Method for floating fluorite, oxidized ores

Abstract

The present application belongs to the field of mineral flotation, and particularly relates to a method for flotation of fluorite and oxidized ore, wherein the target mineral concentrate is obtained by mixing the to-be-flotation mineral containing at least one target mineral of fluorite and oxidized ore and flotation reagents for flotation treatment; the method is characterized in that the flotation reagents contain at least one collector of formula 1 and formula 2. 1 -S-R 2 -COOM formula 1; R 1 is a C6-C 24 alkyl or O-atom-containing C6-C 24 alkyl, R 2 is a C2-C8 alkyl; and M is H, Na or K. The present application innovatively uses the collector of formula 1 and / or formula 2 for flotation of fluorite and oxidized ore, and can efficiently and selectively target capture fluorite and oxidized ore, and can improve the effect, wherein in particular, formula 2 can still obtain good collecting effect at a lower dosage and lower temperature.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation technology, specifically to flotation methods for fluorite and oxide ores. Background Technology

[0002] In the field of mineral processing, flotation is one of the key technologies for separating and enriching target minerals. Carboxylic acid collectors, due to their environmental friendliness and good collecting ability, are widely used for the flotation separation and enrichment of non-sulfide minerals such as scheelite, fluorite, apatite, barite, hematite, pyrolusite, cassiterite, wolframite, ilmenite, bauxite, rare earth minerals, beryl, spodumene, zircon, ferrite, and garnet. Traditional carboxylic acid collectors are mainly derived from animal and vegetable oils, oxidized paraffin, and talc oil, which are inexpensive but have drawbacks such as limited structural adjustment space, poor low-temperature performance, large reagent dosage, and poor foaming performance. Therefore, developing carboxylic acid collectors with adjustable hydrophobic structures, good low-temperature performance, and controllable foaming properties will help achieve effective flotation separation and enrichment of valuable minerals, improving economic and social benefits.

[0003] Patent CN115957889A discloses a method for preparing a carboxylic acid collector and its application. This collector exhibits good selectivity and strong collecting ability, good solubility and dispersibility in water, and can be adapted to efficient flotation of minerals under both normal and low-temperature conditions, particularly suitable for the flotation of oxidized ores. Patent CN118807987A discloses an α-bromofatty acid collector, which has advantages such as wide availability of raw materials, simple synthesis, convenient use, and good low-temperature resistance, and exhibits strong selectivity for lithium chlorite. Patent CN108435431A discloses a method for preparing a cottonseed oil fatty acid soap collector. This collector has good water solubility and low-temperature resistance, and exhibits strong collecting ability and good selectivity for phosphate rock. Patent CN118635003A discloses a compound containing two carboxyl groups and two amino groups, comprising cationic and anionic functional groups. This compound has high polarity, which enhances the adsorption between the collector and the functional groups on the mineral surface, and exhibits good water solubility and dispersibility at low temperatures, contributing to improved recovery rates under low-temperature conditions. Patent CN108480055A discloses a flotation collector for scheelite and its preparation method. The collector is mainly composed of sulfonated unsaturated fatty acids and hydroxy fatty acids, exhibiting good low-temperature resistance, selectivity, and strong collecting ability, enabling the production of high-grade and high-recovery scheelite concentrate. Although various carboxylic acid collectors have been developed and applied in flotation, problems remain, such as high production costs, difficulty in simultaneously achieving optimal performance in hydrophobicity, low-temperature control, foaming ability, and dispersion. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the first objective of this invention is to provide a method for flotation of fluorite and oxide ores, which aims to improve the flotation effect of fluorite and oxide ores.

[0005] A method for flotation of fluorite and oxide minerals involves mixing a target mineral containing at least one target mineral from fluorite and oxide minerals with flotation reagents and performing flotation treatment to obtain a target mineral concentrate; wherein the flotation reagents include at least one collector from Formula 1 and Formula 2.

[0006] R 1 -SR 2 -COOM Formula 1

[0007]

[0008] R 1 C6~C 24 Hydrocarbon group or C6-C containing an O atom 24 hydrocarbon group, R 2 It is a C2 to C8 hydrocarbon group; M is H, Na or K.

[0009] This invention innovatively employs collectors of Formula 1 and / or Formula 2 for the flotation of fluorite and oxide minerals. This allows for the efficient and highly selective targeting and capture of fluorite and oxide minerals based on the combination of special structures in the collectors, thus improving the performance. In particular, Formula 2 can achieve good collection results even at lower dosages and lower temperatures.

[0010] In this invention, the R 1 C6~C 24 Alkyl groups, C6-C 24 alkenyl, C6-C 24 aryl or R 3 -(O-CH2CH2) n -;R 3 C6~C 24 Alkyl groups, C6-C 24 alkenyl or C6~C 24 The aryl group; n is 1 to 12. Preferably, the R... 1 It is n-octyl, isooctyl, nonyl, decyl, isodecyl, tert-dodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, isotetradecyl, hexadecyl, isohexadecyl, octadecyl, isooctadecyl, or 9-n-octadecenyl. More preferably, the R... 1 It is n-octyl, isooctyl, tert-dodecyl, dodecyl, tetradecyl, hexadecyl, or octadecyl.

[0011] R 2 It is a C2-C8 alkyl, C2-C8 alkenyl, C5-C8 cycloalkyl, or C6-C8 aryl; preferably, R 2It can be ethylene, methyl ethylene, propylene, butylene, pentylene, hexylene, cyclopentyl, or cyclohexyl. R 2 Further preferred are ethylene or methyl ethylene.

[0012] In this invention, the oxide ore is an oxide ore of at least one of rare earth elements, iron, titanium, tungsten, lithium, tin, phosphorus, and manganese. It may further include at least one of scheelite, cassiterite, ilmenite, and fluorite.

[0013] For example, as an optional approach, the collector described in this invention can be used for the selective flotation separation of ilmenite and pyroxene; in addition, it can also be used for the selective flotation separation of scheelite and calcium-containing gangue (such as calcite).

[0014] In this invention, the weight of the ore fed to the flotation is used as the calculation standard, and the dosage of the collector of Formula 1 is 200-3000 g / t, preferably 500-2000 g / t.

[0015] In this invention, the pH of the flotation pulp is 3 to 11, preferably 5 to 10; further, it can be 7.5 to 8.5.

[0016] In this invention, flotation can be achieved over a wide temperature range, for example, the flotation temperature can be 1 to 30°C. Especially under low temperature conditions of 1 to 15°C, the flotation process of this invention can exhibit better collection capacity and selectivity compared with existing technical solutions.

[0017] In this invention, the flotation reagent further includes at least one of an inhibitor, a pH adjuster, and a foaming agent.

[0018] The optional flotation process steps of this invention are, for example:

[0019] Step (1): The ore to be selected is crushed and mixed to obtain a slurry;

[0020] Step (2): Add flotation reagents to the slurry from step (1) for flotation and collect the flotation concentrate; the flotation reagents include at least one collector as described in formulas (I) and (II).

[0021] Beneficial effects

[0022] The collector described in this invention features a wide range of raw material sources, high structural adjustability, and strong commercial potential. It is easy to develop collectors with strong hydrophobicity, weak foaming ability, excellent dispersibility, high selectivity, wide applicable temperature range, and strong collecting ability. These characteristics effectively enhance the flotation separation efficiency of fluorite and oxides such as rare earth, iron, titanium, tungsten, lithium, tin, phosphorus, and manganese, and improve the flotation recovery rate of valuable minerals. Attached Figure Description

[0023] Figure 1 Equation 1a 1 H NRM diagram;

[0024] Figure 2 Equation 2a 1 H NRM diagram;

[0025] Figure 3 Infrared spectrum of Equation 1a;

[0026] Figure 4 Infrared spectrum of Equation 2a. Detailed Implementation

[0027] The following examples are intended to further illustrate the invention, but not to limit the scope of protection of the invention. All parts and percentages in the examples refer to mass unless otherwise specified. The examples use the collector of the present invention for flotation of non-sulfide ores, and the experimental process is a conventional flotation process.

[0028] In this invention, the collector of Formula 1 can be prepared based on conventional substitution or addition reactions.

[0029] For example, an alternative substitution reaction synthesis method is:

[0030] R 1 -S - +XR 2 -COO - →R 1 -SR 2 -COOM

[0031] The addition reaction strategy is, for example:

[0032] R3 can be H, alkyl, etc.

[0033] Formula 2 can be obtained by oxidizing Formula 1, such as by oxidizing it under hydrogen peroxide.

[0034] As an optional embodiment of the present invention, the collector can have the following structural formula as a typical example:

[0035] (See the proton spectrum and infrared spectrum respectively) Figure 1 and Figure 3 );

[0036] (See the proton spectrum and infrared spectrum respectively) Figure 2 and Figure 4 );

[0037]

[0038] In the following cases, unless otherwise stated, the flotation process temperature can be room temperature, specifically 20–30°C.

[0039] In this invention, the amount of collector can be adjusted as needed. Considering the flotation cost, its concentration in the pulp can be controlled at 5.0 × 10⁻⁶. -6 ~5.0×10 -4 mol / L; for example, as an optional scheme, the concentration can be controlled at 5.0 × 10⁻⁶ mol / L. -6 6.0×10 -6 7.0×10 -6 8.0×10 -6 9.0×10 -6 1.0×10 -5 2.0×10 -5 3.0×10 -5 4.0×10 -5 5.0×10 -5 .

[0040] Example 1: Flotation of artificially mixed ilmenite and ilmenite

[0041] When the pulp pH is ~8.0 and the N2 flow rate is 300 mL / min, the effect of formula 1a ( Figure 1 and Figure 3 Equation 2a Figure 2 and Figure 4 The flotation performance of comparative formula 1a, palmitic acid and oleic acid on artificial mixed ilmenite-titanium pyroxene with a flotation time of 3 minutes was compared with that of formula 1a. The results are shown in Table 1.

[0042] In the flotation process, the concentrations of Comparative Formula 1a, oleic acid, and palmitic acid were all 8.0 × 10⁻⁶. -6 mol / L, the concentration of the collectors in both Formula 1a and Formula 2a is 7.0 × 10⁻⁶. -6 mol / L.

[0043] Table 1. Results of Ilmenite Flotation

[0044]

[0045] As shown in Table 1, compared with Comparative Formula 1a, oleic acid and palmitic acid, collectors such as Formula 1a and Formula 2a have higher separation efficiency for ilmenite-titanium pyroxene mixed ore at lower dosages, and Formula 2a can achieve highly selective flotation separation of ilmenite and titanium pyroxene.

[0046] Example 2 Fluorite Flotation

[0047] With a pulp pH of approximately 8.0, a flotation temperature of 10°C, and using Comparative Formula 1a, the concentrations of oleic acid and palmitic acid were both 1.0 × 10⁻⁶.-5 mol / L, the concentration of the collectors in both Formula 1a and Formula 2a is 5.0 × 10⁻⁶. -6 The flotation performance of formulas 1a, 2a, comparative formula 1a, palmitic acid, and oleic acid on 0.038–0.076 mm fluorite was investigated at a flow rate of 300 mL / min and a N2 concentration of mol / L. The flotation time was 3 minutes. The results are shown in Table 2.

[0048] Table 2 Fluorite Flotation Results

[0049] Types of collectors Fluorite flotation recovery rate / % Formula 1a 89.46 Equation 2a 93.86 Comparison 1a 84.79 Palmitic acid 80.27 Oleic acid 83.43

[0050] The results showed that, compared with comparative formula 1a, oleic acid and palmitic acid, formulas 1a and 2a, which were used in only half the amount of oleic acid, significantly improved the flotation recovery of fluorite under low-temperature flotation conditions, with formula 2a showing the best effect.

[0051] Example 3: Flotation of Artificial Mixture of Scheelite and Calcite

[0052] With pulp pH ~8.0, the concentrations of Comparative Formula 1a, oleic acid, and palmitic acid were all 7.0 × 10⁻⁶. -5 mol / L, the concentration of the collectors in both Formula 1a and Formula 2a is 5 × 10⁻⁶. -5 The flotation performance of collectors 1a, 2a, comparative 1a, palmitic acid, and oleic acid on 0.038–0.076 mm scheelite-calcite artificial mixed ore was investigated at a N2 flow rate of 300 mL / min and a flotation time of 3 minutes. The results are shown in Table 3. The results indicate that, compared with comparative 1a, oleic acid, and palmitic acid, collectors 1a and 2a, at lower dosages, showed better separation effects on scheelite-calcite artificial mixed ore, with 2a exhibiting the most significant separation effect.

[0053] Table 3. Flotation results of scheelite

[0054]

[0055] Example 4: Rare Earth Flotation

[0056] With pulp pH ~8.0, the concentrations of Comparative Formula 1a, oleic acid, and palmitic acid were all 6.0 × 10⁻⁶. -5 mol / L, the concentration of the collectors in formulas 1a and 2a is 4.0 × 10⁻⁶. -5 The flotation performance of collectors 1a, 2a, palmitic acid, and oleic acid for rare earth elements (fluorocarbon cerium ore) in the range of 0.038–0.076 mm was investigated at a N2 flow rate of 300 mL / min and a flotation time of 3 minutes. The results are shown in Table 4. This indicates that, compared to oleic acid and palmitic acid, collectors 1a and 2a have stronger collecting ability for rare earth elements at lower dosages.

[0057] Table 4. Rare Earth Flotation Results

[0058] Types of collectors Rare earth flotation recovery rate / % Formula 1a 95.72 Equation 2a 89.46 Comparison 1a 86.27 Palmitic acid 83.76 Oleic acid 85.76

[0059] In summary, the collectors of the present invention can achieve better collection capacity and selectivity at lower dosages, especially the collector of Formula 2, which can achieve even better selectivity. Furthermore, the method of the present invention is also adaptable to the requirements of low-temperature flotation applications.

Claims

1. A method for flotation of fluorite and oxide minerals, comprising mixing a target mineral containing at least one target mineral from fluorite and oxide minerals with flotation reagents for flotation treatment to obtain a target mineral concentrate; characterized in that, The flotation reagents include at least one collector of Formula 1 and Formula 2; R 1 -SR 2 -COOM expression 1 R 1 C6~C 24 hydrocarbon group or C6-C containing an O atom 24 hydrocarbon group, R 2 It is a C2 to C8 hydrocarbon group; M is H, Na or K.

2. The method for flotation of fluorite and oxide ores as described in claim 1, characterized in that, The R mentioned 1 C6~C 24 Alkyl groups, C6-C 24 alkenyl, C6-C 24 aryl or R 3 -(O-CH2CH2) n -;R 2 It is a C2-C8 alkyl, C2-C8 alkenyl, C5-C8 cycloalkyl, or C6-C8 aryl; R 3 C6~C 24 Alkyl groups, C6-C 24 alkenyl or C6~C 24 The aryl group; n is 1 to 12.

3. The method for flotation of fluorite and oxide ores as described in claim 1, characterized in that, The R mentioned 1 It is n-octyl, isooctyl, nonyl, decyl, isodecyl, tert-dodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, isotetradecyl, hexadecyl, isohexadecyl, octadecyl, isooctadecyl or 9-n-octadecenyl; R 2 It can be ethylene, methyl ethylene, propylene, butylene, pentylene, hexylene, cyclopentyl, or cyclohexyl.

4. The method for flotation of fluorite and oxide ores as described in claim 1, characterized in that, The R mentioned 1 It is n-octyl, isooctyl, tert-dodecyl, dodecyl, tetradecyl, hexadecyl, or octadecyl; R 2 Further preferred are ethylene or methyl ethylene.

5. The method for flotation of fluorite and oxide ores as described in claim 1, characterized in that, The oxide ore is an oxide ore of at least one of rare earth, iron, titanium, tungsten, lithium, tin, phosphorus and manganese.

6. The method for flotation of fluorite and oxide ores as described in claim 1, characterized in that, The oxide minerals mentioned include at least one of scheelite, cassiterite, ilmenite, and fluorite.

7. The method for flotation of fluorite and oxide ores as described in claim 1, characterized in that, Based on the weight of the ore fed to the flotation, the dosage of the collector of Formula 1 is 200-3000 g / t, preferably 500-2000 g / t.

8. The method for flotation of fluorite and oxide ores according to claim 1, characterized in that, The pH of the flotation pulp is 3–11, preferably 5–10.

9. The method for flotation of fluorite and oxide ores according to claim 1, characterized in that, The flotation temperature is 1–30℃, and can be further reduced to 1–15℃.

10. The method for flotation of fluorite and oxide ores according to any one of claims 1 to 9, characterized in that, The flotation reagents also include at least one of the following: inhibitor, pH adjuster, and frother.

Images