Iron ion inhibitor composition and application thereof

Abstract

The invention relates to an iron ion inhibitor composition and application thereof. The iron ion inhibitor composition is prepared by combining 2 to 2.5 parts of soluble salt of oxalic acid, 1 to 1.5 parts of ammonium phosphate compound and 1.0 to 1.5 parts of triethanolamine. The iron ion inhibitor composition can be added in the ore grinding process, after ore grinding or in the flotation pulp mixing process of copper-lead-zinc oxide minerals, and then conventional flotation pulp mixing and flotation separation operation is carried out. The concentration of iron ions in ore pulp can be effectively reduced, iron species adsorbed on the surface of the ore can be stripped, accordingly, the flotation recovery rate and the concentrate grade of the copper-lead-zinc oxide ore are remarkably improved, agent consumption is reduced, and the method has the advantages of being simple in process, wide in applicability and the like.

Description

Technical Field

[0001] The present invention relates to the field of mineral processing, and specifically relates to an iron ion inhibitor composition and its application. Background Art

[0002] Oxidized mineral resources of copper, lead, and zinc are widely distributed globally. With the continuous exploitation and consumption of high-grade sulfide minerals, the development and utilization of oxidized mineral resources of copper, lead, and zinc have attracted increasing attention. However, oxidized deposits of copper, lead, and zinc are usually accompanied by a large amount of iron-containing minerals. During the ore crushing and flotation processes, these iron-containing minerals will release a large amount of iron ions (Fe 2+ 、Fe 3+ )and their hydrolysis products into the pulp. Since iron ions will adsorb on the mineral surface, change the electrochemical properties of the mineral surface, and reduce the selective adsorption ability of the collector, resulting in a decrease in recovery rate; it can also activate gangue minerals and make them hydrophobic, resulting in a decrease in concentrate grade, and iron ions will form colloidal hydroxide precipitates under certain pH conditions, covering the mineral surface and hindering the contact between the collector and the mineral surface, affecting the flotation effect.

[0003] In the prior art for the problem of iron ion pollution, usually the pulp pH value is adjusted to weakly alkaline (8 - 10) to form hydroxide precipitates of iron ions and reduce their activity. However, this method often leads to the formation of a large amount of flocs and slimes, which instead exacerbates the problem of mineral surface covering. Or by increasing the dosage of sulfiding agent to offset the consumption of iron ions, but excessive sulfiding agent will have an inhibitory effect on some minerals.

[0004] In summary, the prior art has disadvantages such as low efficiency, limited applicability, or complex processes when dealing with the problem of iron ion pollution in the flotation of oxidized copper, lead, and zinc ores. Therefore, there is an urgent need to develop a simple, efficient, and environmentally friendly method to effectively inhibit the harmful effects of iron ions during the flotation process of oxidized copper, lead, and zinc minerals. Summary of the Invention

[0005] Aiming at the problem that the flotation of oxidized copper, lead, and zinc minerals in the prior art is easily contaminated by iron ions released from associated iron-containing minerals, resulting in a decline in flotation indexes and an increase in reagent consumption, the present invention provides an iron ion inhibitor composition and a flotation method that can efficiently reduce iron ion pollution.

[0006] On the one hand, the present application provides an iron ion inhibitor composition, and the iron ion inhibitor composition includes a soluble salt of oxalic acid, an ammonium phosphate compound, and triethanolamine.

[0007] Further, the mass ratio of the soluble salt of oxalic acid, the ammonium phosphate compound, and triethanolamine is: (2 - 2.5) : (1 - 1.5) : (1.0 - 1.5).

[0008] Further, the soluble salt of oxalic acid is selected from at least one or more of sodium oxalate, potassium oxalate, and ammonium oxalate.

[0009] Further, the ammonium phosphate compound is selected from at least one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and triammonium phosphate.

[0010] On the other hand, the present application also provides a method for reducing iron ions during the mineral flotation process. The steps of the method include: 1) Crushing and screening the mineral sample to obtain mineral powder; The mineral sample is one of malachite, high-iron copper oxide lead-zinc mixed ore, or apatite; 2) Mixing the mineral powder with water at a certain solid-liquid ratio, and then performing wet grinding to obtain an initial pulp; 3) When the mineral is malachite, adding an FeCl3 solution to the initial pulp to simulate the pollution of the mineral by iron ions, and obtaining an iron-ion-polluted pulp after sufficient stirring; When the mineral is one of high-iron copper oxide lead-zinc mixed ore or apatite, the iron-containing minerals in the ore will release iron ions, and these iron ions will adsorb on the surface of the mineral or exist in other forms and have an adverse effect on flotation. After sufficient stirring, an iron-ion-polluted pulp is obtained; 4) Adding the above-mentioned iron-ion inhibitor composition to the iron-ion-polluted pulp to obtain a pulp with inhibited iron-ion pollution; The iron-ion inhibitor composition is composed of a soluble salt of oxalic acid, an ammonium phosphate compound, and triethanolamine; the soluble salt of oxalic acid is selected from one or more of sodium oxalate, potassium oxalate, and ammonium oxalate; the ammonium phosphate compound is selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and triammonium phosphate; 5) When the mineral is malachite or high-iron copper oxide lead-zinc mixed ore, adding sodium sulfide to the pulp with inhibited iron-ion pollution, and obtaining a sulfide pulp after sufficient stirring; adding a collector and a frother to the sulfide pulp in sequence, and obtaining a flotation pulp after sufficient stirring; When the mineral is apatite, adding a collector and a frother to the pulp with inhibited iron-ion pollution in sequence, and obtaining a flotation pulp after sufficient stirring; 6) Aerating and skimming the obtained flotation pulp to obtain flotation concentrate and tailings; Further, when the mineral sample is malachite; The mineral powder in 1) is malachite powder, and the particle size of the malachite powder is 0.074 mm - 0.038 mm; The solid-liquid ratio in 2) is 1:20 (g / ml); the wet grinding time is 2 mm; The iron ion inhibitor composition in 4) is composed of potassium oxalate, diammonium hydrogen phosphate and triethanolamine, and the mass ratio thereof is 2.5:1:1.5; The amount of sodium sulfide added in 5) is 1×10 -3 mol / L; The collector in 5) is isopentyl xanthate, added in an amount of 100 mg / L; the foaming agent is pine oil, added in an amount of 50 mg / L.

[0011] Further, when the mineral sample is a high-iron copper oxide lead-zinc mixed ore; The mineral powder in 1) is a high-iron copper oxide, lead and zinc mixed ore powder, the particle size of which is less than 2 mm, and the metal grades are 0.73% copper, 3.21% lead, 1.45% zinc, and 17.97% iron; The solid concentration of the uncontaminated slurry in 2) is 60%, and the ore particles with a particle size of less than 0.074 mm account for 75%; Directly adding the iron ion inhibitor composition in 4) during the wet grinding process in 2) in an amount of 500 g / t of the original ore weight to obtain a slurry with suppressed iron ion contamination; The iron ion inhibitor composition in 4) is composed of ammonium oxalate, diammonium phosphate and triethanolamine, and the mass ratio thereof is 2:1.5:1; The amount of sodium sulfide added in 5) is 1000g / t; In the step 5), before adding the collector, an activator is added; the activator is copper sulfate, and the amount added is 100 g / t; The collector in 5) and the amount thereof added are 600 g / t of amyl xanthate and 200 g / t of butyl ammonium black medicine; the foaming agent is pine oil, and the amount added is 60 g / t.

[0012] Further, when the mineral sample is apatite, the method comprises the following steps: (1) Selecting apatite with a phosphorus pentoxide content of 3.12%, an iron content of 14.97%, and a particle size of -0.074 mm accounting for 78% of the ore sample, and mixing it with water to obtain a mixed ore slurry; (2) adding sodium carbonate to the mixed slurry in an amount of 1000 g / t of the original ore weight to obtain adjusted slurry I; (3) adding the iron ion inhibitor composition to the adjusted slurry I and stirring to obtain a pretreated slurry; The amount of the iron ion inhibitor composition added is 500 g / t of the original ore mass; The iron ion inhibitor composition is composed of sodium oxalate, ammonium phosphate and triethanolamine, and the mass ratio thereof is 2:1:1.5; (4) Add water glass to the pretreated pulp and stir to obtain adjusted pulp II; The addition amount of the water glass is 250 g / t of the mass of the raw ore.

[0013] (5) Add oxidized paraffin soap to the adjusted pulp II and stir to obtain flotation pulp; The addition amount of the oxidized paraffin soap is 800 g / t of the mass of the raw ore.

[0014] (6) Carry out roughing - cleaning open - circuit large - scale and closed - circuit small - scale circulating flotation on the obtained flotation pulp; finally obtain phosphorus concentrate.

[0015] On the other hand, the present application also provides an application of the iron ion inhibitor composition as described above in eliminating the interference of iron ions during mineral flotation.

[0016] On the other hand, the present application also provides an application of the above - mentioned iron ion inhibitor composition in the process of mineral flotation.

[0017] Beneficial effects

[0018] High - efficiency inhibition of iron ions: Through the synergistic effect of the complexing action of oxalic acid (or its salt), the precipitation / dispersion action of ammonium phosphate (or phosphate), and the pH buffering / complexing / dispersion action of triethanolamine, the concentration of free iron ions in the pulp is effectively reduced, and part of the iron species adsorbed on the mineral surface can be stripped, significantly reducing the interference of iron ions on the flotation process.

[0019] Significantly improve flotation indexes: The results of the examples show that compared with not using the inhibitor composition of the present invention, adopting the method of the present invention can increase the recovery rate of oxidized copper - lead - zinc minerals by about 4% - 15% and increase the concentrate grade by about 0.5% - 5%.

[0020] Reduce reagent consumption: Pre - inhibit iron ions, reduce the ineffective consumption of subsequent sulfiding agents and collectors, and the overall reagent cost is reduced by 10% - 20%.

[0021] Strong process adaptability: The method of the present invention has simple steps, is easy to be integrated into the existing flotation process of oxidized copper - lead - zinc ores, does not require complex pretreatment, has less equipment investment, and is easy to operate.

[0022] Less environmental impact: The main reagents used are relatively low - toxic or are easy to be treated in the treatment of ore - dressing wastewater.

[0023] Wide application range: It shows good adaptability to oxidized copper - lead - zinc ores of different types and different iron contents.

[0024] It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present application. Description of the drawings

[0025] The above and other objects, features, and advantages of the present application will become more apparent by describing the exemplary embodiments of the present application in more detail with reference to the accompanying drawings, wherein, in the exemplary embodiments of the present application, the same reference numerals generally represent the same components.

[0026] Figure 1 It is the effect diagram of the iron ion inhibitor effectively weakening the adverse effect of iron ions on malachite flotation, including: a is the effect of different iron ion concentrations on the recovery rate of malachite; b is the effect of different concentrations of iron ion inhibitors on the recovery rate of malachite in the presence of iron ions; c is the comparison of the recovery rate of malachite with and without the addition of iron ion inhibitors in the presence of iron ions; d and e are the surface analysis results of malachite without the addition of iron ion inhibitor (d) and with the addition of iron ion inhibitor (e) under the condition of iron ion pollution, respectively, including: scanning electron microscope images (d-1, d-2, e-1, e-2); energy spectrum analysis results (d-3, e-3); atomic force microscope images (d-4, e-4); mass spectrometry and iron element ion imaging diagrams of time-of-flight secondary ion mass spectrometry (d-5, e-5).

[0027] Figure 2 It is the flow chart of copper oxide lead-zinc mixed ore.

[0028] Figure 3 It is the flow chart of apatite flotation. Specific Embodiments

[0029] The embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although the embodiments of the present application are shown in the drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to make the present application more thorough and complete, and to fully convey the scope of the present application to those skilled in the art.

[0030] The iron ion inhibitor of the present invention achieves efficient reduction of iron ion pollution through the following mechanism: The synergistic effect of the three components can not only effectively reduce the free iron ions in the pulp, but also strip the iron ions adsorbed on the mineral surface, restoring the original properties of the mineral surface, thereby significantly improving the flotation effect.

[0031] The method of the present invention is not only applicable to the flotation of single ore types, but also applicable to the flotation separation of mixed ores, and can be flexibly applied in different ore conditions and flotation processes, having broad industrial promotion value.

[0032] Example 1 Preparation of Iron Ion Inhibitor

[0033] 1. Selection and Basis of Components When designing the iron ion inhibitor of the present invention, based on the known adverse effects of iron ions during the flotation process and combined with the characteristics of common chemical reagents, it aims to efficiently and economically solve the problem of iron ion pollution through the synergy of various chemical actions. Therefore, potassium oxalate, diammonium hydrogen phosphate, and triethanolamine are selected as the key materials for preparing the iron ion inhibitor of the present invention, and the main basis is as follows: Soluble salts of oxalic acid (e.g., ammonium oxalate). This component is selected for the characteristic of its oxalate ion as a strong chelating agent. Theoretically, the oxalate ion can form stable soluble iron oxalate complexes with iron ions in the pulp (especially Fe 3+ ), which helps prevent the migration and adsorption of iron ions to the mineral surface. At the same time, based on the chemical properties of oxalic acid, it is expected to dissolve and strip the iron hydroxide that has been adsorbed on the mineral surface, thereby restoring the original properties of the mineral surface.

[0034] Ammonium phosphate compounds (e.g., ammonium phosphate): This component is selected for its ability to precipitate iron ions with its phosphate ion. The phosphate ion can react with iron ions to form stable insoluble iron phosphate precipitates, which is considered an effective way to reduce the concentration of free iron ions in the pulp. In addition, phosphate substances often also exhibit certain dispersibility, so it is expected to help prevent the mineral surface from being overly covered by iron precipitates.

[0035] Triethanolamine component: This component is selected considering its various auxiliary functions. As an organic amine, triethanolamine has weak alkalinity and can adjust the local pH value, which is beneficial for optimizing the chelating effect of oxalate and the precipitation effect of phosphate. At the same time, triethanolamine is also a known weak complexing agent, which can form complexes with iron ions and is expected to reduce the agglomeration of iron precipitates by improving dispersibility, further preventing the precipitates from covering the mineral surface.

[0036] Through the combination of the above components with different action mechanisms, the present invention aims to achieve multi-faceted control of iron ions, thereby achieving excellent inhibition effects.

[0037] 2. Screening of component ratios In a preferred embodiment, the soluble oxalate component, ammonium phosphate component, and triethanolamine in the iron ion inhibitor of the present invention are in a mass ratio of 2:1:1 respectively. The setting of this ratio is based on a comprehensive consideration of the functional characteristics of each component and the expected synergistic effect, aiming to maximize the iron ion inhibition effect in an economical and effective manner.

[0038] The proportion of the oxalic acid soluble salt component is relatively high. The oxalate ion in the oxalic acid soluble salt component is the main powerful chelating agent, which is responsible for forming stable soluble complexes with free iron ions in the pulp and can effectively strip the iron hydroxide adsorbed on the mineral surface. Considering the stoichiometric requirements of the iron ion chelation reaction and ensuring sufficient chelation and stripping ability, setting a relatively high proportion of the oxalic acid soluble salt component helps to rapidly reduce the concentration of free iron ions and clean the mineral surface. In addition, from a kinetic perspective, a higher concentration of the oxalic acid soluble salt component is beneficial to increasing its reaction rate and chelation efficiency with iron ions.

[0039] The proportion of the ammonium phosphate compound component is medium. The phosphate ion in ammonium phosphate can react with iron ions to form insoluble iron phosphate precipitates, which, as a supplement to the chelation effect of oxalate ions, further reduces the total iron ion concentration. At the same time, an appropriate amount of phosphate helps to disperse the slime and the newly formed precipitates, preventing them from overly covering the minerals. Its dosage is set to be half of that of potassium oxalate to avoid the negative impacts that may be brought about by excessive precipitation while effectively precipitating iron ions. Moreover, for the balance of cost and effectiveness, as an auxiliary precipitant, its dosage takes into account cost - effectiveness on the premise of ensuring the effect.

[0040] The proportion of triethanolamine is medium. As a weak base and weak complexing agent, triethanolamine can adjust the pH environment, providing more suitable conditions for the chelation of oxalate ions and the precipitation of phosphate ions. At the same time, its own weak complexing ability and the property of preventing precipitate aggregation can produce a synergistic effect with oxalic acid and ammonium phosphate, further improving the overall effectiveness of the inhibitor and the properties of the pulp. Moreover, as an auxiliary component, the dosage of triethanolamine is equivalent to that of diammonium hydrogen phosphate, which is sufficient to play its roles of pH buffering, weak complexing and improving dispersibility, while excessive dosage may unnecessarily increase costs or introduce other complex factors.

[0041] Therefore, a mass ratio of 2:1:1 is considered an optimized balance point for the functions of each component, enabling the inhibitor to act synergistically in multiple aspects such as chelation, precipitation, pH adjustment and dispersion, thereby efficiently inhibiting the adverse effects of iron ions.

[0042] Of course, those skilled in the art should understand that according to the different actual ore properties, iron ion pollution degrees and specific flotation process conditions, the above - mentioned ratios can be adjusted within a certain range to achieve the best effect. For example, the mass fraction of the oxalic acid soluble salt component can be between 2 - 2.5, the ammonium phosphate compound can be between 1 - 1.5, and triethanolamine can be between 1 - 1.5, but this does not deviate from the core concept of the present invention.

[0043] Example 2

[0044] This embodiment provides a method for reducing the adsorption of iron ions on the surface of malachite, a typical copper oxide mineral, by using the iron ion inhibitor of the present invention, and a method for characterizing the ability of this inhibitor to reduce the adsorption of iron ions on the surface of copper oxide minerals ( Figure 1 ) The specific steps are as follows: (1) Potassium oxalate, diammonium hydrogen phosphate and triethanolamine are mixed in a mass ratio of 2.5:1:1.5 to prepare an iron ion inhibitor.

[0045] (2) Take a malachite sample with a purity greater than 95%. The ore is crushed, ground and screened to obtain malachite powder with a particle size of 0.074 mm to 0.038 mm.

[0046] (3) After mixing 2 grams of malachite powder and 40 ml of deionized water, place them in a hanging trough flotation machine and stir for 2 minutes to obtain an initial pulp.

[0047] (4) Add FeCl3 solution to the initial pulp, and the concentration of FeCl3 is 0 - 2.5×10 -4 mol / L, which is used as the source of iron ions. Stir and react for 5 minutes to obtain iron ion-contaminated pulp.

[0048] (5) In the iron ion-contaminated pulp, add different doses of iron ion inhibitor as needed. The concentration of this inhibitor is 0 - 5×10 -3 mol / L to obtain iron ion-inhibited pulp.

[0049] (6) Add 1×10 -3 mol / L sodium sulfide to the iron ion-inhibited pulp, stir and react for 5 minutes to obtain sulfide pulp.

[0050] (7) Add isopentyl xanthate as a collector to the sulfide pulp. The concentration of this collector is 50 - 300 mg / L, stir and react for 3 minutes; then add a foaming agent: pine oil 50 mg / L, stir and react for 2 minutes to obtain floated pulp.

[0051] (9) Aerate and scrape the foam from the obtained floated pulp to obtain flotation concentrate and tailings, and calculate the recovery rate of malachite.

[0052] (9) Figure 1 The results of a clearly show that the presence of iron ions significantly inhibits the flotation of malachite. As the iron ion concentration increases from 0 to 2×10 -5 mol / L, the recovery rate of malachite gradually decreases from about 67% to about 18%. This indicates that iron ions significantly inhibit the flotation of malachite, and even at low iron ion concentrations, it will cause a significant reduction in its flotation efficiency.

[0053] (10)Figure 1 Figure b shows that the iron ion inhibitor can effectively weaken the adverse effect of iron ions on the flotation of malachite. As the total concentration of the inhibitor increases from 0 to 2×10 -3 mol / L, the flotation recovery rate of malachite increases from about 30% to 57%.

[0054] (11) Figure 1 Figure c shows the results of the change in the recovery rate of malachite with the concentration of isoamyl xanthate under the conditions with and without the iron ion inhibitor. Without the iron ion inhibitor, the recovery rate of malachite is about 22% under the condition of 250 mg / L isoamyl xanthate. While with the iron ion inhibitor, at the same concentration of isoamyl xanthate, the recovery rate significantly increases to about 92%. This indicates that the iron ion inhibitor significantly reduces the adverse effect of iron ions on the sulfidation-xanthate flotation system of malachite.

[0055] (12) The morphological changes of the surface of malachite contaminated by iron ions before and after treatment with the iron ion inhibitor were comprehensively characterized using field emission scanning electron microscopy-energy dispersive spectroscopy and atomic force microscopy ( Figure 1 d-1, 1d-2, 1d-3, 1e-1, 1e-2, 1e-3). There are significant depressions on the surface of malachite after treatment with the iron ion inhibitor, while there are none on the surface of the sample only contaminated by iron ions. Analyzed by ImageJ software, the porosity of the malachite surface before treatment with the iron ion inhibitor is 29.30%, and it increases to 36.40% after treatment. In addition, the iron element distribution map shows that the iron atom concentration on the surface of malachite after treatment with the iron ion inhibitor decreases from 0.46% to 0.25%.

[0056] (13) Atomic force microscopy analysis clearly shows that after treatment with the iron ion inhibitor, the surface roughness parameters Ra and Rq of the malachite surface increase significantly from 12.50±0.50 nm and 17.50±0.50 nm to 68.20±0.50 nm and 86.60±0.50 nm respectively ( Figure 1 d-4, 1e-4). The results of morphological and elemental analysis fully show that the treatment with the iron ion inhibitor not only effectively dissolves and etches the surface of malachite, desorbs FeOOH from the mineral surface, but also exposes the fresh mineral surface, significantly increases the surface roughness of malachite, and promotes a significant increase in the content of active copper sites on the malachite surface. This improvement in the surface structure and state not only enhances the contact and binding efficiency of sulfide and xanthate on the malachite surface, but also provides a more favorable physicochemical environment for the subsequent flotation process, thus significantly increasing the flotation recovery rate.

[0057] (14) To further evaluate the change in the content of iron substances on the malachite surface, time-of-flight secondary ion mass spectrometry analysis was carried out, and the results are as Figure 1as shown in d-5 and 1e-5. A variety of iron ion fragments (such as Fe + , FeOH + , Fe2O + , CuOFe + and FeOOH + ) were detected on the surface of malachite contaminated with iron ions. Mass spectrometry data and secondary ion imaging results showed that after treatment with the iron ion inhibitor, the intensities of these iron-containing fragments decreased significantly, with a decrease range between 30% - 50%. These results clearly indicated that the treatment with the iron ion inhibitor significantly reduced the content of iron substances adsorbed on the surface of malachite, further confirming the effectiveness of the iron ion inhibitor in improving the flotation performance of malachite under iron ion contamination conditions. Therefore, Fe 3+ mainly exists in the form of FeOOH (including α-FeOOH and γ-FeOOH) on the surface of malachite. These iron substances reduced the hydrophobicity of the malachite surface, thus affecting its flotation performance. The treatment with the iron ion inhibitor reduced the hydrophilicity of the malachite surface by reducing the content of surface α-FeOOH and the surface hydroxyl content, and finally improved its flotation performance.

[0058] Example 3

[0059] This example discloses a method for using the iron ion inhibitor of the present invention to improve the flotation indexes of a typical metal oxide ore - high-iron copper oxide lead-zinc mixed ore ( Figure 2 ), and the specific steps are as follows: (1) Ammonium oxalate, ammonium dihydrogen phosphate and triethanolamine were mixed in a mass ratio of 2:1.5:1 to prepare an iron ion inhibitor.

[0060] (2) A copper oxide lead-zinc mixed ore was taken, and its main metal grades were copper 0.73%, lead 3.21%, zinc 1.45%, and the iron content was 17.97%. The ore was crushed to a particle size less than 2 mm.

[0061] (3) The crushed ore was placed in a ball mill and wet-ground with water. The grinding fineness was controlled so that the ore particles with a particle size less than 0.074 mm accounted for 75%, and the solid concentration was 60% to obtain a ground ore pulp.

[0062] (4) During the above grinding process (in step (3)), an iron ion inhibitor was added to the ball mill, and the addition amount was 500 g / t (based on the weight of the original ore). After grinding, the pH value of the ore pulp was about 8.0, and a ground pre-treated ore pulp (ore pulp inhibiting iron ion contamination) was obtained.

[0063] (5) A sulfiding agent: sodium sulfide 1000 g / t was added to the adjusted ore pulp, and stirred and reacted for 5 minutes to obtain a sulfided ore pulp.

[0064] (6) Add an activator to the sulfide slurry: 100 g / t copper sulfate, stir and react for 5 minutes to obtain an activated slurry.

[0065] (7) Collectors: 600 g / t of amyl xanthate and 200 g / t of butyl ammonium black powder were added to the activated slurry in sequence, and the mixture was stirred for reaction for 3 minutes. Subsequently, a frother: 60 g / t of pine oil was added, and the mixture was stirred for reaction for 2 minutes to obtain a flotation slurry.

[0066] (8) The obtained flotation pulp is subjected to a closed-circuit flotation of roughing-cleaning-scavenging. The final copper-lead-zinc mixed concentrate has the following technical indicators: Cu grade 8.97%, recovery rate 78.51%; Pb grade 26.77%, recovery rate 78.46%; Zn grade 10.15%, recovery rate 44.16%.

[0067] This example verifies the application effect of the present invention in the flotation of a typical metal oxide ore - copper oxide, lead oxide, and zinc mixed ore.

[0068] Example 4

[0069] This embodiment discloses a method for improving the flotation index of apatite, a typical non-metallic oxide ore, by using the iron ion inhibitor of the present invention. Figure 3 ), the specific steps are as follows: (1) Sodium oxalate, ammonium phosphate and triethanolamine are mixed in a mass ratio of 2:1:1.5 to prepare an iron ion inhibitor.

[0070] (2) Take a high-iron apatite after magnetic iron separation, whose phosphorus pentoxide content is 3.12% and iron content is 14.97%. The -0.074 mm particle size of the ore sample accounts for 78%. Place the sample in a flotation machine and mix it thoroughly with water to obtain a mixed slurry (uncontaminated slurry).

[0071] (3) 1000 g / t sodium carbonate (based on the weight of the original ore) was added to the above mixed slurry, and the pH value of the slurry was about 10.0 to obtain adjusted slurry I.

[0072] (4) Add 500 g / t of iron ion inhibitor to the adjusted slurry I. Stir and react for 5 minutes to obtain a pretreated slurry.

[0073] (5) Add 250 g / t of water glass to the pretreated slurry and stir the mixture for 3 minutes to obtain adjusted slurry II.

[0074] (6) Add oxidized paraffin soap in an amount of 800 g / t to the adjusted pulp II, stir and react for 3 minutes to obtain flotation pulp.

[0075] (7) Subject the obtained floated ore pulp to roughing - cleaning open - circuit large - scale and closed - circuit small - scale circulating flotation. The obtained phosphorus concentrate has the following technical indicators: phosphorus pentoxide grade 32.63% and recovery rate 81.63%.

[0076] This example verifies the application effect of the present invention in the flotation of typical non - metallic oxide ore - apatite.

[0077] Comparative Example 1

[0078] The operation steps of this comparative example are the same as those of Example 3, and the only difference is that the iron ion inhibitor described in the present invention is not added in step (4).

[0079] Repeat the operations of steps (2) to (8) of Example 1, but add sodium carbonate and sodium hexametaphosphate as inhibitors during the grinding process in step (4). Conduct flotation according to the closed - circuit circulating flotation process shown in step (9) of Example 1.

[0080] The flotation results of the finally obtained copper - lead - zinc bulk concentrate are as follows: Cu grade 7.12%, recovery rate 74.21%; Pb grade 23.54%, recovery rate 75.15%; Zn grade 9.51%, recovery rate 46.37%.

[0081] Effect Verification and Comparative Analysis Comparison between Example 2 and Comparative Example 3 (copper - oxide - lead - zinc mixed ore) When treating copper - oxide - lead - zinc mixed ore, the results compared with Comparative Example 4 without adding inhibitor are shown in Table 1.

[0082] Table 1 Comparison of test results between Example 1 and Comparative Example 4 In the obtained copper - lead - zinc bulk concentrate, although the recovery rate of Zn decreased slightly, the recovery rates of Cu and Pb increased, and the grades of Cu, Pb, and Zn increased by 1.85 percentage points, 3.23 percentage points, and 0.64 percentage points respectively. This shows that the method of the present invention effectively overcomes the adverse effects of high - content iron ions on the combined flotation recovery of copper - oxide - lead - zinc minerals and improves the total recovery efficiency of valuable metals.

[0083] Comparative Example 2

[0084] The operation steps of this comparative example are the same as those of Example 4, and the only difference is that the iron ion inhibitor described in the present invention is not added in step (4).

[0085] Repeat the operations of steps (2) to (7) of Example 4, but add sodium hexametaphosphate as an inhibitor during the grinding process in step (4). Conduct flotation according to the closed - circuit circulating flotation process shown in step (7) of Example 3.

[0086] The finally obtained phosphate concentrate has the following technical indicators: the grade of phosphorus pentoxide is 28.56%, and the recovery rate is 78.54%.

[0087] Effect verification and comparative analysis Comparison between Example 4 and Comparative Example 5 (apatite): When treating high-iron apatite after magnetic separation of iron, the results compared with Comparative Example 2 without adding inhibitor are shown in Table 2.

[0088] Table 2 Comparison of test results between Example 1 and Comparative Example 4

[0089] In the obtained phosphate concentrate, by adding this iron ion inhibitor, the grade of phosphorus pentoxide in the phosphate concentrate increased by 4.07 percentage points, and the recovery rate increased by 3.09 percentage points. This shows that the method of the present invention effectively overcomes the adverse effects of high-content iron ions on the flotation recovery of apatite and improves the total recovery efficiency.

[0090] In addition, since the pollution of iron ions to flotation is a common phenomenon, it not only exists in the flotation of copper, lead, and zinc oxide ores and apatite, but also widely exists in other flotation systems affected by the association of iron minerals or iron pollution. The core problem is that dissolved iron ions or their hydrolysis products (such as iron hydroxide) will activate gangue minerals such as silicate and carbonate, or inhibit the target minerals.

[0091] Based on the action mechanism of the iron ion inhibitor and the universality of iron ion pollution, this inhibitor can theoretically be applied to the following flotation systems that may be interfered by iron ions: 1) Reverse flotation of iron oxide ore: When using amine collectors for reverse flotation of silica to improve the grade of iron concentrate, dissolved iron ions or iron sludge will activate silica and reduce the reverse flotation effect. The inhibitor can chelate iron ions to reduce the activation of silica.

[0092] 2) Flotation of tungsten ore (scheelite, wolframite): Fatty acids or chelating collectors are commonly used in the flotation of tungsten ore. Scheelite is often associated with calcite, apatite, silicate and a small amount of iron minerals. Dissolved iron ions and calcium ions may both have adverse effects on flotation, activating gangue or reacting with collectors. The oxalate and phosphate components in the inhibitor may have inhibitory effects on both iron ions and calcium ions, which helps to improve selectivity.

[0093] 3) Flotation of fluorite and barite: Fatty acid collectors are also commonly used in the flotation of these minerals, which are easily interfered by iron, calcium, magnesium and other ions, and iron ions will activate gangue such as silica. This inhibitor may be effective.

[0094] 4) Flotation of titanium ores (ilmenite, rutile): Especially for ilmenite, although it contains iron itself, the dissolution and hydrolysis products of iron and the activation of associated silicates are still common problems during the flotation process. This inhibitor may help to improve the situation.

[0095] 5) Purification of certain non-metallic ores (removing iron staining): Such as quartz, feldspar, kaolin, etc. In order to obtain high-purity products, it is necessary to remove the iron staining on the surface or the associated iron-containing minerals. In some cases, the flotation method is used, and the dissolved iron ions may also interfere with the action of the reagents or reattach. This inhibitor may be useful.

[0096] The embodiments of the present application have been described above. The above description is exemplary and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of the terms used herein is intended to best explain the principles of the embodiments, practical applications, or improvements to the technologies in the market, or to enable other ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. An iron ion inhibitor composition, characterized in that, The iron ion inhibitor composition includes soluble salts of oxalic acid, ammonium phosphate compounds, and triethanolamine.

2. The ferric ion inhibitor composition according to claim 1, wherein The mass ratio of the soluble salts of oxalic acid, ammonium phosphate compounds, and triethanolamine is: (2 - 2.5) : (1 - 1.5) : (1.0 - 1.5).

3. The iron ion inhibitor composition according to claim 1, characterized in that, The soluble salts of oxalic acid are selected from one or more of sodium oxalate, potassium oxalate, and ammonium oxalate.

4. The ferric ion inhibitor composition according to claim 1, wherein The ammonium phosphate compounds are selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.

5. A method for reducing iron ions during the mineral flotation process, characterized in that, The steps of the method include: 1) Crushing and screening the mineral sample to obtain mineral powder; The mineral sample is one of malachite, high-iron copper oxide lead-zinc mixed ore, or apatite; 2) Mixing the mineral powder with water at a certain solid-liquid ratio, and then performing wet grinding to obtain an initial pulp; 3) When the mineral is malachite, adding an FeCl3 solution to the initial pulp to simulate the pollution of the mineral by iron ions, and obtaining an iron-ion-polluted pulp after sufficient stirring; When the mineral is one of high-iron copper oxide lead-zinc mixed ore or apatite, the iron-containing minerals in the ore will release iron ions, and these iron ions will adsorb on the surface of the mineral or exist in other forms and have an adverse effect on flotation. After sufficient stirring, an iron-ion-polluted pulp is obtained; 4) Adding the iron ion inhibitor composition as described in claim 1 to the iron-ion-polluted pulp to obtain an iron-ion-pollution-inhibited pulp; The iron ion inhibitor composition is composed of soluble salts of oxalic acid, ammonium phosphate compounds, and triethanolamine; the soluble salts of oxalic acid are selected from one or more of sodium oxalate, potassium oxalate, and ammonium oxalate; the ammonium phosphate compounds are selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate; 5) When the mineral is malachite or high-iron copper oxide lead-zinc mixed ore, adding sodium sulfide to the iron-ion-pollution-inhibited pulp, and obtaining a sulfide pulp after sufficient stirring; adding a collector and a frother to the sulfide pulp in sequence, and obtaining a flotation pulp after sufficient stirring; When the mineral is apatite, adding a collector and a frother to the iron-ion-pollution-inhibited pulp in sequence, and obtaining a flotation pulp after sufficient stirring; 6) Aerating and skimming the obtained flotation pulp to obtain flotation concentrate and tailings.

6. A method according to claim 5, wherein When the mineral sample is malachite; The mineral powder in 1) is malachite powder, and the particle size of the malachite powder is 0.074 mm - 0.038 mm; The solid-liquid ratio in 2) is 1:20 (g / ml); the wet grinding time is 2 mm; In 4), the iron ion inhibitor composition is composed of potassium oxalate, diammonium hydrogen phosphate, and triethanolamine, and their mass ratio is: 2.5:1:1.5; The addition amount of sodium sulfide in the above (5) is 1×10 -3 mol / L; The collector in 5) is isoamyl xanthate, and the addition amount is 100 mg / L; the frother is pine oil, and the addition amount is 50 mg / L.

7. A method according to claim 5, characterized in that, When the mineral sample is high-iron copper oxide lead-zinc mixed ore; The mineral powder in 1) is high-iron copper oxide lead-zinc mixed ore powder, its particle size is less than 2 mm, the metal grades are copper 0.73%, lead 3.21%, zinc 1.45%, and the iron content is 17.97%; The solid concentration of the uncontaminated pulp in 2) is 60%, and the ore particles with a particle size less than 0.074 mm account for 75%. During the wet grinding process in 2), the iron ion inhibitor composition in 4) is directly added, and the addition amount is 500 g / t of the weight of the original ore; the pulp with inhibited iron ion contamination is obtained. The iron ion inhibitor composition in 4) is composed of ammonium oxalate, ammonium dihydrogen phosphate and triethanolamine, and their mass ratio is: 2:1.5:

1. The addition amount of sodium sulfide in 5) is 1000 g / t. In 5), before adding the collector, an activator is added; the activator is copper sulfate, and the addition amount is 100 g / t. The collector in 5) and its addition amount are amyl xanthate 600 g / t and butyl ammonium black medicine 200 g / t; the foaming agent is pine oil alcohol, and the addition amount is 60 g / t.

8. A method according to claim 5, characterized in that, When the mineral sample is apatite; the method includes the following steps: (1) Select apatite with a phosphorus pentoxide content of 3.12%, an iron content of 14.97%, and the -0.074 mm particle size of the ore sample accounting for 78%, and mix it with water to obtain a well-mixed pulp. (2) Add sodium carbonate to the well-mixed pulp, and the addition amount is 1000 g / t of the weight of the original ore to obtain adjusted pulp I. (3) Add the iron ion inhibitor composition to the adjusted pulp I and stir to obtain pretreated pulp. The addition amount of the iron ion inhibitor composition is 500 g / t of the mass of the original ore. The iron ion inhibitor composition is composed of sodium oxalate, ammonium phosphate and triethanolamine, and their mass ratio is 2:1:1.

5. (4) Add water glass to the pretreated pulp and stir to obtain adjusted pulp II. The addition amount of the water glass is 250 g / t of the mass of the original ore. (5) Add oxidized paraffin soap to the adjusted pulp II and stir to obtain floating pulp. The addition amount of the oxidized paraffin soap is 800 g / t of the mass of the original ore. (6) Conduct roughing - cleaning open-circuit and small closed-circuit circulating flotation on the obtained floating pulp; finally obtain phosphorus concentrate.

9. Application of an iron ion inhibitor composition as described in claim 1 in eliminating the interference of iron ions during mineral flotation.

10. Application of an iron ion inhibitor composition as described in claim 1 during mineral flotation.

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