inhibitor is a composite complex obtained by complexing sodium hexametaphosphate with a water glass solution.

[0022] The present invention also proposes a method for preparing a flotation agent for improving the separation efficiency of indium tin antimony ore as described in the above technical solution. The method for preparing an activator in the flotation agent comprises the following steps:

[0023] Triethylphosphine and 2-chloroethanol are stirred and mixed under the protection of an inert gas to obtain an activator base liquid;

[0024] Adding a basic catalyst to the activator base liquid and reacting at room temperature for 3 to 5 hours to obtain (2-hydroxyethoxy)phosphonate;

[0025] (2-hydroxyethoxy)phosphonate is mixed with ethyl bromide, and heated under reflux under alkaline conditions to carry out ethylation reaction to obtain diethyl ((2-hydroxyethoxy)methyl)phosphonate (DEHEMP);

[0026] Diethyl ((2-hydroxyethoxy)methyl)phosphonate is mixed with water to give the activator.

[0027] Furthermore, the preparation method of the collector in the flotation reagent comprises the following steps:

[0028] Dissolving diethylamine in water under stirring to obtain a diethylamine aqueous solution;

[0029] At room temperature, slowly add carbon disulfide to the diethylamine aqueous solution, and at the same time add sodium hydroxide solution to ensure that the reaction mixture is alkaline;

[0030] The solution was concentrated to dryness to obtain diethyldithiocarbamate (sodium diethyldithiocarbamate, DDTC).

[0031] Furthermore, the method for preparing the collector in the flotation reagent further comprises the following steps:

[0032] Dissolve aniline in anhydrous ethanol in an ice bath, slowly add acetamide and maintain the temperature at 0-5°C with continuous stirring to generate N-phenylacetamide;

[0033] Dissolve N-phenylacetamide in anhydrous ethanol, add hydroxylamine hydrochloride and an alkali agent, so that hydroxylamine exists in the form of free hydroxylamine;

[0034] After heating under reflux for 4 to 8 hours, cool to room temperature and adjust the pH value of the solution to neutral;

[0035] After filtering, washing and drying, N-phenylacetylhydroxamic acid crystals are obtained;

[0036] Ethiocarb is mixed with N-phenylacetoisoxamic acid (NPHA), sodium carbonate and water to obtain a collector.

[0037] Furthermore, the method for preparing the inhibitor in the flotation reagent comprises the following steps:

[0038] The sodium dihydrogen phosphate is heated to 600-700°C and maintained at this temperature to dehydrate and polymerize to form a sodium hexametaphosphate melt;

[0039] The melt is rapidly cooled to form a glassy solid, and the cooled glassy solid is crushed into powder to obtain a sodium hexametaphosphate product;

[0040] Mix quartz sand and sodium carbonate in a mass ratio of about 1:1, and heat them in a high-temperature furnace to 1300-1400°C to melt the mixture and react. After the reaction is completed, molten water glass is obtained;

[0041] Cooling the molten water glass to obtain solid water glass, and then dissolving the solid water glass in hot water to obtain a water glass solution of desired concentration;

[0042] Sodium hexametaphosphate and water glass solution are dissolved in water at a ratio of 1:1.5 to prepare a 10% to 20% composite complex solution to obtain an inhibitor.

[0043] In the present invention, diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) is used as an activator to enhance the effect of indium tin antimony minerals and collectors, thereby improving the flotation recovery rate; a mixed solution prepared by ethylthiocyanate, N-phenylacetoisoxamic acid (NPHA) and sodium carbonate in a certain proportion is used as a collector to improve the selective collection of indium, tin and antimony minerals and reduce the flotation of impurity minerals; a complex of sodium hexametaphosphate and water glass is used as an inhibitor to inhibit the flotation of gangue minerals and improve the concentrate grade. The present invention achieves the effect of improving the efficiency of the flotation process, and in the development of complex metal resources, it can effectively avoid the waste of metal resources, reduce production costs, and improve production benefits. DETAILED DESCRIPTION

[0044] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0045] It should be noted that all directional indications in the embodiments of the present invention (such as up, down, left, right, front, back, etc.) are only used to explain the relative position relationship, movement status, etc. between the components in a certain specific posture. If the specific posture changes, the directional indication will also change accordingly.

[0046] In addition, the descriptions of "first", "second", etc. in the present invention are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in the field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0047] The specific components of the selected activator involved in the present invention are diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP, with a structural formula such as Formula 1); the specific components of the collector are ethylthiocyanate (with a structural formula such as Formula 2), N-phenylacetylisoxamic acid (NPHA, with a structural formula such as Formula 3), and sodium carbonate; and the specific components of the inhibitor are a complex of sodium hexametaphosphate and water glass.

[0048]

[0049]

[0050] Among them, the phosphonate group in DEHEMP has good metal ion complexing ability and can form stable complexes with metal ions such as indium, tin, and antimony. The molecule contains hydrophilic and hydrophobic groups, which is conducive to selective adsorption on the surface of minerals. The chemical name of ethyl dithiocarbamate is sodium diethyl dithiocarbamate (DDTC). It has good capture performance for metal sulfide minerals, and its capture ability for some non-metallic minerals is weak, which is conducive to improving flotation selectivity. N-phenylacetyl isoxime (NPHA) has good capture ability for oxidized minerals and some metal minerals. Its hydroxamic acid group can form stable chelates with metal ions. Sodium carbonate is used to adjust the pH value of the pulp, improve the activity of the collector, help disperse mineral particles, and prevent flocculation. The mixed use of ethyl dithiocarbamate and NPHA can produce a synergistic capture effect on metal minerals of different properties and improve the recovery rate. Sodium hexametaphosphate can complex metal ions in the slurry, prevent the agglomeration of mineral particles, and inhibit the surface of gangue minerals such as iron, calcium, and magnesium. At the same time, it improves the stability of the slurry, prevents the sedimentation of mineral particles, and has a synergistic inhibitory effect. By compounding sodium hexametaphosphate with water glass, the inhibitory effect on gangue minerals can be enhanced and the concentrate grade can be improved. The foaming agent is pine alcohol oil (MIBC), the pH regulator is sodium carbonate (Na2CO3), and the auxiliary agent is sodium sulfide (Na2S·9H2O).

[0051] The present invention also discloses specific application examples 1-3 and flotation reagent formulas and performance comparison experiments of control examples 1-2 using the prior art, which are as follows:

[0052] raw material:

[0053] 1. Indium tin antimony slurry: Grind the indium tin antimony ore until the particles with a diameter of less than 0.074 mm account for 70%, and adjust the slurry to a slurry concentration of 30%.

[0054] 2. Flotation reagent: Activator: Diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP)

[0055] Collectors: DDTC, N-phenylacetohydroxamic acid (NPHA)

[0056] Inhibitor: Sodium hexametaphosphate (SHMP) and water glass (Na2SiO3) complex

[0057] Foaming agent: pine alcohol oil (MIBC)

[0058] pH adjuster: sodium carbonate (Na2CO3)

[0059] Auxiliary agent: sodium sulfide (Na2S·9H2O)

[0060] Embodiment 1:

[0061] Table 1 Flotation reagent formula of Example 1 (g / t)

[0062] Drug Name Dosage(g / t) Activator DEHEMP 150 Collector DDTC 100 Collector NPHA 200 SHMP inhibitor 300 Inhibitor water glass 400 Foaming agent MIBC 50 <![CDATA[pH regulator Na2CO3]]> 800 <![CDATA[Auxiliary agent Na2S·9H2O]]> 80

[0063] Embodiment 2:

[0064] Table 2 Flotation reagent formula of Example 2 (g / t)

[0065] Drug Name Dosage(g / t) Activator DEHEMP 200 Collector DDTC 120 Collector NPHA 250 SHMP inhibitor 350 Inhibitor water glass 450 Foaming agent MIBC 60 <![CDATA[pH regulator Na2CO3]]> 850 <![CDATA[Auxiliary agent Na2S·9H2O]]> 90

[0066] Embodiment 3:

[0067] Table 3 Flotation reagent formula of Example 3 (g / t)

[0068]

[0069]

[0070] Comparative Example 1:

[0071] Table 4 Flotation reagent formula of comparative example 1 (g / t)

[0072] Drug Name Dosage(g / t) Collector Xanthate 200 Collector black medicine 150 Inhibitor water glass 600 Foaming agent 2# oil 60 pH adjuster lime 1000 No auxiliary agent -

[0073] Comparative Example 2:

[0074] Table 5 Flotation reagent formula of comparative example 2 (g / t)

[0075]

[0076] In order to verify the effect of the flotation reagent formula proposed in the present invention on the flotation effect of indium tin antimony ore, the present invention designed the above three groups of examples and two groups of control examples. Examples 1-3 respectively used different proportions of activators, collectors, inhibitors, frothers, pH regulators, and auxiliary agents to obtain products obtained according to the technical means of the present invention and to verify the corresponding data. Control examples 1-2 used the current existing technology. It is also necessary to measure and compare the flotation indicators of each group, including concentrate grade, recovery rate, etc., through quantitative sample tests.

[0077] (II) Performance comparison experiment

[0078] The specific steps of flotation are as follows:

[0079] S1. Grind the indium, tin and antimony ore until the particle diameter is less than 0.074 mm, accounting for 70%, and adjust the slurry to a slurry concentration of 30%;

[0080] S2, add pH regulator Na2CO3, adjust pH to 8.5;

[0081] S3, adding the compound complex of inhibitor SHMP and water glass, stirring for 30 minutes;

[0082] S4, add activator DEHEMP and stir for 50 minutes;

[0083] S5, add auxiliary agent sodium sulfide, stir for 20 minutes;

[0084] S6, add collector DDTC and stir for 20 minutes, then add NPHA and stir for 20 minutes;

[0085] S7, adding frother MIBC, stirring for 10 minutes and then flotation;

[0086] S8. Filter, wash and dry the foamed ore product obtained after flotation to obtain concentrate, and calculate the recovery rate and concentrate grade according to the formula.

[0087] The calculation formula of recovery rate is:

[0088] Recovery rate (%) = (mass of target element in concentrate) / (total mass of target element in raw ore) * 100%

[0089] The formula for calculating the concentrate grade is:

[0090] Concentrate grade (%) = (mass of target element in concentrate) / (total mass of concentrate) * 100%

[0091] Table 6 Metal recovery and concentrate grade test data

[0092]

[0093] Data Analysis:

[0094] Recovery rate and grade of tin: The grade and recovery rate of the tin concentrate of Examples 1-3 are significantly higher than those of Control Examples 1-2. With the increase in the dosage of the reagent (Examples 1-3), the recovery rate and grade are improved.

[0095] Recovery rate and grade of antimony: The grade and recovery rate of the antimony concentrate of Examples 1-3 are also significantly better than those of the control example, and also show a trend of increasing with the increase in the dosage of the reagent.

[0096] Recovery rate and grade of indium: The grade and recovery rate of the indium concentrate in Examples 1-3 were improved more significantly, indicating that the proposed reagent formula has a better effect on the enrichment of indium.

[0097] Experimental conclusion:

[0098] Through the experimental data of the above three groups of embodiments and two groups of control embodiments, it can be seen that the advantage of the flotation reagent formula in the present invention compared with the traditional technology is that it fully considers the mineral characteristics of the indium tin antimony ore and proposes the targeted use of DEHEMP as an activator, DDTC and NPHA as collectors, and SHMP and water glass composite inhibitor, which can significantly improve the flotation effect of the indium tin antimony ore, and the addition of sodium sulfide nonahydrate as an auxiliary agent is beneficial to activate the mineral surface and improve the flotation efficiency. Using pine alcohol oil (MIBC) as a frother, the foam is fine and stable, which is beneficial to improve the quality of the concentrate.

[0099] In combination with all the above embodiments, the present invention adopts diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) as an activator to enhance the effect of indium tin antimony minerals and collectors, thereby improving the flotation recovery rate; a mixed solution prepared by ethylthiocyanate, N-phenylacetoisoxamic acid (NPHA), and sodium carbonate in a certain proportion is used as a collector to improve the selective capture of indium, tin, and antimony minerals and reduce the flotation of impurity minerals; a complex of sodium hexametaphosphate and water glass is used as an inhibitor to inhibit the flotation of gangue minerals and improve the concentrate grade. The present invention achieves the effect of improving the efficiency of the flotation process, and in the development of complex metal resources, it can effectively avoid the waste of metal resources, reduce production costs, and improve production efficiency.

[0100] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification under the inventive concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A flotation agent for improving the separation efficiency of indium, tin and antimony ore, characterized in that: The flotation reagent includes an activator, a collector, an inhibitor, a frother, a pH regulator and an auxiliary agent, including the following raw materials in parts by weight: Activator: diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) 5-15 wt%, water 95-85 wt%; Collector: 8-12 wt% of ethylthiocyanate, 18-22 wt% of N-phenylacetoisoxamic acid (NPHA), 25-35 wt% of sodium carbonate, and 31-49 wt% of water; Inhibitor: sodium hexametaphosphate 25-35wt%, water glass solution 43-53wt%, water 32-12wt%; Foaming agent: methyl isobutyl carbinol 4-7wt%, water 96-93wt%; pH regulator: sodium carbonate 5-20wt%, water 80-95wt%; Auxiliary agent: sodium sulfide nonahydrate 8-12wt%, 88-92wt%.

2. The flotation agent for improving the separation efficiency of indium tin antimony ore according to claim 1, characterized in that: The flotation reagent includes the following raw materials by mass fraction: Activator: diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) 5-15 wt%, water 95-85 wt%; Collector: 8-12 wt% of ethylthiocyanate, 18-22 wt% of N-phenylacetoisoxamic acid (NPHA), 25-35 wt% of sodium carbonate, and 31-49 wt% of water; Inhibitor: sodium hexametaphosphate 30wt%, water glass solution 50wt%, water 20wt%; Foaming agent: methyl isobutyl carbinol 5wt%, water 95wt%; pH adjuster: sodium carbonate 10wt%, water 90wt%; Auxiliary agent: sodium sulfide nonahydrate 10wt%, 90wt%.

3. The flotation agent for improving the separation efficiency of indium tin antimony ore according to claim 1, characterized in that: The water glass solution is a Na2SiO3 solution with a solid content of 30%.

4. The flotation agent for improving the separation efficiency of indium tin antimony ore according to claim 1, characterized in that: The solute in the inhibitor is a composite complex obtained by complexing sodium hexametaphosphate with a water glass solution.

5. A method for preparing a flotation agent for improving the separation efficiency of indium tin antimony ore as claimed in claims 1 to 4, characterized in that: The preparation method of the activator in the flotation reagent comprises the following steps: Triethylphosphine and 2-chloroethanol are stirred and mixed under the protection of an inert gas to obtain an activator base liquid; Adding a basic catalyst to the activator base liquid and reacting at room temperature for 3 to 5 hours to obtain (2-hydroxyethoxy)phosphonate; (2-hydroxyethoxy)phosphonate is mixed with ethyl bromide and heated under reflux under alkaline conditions to carry out ethylation reaction to obtain diethyl ((2-hydroxyethoxy)methyl)phosphonate (DEHEMP); Diethyl ((2-hydroxyethoxy)methyl)phosphonate is mixed with water to give the activator.

6. The method for preparing a flotation agent for improving the separation efficiency of indium tin antimony ore according to claim 5, characterized in that: The preparation method of the collector in the flotation reagent comprises the following steps: Dissolving diethylamine in water under stirring to obtain a diethylamine aqueous solution; At room temperature, slowly add carbon disulfide to the diethylamine aqueous solution, and at the same time add sodium hydroxide solution to ensure that the reaction mixture is alkaline; The solution was concentrated to dryness to obtain diethyldithiocarbamate (sodium diethyldithiocarbamate, DDTC).

7. The method for preparing a flotation agent for improving the separation efficiency of indium tin antimony ore according to claim 6, characterized in that: The method for preparing the collector in the flotation reagent also includes the following steps: Dissolve aniline in anhydrous ethanol in an ice bath, slowly add acetamide and maintain the temperature at 0-5°C with continuous stirring to generate N-phenylacetamide; Dissolve N-phenylacetamide in anhydrous ethanol, add hydroxylamine hydrochloride and an alkali agent, so that hydroxylamine exists in the form of free hydroxylamine; After heating under reflux for 4 to 8 hours, cool to room temperature and adjust the pH value of the solution to neutral; After filtering, washing and drying, N-phenylacetylhydroxamic acid crystals are obtained; Ethiocarb is mixed with N-phenylacetoisoxamic acid (NPHA), sodium carbonate and water to obtain a collector.

8. The method for preparing a flotation agent for improving the separation efficiency of indium tin antimony ore according to claim 5, characterized in that: The method for preparing the inhibitor in the flotation reagent comprises the following steps: The sodium dihydrogen phosphate is heated to 600-700°C and maintained at this temperature to dehydrate and polymerize to form a sodium hexametaphosphate melt; The melt is rapidly cooled to form a glassy solid, and the cooled glassy solid is crushed into powder to obtain a sodium hexametaphosphate product; Mix quartz sand and sodium carbonate in a mass ratio of about 1:1, and heat them in a high-temperature furnace to 1300-1400°C to melt the mixture and react. After the reaction is completed, molten water glass is obtained; Cooling the molten water glass to obtain solid water glass, and then dissolving the solid water glass in hot water to obtain a water glass solution of desired concentration; Sodium hexametaphosphate and water glass solution are dissolved in water at a ratio of 1:1.5 to prepare a 10% to 20% composite complex solution to obtain an inhibitor.

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