A flotation reagent for improving the separation efficiency of indium tin antimony ore and a preparation method thereof

Abstract

The present application relates to the technical field of mineral processing, and particularly relates to a flotation reagent for improving the separation efficiency of indium-tin-antimony ore and a preparation method thereof, the flotation reagent comprises an activator, a collector, an inhibitor, a foaming agent, a pH regulator and an auxiliary agent, and comprises: the activator is diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP), the collector is a mixed solution of ethion, N-phenylacetyl isoxazoline (NPHA) and sodium carbonate, and the inhibitor is a complex compound of sodium hexametaphosphate and water glass.The present application uses diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) as the activator, a mixed solution of ethion, N-phenylacetyl isoxazoline (NPHA) and sodium carbonate prepared according to a certain proportion as the collector, and a complex compound of sodium hexametaphosphate and water glass as the inhibitor, so that the efficiency of the flotation process is improved, metal resources can be effectively avoided from being wasted, production cost is reduced, and production benefit is improved.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, and in particular to a flotation reagent for improving the separation efficiency of indium-tin-antimony ore and its preparation method. Background Technology

[0002] Indium-tin-antimony ore has always been a challenge in mineral processing due to its complex mineral composition and fine-grained dispersive characteristics. Currently, industrial beneficiation of this type of polymetallic sulfide ore mainly relies on flotation processes. Commonly used flotation reagents include traditional sulfur-based collectors such as xanthates and diammonium phosphates, as well as depressants such as water glass.

[0003] However, while these reagents can separate some metallic minerals to a certain extent, their recovery efficiency for elements such as indium, tin, and antimony is not ideal. Indium, in particular, as a rare and dispersed element, often exists in the ore in the form of fine particles, making it difficult for traditional reagents to effectively capture. Furthermore, current inhibitors have limited effectiveness against gangue minerals, failing to effectively reduce the flotation of impurities and affecting the quality of the concentrate. Regarding activators, commonly used inorganic activators such as copper sulfate have limited activation effects on some minerals. The interactions between reagents are complex, making formulation optimization difficult and failing to meet the separation requirements of complex ores. These problems severely restrict the efficient recovery of indium, tin, and antimony ores.

[0004] Therefore, there is a need for a highly efficient and environmentally friendly flotation reagent to improve the separation efficiency of indium-tin-antimony ore. Summary of the Invention

[0005] The main objective of this invention is to provide a flotation reagent and its preparation method for improving the separation efficiency of indium-tin-antimony ore, aiming to solve the problem of low efficiency in existing indium-tin-antimony ore separation processes.

[0006] To achieve the above objectives, this invention proposes a flotation reagent for improving the separation efficiency of indium-tin-antimony ore. The flotation reagent comprises an activator, a collector, an inhibitor, a frother, a pH adjuster, and auxiliary agents, including the following raw materials in parts by weight:

[0007] Activator: Diethyl ((2-hydroxyethoxy)methyl)phosphonic acid ester (DEHEMP) 5-15 wt%, water 95-85 wt%;

[0008] Collector: 8-12 wt% ethyl thiocyanate, 18-22 wt% N-phenylacetylisoxamic acid (NPHA), 25-35 wt% sodium carbonate, 31-49 wt% water;

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

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

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

[0012] Additives: Sodium sulfide nonahydrate 8-12 wt%, 88-92 wt%.

[0013] Furthermore, the flotation reagent comprises raw materials in the following mass fractions:

[0014] Activator: Diethyl ((2-hydroxyethoxy)methyl)phosphonic acid ester (DEHEMP) 5-15 wt%, water 95-85 wt%;

[0015] Collector: 8-12 wt% ethyl thiocyanate, 18-22 wt% N-phenylacetylisoxamic acid (NPHA), 25-35 wt% sodium carbonate, 31-49 wt% water;

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

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

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

[0019] Additives: 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 complex obtained by complexing sodium hexametaphosphate with water glass solution.

[0022] This invention also proposes a method for preparing flotation reagents to improve the separation efficiency of indium-tin-antimony ore as described in the above technical solution, wherein the preparation method of the activator in the flotation reagent includes the following steps:

[0023] Triethylphosphine and 2-chloroethanol were stirred and mixed under inert gas protection to obtain the activator base solution;

[0024] An alkaline catalyst was added to the activator base solution, and the reaction was carried out at room temperature for 3 to 5 hours to obtain (2-hydroxyethoxy)phosphonate.

[0025] (2-hydroxyethoxy)phosphonate was mixed with bromoethane and heated under alkaline conditions under reflux to carry out an ethylation reaction, yielding diethyl ((2-hydroxyethoxy)methyl)phosphonate (DEHEMP);

[0026] An activator is obtained by mixing diethyl((2-hydroxyethoxy)methyl)phosphonic acid ester with water.

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

[0028] Diethylamine was dissolved in water under stirring to obtain an aqueous solution of diethylamine.

[0029] At room temperature, carbon disulfide was slowly added to an aqueous solution of diethylamine, while sodium hydroxide solution was added simultaneously to ensure that the reaction mixture was alkaline.

[0030] The solution was concentrated and dried to obtain ethyl thiocyanate (sodium diethyl dithiocarbamate, DDTC).

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

[0032] Aniline was dissolved in anhydrous ethanol under ice bath conditions, acetamide was slowly added and the temperature was maintained at 0-5°C while stirring continuously to generate N-phenylacetamide.

[0033] N-phenylacetamide was dissolved in anhydrous ethanol, and hydroxylamine hydrochloride and an alkaline agent were added to allow hydroxylamine to exist in the form of free hydroxylamine.

[0034] After heating and refluxing for 4–8 hours, cool to room temperature and adjust the pH of the solution to neutral.

[0035] After filtration, washing, and drying, N-phenylacetylhydroxamic acid crystals were obtained;

[0036] A collector is obtained by mixing ethyl thiocyanate with N-phenylacetylisoxamic acid (NPHA), sodium carbonate, and water.

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

[0038] Sodium dihydrogen phosphate is heated to 600-700°C and maintained at this temperature to dehydrate and polymerize, producing sodium hexametaphosphate melt.

[0039] The melt is rapidly cooled to form a glassy solid. The cooled glassy solid is then crushed into powder to obtain sodium hexametaphosphate.

[0040] Quartz sand and sodium carbonate are mixed in a mass ratio of approximately 1:1 and heated in a high-temperature furnace to 1300–1400°C to melt the mixture and allow it to react. After the reaction is complete, molten water glass is obtained.

[0041] The molten water glass is cooled to obtain solid water glass, which is then dissolved in hot water to obtain a water glass solution of the desired concentration.

[0042] Sodium hexametaphosphate and water glass solution were dissolved in water at a ratio of 1:1.5 to prepare a 10%–20% complex solution, which yielded the inhibitor.

[0043] This invention employs diethyl ((2-hydroxyethoxy)methyl)phosphonic acid ester (DEHEMP) as an activator to enhance the interaction between indium, tin, and antimony minerals and the collector, thereby improving flotation recovery. A mixed solution prepared from ethyl thiocyanate, N-phenylacetylisoxamic acid (NPHA), and sodium carbonate in a specific ratio 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 acts as an inhibitor, suppressing the flotation of gangue minerals and improving concentrate grade. This invention achieves the effect of improving the efficiency of the flotation process, effectively avoiding waste of metal resources, reducing production costs, and improving production efficiency in the development of complex metal resources. Detailed Implementation

[0044] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

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

[0046] Furthermore, the use of terms such as "first" and "second" in this invention is for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of that feature. Additionally, the technical solutions of the various embodiments can be combined with each other, but only on the basis of being achievable by those skilled in the art. When the combination of technical solutions is contradictory or impossible to implement, such a combination of technical solutions should be considered non-existent and not within the scope of protection claimed by this invention.

[0047] The specific components of the activator used in this invention are diethyl ((2-hydroxyethoxy)methyl)phosphonic acid ester (DEHEMP, structural formula as shown in Formula 1); the specific components of the collector are ethyl thiocyanate (structural formula as shown in Formula 2), N-phenylacetylisoxamic acid (NPHA, structural formula as shown in Formula 3), and sodium carbonate; and the specific components of the inhibitor are sodium hexametaphosphate and water glass complex.

[0048]

[0049]

[0050] DEHEMP contains phosphonate groups, which exhibit excellent metal ion complexing ability, forming stable complexes with metal ions such as indium, tin, and antimony. Its molecules also contain both hydrophilic and hydrophobic groups, facilitating selective adsorption on mineral surfaces. Diethyl thiocyanate (DDTC) has excellent collecting properties for metal sulfide minerals, but its collecting ability for some non-metallic minerals is weaker, thus improving flotation selectivity. N-Phenylacetylisoxamic acid (NPHA) has good collecting ability for oxidized minerals and some metallic minerals. Its hydroxamic acid groups can form stable chelates with metal ions. Sodium carbonate is used to adjust the pH of the pulp, improve the activity of the collector, aid in mineral particle dispersion, and prevent flocculation. Furthermore, the combined use of ethyl thiocyanate and NPHA can produce a synergistic collecting effect on metallic minerals with different properties, improving recovery rates. Sodium hexametaphosphate can complex metal ions in the slurry, preventing the aggregation of mineral particles and inhibiting the surface formation of gangue minerals such as iron, calcium, and magnesium. It also improves the stability of the slurry, prevents mineral particle sedimentation, and has a synergistic inhibitory effect. By combining sodium hexametaphosphate with water glass, the inhibitory effect on gangue minerals can be enhanced, improving the concentrate grade. The frother is pine oil (MIBC), the pH adjuster 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 comparative flotation reagent formulations and performance experiments using prior art control examples 1-2, as detailed below:

[0052] raw material:

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

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

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

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

[0057] Foaming agent: MIBC (pine oil)

[0058] pH adjuster: Sodium carbonate (Na₂CO₃)

[0059] Additive: Sodium sulfide (Na2S·9H2O)

[0060] Example 1:

[0061] Table 1. Flotation reagent formulation for Example 1 (g / t)

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

[0063] Example 2:

[0064] Table 2. Flotation reagent formulation (g / t) for Example 2

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

[0066] Example 3:

[0067] Table 3. Flotation reagent formulation (g / t) for Example 3

[0068]

[0069]

[0070] Comparative Example 1:

[0071] Table 4. Flotation reagent formulation (g / t) for Comparative Example 1

[0072] Drug Name Dosage (g / t) xanthate, a collector 200 Harvester Black Medicine 150 Inhibitor water glass 600 Foaming agent #2 oil 60 pH adjuster lime 1000 No adjuvants -

[0073] Comparative Example 2:

[0074] Table 5. Flotation reagent formulation (g / t) for Comparative Example 2

[0075]

[0076] To verify the effect of the flotation reagent formulation proposed in this invention on the flotation effect of indium-tin-antimony ore, this invention designed the above three sets of exemplary formulations and two sets of control formulations. Examples 1-3 used different proportions of activator, collector, inhibitor, frother, pH adjuster, and auxiliary agent, respectively, obtaining products according to the technical means of this invention and verifying the corresponding data. Control examples 1-2 used existing technology. Further quantitative sample experiments are needed to determine and compare the flotation indicators of each group, including concentrate grade and recovery rate.

[0077] (II) Performance Comparison Experiment

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

[0079] S1. Grind the indium-tin-antimony ore until 70% of the particles have a diameter of less than 0.074 mm, and adjust the slurry to a slurry concentration of 30%.

[0080] S2. Add pH adjuster Na2CO3 to adjust the pH to 8.5;

[0081] S3. Add the complex of the inhibitor SHMP and water glass, and stir for 30 minutes;

[0082] S4. Add activator DEHEMP and stir for 50 minutes;

[0083] S5. Add sodium sulfide as an auxiliary agent and stir for 20 minutes;

[0084] S6. After adding the collector DDTC and stirring for 20 minutes, add NPHA and stir for 20 minutes.

[0085] S7. Add frother MIBC, stir for 10 minutes, and then perform flotation.

[0086] S8. The frothy mineral product obtained after flotation is filtered, washed, and dried to obtain concentrate. The recovery rate and concentrate grade are calculated according to the formula.

[0087] The formula for calculating the recovery rate is as follows:

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

[0089] The formula for calculating concentrate grade is:

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

[0091] Table 6. Recovery rates of various metals and their concentrate grades.

[0092]

[0093] Data Analysis:

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

[0095] Antimony recovery rate and grade: The antimony concentrate grade and recovery rate of Examples 1-3 were also significantly better than those of the control example, and similarly showed an increasing trend with the increase of reagent dosage.

[0096] Indium recovery rate and grade: The indium concentrate grade and recovery rate of Examples 1-3 showed a more significant increase, indicating that the proposed reagent formulation has a better effect on indium enrichment.

[0097] Experimental conclusion:

[0098] Based on the experimental data from the three sets of embodiments and two sets of comparative embodiments described above, it can be seen that the advantage of the flotation reagent formulation in this invention compared to traditional technologies lies in its comprehensive consideration of the mineral characteristics of indium tin antimony ore. It employs DEHEMP as an activator, DDTC and NPHA as collectors, and a composite inhibitor of SHMP and water glass, which significantly improves the flotation effect of indium tin antimony ore. Furthermore, the addition of sodium sulfide nonahydrate as an auxiliary agent helps activate the mineral surface and improve flotation efficiency. The use of pine oil (MIBC) as a frother results in fine and stable foam, which is beneficial for improving concentrate quality.

[0099] In combination with all the above embodiments, this invention employs diethyl ((2-hydroxyethoxy)methyl)phosphonic acid ester (DEHEMP) as an activator to enhance the interaction between indium, tin, and antimony minerals and the collector, thereby improving flotation recovery. A mixed solution prepared from ethyl thiocyanate, N-phenylacetylisoxamic acid (NPHA), and sodium carbonate in a certain proportion serves as the collector, improving the selective collection of indium, tin, and antimony minerals and reducing the flotation of impurity minerals. A complex of sodium hexametaphosphate and water glass acts as an inhibitor, suppressing the flotation of gangue minerals and improving concentrate grade. This invention achieves the effect of improving the efficiency of the flotation process, effectively avoiding waste of metal resources, reducing production costs, and improving production efficiency in the development of complex metal resources.

[0100] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

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

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

3. The flotation reagent for improving the separation efficiency of indium tin antimony ore according to claim 1, wherein The water glass solution is Solution, solid content 30%.

4. The flotation reagent for improving the separation efficiency of indium tin antimony ore according to claim 1, wherein The solute in the depressor is a complex compound obtained by complexing sodium hexametaphosphate and water glass solution.

5. A method of preparing a flotation reagent for improving the separation efficiency of indium-tin-antimony ore according to any one of claims 1 to 4, characterized in that, The preparation method of the activator in the flotation reagent comprises the following steps: Triethyl phosphine and 2-chloroethanol are mixed under inert gas protection to obtain activator base solution; An alkaline catalyst is added to the activator base solution, and a (2-hydroxyethoxy) phosphonate is obtained by reacting at room temperature for 3-5 hours; The (2-hydroxyethoxy) phosphonate is mixed with bromoethane, and ethylation reaction is carried out under alkaline conditions and heating reflux to obtain diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP); The diethyl ((2-hydroxyethoxy) methyl) phosphonate is mixed with water to obtain the activator.

6. The method for preparing the flotation reagent for improving the separation efficiency of indium-tin-antimony ore as described in claim 5, characterized in that, The preparation method of the collector in the flotation reagent comprises the following steps: Diethylamine is dissolved in water under stirring to obtain diethylamine aqueous solution; Carbon disulfide is slowly added to the diethylamine aqueous solution under room temperature, and sodium hydroxide solution is added at the same time to ensure that the reaction mixture is alkaline; The solution is concentrated and dried to obtain ethyldithiocarbamic acid (sodium diethyldithiocarbamate, DDTC).

7. The method for preparing the flotation reagent for improving the separation efficiency of indium-tin-antimony ore as described in claim 6, characterized in that, The preparation method of the collector in the flotation reagent further comprises the following steps: Aniline is dissolved in anhydrous ethanol under ice bath condition, acetic amide is slowly added and the temperature is maintained at 0-5℃, and stirring is continuously carried out to generate N-phenylacetamide; N-phenylacetamide is dissolved in anhydrous ethanol, hydroxylamine hydrochloride and alkali agent are added to make hydroxylamine exist in free hydroxylamine form; After heating and refluxing for 4-8 hours, the solution is cooled to room temperature, and the pH value of the solution is adjusted to neutral; After filtration, washing and drying, N-phenyl acetyl hydroxamic acid crystals are obtained; Ethylthiourea is mixed with N-phenyl acetyl hydroxamic acid (NPHA), sodium carbonate and water to obtain a collector.

8. The method for preparing the flotation reagent for improving the separation efficiency of indium-tin-antimony ore as described in claim 5, characterized in that, The preparation method of the depressor in the flotation reagent comprises the following steps: Sodium dihydrogen phosphate is heated to 600-700 DEG C and kept at this temperature to make it 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 sodium hexametaphosphate product; Quartz sand is mixed with sodium carbonate at a mass ratio of 1:1, and heated to 1300-1400 DEG C in a high-temperature furnace to melt and react the mixture; after the reaction is completed, a molten water glass is obtained; The molten water glass is cooled to obtain solid water glass, which is then dissolved in hot water to obtain a water glass solution with a desired concentration; Sodium hexametaphosphate and the water glass solution are dissolved in water at a ratio of 1:1.5 to prepare a 10%-20% complex compound solution to obtain the depressor.

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