Carboxylic acid flotation collector as well as synthesis method and application thereof

Abstract

The invention discloses a carboxylic acid flotation collecting agent and a synthesis method and application thereof, the application is that an amino carboxylic acid compound is used as a mineral flotation collecting agent to be applied to flotation recovery of valuable metals in oxidized minerals containing rare earth, cassiterite, copper oxide and the like, and two functional groups are connected through an amino group and a hydrocarbon chain; the repulsive force between coordination groups and the repulsive force between surrounding hydration layers are weakened, the hydrophobicity of the mineral surface is effectively improved, and the mineral flotation recovery performance can be remarkably improved. When being applied to flotation separation of non-ferrous metal and precious metal ores as a non-ferrous metal and precious metal ore collecting agent, the flotation separation and recovery of non-ferrous metal and precious metal are expected to be effectively realized. Compared with a common flotation collecting agent in the prior art (the common flotation collecting agent is suitable for being used under the strong acid condition, the strong acid can corrode equipment, and inconvenience is brought to research), enrichment and recovery of non-ferrous metal and precious metal minerals such as rare earth, cassiterite and copper oxide can be effectively improved under the weak alkaline condition.

Description

Technical Field

[0001] This invention belongs to the field of metal beneficiation technology, and relates to a carboxylic acid flotation collector, its synthesis method and application, specifically the application of a carboxylic acid flotation collector in the flotation recovery of valuable metals from oxidized minerals. Background Technology

[0002] Carboxylic acid compounds possess biological activity. As pharmaceuticals, they play an irreplaceable role in preventing and controlling pests and diseases, regulating plant growth, and ensuring global food production. The active ingredients of carboxylic acid compounds are crucial in pesticides, but their low water solubility and poor bioavailability must be overcome. Emulsion concentrates, as modified products of carboxylic acid compounds, are among the most widely used pesticide formulations, offering advantages such as good storage stability, high biological activity, and convenient production. However, the large-scale release of organic solvents into the environment pollutes it and harms human health. Compared to acyl chains, the presence of fatty acids leads to a lower critical micelle concentration, and an increase of six carbon atoms in the alkyl chain length of fatty acids results in an order-of-magnitude decrease.

[0003] Carboxylic acid compounds have wetting properties. When a solid and a liquid come into contact, an interface is formed, and surface energy adsorption occurs, causing the liquid to spread across the solid surface. This spreading of the liquid on the solid surface is called wetting, and the ability of the liquid to spread on the solid surface is called the wettability of the liquid on the solid. Simulation studies have shown that a beneficial surfactant (cocamidopropyl betaine) primarily acts on the coal-water interface, promoting the diffusion of water molecules at the coal interface. As the degree of coal metamorphism increases, the wetting effect of the surfactant on coal first decreases, then increases, and then decreases again. During the wetting process, surfactant molecules interact, migrate, and penetrate into the coal matrix. Coal dust has a serious impact on mine safety and miners' occupational safety and health; therefore, this research has significant theoretical and practical value for improving safe and clean production in mines. The study also demonstrated the wetting behavior of surfactant aqueous solutions on dimethyldichlorosilane-treated quartz sand. The results showed that the wettability of the aqueous solution increased with increasing surfactant concentration, and the droplet penetration time shortened when the surfactant concentration was higher than the CMC (compound maximum concentration). Since the organic matter in natural soil particles leads to soil hydrophobicity, it reduces soil surface energy and affinity for water, affecting crop germination and causing poor crop growth and development. Therefore, these research findings provide ideas for the modeling, design and application of hydrophobic sand as a functional building material.

[0004] Carboxylic acid compounds are anionic collectors with stable chelating properties, and can be used for the flotation of tungsten, tin, copper, rare metal minerals, and oxide ores. A study on the flotation performance and mechanism of smithsonite with oleic acid showed that oleic acid had the best flotation effect on smithsonite at pH 10. Contact angle measurements showed that the contact angle between smithsonite and oleic acid increased to 105°, indicating enhanced interaction between the smithsonite surface and oleic acid, which is beneficial for the flotation separation of smithsonite. Zeta potential detection results showed that the Zeta potential of the smithsonite surface decreased after the reaction with oleic acid. FT-IR spectroscopy also confirmed the formation of zinc oleate (zinc oleate) on the smithsonite surface after the reaction with oleic acid. Pure mineral experiments were conducted to explore the mechanism of sodium oleate in the flotation process of heterodyne ores. Experimental results showed that when the pulp pH was in the range of 4-8 and 11 and the molar concentration of sodium oleate was 3×10⁻⁶, the flotation effect was optimal. -4 At a concentration of mol / L, the flotation recovery of hemimorphite remained stable at approximately 80%. Further analysis using Zeta potential and infrared spectroscopy revealed that sodium oleate primarily interacts with the hemimorphite surface through chemisorption, accompanied by a certain degree of physisorption.

[0005] Carboxylic acid collectors utilize their carboxylic acid groups (-COOH) to interact with the active sites of calcium ions on the surface of tungsten ore, forming a collector bilayer or oleic acid-metal ion precipitate that adheres to the mineral surface, altering its hydrophilicity or hydrophobicity to achieve the collection of scheelite. Numerous research reports both domestically and internationally have documented the use of fatty acids in the collection of scheelite, with oleic acid and sodium oleate being the most widely applied. The mechanism of sodium oleate flotation of salt minerals suggests that NaOL undergoes chemical adsorption on the mineral surface, generating metal fatty acid salts that hydrophobize the mineral surface. However, due to the high similarity of surface properties between other calcium-bearing gangue minerals and scheelite, these agents also adsorb onto the surfaces of fluorite and calcite. In existing technologies, oleic acid is used as a flotation collector for a calcium-bearing scheelite. Zeta potential analysis revealed a negative potential shift in oleic acid on the surfaces of scheelite, fluorite, and calcite, indicating chemisorption on the calcium-bearing mineral surfaces. However, in a study of a foreign scheelite, adding 60 mg of NaOL as a collector resulted in a concentrate product with recoveries of over 95% for both calcite and scheelite, but failed to separate the scheelite. This demonstrates that oleic acid and NaOL possess strong collecting properties but poor selectivity. To address this issue of poor selectivity, researchers conducted compound experiments with different surfactants. Studies showed that the combination of oleic acid and naphthenic acid exhibited higher selectivity than sodium oleate, while the combination of sodium oleate and sodium hydrocarbon fatty acids significantly improved selectivity. However, the practical application of these combined reagents is complex due to the influence of the addition method or order. Therefore, many researchers are dedicated to developing new multifunctional collectors, introducing different or the same functional groups into the same molecular structure, so that the collector has multifunctional properties and improves the interaction ability with minerals.

[0006] Extensive practical experience has proven that carboxylic acids are a class of oxide mineral collectors with high selectivity, strong collecting ability, and low toxicity and environmental friendliness, showing promising application prospects in the field of mineral flotation. Currently, they are used in the beneficiation industries of iron oxide ores, zinc oxide ores, niobium iron ore, lead-zinc ore, rare earth ores, tantalum-niobium ore, tungsten ore, cassiterite, and copper oxide ores.

[0007] Currently, there are no reports in existing technologies regarding the use of naphthylaminocarboxylic acid compounds as mineral flotation collectors. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a carboxylic acid flotation collector, its synthesis method, and its application.

[0009] The first objective of this invention is to provide a carboxylic acid flotation collector, wherein the carboxylic acid flotation collector is a naphthylaminocarboxylic acid compound having the structure of formula (1). Equation (1) Wherein, R1 is an alkane group, an olefin group, an aromatic group, or an alkoxyether group, and R2 is an alkane group, an olefin group, an aromatic group, or an alkoxyether group.

[0010] Preferably, R1 is a C1-C8 alkane group or a C2-C... 10 olefinic group, C6-C 12 The aromatic group, or the alkoxy ether group having the structure of formula (2), wherein R2 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2); Equation (2) In this context, R3 and R4 are ethylidene or propyleneide, respectively, and n is 1-3.

[0011] Preferably, R1 is methylene, ethylene, propylene, hexylene, heptylene, nonylene, allylene, or allenebutyryl.

[0012] A second objective of this invention is to provide a method for synthesizing the above-mentioned carboxylic acid flotation collector, the synthetic route of which is as follows: S1: Add methanol and naphthylamine to the reaction vessel, stir to disperse evenly, keep at room temperature, then slowly add methyl chloroalkyl / aromatic carboxylate, heat to 50°C, react for 3 hours to obtain methyl naphthylamine carboxylate; S2: Add pure water to hydrolyze, then distill the product under reduced pressure to obtain a carboxylic acid flotation collector; or, T1: Naphthylamine, chloroalkyl / aromatic carboxylic acid, and sodium hydroxide are stirred and dispersed evenly, heated to 25°C, and reacted for 3 hours to obtain sodium naphthylamine carboxylic acid; T2: Add hydrochloric acid to it, and then distill the product under reduced pressure to obtain a carboxylic acid flotation collector.

[0013] A third objective of this invention is to provide the application of the aforementioned carboxylic acid flotation collector in the flotation recovery of valuable metals from non-ferrous and precious metal minerals containing rare earth elements, cassiterite, and copper oxide.

[0014] Preferably, the non-ferrous and precious metal minerals contain one or more of cerium, tin, and copper.

[0015] The beneficial effects of this invention are as follows: This invention is the first to apply naphthylaminocarboxylic acid compounds to the flotation collection of valuable metals in minerals. It is particularly suitable for the enrichment and recovery of valuable metals in oxidized minerals such as rare earth, cassiterite and copper oxide. Compared with existing commonly used collectors (phthalic acid), it can improve the recovery rate of valuable metals. Attached Figure Description

[0016] Figure 1 This is a comparison chart showing the effect of pulp pH on the flotation of fluorocarbon cerium ore using F306 and phthalic acid in Example 1.

[0017] Figure 2 This is a comparison chart showing the effect of pulp pH on the flotation of monazite using F306 and phthalic acid in Example 2.

[0018] Figure 3 This is a comparison chart showing the effect of pulp pH on the flotation of cassiterite using F306 and phthalic acid in Example 3.

[0019] Figure 4 Naphthylaminodiethylcarboxylic acid 1 H NMR spectrum.

[0020] Figure 5 Naphthylaminodiethylcarboxylic acid 13 C NMR spectrum. Detailed Implementation

[0021] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0022] The technical solution of the present invention is as follows: A carboxylic acid flotation collector, wherein the carboxylic acid flotation collector is a naphthylaminocarboxylic acid compound having the structure of formula (1), Equation (1) Wherein, R1 is an alkane group, an olefin group, an aromatic group, or an alkoxyether group, and R2 is an alkane group, an olefin group, an aromatic group, or an alkoxyether group.

[0023] In some embodiments, R1 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group, or the alkoxy ether group having the structure of formula (2), wherein R2 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2); Equation (2) In this context, R3 and R4 are ethylidene or propyleneide, respectively, and n is 1-3.

[0024] In some embodiments, R1 is methylene, ethylene, propylene, hexylene, heptylene, nonylene, allylene, or allenylene.

[0025] The synthetic route for the above-mentioned carboxylic acid flotation collectors is as follows: S1: Add methanol and naphthylamine to the reaction vessel, stir to disperse evenly, keep at room temperature, then slowly add methyl chloroalkyl / aromatic carboxylate, heat to 50°C, react for 3 hours to obtain methyl naphthylamine carboxylate; S2: Add pure water to hydrolyze, then distill the product under reduced pressure to obtain a carboxylic acid flotation collector; or, T1: Naphthylamine, chloroalkyl / aromatic carboxylic acid, and sodium hydroxide are stirred and dispersed evenly, heated to 25°C, and reacted for 3 hours to obtain sodium naphthylamine carboxylic acid; T2: Add hydrochloric acid to it, and then distill the product under reduced pressure to obtain a carboxylic acid flotation collector.

[0026] The above-mentioned carboxylic acid flotation collectors are used in the flotation and recovery of valuable metals from non-ferrous and precious metal minerals containing rare earth elements, cassiterite, and copper oxide.

[0027] In some embodiments, the non-ferrous and precious metal minerals contain one or more of cerium, tin, and copper.

[0028] Unless otherwise specified, all parts and percentages in the examples refer to mass. The flotation and collection processes for the minerals in the examples are conventional processes, except that the phthalic acid compounds of the present invention are used to replace conventional collectors.

[0029] Example 1 The concentrations of naphthylaminodiethylcarboxylic acid (F306) and phthalic acid were both 6 × 10⁻⁶. -5 A flotation of fluorocarbon cerium ore with a particle size of -0.076 mm to +0.038 mm was performed for 3 minutes using a frother (methyl isobutyl methanol, 15 mg / L) at a concentration of mol / L. The pH of the pulp was adjusted, and the flotation results are as follows: Figure 1 As shown, the highest flotation recovery rate of F306 was at pH=7, and the highest flotation recovery rate of phthalic acid was at pH=3. The flotation recovery rates of fluorocarbon cerium ore were 95.05% and 24.25%, respectively.

[0030] Example 2 The concentrations of naphthylaminodiethylcarboxylic acid (F306) and phthalic acid were both 6 × 10⁻⁶. -5 A flotation of monazite particles with a particle size of -0.076 mm to +0.038 mm was performed for 3 minutes at a concentration of mol / L and 15 mg / L of frother MIBC. The pH of the pulp was adjusted, and the results were as follows: Figure 2 As shown, the highest flotation recovery rate of F306 was at pH=8, and the highest flotation recovery rate of phthalic acid was at pH=4. The flotation recovery rates of monazite were 82.63% and 29.34%, respectively.

[0031] Example 3 The concentrations of naphthylaminodiethylcarboxylic acid (F306) and phthalic acid were both 6 × 10⁻⁶. -5 A flotation of cassiterite with a particle size of -0.076 mm to +0.038 mm was performed for 3 minutes using a mol / L ... Figure 3 As shown, the highest flotation recovery rate of F306 was at pH=7, and the highest flotation recovery rate of phthalic acid was at pH=2. At these values, the flotation recovery rates of cassiterite were 95.6% and 32.96%, respectively.

[0032] Figure 4 and Figure 5 The results show that the quantity and position of hydrogen and carbon in the synthesized substance correspond to those in the target product, proving that the synthesized product is indeed the target substance.

[0033] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or basic characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0034] Where there is no conflict, the embodiments and features described above can be combined with each other. The above descriptions are merely preferred embodiments of the present invention and are not intended to limit the invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

[0035] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A carboxylic acid-based flotation collector, characterized in that, The carboxylic acid flotation collector is a naphthylaminocarboxylic acid compound with the structure of formula (1). Equation (1) Wherein, R1 is an alkane group, an olefin group, an aromatic group, or an alkoxyether group, and R2 is an alkane group, an olefin group, an aromatic group, or an alkoxyether group.

2. The carboxylic acid flotation collector as described in claim 1, characterized in that, R1 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group, or the alkoxy ether group having the structure of formula (2), wherein R2 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2); Equation (2) In this context, R3 and R4 are ethylidene or propyleneide, respectively, and n is 1-3.

3. The carboxylic acid flotation collector as described in claim 2, characterized in that, R1 can be methylene, ethylene, propylene, hexylene, heptylene, nonylene, allylene, or allenebutylene.

4. A method for synthesizing a carboxylic acid flotation collector as described in any one of claims 1-3, characterized in that, Its synthetic route is as follows: S1: Add methanol and naphthylamine to the reaction vessel, stir to disperse evenly, keep at room temperature, then slowly add methyl chloroalkyl / aromatic carboxylate, heat to 50°C, react for 3 hours to obtain methyl naphthylamine carboxylate; S2: Add pure water to hydrolyze, then distill the product under reduced pressure to obtain a carboxylic acid flotation collector; or, T1: Naphthylamine, chloroalkyl / aromatic carboxylic acid, and sodium hydroxide are stirred and dispersed evenly, heated to 25°C, and reacted for 3 hours to obtain sodium naphthylamine carboxylic acid; T2: Add hydrochloric acid to it, and then distill the product under reduced pressure to obtain a carboxylic acid flotation collector.

5. The application of a carboxylic acid flotation collector as described in any one of claims 1-3, characterized in that, Application in the flotation and recovery of valuable metals from non-ferrous and precious metal minerals containing rare earth elements, cassiterite, and copper oxide.

6. The application of a carboxylic acid flotation collector as described in claim 5, characterized in that, The non-ferrous and precious metal minerals contain one or more of cerium, tin, and copper.

Images