Method for the flotation of non-sulphidic ores

Abstract

The application belongs to the field of mineral flotation, and specifically discloses a flotation method for non-sulfide ores, which comprises the following steps: carrying out flotation on the non-sulfide ores in a flotation reagent containing a collector of formula 1 to obtain a non-sulfide ore concentrate. The collector of formula 1 has good collecting activity and low-temperature adaptability, and can achieve good collecting effect on the non-sulfide ores even at a lower temperature and in a lower dosage.

Description

Technical Field

[0001] This invention relates to the field of mineral beneficiation, specifically to the flotation of non-sulfide minerals. Background Technology

[0002] Carboxylic acid collectors, containing carboxyl functional groups, are common collectors in the flotation of non-sulfide minerals. They are widely used for the flotation separation and enrichment of minerals such as scheelite, fluorite, apatite, barite, hematite, pyrolusite, cassiterite, wolframite, ilmenite, bauxite, rare earth minerals, beryl, spodumene, zircon, hedonicite, and garnet. Traditional carboxylic acid collectors are mainly derived from animal and vegetable oils, oxidized paraffins, and talc oils, which are relatively inexpensive. However, they have drawbacks such as limited structural adjustment capabilities, poor low-temperature adaptability, high reagent dosage, and poor foaming performance. Therefore, developing novel structural carboxylic acid collectors to improve flotation performance is of great significance for achieving efficient mineral separation and improving economic and social benefits.

[0003] Patent publication CN 104447321 A discloses a method for synthesizing alcohol ether ester carboxylate compounds. These compounds are prepared from alkyl alcohol ethers and oxalic acid via esterification and salt formation reactions, exhibiting good dispersing and emulsifying properties. Patent publication CN 116532243A discloses the preparation of a calcium and magnesium ion-resistant surfactant and its application in the flotation of refractory scheelite. The collector is sodium alkyl succinate sulfonate (SDMA), which shows good flotation recovery effects on scheelite.

[0004] The aforementioned novel carboxylic acid collectors exhibit excellent collecting performance, which can improve the flotation separation efficiency of valuable minerals. However, these novel carboxylic acid collectors have high preparation costs, low atom utilization, and some require chlorides as raw materials, posing potential environmental pollution. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a flotation method for non-sulfide minerals, aiming to improve the flotation effect of non-sulfide minerals.

[0006] A flotation method for non-sulfide minerals involves flotating the non-sulfide minerals in a flotation reagent containing a collector of Formula 1 to obtain a non-sulfide mineral concentrate.

[0007]

[0008] R1 is C3~C 24 Hydrocarbon group or C3-C containing an O atom 24 Hydrocarbon group; R2 is H, C1-C 24 Hydrocarbon group or C3-C containing an O atom 24 Hydrocarbon group; M is H, Na or K.

[0009] This invention demonstrates that the combination of the -COO- and -CONR- groups at the ortho position of the benzene ring and the spatial domain in the structure of Formula 1 can unexpectedly improve the flotation collecting ability and selectivity of non-sulfide ores, achieving excellent collecting effects at low temperatures and low dosages. Furthermore, the collector of Formula 1 described in this invention has a simple preparation process and the raw materials are readily available.

[0010] The R1 is preferably phenyl, benzyl, methylphenyl, 4-methoxybenzyl, phenethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octyloxypropyl, tridecyl, isotridecyl, cocoyl, tetradecyl, isotetradecyl, hexadecyl, octadecyl, 9-n-octadecenyl, N-oleo-3-propylidene, N-octadecyl-3-propene, mustardyl, or behenyl; more preferably n-octyl, isooctyl, decyl, dodecyl, cocoyl, octyloxypropyl, tridecyl, tetradecyl, hexadecyl, octadecyl, or 9-n-octadecenyl; preferably C 10 ~C 20 The linear alkyl group. Studies have shown that the preferred R1 can further synergize with the structure of Formula 1, which helps to further enhance the harvesting effect of the collector at low temperatures.

[0011] R 2 Preferably, H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, n-octyl, nonyl, decyl, dodecyl, octyloxypropyl, tridecyl, cocoyl, tetradecyl, hexadecyl, or octadecyl; more preferably, H, methyl, n-octyl, isooctyl, decyl, isodecyl, dodecyl, octyloxypropyl, cocoyl, tetradecyl, hexadecyl, or octadecyl.

[0012] The collector of Formula 1 is obtained by reacting with Formulas 2 and 3;

[0013]

[0014] The flotation method of the present invention includes the following steps:

[0015] Step (1): The ore is crushed and mixed to obtain a slurry;

[0016] 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 formula (I).

[0017] 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 100-3000 g / t, preferably 500-2000 g / t.

[0018] In this invention, the pH of the flotation pulp is 4 to 11, preferably 5 to 10; more preferably 7.5 to 9.

[0019] In this invention, there are no special requirements for the flotation temperature. For example, it can be 1 to 30°C. Especially at low temperatures of 1 to 5°C, the collection method of this invention can show superior collection advantages compared with existing reagents.

[0020] In this invention, the flotation reagent further includes at least one flotation aid selected from inhibitors and pH adjusters.

[0021] In this invention, no additional frother is required in the flotation reagent.

[0022] Beneficial effects

[0023] The compound of Formula 1 in this invention has the advantages of wide availability of raw materials, high structural tunability, and strong commercialization potential. It is easy to develop environmentally friendly collectors with good water solubility, excellent dispersibility, high selectivity, wide operating temperature range, good low-temperature resistance, and strong collecting ability. This invention innovatively applies the collector of Formula 1 to the flotation of non-sulfide minerals, which can effectively enhance the flotation separation efficiency of fluorite and oxide minerals such as rare earth, iron, titanium, tungsten, lithium, tin, phosphorus, and manganese, and improve the flotation recovery rate of valuable minerals; even at lower dosages and lower temperatures, good collecting effect can still be obtained. Attached Figure Description

[0024] Figure 1 For Equation 1A 1 HNRM diagram;

[0025] Figure 2 For Equation 1B 1 H NRM diagram;

[0026] Figure 3 For Equation 1C 1 H NRM diagram;

[0027] Figure 4 For Equation 1D 1 H NRM diagram; Detailed Implementation

[0028] 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 Formula 1 of the present invention for mineral flotation, and the experimental process is a conventional flotation process.

[0029] In the following cases, collectors with the following structures are used for the flotation of non-sulfide minerals.

[0030] (That is, R1 is n-dodecyl and R2 is H, formula 1);

[0031] (That is, R1 is tetradecyl and R2 is H, formula 1);

[0032] (That is, R1 is n-hexadecyl and R2 is H, formula 1);

[0033] (That is, R1 is n-octadecyl and R2 is H, formula 1);

[0034]

[0035]

[0036] Example 1: Flotation of Scheelite

[0037] With a pulp pH of approximately 8.0, the collector concentration was 2.0 × 10⁻⁶. -5 At a flow rate of 300 mL / min and mol / L N2, scheelite of 200–400 mesh was floated for 4 minutes. The results are shown in Table 1.

[0038] Table 1. Flotation results of scheelite

[0039] Types of collectors Scheelite flotation recovery rate / % Formula 1A 80.83 Formula 1B 84.54 Formula 1C 89.76 Formula 1D 95.24 Comparison A 61.54 Comparative B 64.86 Comparative C 70.39 Oleic acid 73.65

[0040] As shown in Table 1, the collector of Formula 1 of the present invention, based on the combination of benzene ring and its adjacent -COOH and -CONR, can achieve synergy and enhance the collection ability of scheelite.

[0041] Example 2 Rare Earth Flotation

[0042] With a pulp pH of approximately 8.0, the collector concentration was 4.0 × 10⁻⁶. -5 The flotation performance of each collector on 200-400 mesh rare earth (fluorocarbon cerium ore) was investigated at a flow rate of 300 mL / min and a N2 concentration of mol / L. The flotation time was 4 minutes. The results are shown in Table 2.

[0043] Table 2 Rare Earth Flotation Results

[0044]

[0045]

[0046] As shown in Table 2, the collector of Formula 1 of the present invention can achieve synergy and enhance the collection ability of rare earth elements based on the combination of benzene ring and its adjacent -COOH and -CONR.

[0047] Example 3: Cassiterite Flotation

[0048] With a pulp pH of approximately 8.0, the collector concentration was 5.0 × 10⁻⁶. -4 The flotation performance of each collector on -400 mesh cassiterite was investigated at a flow rate of 300 mL / min and a N2 flow rate of mol / L. The flotation time was 4 minutes. The results are shown in Table 3.

[0049] Table 3. Results of Cassiterite Flotation

[0050] Types of collectors Cassiterite flotation recovery rate / % Formula 1A 76.89 Formula 1B 81.76 Formula 1C 85.45 Formula 1D 86.87 Comparison A 61.54 Comparative B 54.63 Comparative C 66.38 Oleic acid 72.34

[0051] As shown in Table 3, the collector of Formula 1 of the present invention can achieve synergistic effect and enhance the collection ability of cassiterite based on the combination of benzene ring and its adjacent -COOH and -CONR.

[0052] Example 4: Ilmenite Flotation

[0053] With a pulp pH of approximately 8.0, the collector concentration was 6.0 × 10⁻⁶. -6 The flotation performance of each collector on 200-400 mesh ilmenite was investigated at a flow rate of 300 mL / min and a N2 flow rate of 300 mL / min. The flotation time was 4 minutes. The results are shown in Table 4.

[0054] Table 4. Results of Ilmenite Flotation

[0055] Types of collectors ilmenite flotation recovery rate / % Formula 1A 96.85 Formula 1B 97.89 Formula 1C 98.68 Formula 1D 98.36 Comparison A 74.89 Comparative B 79.54 Comparative C 84.39 Oleic acid 89.73

[0056] As shown in Table 4, the collector of Formula 1 of the present invention, based on the combination of the benzene ring and the adjacent -COOH and -CONR, can achieve synergistic effect and enhance the collection ability of ilmenite.

[0057] Example 5: Fluorite Ore Flotation

[0058] A certain tailings contains 13.70% CaF2. During flotation, 200g of ore sample is taken each time, of which 70% consists of mineral particles of 200-400 mesh. Water is added to adjust the pulp concentration to 45%. The dosage is 700g / t of sulfuric acid, 1000g / t of water glass, and the pulp pH is 8.0. The collector dosage is 200g / t. A single roughing process is used, with a flotation temperature of 2℃ and a flotation time of 5 minutes.

[0059] Table 5. Results of comparative flotation tests for a fluorite ore mine

[0060]

[0061]

[0062] The flotation results are shown in Table 5, which indicate that the collector of the present invention, which is only half the amount of oleic acid compared to 400 g / t oleic acid, significantly improves the flotation recovery rate of CaF2 in fluorite ore under low temperature flotation conditions.

Claims

1. A flotation method for non-sulfide minerals, characterized in that, Non-sulfide minerals are floated in a flotation reagent containing a collector of Formula 1 to obtain non-sulfide mineral concentrate; R1 is C3~C 24 Hydrocarbon group or C3-C containing an O atom 24 Hydrocarbon group; R2 is H, C1-C 24 Hydrocarbon group or C3-C containing an O atom 24 Hydrocarbon group; M is H, Na or K.

2. The flotation method for non-sulfide ores according to claim 1, characterized in that, R1 is phenyl, benzyl, methylphenyl, 4-methoxybenzyl, phenethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octyloxypropyl, tridecyl, isotridecyl, cocoyl, tetradecyl, isotetradecyl, hexadecyl, octadecyl, 9-n-octadecenyl, N-oleo-3-propylidene, N-octadecyl-3-propene, mustardyl, or behenyl; preferably C 10 ~C 20 Straight-chain alkyl groups.

3. The flotation method for non-sulfide ores according to claim 1, characterized in that, R2 is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, n-octyl, nonyl, decyl, dodecyl, cocoyl, octyloxypropyl, tridecyl, tetradecyl, hexadecyl, or octadecyl.

4. The flotation method for non-sulfide ores according to claim 1, characterized in that, The collector of Formula 1 is obtained by reacting with Formulas 2 and 3; 5. The flotation method for non-sulfide ores according to claim 1, characterized in that, The non-sulfide mineral is fluorite and / or oxide mineral; the oxide mineral is an oxide mineral of at least one of rare earth, iron, titanium, tungsten, lithium, tin, phosphorus and manganese.

6. The flotation method for non-sulfide ores according to claim 5, characterized in that, The oxide minerals mentioned include at least one of scheelite, cassiterite, ilmenite, and fluorite.

7. The flotation method for non-sulfide ores according to 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 100-3000 g / t, preferably 500-2000 g / t.

8. The flotation method for non-sulfide ores according to claim 1, characterized in that, The pH of the flotation pulp is 4–11, preferably 5–10.

9. The flotation method for non-sulfide ores according to claim 1, characterized in that, The flotation temperature is 1–30℃, and can be further reduced to 1–5℃.

10. The flotation method for non-sulfide ores according to any one of claims 1 to 9, characterized in that, The flotation reagents also include at least one flotation aid selected from inhibitors and pH adjusters.

Images