Application of halogenated organic oxidant in iron oxide ore flotation
By leveraging the synergistic effect of halogenated organic oxidants and collectors, the problems of environmental pollution and low recovery rate in the flotation of iron oxide ore have been solved, achieving a highly efficient and selective flotation process for iron oxide ore.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- KUNMING UNIV OF SCI & TECH
- Filing Date
- 2026-02-27
- Publication Date
- 2026-04-14
AI Technical Summary
Existing inorganic oxidants pose environmental pollution problems in the flotation of iron oxide ore, and their oxidation efficiency and selectivity are insufficient, resulting in low recovery rates.
By employing the synergistic effect of halogenated organic oxidants and collectors, low-valent iron on the mineral surface is oxidized to high-valent iron through an oxidation reaction, generating stable chelates and improving the floatability of the minerals.
It significantly enhances the separation selectivity and recovery rate of iron oxide ores, and the process is simple, environmentally friendly, and applicable to a variety of iron oxide ores. It does not require high-temperature and high-pressure equipment and requires low equipment investment.
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Figure CN121847342A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of mineral flotation technology, specifically to the application of a halogenated organic oxidant in the flotation of iron oxide ore. Background Technology
[0002] Contains Fe 2+ The minerals include ilmenite, wolframite, and siderite, and the active sites on the surface are mainly Fe. 2+ Its Fe 2+ Its chelating ability with collectors is relatively weak. Compared to Fe... 2+ (pKa=9.5), Fe 3+ (pKa=2.2) It has stronger Lewis acidity, which significantly enhances its complexing ability with collectors.
[0003] Currently, commonly used inorganic oxidants include metal ions, non-metallic elements, oxyacids and oxyacid salts, and peroxides. Among them, potassium permanganate, potassium dichromate, and concentrated sulfuric acid are widely used in mineral processing. However, potassium permanganate and potassium dichromate contain heavy metal ions, and improper treatment of the heavy metal-containing wastewater and waste residue generated after the reaction can cause soil and water pollution; concentrated sulfuric acid is highly corrosive and requires sophisticated equipment.
[0004] Therefore, developing oxidants that combine high oxidation efficiency, good selectivity, mild reaction conditions, and environmental friendliness to achieve efficient flotation of iron oxide ores and simultaneously improve recovery rate and concentrate grade has become a key issue that urgently needs to be addressed in this field. Summary of the Invention
[0005] To solve the problem of Fe-containing 2+ The direct flotation separation efficiency in mineral flotation is insufficient, and inorganic oxidants cause environmental pollution. The purpose of this invention is to provide an application of a halogenated organic oxidant in the flotation of iron oxide ores, specifically including the following steps: (1) Iron oxide ore is crushed, mixed into a slurry, and then a slurry is prepared.
[0006] (2) Add a halogenated organic oxidant to the slurry to carry out an oxidation reaction.
[0007] (3) After the oxidation reaction is completed, a collector and a frother are added to the slurry, and the concentrate is obtained by flotation.
[0008] Preferably, the iron oxide ore in step (1) of the present invention is one of ilmenite, wolframite, hematite, and siderite.
[0009] Preferably, the pH of the slurry in step (1) of the present invention is 4.0~10.0.
[0010] Preferably, the structural formula of the halogenated organic oxidant in step (2) of the present invention is shown in formula (I) or formula (II): , In equations (I) and (II), X is one of F and Cl.
[0011] Preferably, the amount of halogenated organic oxidant added in step (2) of the present invention is 0.5 × 10⁻⁶. -4 ~2.0×10 - 4 mol / L.
[0012] Preferably, the oxidation reaction time in step (2) of the present invention is 2 to 10 minutes.
[0013] Preferably, the collector in step (3) of the present invention is one of benzohydroxyxamic acid, sodium oleate, and octylhydroxyxamic acid, and the amount of collector added is 5.0 × 10⁻⁶. -4 ~2.0×10 -3 mol / L.
[0014] Preferably, the foaming agent in step (3) of the present invention is methyl isobutyl methanol, and the amount of foaming agent added is 1×10 -4 mol / L.
[0015] Preferably, the flotation time in step (3) of the present invention is 1 to 5 minutes; more preferably, the flotation time is 3 minutes.
[0016] This invention provides an application of a halogenated organic oxidant in the flotation of iron oxide ore, which has the following beneficial effects: (1) The halogenated organic oxidant of the present invention can precisely remove low-valent iron (Fe) from the surface of minerals. 2+ ) is oxidized to high-valence iron (Fe) 3+ Through the synergistic effect of oxidants and collectors, a highly stable chelate is generated, which significantly enhances the floatability of iron oxide ore and improves the separation selectivity between minerals and gangue. Its separation effect is superior to traditional flotation and roasting processes.
[0017] (2) The halogenated organic oxidant of the present invention is characterized by its economical price, wide availability of raw materials and good water solubility.
[0018] (3) The flotation process of the present invention is applicable to a variety of iron oxide ores, including ilmenite, wolframite, hematite, siderite, etc., and the pulp pH range is wide, which has good universality for different types of ore. It can be carried out at normal temperature and pressure without the need for high temperature or high pressure equipment. The process is simple, the equipment investment is small, and it is easy to implement industrially. Attached Figure Description
[0019] Figure 1 This is a schematic diagram of the flotation process of the present invention. Detailed Implementation
[0020] 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.
[0021] Example 1 In this embodiment, the halogenated organic oxidant used is cyanuric chloride, the collector is octyl hydroxamic acid, and the frother is methyl isobutyl methanol; 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).
[0022] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 0.5 × 10⁻⁶. -4 mol / L, oxidize for 10 minutes.
[0023] (3) 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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0024] In this embodiment, the ilmenite recovery rate is 97.7%.
[0025] Example 2 In this embodiment, the halogenated organic oxidant used is cyanuric chloride, the collector is sodium oleate, and 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).
[0026] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 1×10 -4 mol / L, oxidize for 10 minutes.
[0027] (3) 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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0028] In this embodiment, the recovery rate of ilmenite was 99.0%.
[0029] Example 3 In this embodiment, the halogenated organic oxidant used is cyanuric chloride, the collector is sodium oleate, and 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).
[0030] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 2.0 × 10⁻⁶. -4 mol / L, oxidize for 2 minutes.
[0031] (3) 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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0032] In this embodiment, the ilmenite recovery rate is 85.3%.
[0033] Example 4 In this embodiment, the halogenated organic oxidant used is trichloromelamine, the collector is octyl hydroxamic acid, and the frother is methyl isobutyl methanol. 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 10.0).
[0034] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 2 × 10⁻⁶. -4 mol / L, oxidize for 10 minutes.
[0035] (3) 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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0036] In this embodiment, the ilmenite recovery rate is 95.2%.
[0037] Example 5 In this embodiment, the halogenated organic oxidant used is cyanuric chloride, the collector is octyl hydroxamic acid, and the frother is methyl isobutyl methanol. Hematite is flotated, and the flotation process 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 4.0).
[0038] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 0.5 × 10⁻⁶. -4 mol / L, oxidize for 5 minutes.
[0039] (3) Add a collector to the slurry. The amount of collector added is 2.0 × 10⁻⁶. -3 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0040] In this embodiment, the hematite recovery rate was 94.9%.
[0041] Example 6 In this embodiment, the halogenated organic oxidant used is trichloromelamine, the collector is benzohydroxyxamic acid, and the frother is methyl isobutyl methanol; the flotation process for wolframite is as follows: Figure 1 As shown, the specific steps are as follows: (1) The wolframite is crushed to a particle size of -200~+400 mesh, and the slurry is prepared (the pH of the slurry is 8.0).
[0042] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 2.0 × 10⁻⁶. -4 mol / L, oxidize for 2 minutes.
[0043] (3) Add a collector to the slurry. The amount of collector added is 1.0 × 10⁻⁶. -3 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0044] In this embodiment, the recovery rate of wolframite was 93.6%.
[0045] Example 7 In this embodiment, the halogenated organic oxidant used is cyanuric fluoride, the collector is benzyl hydroxamic acid, and the frother is methyl isobutyl methanol. 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).
[0046] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 1.0 × 10⁻⁶. -4 mol / L, oxidize for 2 minutes.
[0047] (3) Add a collector to the slurry. The amount of collector added is 1.0 × 10⁻⁶. -3 mol / L; and add a foaming agent, the amount of which is 1.0 × 10 mol / L. -4 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0048] In this embodiment, the siderite recovery rate is 90.3%.
[0049] Example 8 In this embodiment, the halogenated organic oxidant used is cyanuric chloride, the collector is octyl hydroxamic acid, and the frother is methyl isobutyl methanol. Oxidative flotation is used to separate a mixed ore of ilmenite and diopside (ilmenite to diopside mass ratio of 1:1). The flotation process is as follows: Figure 1 As shown, the specific steps are as follows: (1) The mixed ore of ilmenite and diopside is crushed to a particle size of -200~+400 mesh, and the slurry is prepared (the pH of the slurry is 8.0).
[0050] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 0.5 × 10⁻⁶. -4 mol / L, oxidize for 10 minutes.
[0051] (3) 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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0052] In this embodiment, the ilmenite recovery rate is 90.9%.
[0053] Example 9 In this embodiment, the halogenated organic oxidant used is cyanuric chloride, the collector is sodium oleate, and the frother is methyl isobutyl alcohol. Oxidative flotation is used to separate a mixed ore of ilmenite and diopside (ilmenite to diopside mass ratio of 1:1). The flotation process is as follows: Figure 1 As shown, the specific steps are as follows: (1) The mixed ore of ilmenite and diopside is crushed to a particle size of -200~+400 mesh, and the slurry is prepared (the pH of the slurry is 10.0).
[0054] (2) Add a halogenated organic oxidant to the slurry. The amount of halogenated organic oxidant added is 0.5 × 10⁻⁶.-4 mol / L, oxidize for 10 minutes.
[0055] (3) 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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0056] In this embodiment, the ilmenite recovery rate was 91.1%.
[0057] 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).
[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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0059] In this comparative example, the recovery rate of ilmenite was 74.1%.
[0060] Comparative Example 2 This comparative example uses octyl hydroxamic acid as the collector, 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 8.0).
[0061] (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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0062] In this comparative example, the recovery rate of ilmenite was 77.5%.
[0063] Comparative Example 3 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).
[0064] (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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0065] In this comparative example, the hematite recovery rate was 49.3%.
[0066] Comparative Example 4 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).
[0067] (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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0068] In this comparative example, the hematite recovery rate was 38.4%.
[0069] Comparative Example 5 This comparative example uses benzohydroxyxamic acid as a collector and methyl isobutyl methanol as a frother to float wolframite. The specific steps are as follows: (1) The wolframite is crushed to a particle size of -200~+400 mesh, and the slurry is prepared (the pH of the slurry is 8.0).
[0070] (2) Add a collector to the slurry. The amount of collector added is 1.0 × 10⁻⁶. -3 mol / L; and add a foaming agent, the amount of which is 1×10 mol / L. -4 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0071] In this comparative example, the recovery rate of wolframite was 54.8%.
[0072] Comparative Example 6 The oxidant used in this comparative example is sodium hypochlorite, the collector is octyl hydroxamic acid, the frother is methyl isobutyl methanol, and the flotation is carried out on 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).
[0073] (2) Add an oxidant to the slurry. The amount of oxidant added is 0.5 × 10⁻⁶. -4 mol / L; (3) 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 mol / L, aerated flotation for 3 minutes, to separate and obtain concentrate.
[0074] In this comparative example, the recovery rate of ilmenite was 85.6%.
[0075] In summary, this invention significantly improves the floatability of iron oxide ore through the synergistic effect of halogenated organic oxidants and collectors, enabling efficient flotation of iron oxide ore. It has outstanding advantages such as good selectivity, high recovery rate, low dosage, and environmental friendliness.
[0076] 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. The application of a halogenated organic oxidant 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 halogenated organic oxidant to the slurry to carry out an oxidation reaction; (3) After the oxidation reaction is completed, a collector and a frother are added to the slurry, and the concentrate is obtained by flotation.
2. The application of the halogenated organic oxidant according to claim 1 in the flotation of iron oxide ore, characterized in that, The iron oxide ore mentioned in step (1) is one of ilmenite, wolframite, hematite, and siderite.
3. The application of the organic oxidant 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.
4. The application of the organic oxidant according to claim 1 in the flotation of iron oxide ore, characterized in that, The structural formula of the halogenated organic oxidant mentioned in step (2) is shown in formula (I) or formula (II): , In equations (I) and (II), X is one of F and Cl.
5. The application of the halogenated organic oxidant according to claim 1 in the flotation of iron oxide ore, characterized in that, The amount of halogenated organic oxidant added in step (2) is 0.5 × 10⁻⁶. -4 ~2.0×10 -4 mol / L.
6. The application of the halogenated organic oxidant according to claim 1 in the flotation of iron oxide ore, characterized in that, The oxidation reaction in step (2) takes 2 to 10 minutes.
7. The application of the halogenated organic oxidant according to claim 1 in the flotation of iron oxide ore, characterized in that, The collector mentioned in step (3) is one of benzohydroxyxamic acid, sodium oleate, and octylhydroxyxamic acid, and the amount of collector added is 5.0 × 10⁻⁶. -4 ~2.0×10 -3 mol / L.
8. The application of the halogenated organic oxidant according to claim 1 in the flotation of iron oxide ore, characterized in that, The foaming agent mentioned in step (3) is methyl isobutyl alcohol, and the amount of foaming agent added is 1×10 -4 mol / L.
9. The application of the halogenated organic oxidant according to claim 1 in the flotation of iron oxide ore, characterized in that, The flotation time in step (3) is 1 to 5 minutes.