Application of phosphonate-carboxylic acid compound in flotation of non-ferrous metal and precious metal minerals

Abstract

The invention discloses application of a phosphonate-carboxylic acid compound in flotation of non-ferrous metal and precious metal minerals, and belongs to the technical field of metal mineral separation of the non-ferrous metal and the precious metal minerals. According to the method, the phosphonate-carboxylic acid compound is applied to flotation collection of the valuable metal in the mineral for the first time, the method is particularly suitable for enrichment and recovery of the valuable metal in the mineral containing cerium, tin, niobium, scandium, copper, silver or gold, compared with an existing common collecting agent, the recovery rate of the valuable metal can be increased, and damage to equipment cannot be caused.

Description

Technical Field

[0001] This invention belongs to the field of metal beneficiation technology for non-ferrous and precious metal minerals, and in particular relates to the application of a phosphonate-carboxylic acid compound in the flotation of non-ferrous and precious metal minerals. Background Technology

[0002] Phosphate esters and carboxylic acid compounds possess biological activity and chelating properties. In agriculture, they can be used as herbicides, insecticides, and plant growth regulators, and can also be used to control diseases such as rice bacterial blight, citrus canker, and tomato bacterial wilt. In the biopharmaceutical field, they are mainly used for sterilization, anti-inflammation, anti-cancer, antihypertensive, cholesterol-lowering, anti-tuberculosis, and anticonvulsant effects. In addition, because the synthesized phosphonate-carboxylic acid compounds contain two functional groups, P=O and C(=O)NHOH, they have strong coordination ability and can act as polydentate ligands to chelate various ions such as copper, cerium, tin, lead, silver, nickel, and mercury, which can be applied to anti-corrosion, anti-friction, and analytical chemistry.

[0003] Fan, H, et al. studied the good flotation performance of phosphonic acid and phosphate ester collectors for rare earth elements (Fan, H., Yang, X., Qi, J., Liu, G., Qin, J., 2021. A comparative investigation into floatability of bastnaesite with three di / trialkyl phosphate surfactants[J].J.Rare Earths.39 (11), 1442-1449.; Fan, H., Tan, W., Liu, G., 2021. 1-Hydroxydodecylidene-1,1-diphosphonic acid flotation of bastnasite:Performance and mechanism. Colloids Surfaces A: Physicochem. Eng. Aspects.609, 125623.).

[0004] Zheng et al. discovered that 1-hydroxyoctyl diphosphonic acid is chemically adsorbed onto the surface of niobite via its -P=O and -PO- groups (Zheng XP, Misra M, Smith RW, et al. Fersmite flotation with diphosphonic acid and other collectors[J]. Minerals Engineering, 2015, 9(3):331-341). Chen reported on the flotation study of 1-hydroxyoctyl diphosphonic acid on niobite and dolomite. The study found that, at the same dosage, 1-hydroxyoctyl diphosphonic acid had a higher recovery rate than benzylarsonic acid, styrenephosphonic acid, and diisobutyl sulfosuccinate (Chen GL, Tao D, Ren H, et al. An investigation of niobiteflotation with octyl diphosphonic acid as collector[J]. International Journal of Mineral Processing, 2005, 76(1):111-122.). Zhang et al. reported the flotation of cassiterite with heptaphosphate monoester. The results showed that heptaphosphate monoester had a strong collecting ability for cassiterite, with a recovery rate of about 80% (Zhang BR, Zhang L, Li FT, et al. Testing the formation of Ca-phosphonate precipitates and evaluating the anionic polymers as Ca-phosphonate precipitates and CaCO3 scale inhibitor in simulated cooling water[J]. Corrosion science, 2010, 52(12): 3883-3890). Bulatovic et al. studied C 12 -C 16 The flotation performance of phosphate esters for ilmenite, rutile, and perovskite (Bulatovic S, Wyslouzil D M. Process development for treatment of complex perovskite, ilmenite and rutile ores[J].Minerals Engineering, 1999, 12(12): 1407-1417). The results show that adding C12 -C 16 The combined use of phosphate esters and sulfonated paraffin soaps exhibits a strong harvesting ability for ilmenite, superior to C. 12 -C 16 The efficacy of phosphate esters when used alone, and the significant reduction in C when used in combination with other drugs. 12 -C 16 The amount of phosphate ester used. Compared to talc oil and oleic acid, C 12 -C 16 Phosphate esters have a stronger ability to collect perovskite.

[0005] 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 (Yoon H, Shin S, Park S, et al. Low-viscosity quaternary ammonium-based ionic liquid electrolytes for lithium air batteries. Journal of Molecular Liquids, 2022, 359: 119352.). The active components of carboxylic acid compounds play a crucial role in pesticides, but their low solubility in water and poor bioavailability must be overcome (Pal A, Yadav A. Mixed micellization of a trisubstituted surfaceactive ionic liquid 1-dodecyl-2,3-dimethylimidazolium chloride [C 12[bmim][Cl]with an amphiphilic drug amitriptylinehydrochloride AMT: A detailed insights from conductance and surface tension measurements. Journal of Molecular Liquids, 2019, 279: 43-50.). Emulsion concentrates, as modified products of carboxylic acid compounds, are among the most widely used pesticide formulations, possessing advantages such as good storage stability, high biological activity, and convenient production (Plechkova NV, Seddon K R. Applications of ionic liquids in the chemical industry. Chemical Society Reviews, 2008, 37: 123-150). However, the large-scale discharge of organic solvents into the environment can pollute the environment and harm human health (Egorova KS, Seitkalieva MM, Posvyatenko AV, et al. An unexpected increase of toxicity of amino acid-containing ionic liquids. Toxicology Research, 2015, 4: 152-159.). Studies by Ferrer et al. have shown that the presence of fatty acids leads to a lower critical micelle concentration compared to acyl chains, and that when the alkyl chain length of fatty acids increases by 6 carbon atoms, it shows an order of magnitude decrease (Ferrer M, Comelles F, J. Plou F, et al. Comparative surfaceactivities of Di- and trisaccharide fatty acid esters. Langmuir, 2002, 18:667-673.).

[0006] 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 a liquid to spread on a solid surface is called the wettability of the liquid on the solid. Zhang et al., through simulation studies, found that a benign surfactant (cocamidopropyl betaine) mainly 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 can have a serious impact on mine safety and occupational health, so this study has important theoretical significance and practical value for improving mine safety and clean production (Zhang Q, Wang B, Xing X, et al. Wetting characteristics and kinetic behavior of amphoteric

[56] ionic sufactant on the microscopic “'solid-liquid" interface of coal-A case study. Journal of Molecular Liquids, 2023, 392: 123497.). Xing et al.'s study demonstrated the wetting behavior of surfactant aqueous solution on dimethyldichlorosilane-treated quartz sand. The results showed that as the surfactant concentration increased, the wettability of the aqueous solution increased, and when the surfactant concentration was higher than CMC, the droplet penetration time was shortened. Because 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 insights for the modeling, design, and application of hydrophobic sand as a functional building material (Xing X, Lourenço SD N. The wetting behavior of a nonionic surfactant on hydrophobizedquartz sand. Colloids and Surfaces A:Physicochemical and Engieering Aspects, 2024, 684: 133109.).

[0007] Carboxylic acid compounds are anionic collectors and also have stable chelating properties, which can be used for the flotation of tungsten, tin, copper, and rare metal minerals and oxide ores (Bu Xianzong, Chen Yao. Research progress on beneficiation technology of lead-zinc oxide ore in my country [J]. Metal Mines, 2019(7): 118-123.). Hosseinil studied the flotation performance and mechanism of oleic acid on smithsonite. The results showed that oleic acid had the best flotation effect on smithsonite at pH 10. At the same time, the contact angle measurement results showed that the contact angle between smithsonite and oleic acid increased to 105°, indicating that the interaction between the surface of smithsonite and oleic acid was enhanced, which was beneficial to the flotation separation of smithsonite. The Zeta potential detection results showed that the Zeta potential of the mineral surface decreased after the interaction of smithsonite and oleic acid. FT-IR spectroscopy also confirmed that zinc oleate (zinc oleate) forms on the surface of smithsonite after reaction with oleic acid (S.H. Hosseini, Wang Jingliang, Lin Sen. Adsorption study of smithsonite flotation using dodecylamine and oleic acid [J]. Foreign Metal Mineral Processing, 2006, 43(12): 6.). Liu Cheng et al. explored the mechanism of sodium oleate in the flotation process of heterodyne ore through pure mineral experiments. The 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 effect of sodium oleate on the flotation process of heterodyne ore was achieved. -4 At a concentration of mol / L, the flotation recovery of hemimorphite can be stably maintained at about 80%. Further analysis using Zeta potential and infrared spectroscopy revealed that sodium oleate mainly interacts with the surface of hemimorphite through chemical adsorption, accompanied by a certain degree of physical adsorption (Liu Cheng, Feng Qiming, Zhang Guofan. Flotation behavior and mechanism of hemimorphite under the action of sodium oleate [J]. Chinese Journal of Nonferrous Metals, 2016, 26(4): 878-883.).

[0008] 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 and hydrophobicity to achieve the collection of scheelite (BULATOVIC S M. Handbook of Flotation Reagents: Chemistry, Theory and Practice Flotation of Sulfde Ores[J]. Chinese Journal of Chemical Engineering: English Edition, 2008, 16(05): 685.). Numerous research reports on fatty acid collection of scheelite have been published both domestically and internationally, with oleic acid and sodium oleate being the most widely used. Hu Yuehua et al. studied the mechanism of sodium oleate flotation of salt minerals, concluding 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, this type of reagent can also be adsorbed on the surfaces of fluorite and calcite (Hu Yuehua, Wang Dianzuo. Solution Chemistry and Flotation Separation Control of Reagent-Salt Mineral System [J]. Journal of Central South Institute of Mining and Metallurgy, 1992, (01): 24-30.). Kim et al. used oleic acid as a flotation collector for a certain calcium-bearing scheelite and found through Zeta potential that oleic acid showed a negative potential shift on the surfaces of scheelite, fluorite and calcite, and chemical adsorption occurred on the surfaces of calcium-bearing minerals (KIM S, BAEK SH, HAN Y, et al. Laboratory Testing of Scheelite Flotation from Raw Ore in Sangdong Mine for Process Development [J]. Minerals, 2020, 10(11):971.). Feng et al. used a foreign scheelite mine as a research object, adding 60 mg of NaOL as a collector, and finally obtained a concentrate product with a recovery rate of over 95% for both calcite and scheelite, but failed to separate the scheelite. This shows that oleic acid and NaOL have the characteristics of strong collecting performance but poor selectivity. To solve the problem of poor selectivity, researchers conducted compound experiments with the addition of different surfactants (FENG B, LUO XP, WANG JQ, et al. The flotation separation of scheelite from calcite using acidified sodium silicate as depressant [J]. Minerals Engineering, 2015, 80:45-49.).Studies have shown that the selectivity of oleic acid and naphthenic acid combination agents is higher than that of sodium oleate, and the selectivity of sodium oleate and sodium hydrocarbon fatty acid combination agents is significantly improved (FILIPPOVL O, FOUCAUD Y, FILIPPOVAIV, et al. Newreagent formulations for selective flotation of scheelite from a skann ore with complex calcium minerals gangue[J]. Minerals Engineering, 2018, 123: 85-94.). Due to the influence of the addition method or order, the operation of combination agents is complex in actual production. Therefore, many researchers are committed to developing novel multifunctional collectors, introducing different or the same functional groups into the same molecular structure, giving the collector multifunctional properties and improving its interaction with minerals.

[0009] Conventional phosphate esters exhibit good selectivity, but only demonstrate good flotation performance for minerals under strong acid conditions. Strong acid conditions corrode flotation equipment, complicating flotation experimental research (Zeng Qinghua, Zhang Xiuhua, Jiang Erlong. Mechanism of Aerosol-22 in cassiterite flotation [J]. Nonferrous Metals Engineering, 1996, 4: 29-34). Traditional carboxylic acid flotation collectors are non-toxic, highly hydrophobic, and inexpensive, but their selectivity is poor and they are very sensitive to temperature, leading to their gradual replacement by other reagents (Wang ZJ, Wu HQ, Xu YB, et al. The effect of dissolved calcite species on the flotation of bastnaesite using sodium oleate [J]. Miner. Eng., 2020, 145:106095.).

[0010] Currently, there are no reports in existing technologies regarding the use of phosphonate-carboxylic acid bifunctional compounds as mineral flotation collectors. Summary of the Invention

[0011] To address the aforementioned problems, this invention provides an application of phosphonate-carboxylic acid compounds in the flotation of non-ferrous and precious metal minerals. These phosphonate-carboxylic acid compounds can effectively improve the enrichment and recovery efficiency of valuable metals in ores containing minerals such as cerium, tin, niobium, scandium, copper, silver, or gold.

[0012] To achieve the above-mentioned objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides an application of a phosphonate-carboxylic acid compound in the flotation of non-ferrous and precious metal minerals, wherein the chemical formula of the phosphonate-carboxylic acid compound is: ; R1 is selected from C1~C17 alkane group, C2~C17 olefin group, C6~C12 aromatic group or alkoxy ether group; R2 is selected from C1~C17 alkylene group, C2~C17 olefinene group, C6~C12 aryl group, naphthyl group, or alkylene ether group.

[0013] Introducing carboxylic acid groups into phosphate ester molecules yields bifunctional collectors, which enhance the interaction between the collector and the mineral interface, thereby improving flotation efficiency. Phosphate ester-carboxylic acid collectors are a promising type of mineral collector.

[0014] Furthermore, the non-ferrous and precious metal minerals are ores containing cerium, tin, niobium, scandium, copper, silver, or gold.

[0015] Furthermore, the phosphonate-carboxylic acid compound is diphenyl phosphonate benzoic acid.

[0016] Secondly, the present invention provides a flotation method for non-ferrous and precious metal minerals, comprising the following steps: pre-treating the non-ferrous and precious metal minerals, adding them to water to prepare a slurry; adding phosphonate-carboxylic acid compounds and frothers to the slurry, and then performing stirring and aeration flotation to obtain the target minerals; The chemical formula of the phosphonate-carboxylic acid compound is: ; R1 is selected from C1~C17 alkane group, C2~C17 olefin group, C6~C12 aromatic group or alkoxy ether group; R2 is selected from C1~C17 alkylene group, C2~C17 olefinene group, C6~C12 aryl group, naphthyl group, or alkylene ether group.

[0017] Furthermore, the pretreatment of the non-ferrous and precious metal minerals is as follows: the non-ferrous and precious metal minerals are subjected to gravity separation to obtain concentrate, middlings and tailings, and then the concentrate is subjected to magnetic separation.

[0018] The gravity separation process includes the following steps: crushing and grinding the non-ferrous and precious metal minerals to liberate the useful minerals from the gangue; then feeding them into a gravity separation device (shaking table or jig), where, under the action of gravity and medium flow (water / air), the denser minerals settle and rapidly aggregate into layers, while the less dense minerals are washed away, separating the mineral layers of different densities to obtain concentrate, middlings and tailings.

[0019] The magnetic separation process is as follows: the concentrate is ground and dissociated, and then the slurry is adjusted to ensure the dispersion of individual minerals; the resulting slurry is passed through the magnetic field zone of the magnetic separator, where strongly magnetic minerals are adsorbed by the magnetic poles, and weakly magnetic or non-magnetic minerals are carried away with the slurry; the adsorbed magnetic minerals are collected after leaving the magnetic field zone to obtain the target concentrate, and the non-magnetic portion is tailings, which are then subjected to multi-stage separation and purification as needed.

[0020] Furthermore, the mineral particle size used for flotation after pretreatment of the non-ferrous and precious metal minerals is -0.076 mm to +0.038 mm.

[0021] Furthermore, the pH of the slurry is 7-9; the concentration of the diphenyl phosphonate benzoic acid in the slurry is 6 × 10⁻⁶. - 5 The frother concentration in the slurry is 1 × 10 mol / L. -4 mol·L -1 The stirring and aeration flotation time is 3 minutes.

[0022] Furthermore, when the non-ferrous and precious metal minerals are bastnaesite, the pH of the slurry is 8.0.

[0023] Furthermore, when the non-ferrous and precious metal minerals are monazite, the pH of the slurry is 9.0.

[0024] Furthermore, when the non-ferrous and precious metal minerals are cassiterite, the pH of the slurry is 7.0.

[0025] The P=O and -COOH groups in the phosphonate-carboxylic acid compounds provided by this invention react with active atoms at the mineral interface, thereby adsorbing onto the mineral interface and playing a collecting role.

[0026] Each compound has a pulp pH value corresponding to its optimal flotation result. Changing the pulp pH value will reduce the flotation recovery rate. Therefore, this invention strictly limits the pH of the pulp.

[0027] Compared with the prior art, the present invention has the following advantages and technical effects: This invention is the first to apply phosphonate-carboxylic acid compounds to the flotation collection of valuable metals in minerals. It is particularly suitable for the enrichment and recovery of valuable metals in ores containing cerium, tin, niobium, scandium, copper, silver or gold minerals. Compared with existing commonly used collectors, it can improve the recovery rate of valuable metals and will not damage the equipment. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 The synthetic route diagram of diphenyl phosphonate benzoic acid is used as a reference in this invention; Figure 2 The diphenyl phosphonate benzoic acid prepared according to the present invention 1 H NMR spectrum; Figure 3 The flotation recovery rate of benzoic acid diphosphonate on bastnaesite at different pH values ​​is given. Figure 4 The flotation recovery of monazite by diphenyl phosphonate benzoic acid at different pH values; Figure 5 The flotation recovery rate of benzoic acid diphosphonate on cassiterite at different pH values ​​is given. Detailed Implementation

[0030] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0031] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0032] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0033] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This specification and embodiments are merely exemplary.

[0034] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0035] In the embodiments of this invention, the raw ores of bastnaesite, monazite and cassiterite were all purchased from the market. The above-mentioned raw ores were pre-treated. The pre-treatment of the non-ferrous metal and precious metal minerals was as follows: the non-ferrous metal and precious metal minerals were subjected to gravity separation to obtain concentrate, middlings and tailings, and then the concentrate was subjected to magnetic separation.

[0036] The gravity separation process includes the following steps: crushing and grinding the non-ferrous and precious metal minerals to liberate the useful minerals from the gangue; then feeding them into a gravity separation device (shaking table or jig), where, under the action of gravity and medium flow (water / air), the denser minerals settle and rapidly aggregate into layers, while the less dense minerals are washed away, separating the mineral layers of different densities to obtain concentrate, middlings and tailings.

[0037] The magnetic separation process is as follows: the concentrate is ground and dissociated, and then the slurry is adjusted to ensure the dispersion of individual minerals; the resulting slurry is passed through the magnetic field zone of the magnetic separator, where strongly magnetic minerals are adsorbed by the magnetic poles, and weakly magnetic or non-magnetic minerals are carried away with the slurry; the adsorbed magnetic minerals are collected after leaving the magnetic field zone to obtain the target concentrate, and the non-magnetic portion is tailings, which are then subjected to multi-stage separation and purification as needed.

[0038] The above pretreatment yields bastnaesite (particle size -0.076mm to +0.038mm), monazite (particle size -0.076mm to +0.038mm), and cassiterite powder (particle size -0.076mm to +0.038mm) suitable for flotation.

[0039] The phosphonate-carboxylic acid compound used in this embodiment of the invention is diphenyl phosphonate benzoic acid. Its preparation method refers to the synthetic route of phosphonate-carboxylic acid compounds provided in the prior art "Preparation of Sodium Phosphate Dithiocarboxylate and Quantum Chemical Study on its Flotation Performance" (Lin Qiang, Wang Dianzuo, Yang Xiaoling, Ji Fuguang, Nonferrous Metals, 1991, 43(2): 28-29), such as... Figure 1As shown, the specific process for preparing diphenyl phosphonate benzoic acid in this invention is as follows: Tetrahydrofuran and 0.1-0.5 mol sodium hydride are added to a four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux device. The mixture is stirred until it is evenly dispersed and kept at room temperature. Then, 0.1-0.5 mol diphenyl phosphite is slowly added dropwise until no hydrogen gas is released. Then, 0.1-0.5 mol sodium hydroxide and 4-chlorobenzoic acid or methyl 4-chlorobenzoate are slowly added. The reaction is maintained at the above temperature for 2-4 hours. Then, the temperature is lowered to 5°C, and hydrochloric acid is added for acidification (or hydrolysis) under these conditions to prepare diphenyl phosphonate benzoic acid.

[0040] Figure 2 The diphenyl phosphonate benzoic acid prepared according to the present invention 1 H NMR spectrum.

[0041] The recovery rate calculation formula in this embodiment of the invention is shown below.

[0042] In the formula, ɛ represents the mineral flotation recovery rate, and m c and m t These represent the product quality of the dried concentrate and tailings, respectively, in grams.

[0043] The pH adjusters used in the embodiments of the present invention include NaOH solution (0.1 mol / L or 1 mol / L) and hydrochloric acid (0.1 mol / L or 1 mol / L).

[0044] The specific operation of the agitation and aeration flotation in this embodiment of the invention can be achieved by conventional technical means, and will not be described in further detail.

[0045] Example 1 Pretreated bastnaesite was added to water to prepare a slurry (66.7 mg / L). Six parallel batches were prepared, and the pH of the slurries was adjusted to 6, 7, 8, 9, 10, and 11 respectively using a pH adjuster. Then, diphenyl phosphonate benzoic acid and foaming agent methyl isobutyl alcohol were added to each batch, ensuring that the concentration of diphenyl phosphonate benzoic acid was 6 × 10⁻⁶. -5 The concentration of the foaming agent is 1×10 mol / L. -4 mol·L -1 The mixture was stirred and aerated for flotation, and each flotation lasted for 3 minutes. Figure 3 The flotation recovery rates of diphenyl phosphonate benzoic acid on fluorocarbon cerium ore at different pH values ​​were determined by... Figure 3 It can be seen that when the pulp pH is 8.0, the flotation recovery rate of fluorocarbon cerium ore reaches 93.95%.

[0046] Example 2 Pretreated monazite was added to water to prepare a slurry (66.7 mg / L). Six parallel batches were prepared, and the pH of the slurries was adjusted to 6, 7, 8, 9, 10, and 11 respectively using a pH adjuster. Then, diphenyl phosphonate benzoic acid and foaming agent methyl isobutyl alcohol were added to each batch, ensuring that the concentration of diphenyl phosphonate benzoic acid was 6 × 10⁻⁶. -5 The concentration of the foaming agent is 1×10 mol / L. -4 mol·L -1 The mixture was stirred and aerated for flotation, and each flotation lasted for 3 minutes. Figure 4 To determine the flotation recovery rate of benzoic acid diphosphonate on monazite at different pH values, the following methods were used: Figure 4 It can be seen that when the pulp pH is 9.0, the flotation recovery rate of monazite reaches 89.65%.

[0047] Example 3 Pretreated cassiterite was added to water to prepare a slurry (66.7 mg / L). Six parallel batches were prepared, and the pH of the slurries was adjusted to 6, 7, 8, 9, 10, and 11 respectively using a pH adjuster. Then, diphenyl phosphonate benzoic acid and foaming agent methyl isobutyl alcohol were added to each batch, ensuring that the concentration of diphenyl phosphonate benzoic acid was 6 × 10⁻⁶. -5 The concentration of the foaming agent is 1×10 mol / L. -4 mol·L -1 The mixture was stirred and aerated for flotation, and each flotation lasted for 3 minutes. Figure 5 The flotation recovery rate of benzoic acid diphosphonate on cassiterite at different pH values ​​was determined by... Figure 5 It can be seen that when the pulp pH is 7.0, the flotation recovery rate of cassiterite reaches 95.56%.

[0048] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. The application of a phosphonate-carboxylic acid compound in the flotation of non-ferrous and precious metal minerals, characterized in that, The chemical formula of the phosphonate-carboxylic acid compound is: ; R1 is selected from C1~C17 alkane group, C2~C17 olefin group, C6~C12 aromatic group or alkoxy ether group; R2 is selected from C1~C17 alkylene group, C2~C17 olefinene group, C6~C12 aryl group, naphthyl group, or alkylene ether group.

2. The application according to claim 1, characterized in that, The non-ferrous and precious metal minerals are ores containing cerium, tin, niobium, scandium, copper, silver, or gold.

3. The application according to claim 1, characterized in that, The phosphonate-carboxylic acid compound is diphenyl phosphonate benzoic acid.

4. A flotation method for non-ferrous and precious metal minerals, characterized in that, The process includes the following steps: pretreating the non-ferrous and precious metal minerals, then adding them to water to prepare a slurry; adding phosphonate-carboxylic acid compounds and a frother to the slurry, followed by stirring, aeration, and flotation to obtain the target mineral; The chemical formula of the phosphonate-carboxylic acid compound is: ; R1 is selected from C1~C17 alkane group, C2~C17 olefin group, C6~C12 aromatic group or alkoxy ether group; R2 is selected from C1~C17 alkylene group, C2~C17 olefinene group, C6~C12 aryl group, naphthyl group, or alkylene ether group.

5. The flotation method for non-ferrous and precious metal minerals according to claim 4, characterized in that, The pretreatment of the non-ferrous and precious metal minerals is as follows: the non-ferrous and precious metal minerals are subjected to gravity separation to obtain concentrate, middlings and tailings, and then the concentrate is subjected to magnetic separation.

6. The flotation method for non-ferrous and precious metal minerals according to claim 4, characterized in that, The pretreated non-ferrous and precious metal minerals used for flotation have a particle size of -0.076 mm to +0.038 mm.

7. The application according to claim 4, characterized in that, The pH of the slurry is 7-9; the concentration of benzoic acid diphosphonate in the slurry is 6 × 10⁻⁶. -5 The frother concentration in the slurry is 1 × 10 mol / L. -4 mol·L -1 The stirring and aeration flotation time is 3 minutes.

8. The flotation method for non-ferrous and precious metal minerals according to claim 4, characterized in that, When the non-ferrous and precious metal minerals are bastnaesite, the pH of the slurry is 8.

0.

9. The flotation method for non-ferrous and precious metal minerals according to claim 4, characterized in that, When the non-ferrous and precious metal minerals are monazite, the pH of the slurry is 9.

0.

10. The flotation method for non-ferrous and precious metal minerals according to claim 4, characterized in that, When the non-ferrous and precious metal minerals are cassiterite, the pH of the slurry is 7.0.

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