Iron oxide ore combined collecting agent and application thereof

Abstract

The invention discloses an iron oxide ore combined collecting agent and application thereof, and belongs to the technical field of mineral flotation. According to the combined collecting agent, a multi-element mixed coordination field is constructed through dihydroxamic acid and oximido, a stable composite adsorption layer is formed, and meanwhile, a dense hydrophobic layer is constructed on the surface of a mineral through the hydrophobic synergistic effect of a flexible aliphatic chain and a rigid benzene ring. The application of the combined collecting agent in iron oxide ore flotation comprises the steps that after iron oxide ore is smashed and subjected to size mixing, the combined collecting agent and a foaming agent are added, an oxidizing agent can also be added, and concentrate is obtained after air inflation flotation. The combined collecting agent can achieve efficient flotation of ilmenite, hematite and siderite under the mild condition, and has the advantages of being good in selectivity, high in recovery rate, small in dosage and environmentally friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral flotation, in particular to a combined collector for oxidized iron ore and application thereof. BACKGROUND

[0002] Iron ore flotation process is mainly divided into direct flotation and reverse flotation. In the direct flotation process, anionic collectors such as fatty acid and its soap, sulfonic acid, etc. are often used, and this process has good separation effect on oxidized iron ore with single composition, low primary slime content and difficult to float gangue minerals. In industrial practice, fatty acid collectors are widely used, and sodium oleate is one of the typical representatives. However, sodium oleate has significant limitations: in the system where iron ore coexists with gangue minerals such as feldspar, quartz and augite, sodium oleate not only can chelate with Fe 2+ on the surface of iron ore, but also easily combines with Ca 2+ , Mg 2+ and other impurity ions on the surface of gangue minerals, resulting in the gangue minerals floating with the iron ore, poor selectivity and seriously affecting the concentrate grade; sodium oleate has poor water solubility and is easy to form micelles in the flotation process, which not only reduces its dispersibility and effective utilization rate in the ore slurry, but also the agglomerates may form an over-thick adsorption layer on the surface of iron ore, which in turn inhibits the flotation effect, in addition, in the closed loop cycle, the sodium oleate and its hydrolysis products that have not completely reacted in the backwater continue to accumulate, which will exacerbate the emulsification of the ore slurry and interfere with the stability of the subsequent flotation process.

[0003] When benzhydroxamic acid is applied to industrial flotation of iron ore, in terms of collecting ability, the planar rigid structure of benzene ring results in its hydrophobicity being inferior to that of straight-chain alkyl, which cannot provide sufficient hydrophobicity for iron ore particles, and the collecting force is thus limited; in terms of applicability, benzhydroxamic acid has poor solubility, which affects its dispersion and performance in the ore slurry, and restricts its application range. Currently, in the face of the flotation demand of "poor, fine and impure" iron ore resources, the lack of high-efficiency and high-selectivity collectors has become a key factor restricting the development of technology.

[0004] Therefore, it has become a key problem to be solved in this field to develop a collector with good collecting performance and high selectivity to realize efficient flotation of iron ore and simultaneously improve the recovery rate and concentrate grade. SUMMARY

[0005] To solve the problems of poor selectivity, low solubility and insufficient adaptability, which restrict the utilization of poor, fine and impure resources, the purpose of the present application is to provide a combined collector for oxidized iron ore, which is composed of collector A and collector B, the structural formula of collector A is shown as formula (I), and the structural formula of collector B is shown as formula (II): , ; R in formula (I) is C7~C 16It is one of alkyl, phenyl or cyclohexyl groups, wherein M is sodium, potassium, ammonium or hydrogen in formulas (I) and (II).

[0006] Another object of the present invention is to provide an application of a combined collector in the flotation of iron oxide ore, specifically including the following steps: (1) Iron oxide ore is crushed, mixed into a slurry, and then a slurry is prepared.

[0007] (2) Add a combination of collector and frother to the slurry, and then perform aeration flotation to separate and obtain concentrate.

[0008] Preferably, the iron oxide ore in step (1) of the present invention is one of ilmenite, siderite and hematite.

[0009] Preferably, the pH of the slurry in step (1) of the present invention is 4.0~10.0.

[0010] Preferably, in step (2) of the present invention, the molar ratio of collector A and collector B in the combined collector is 1~5:5~1.

[0011] Preferably, the amount of the combined collector added to the slurry in step (2) of the present invention is 1.0 × 10⁻⁶. -4 ~1.0×10 - 2 mol / L.

[0012] Preferably, in step (2) of the present invention, an oxidant may be added for further aeration and flotation, and the amount of oxidant added is 0.5 × 10⁻⁶. -4 ~1.0×10 -2 mol / L.

[0013] Preferably, the oxidant of the present invention is one of ammonium persulfate, potassium persulfate, sodium persulfate, hypochlorous acid, sodium hypochlorite, calcium hypochlorite, and aqueous solution of hydrogen peroxide.

[0014] Preferably, the foaming agent in step (2) of the present invention is methyl isobutyl methanol, and the amount of foaming agent added is 0~1×10 -3 mol / L.

[0015] Preferably, the time for aeration flotation in step (2) of the present invention is 2 to 5 minutes.

[0016] Compared with the prior art, the present invention provides a combined collector for iron oxide ore and its application, which has the following beneficial effects: (1) This invention utilizes the synergistic effect of collectors A and B to construct a multi-component mixed coordination field. Based on the complementary coordination mechanism of the diisohydroxamic acid functional group and the oxime group, it achieves all-round coverage of iron sites on the mineral surface. The diisohydroxamic acid structure can form a stable double five-membered ring chelate configuration, while the oxime group, with its unique electron cloud distribution and spatial configuration, can effectively adapt to the surface sites with weak affinity for hydroxamic acid, and can also strengthen the interfacial interaction through secondary bonding. This synergistic coordination mode forms a dense and stable composite adsorption layer on the mineral surface, significantly improving the adsorption density and structural strength of the interfacial complex, thereby achieving a significant increase in the recovery rate of various iron oxide ores under the same or lower dosage conditions.

[0017] (2) This invention constructs a dense and stable composite hydrophobic layer by hydrophobic association between the flexible aliphatic hydrocarbon chain of collector A and the rigid benzene ring of collector B at the solid-liquid interface. This structure significantly improves bubble mineralization efficiency, enabling simultaneous growth in flotation rate and recovery rate. On the other hand, due to its low sensitivity to the surface characteristics of gangue minerals, it effectively inhibits gangue entrainment while enhancing the hydrophobicity of target minerals, successfully overcoming the technical bottleneck of traditional collectors where "collecting capacity and selectivity are difficult to balance".

[0018] (3) The combined collector of this invention has a high efficiency in collecting major iron oxide ores such as ilmenite, hematite, and siderite, demonstrating excellent process versatility and proving the wide adaptability of the mixed coordination field strategy to various occurrence states of iron ions. When used in conjunction with surface modification processes, this system can maximize the utilization of the newly generated Fe produced by the pre-oxidation of the oxidant. 3+ The active sites, with their multi-coordination mechanism, exhibit a response efficiency to surface modification far exceeding that of traditional collectors, potentially boosting recovery rates to near theoretical limits. Furthermore, this system achieves highly efficient separation under neutral to weakly alkaline conditions, overcoming the dependence of traditional flotation on high-alkaline environments. While ensuring optimal flotation performance, it significantly reduces reagent costs and environmental impact. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the flotation process using combined collectors according to the present invention.

[0020] Figure 2 This is a schematic diagram of the flotation process using a combination of collectors and oxidants according to the present invention. Detailed Implementation

[0021] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Example 1 In this embodiment, the combined collector is composed of collector A and collector B in a molar ratio of 5:1, wherein collector A is octanoyl diisohydroxyoxime acid and collector B is α-benzoic acid oxime; the frother is methyl isobutyl alcohol; the flotation process for ilmenite is as follows: Figure 1 As shown, the specific steps are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0023] (2) Add a combined collector to the slurry. The amount of the combined collector added is 1.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0024] In this embodiment, the ilmenite recovery rate was 97.6%.

[0025] Example 2 In this embodiment, the combined collector is composed of collector A and collector B in a molar ratio of 5:1, wherein collector A is octanoyl diisohydroxyoxime acid and collector B is α-benzoic acid oxime; the frother is methyl isobutyl alcohol; the flotation process for siderite is as follows: Figure 1 As shown, the specific steps are as follows: (1) Crush the siderite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0026] (2) Add a combined collector to the slurry. The amount of the combined collector added is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -3 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0027] In this embodiment, the siderite recovery rate is 98.5%.

[0028] Example 3 In this embodiment, the combined collector is composed of collector A and collector B in a molar ratio of 5:1, wherein collector A is octanoyl diisohydroxyoxime acid and collector B is α-benzoic acid oxime; the frother is methyl isobutyl alcohol; the flotation process for hematite is as follows: Figure 1 As shown, the specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0029] (2) Add a combined collector to the slurry, wherein the combined collector is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The concentrate was obtained by flotation with N2 for 2 minutes (N2 gas flow rate of 200 mL / min) at a concentration of mol / L.

[0030] In this embodiment, the hematite recovery rate was 92.4%.

[0031] Example 4 In this embodiment, the combined collector is composed of collector A and collector B in a 1:1 molar ratio. Collector A is octanoyl diisohydroxyoxime acid, and collector B is α-benzoic acid oxime. The oxidant is an aqueous hydrogen peroxide solution (30% by mass). The frother is methyl isobutyl methanol. The flotation process for ilmenite is as follows: Figure 2 As shown, the specific steps are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0032] (2) Add a combined collector and an oxidant to the slurry, wherein the amount of the combined collector added is 6.0 × 10⁻⁶. - 4 mol / L, the amount of oxidant added is 0.5 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1×10 mol / L. -4 The concentrate was obtained by flotation with N2 for 5 minutes (N2 gas flow rate of 200 mL / min) at a concentration of mol / L.

[0033] In this embodiment, the ilmenite recovery rate is 98.6%.

[0034] Example 5 In this embodiment, the combined collector is composed of collector A and collector B in a molar ratio of 1:5, wherein collector A is octanoyl diisohydroxyoxime acid and collector B is α-benzoic acid oxime; the oxidant is an aqueous solution of hydrogen peroxide (mass fraction of 30%); the frother is methyl isobutyl methanol; and the flotation process for siderite is as follows. Figure 2 As shown, the specific steps are as follows: (1) Crush the siderite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0035] (2) Add a combined collector and an oxidant to the slurry, wherein the amount of the combined collector added is 1×10 -2 mol / L, the amount of oxidant added is 1.0 × 10⁻⁶. -4 mol / L; without adding frother, N2 flotation was carried out for 3 minutes (N2 gas flow rate of 200 mL / min) to obtain concentrate.

[0036] In this embodiment, the siderite recovery rate is 99.3%.

[0037] In this embodiment, during the flotation process, the oxidant hydrogen peroxide oxidizes the Fe on the surface of the siderite. 2+ Oxidized to Fe 3+ This significantly increases the number of surface active sites; in the combined collector, collector A (octanoyl bis(hydroxyoxime)) and collector B synergistically adsorb, forming a high-density, high-stability composite adsorption layer; the flexible aliphatic chain of collector A (octanoyl bis(hydroxyoxime)) and the rigid benzene ring undergo hydrophobic association at the interface, constructing a dense hydrophobic surface, which greatly enhances the inherent hydrophobicity of the mineral particles.

[0038] Example 6 In this embodiment, the combined collector is composed of collector A and collector B in a 1:1 molar ratio, wherein collector A is octanoyl diisohydroxyoxime acid and collector B is α-benzoic acid oxime; the oxidant is an aqueous solution of hydrogen peroxide (mass fraction 30%); the frother is methyl isobutyl methanol; and the flotation process for hematite is as follows. Figure 2 As shown, the specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0039] (2) Add a combined collector and an oxidant to the slurry, wherein the amount of the combined collector added is 6.0 × 10⁻⁶. - 4 The concentration of mol / L and the amount of oxidant added is 0.75 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1×10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0040] In this embodiment, the hematite recovery rate was 93.2%.

[0041] Example 7 In this embodiment, the combined collector is composed of collector A and collector B in a molar ratio of 5:1, wherein collector A is sebacyl diisohydroxyoxime acid and collector B is α-benzoic acid oxime; the oxidant is an aqueous solution of hydrogen peroxide (mass fraction of 30%); the frother is methyl isobutyl methanol; and the flotation process for hematite is as follows. Figure 2 As shown, the specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0042] (2) Add a combined collector and an oxidant to the slurry, wherein the amount of the combined collector added is 6.0 × 10⁻⁶. - 4 mol / L, the amount of oxidant added is 1.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1×10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0043] In this embodiment, the hematite recovery rate is 99.2%.

[0044] Comparative Example 1 This comparative example uses sodium oleate as a collector, methyl isobutyl alcohol as a frother, and flotation of ilmenite. The specific steps are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0045] (2) Add a collector to the slurry. The amount of collector added is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0046] In this comparative example, the recovery rate of ilmenite was 71.1%.

[0047] Comparative Example 2 This comparative example uses benzohydroxyxamic acid as a collector, methyl isobutyl methanol as a frother, and flotation of ilmenite. The specific steps are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0048] (2) Add a collector to the slurry. The amount of collector added is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L.-4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0049] In this comparative example, the recovery rate of ilmenite was 77.5%.

[0050] As shown in Example 1 and Comparative Examples 1-2, sodium oleate in Comparative Example 1 has limited collecting ability and poor selectivity, and easily reacts with calcium and magnesium ions in gangue minerals. Although benzyl hydroxamic acid in Comparative Example 2 can chelate with iron ions, it is only a single-point adsorption, and the resulting adsorption layer is not dense and strong enough. Moreover, its hydrophobic group (benzene ring) configuration is simple, and the effect of constructing a hydrophobic layer is limited. Example 1, through the synergistic coordination of combined collectors, forms a more complete and stronger adsorption layer on the surface of ilmenite. Furthermore, the flexible chain of collector A and the rigid benzene ring of collector B jointly construct a highly efficient composite hydrophobic layer, thereby achieving efficient recovery.

[0051] Comparative Example 3 This comparative example uses sodium oleate as a collector, methyl isobutyl methanol as a frother, and siderite flotation. The specific steps are as follows: (1) Crush the siderite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0052] (2) Add a collector to the slurry. The amount of collector added is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0053] In this comparative example, the recovery rate of siderite was 57.3%.

[0054] Comparative Example 4 This comparative example uses benzohydroxyxamic acid as a collector, methyl isobutyl methanol as a frother, and siderite flotation. The specific steps are as follows: (1) Crush the siderite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0055] (2) Add a collector to the slurry. The amount of collector added is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0056] In this comparative example, the recovery rate of siderite was 36.2%.

[0057] Comparative Example 5 This comparative example uses octanoyl diisohydroxamic acid as the collector, methyl isobutyl methanol as the frother, and siderite flotation. The specific steps are as follows: (1) Crush the siderite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0058] (2) Add a collector to the slurry. The amount of collector added is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0059] In this comparative example, the recovery rate of siderite was 88.7%.

[0060] Comparative analysis of Example 2 and Comparative Example 5 shows that collector A (octanoyl bis(hydroxyoxime)) and collector B work synergistically to improve the overall collecting performance. The oxime functional groups contained in collector B can act on mineral surface sites that collector A has difficulty effectively bonding to or where the effect is weak, thereby expanding the adsorption range and enhancing interfacial forces, significantly improving the adsorption layer coverage density and stability.

[0061] Comparative Example 6 This comparative example uses sodium oleate as a collector, methyl isobutyl methanol as a frother, and hematite flotation. The specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 10.0).

[0062] (2) Add a collector to the slurry. The amount of collector added is 6.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0063] In this comparative example, the hematite recovery rate was 49.3%.

[0064] Comparative Example 7 This comparative example uses benzohydroxyxamic acid as a collector, methyl isobutyl methanol as a frother, and hematite flotation. The specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 10.0).

[0065] (2) Add a collector to the slurry. The amount of collector added is 6.0 × 10⁻⁶.-4 mol / L; and add a foaming agent, the amount of which is 1×10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0066] In this comparative example, the hematite recovery rate was 38.4%.

[0067] Based on the comparison results between Example 3 and Comparative Examples 6-7, Example 3 showed a significant advantage in recovery rate. Hematite has complex surface chemical properties, making it difficult for traditional collectors to form effective adsorption on its surface. The combined collector of this invention, through a multi-element mixed coordination field, can adapt to the diverse active sites on the hematite surface, forming an adsorption layer with strong binding force and high selectivity. The adsorption structure constructed by the combined collector in Example 3 is dense and highly hydrophobic, thereby significantly improving the floatability of hematite particles.

[0068] Comparative Example 8 This comparative example uses sodium oleate as a collector, hydrogen peroxide aqueous solution (30% by mass) as an oxidant, methyl isobutyl methanol as a frother, and flotation of ilmenite. The specific steps are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 10.0).

[0069] (2) Add collector and oxidant to the slurry, wherein the amount of collector added is 6.0 × 10⁻⁶. -4 mol / L, the amount of oxidant added is 0.5 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0070] In this comparative example, the recovery rate of ilmenite was 59.1%.

[0071] Comparative Example 9 This comparative example uses benzohydroxyxamic acid as the collector, hydrogen peroxide aqueous solution (30% by mass) as the oxidant, methyl isobutyl methanol as the frother, and flotation of ilmenite. The specific steps are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 10.0).

[0072] (2) Add collector and oxidant to the slurry, wherein the amount of collector added is 6.0 × 10⁻⁶. -4 mol / L, the amount of oxidant added is 0.5 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L.-4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0073] In this comparative example, the recovery rate of ilmenite was 48.6%.

[0074] Based on the comparison results between Example 4 and Comparative Examples 8-9, it can be seen that oxidants (such as H2O2) can remove Fe from the mineral surface. 2 + Oxidized to Fe 3+ This creates more active sites that readily bind to the chelating agent. When acting synergistically with the oxidant, collectors A and B can rapidly and fully occupy these newly generated active sites, forming a high-strength adsorption layer, thus achieving near-limited recovery rates. In contrast, the collectors used in Comparative Examples 8 and 9 failed to effectively utilize the new sites generated by oxidation, resulting in lower recovery rates.

[0075] Comparative Example 10 This comparative example uses sodium oleate as a collector, hydrogen peroxide aqueous solution (30% by mass) as an oxidant, methyl isobutyl methanol as a frother, and hematite flotation. The specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 10.0).

[0076] (2) Add collector and oxidant to the slurry, wherein the amount of collector added is 6.0 × 10⁻⁶. -4 mol / L, the amount of oxidant added is 0.5 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0077] In this comparative example, the hematite recovery rate was 59.4%.

[0078] Comparative Example 11 This comparative example uses benzohydroxyxamic acid as the collector, hydrogen peroxide aqueous solution (30% by mass) as the oxidant, methyl isobutyl methanol as the frother, and hematite as the flotation agent. The specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 10.0).

[0079] (2) Add collector and oxidant to the slurry, wherein the amount of collector added is 6.0 × 10⁻⁶. -4 mol / L, the amount of oxidant added is 0.5 × 10⁻⁶. -4mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0080] In this comparative example, the hematite recovery rate was 41.2%.

[0081] Comparative Example 12 This comparative example uses adipicoyl bis(hydroxyoxime) as the collector, methyl isobutyl methanol as the frother, and hydrogen peroxide aqueous solution as the oxidant to float hematite. The specific steps are as follows: (1) Crush the hematite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 10.0).

[0082] (2) Add collector and oxidant to the slurry, wherein the amount of collector added is 6.0 × 10⁻⁶. -4 mol / L, the amount of oxidant added is 1.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0083] In this comparative example, the hematite recovery rate was 46.9%.

[0084] The collector in this comparative example lacked sufficient hydrophobicity to form an effective hydrophobic film on the mineral surface, resulting in the mineral particles failing to float effectively even after chelation. In Example 7, collector A (decanedioyl diisohydroxyxamic acid) and collector B (α-benzoic acid oxime) formed complementary coordination, with the diisohydroxyxamic acid functional group and oxime group respectively adapting to the different Fe content on the hematite surface. 3+ Sites are established to achieve full surface coverage. After adsorption at the mineral interface, the flexible aliphatic chains and rigid benzene rings undergo hydrophobic association, constructing a dense and stable composite hydrophobic layer at the solid-liquid interface. This process occurs within the Fe-rich environment created by oxidant pre-activation. 3+ The surface is strengthened, which significantly improves the adsorption density and structural stability of the interfacial complex. Ultimately, the optimized surface hydrophobicity ensures efficient mineralization of bubbles and significantly improves the recovery rate.

[0085] Comparative Example 13 This comparative example uses sodium oleate and octanoyl diisohydroxamic acid as collectors, methyl isobutyl methanol as a frother, and hydrogen peroxide aqueous solution as an oxidant for the flotation of siderite. The specific steps are as follows: (1) Crush the siderite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0).

[0086] (2) Add collector and oxidant to the slurry, wherein the amount of collector added is 6.0 × 10⁻⁶. -4 mol / L, the amount of oxidant added is 1.0 × 10⁻⁶. -4 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 The solution was mol / L, and N2 was used for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to separate and obtain the concentrate.

[0087] In this comparative example, the recovery rate of siderite was 89.0%.

[0088] The results of Examples 2, 5, and Comparative Example 13 show that sodium oleate and collector A failed to achieve synergistic coordination and hydrophobic association. The carboxyl groups in sodium oleate and the bis(hydroxyoxime) acid collector A lack effective synergy in their mechanism of action, preventing them from constructing a complementary coordination field and forming a dense composite hydrophobic layer. Therefore, their recovery rate is lower than that when using the combined collector of this invention.

[0089] In summary, this invention provides a combined collector for iron oxide ore and its application. Through the synergistic effect of collector A (a diisohydroxyxamic acid) and collector B (an oxime), a multi-element mixed coordination field and a composite hydrophobic layer are successfully constructed. This combined collector can achieve efficient and highly selective flotation recovery of ilmenite, hematite, and siderite under mild pH conditions. This invention overcomes the inherent defects of traditional collectors such as sodium oleate (poor selectivity, easy emulsification) and benzyl hydroxamic acid (weak collecting power, poor solubility), and further enhances the utilization of activated sites on the mineral surface through synergistic use with oxidants, achieving extremely high recovery rates. This invention combines the outstanding advantages of good selectivity, high recovery rate, low dosage, environmental friendliness, and wide applicability, providing a reliable technical solution for the efficient separation of "lean, fine, and complex" iron oxide ore resources.

[0090] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A composite collector for iron oxide ore, characterized in that, The combined collector consists of collector A and collector B. The structural formula of collector A is shown in formula (I), and the structural formula of collector B is shown in formula (II). , In equation (Ⅰ), R is C7~C 16 One of alkyl, phenyl or cyclohexyl groups; M in formulas (I) and (II) is sodium, potassium, ammonium or hydrogen.

2. The application of the combined collector as described in claim 1 in the flotation of iron oxide ore, characterized in that, Specifically, the following steps are included: (1) Iron oxide ore is crushed, mixed into a slurry, and then a slurry is prepared. (2) Add a combination of collector and frother to the slurry, and then perform aeration flotation to separate and obtain concentrate.

3. The application of the combined collector according to claim 2 in the flotation of iron oxide ore, characterized in that, The iron oxide ore mentioned in step (1) is one of ilmenite, siderite and hematite.

4. The application of the combined collector according to claim 2 in the flotation of iron oxide ore, characterized in that, The pH of the slurry in step (1) is 4.0~10.

0.

5. The application of the combined collector according to claim 2 in the flotation of iron oxide ore, characterized in that, In step (2), the molar ratio of collector A to collector B in the combined collector is 1~5:5~1.

6. The application of the combined collector according to claim 2 in the flotation of iron oxide ore, characterized in that, The amount of the combined collector added in step (2) is 1.0 × 10⁻⁶. -4 ~1.0×10 -2 mol / L.

7. The application of the combined collector according to claim 2 in the flotation of iron oxide ore, characterized in that, In step (2), an oxidant can be added before aeration flotation. The amount of oxidant added is 0.5 × 10⁻⁶. -4 ~1.0×10 -2 mol / L.

8. The application of the combined collector according to claim 7 in the flotation of iron oxide ore, characterized in that, The oxidant is one of the following: ammonium persulfate, potassium persulfate, sodium persulfate, hypochlorous acid, sodium hypochlorite, calcium hypochlorite, or aqueous solution of hydrogen peroxide.

9. The application of the combined collector according to claim 2 in the flotation of iron oxide ore, characterized in that, The foaming agent mentioned in step (2) is methyl isobutyl methanol, and the amount of foaming agent added is 0~1×10 -3 mol / L.

10. The application of the combined collector according to claim 2 in the flotation of iron oxide ore, characterized in that, The time for aeration flotation in step (2) is 2 to 5 minutes.

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