Diamino-dihydroximic acid collecting agent and application thereof

Abstract

The invention discloses a diamino-dihydroximic acid collecting agent and application thereof, and belongs to the technical field of mineral flotation. The collecting agent has two amino groups and two hydroxamic acid functional groups, efficient synergy of chelation of the hydroxamic acid groups and electrostatic adsorption of the amino groups is achieved through an intramolecular multi-site synergistic adsorption mechanism, and the adsorption strength and stability of the collecting agent on the surfaces of minerals are remarkably enhanced. The collecting agent is suitable for flotation separation of various metal minerals such as ilmenite, zinc oxide ore, tungsten ore, lead oxide ore, cassiterite and rare earth, has the advantages of being high in collecting capacity, high in acting efficiency and wide in application range, effectively improves the recovery rate of complex metal mineral resources while reducing the dosage of the agent, and is wide in industrial application prospect.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation technology, specifically to a diamino-dihydroxyoxime collector and its application. Background Technology

[0002] Flotation is a key technology for recovering metal ores in mineral processing. Its core principle is to utilize the differences in the physicochemical properties of mineral surfaces and achieve efficient separation of target minerals from gangue through reagent adjustment. In the entire flotation process, the collector, as the most important reagent type, selectively adsorbs onto the surface of the target mineral, enhancing its hydrophobicity, thereby causing the target mineral to float with the bubbles and achieve effective enrichment. The performance of the collector directly determines the selectivity, recovery rate, and final concentrate grade of the flotation process; therefore, developing efficient and specific collectors has always been a key focus of flotation research.

[0003] Benzyl hydroxamic acid, a typical representative of hydroxamic acid collectors, still has significant limitations in practical applications: the hydrophobicity provided by the benzene ring in its molecular structure is limited, especially when flotating minerals with high density or surface energy, often exhibiting insufficient collecting power. To achieve ideal flotation results, it is often used in combination with other collectors in industry, which not only increases reagent costs and operational complexity but also presents problems such as reduced foam stability due to reagent interactions and difficulty in dosage control, thus hindering further improvements in flotation efficiency.

[0004] Therefore, developing a single collector with a novel molecular structure that combines strong selective collecting ability and high hydrophobicity is of great significance for simplifying the flotation process and improving separation efficiency and economic benefits. Summary of the Invention

[0005] To address the limitations of existing collectors in terms of hydrophobicity, reliance on compound formulations, and operational complexity, the present invention aims to provide a diamino-dihydroxyoxime acid collector, the structural formula of which is shown in formula (Ⅰ) below: Where R is C4-C 16 M is one of alkyl, phenyl, or cyclohexyl groups; M is one of sodium, potassium, ammonium, or hydrogen.

[0006] Another object of the present invention is to provide an application of diamino-dihydroxyoxime acid collector in the flotation of metal ores, specifically including the following steps: (1) The metal ore is crushed, mixed into a slurry, and then a slurry is prepared.

[0007] (2) Add collectors and frothers to the slurry, and then perform flotation to separate and obtain concentrate.

[0008] Preferably, the metal ore in step (1) of the present invention is one of ilmenite, zinc oxide ore, tungsten ore, cassiterite, copper oxide ore, copper sulfide ore, lead oxide ore, iron ore, bauxite, nickel ore, lithium ore, rhodochrosite, lead sulfide ore, and zinc sulfide ore.

[0009] Preferably, the pH of the slurry in step (1) of the present invention is 4.0 to 12.0; more preferably, the pH of the slurry is 4.0 to 10.0.

[0010] Preferably, the amount of collector added to the slurry in step (2) of the present invention is 1×10⁻⁶. -6 ~1×10 -2 mol / L, more preferably, the amount of collector added to the slurry is 1×10 mol / L. -5 ~1×10 -3 mol / L.

[0011] Preferably, the foaming agent in step (2) of the present invention is methyl isobutyl methanol (MIBC), and the amount of foaming agent added is 0~1×10 -3 mol / L.

[0012] Preferably, the time for aeration flotation in step (2) of the present invention is 2 to 5 minutes.

[0013] Compared with the prior art, the present invention provides a diamino-dihydroxyoxime acid collector and its application, which has the following beneficial effects: (1) This invention integrates two hydroxamic acid groups and two amino groups in a single molecular skeleton to form a unique two-site adsorption mode. The hydroxamic acid groups form a stable chelate ring with the metal sites on the mineral surface. The amino groups are protonated under the condition of pH=8.0 in the slurry and then undergo electrostatic adsorption. They are simultaneously adsorbed in the two-site in the diamino-dihydroxamic acid molecule with a fixed spatial configuration, which avoids the competitive adsorption problem of traditional physical mixed collectors and significantly enhances the interfacial interaction strength.

[0014] (2) The present invention enables the total adsorption energy to far exceed that of a single functional group collector through multi-site synchronous adsorption, and is higher than the sum of the adsorption energies of physically mixed collectors. This enhanced adsorption is manifested as higher adsorption strength and coverage density, thereby greatly improving the hydrophobicity effect of mineral surfaces and achieving a higher recovery rate.

[0015] (3) Compared with traditional collectors such as benzohydroxyxamic acid and sodium oleate, this product has excellent collecting ability for a variety of metal oxides and carbonate minerals such as ilmenite, wolframite, cerussite, smithsonite and rhodochrosite; the flotation recovery rate is significantly improved, especially for minerals such as rhodochrosite where traditional collectors are not very effective.

[0016] (4) The diamino-dihydroxyoxime acid collector of the present invention provides an efficient solution for complex and difficult-to-process metal oxide ores and carbonate ores. Its stable synergistic effect comes from the internal molecular structure and is not affected by the reagent ratio and the order of addition. It has a wide process operation window and good reproducibility. It creates favorable conditions for optimizing the flotation process, reducing reagent consumption and improving resource utilization. It is particularly suitable for the efficient development of low-grade and complex symbiotic mineral resources. Attached Figure Description

[0017] Figure 1 This is a flow chart of the diamino-dihydroxyoxime flotation process of the present invention.

[0018] Figure 2 It is the 1H NMR spectrum of 1,12-dodecyldiaminodipropylhydroxamic acid.

[0019] Figure 3 This is the 1H NMR spectrum of 1,10-decanediaminodipropylhydroxamic acid.

[0020] Figure 4 It is the 1H NMR spectrum of 1,8-octanediaminodipropylhydroxamic acid. Detailed Implementation

[0021] 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.

[0022] The specific preparation method of diamino-dihydroxyoxime acid used in the embodiments and comparative examples of this invention is as follows: 0.1 mol of alkyl diamine is dissolved in ethanol, and then 0.205 mol of methyl acrylate is added dropwise at -10℃. After the addition is complete, the reaction is carried out at -10℃ for 2 hours. Subsequently, 0.22 mol of hydroxylamine hydrochloride and 0.22 mol of sodium hydroxide solid are added in batches. After complete dissolution, the temperature is raised to 45℃ and reacted for 4-6 hours. After the reaction is completed, the system is cooled to -10℃, and sulfuric acid is slowly added dropwise to adjust the pH to about 7. After filtering to remove the solvent, crude 1,12-dodecyldiaminodipropylhydroxyoxime acid is obtained. The crude product is recrystallized in ethanol solution to obtain pure diamino-dihydroxyoxime acid. The 1H NMR spectrum of 1,12-dodecyldiaminodipropylhydroxyoxime acid is shown below. Figure 2 As shown; the 1H NMR spectrum of 1,10-decanediaminodipropylhydroxamic acid is as follows. Figure 3 As shown; the 1H NMR spectrum of 1,8-octanediaminodipropylhydroxamic acid is as follows. Figure 4As shown, the characteristic chemical shifts in the spectrum correspond one-to-one with the proton types in the target molecule structure, confirming the successful synthesis of the target product.

[0023] Example 1 The flotation of ilmenite with 1,12-dodecyldiaminodipropylhydroxamic acid follows these steps: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0024] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of ilmenite, and the ilmenite recovery rate was 99.6%.

[0025] Example 2 The flotation of ilmenite with 1,8-octanediaminodipropylhydroxamic acid follows these steps: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,8-octanediaminodipropylhydroxamic acid to the slurry (the amount of 1,8-octanediaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0026] In this embodiment, 1,8-octanediaminodipropylhydroxamic acid was used as a collector for flotation of ilmenite, and the ilmenite recovery rate was 93.2%.

[0027] Example 3 The flotation of ilmenite with 1,10-decanediaminodipropylhydroxamic acid follows these steps: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,10-decanediaminodipropylhydroxamic acid to the slurry (the amount of 1,10-decanediaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0028] In this embodiment, 1,10-decanediaminodipropylhydroxamic acid was used as a collector for flotation of ilmenite, and the ilmenite recovery rate was 96.8%.

[0029] Example 4 The flotation of ilmenite with 1,12-dodecyldiaminodipropylhydroxamic acid follows these steps: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 1×10 -5 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 2 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0030] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of ilmenite, and the ilmenite recovery rate was 93.5%.

[0031] Example 5 The flotation of ilmenite with 1,12-dodecyldiaminodipropylhydroxamic acid follows these steps: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 1×10 -3 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -3 (mol / L), and N2 was passed through for flotation for 5 minutes (N2 gas flow rate of 200 mL / min) to obtain the concentrate.

[0032] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of ilmenite, and the ilmenite recovery rate was 98.1%.

[0033] Example 6 The flotation of smithsonite with 1,12-dodecyl diaminodipropyl hydroxamic acid follows these steps: (1) Crush smithsonite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 (mol / L), without adding a frother, N2 was passed through for flotation for 3 minutes (N2 gas flow rate of 200 mL / min) to obtain the concentrate.

[0034] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of smithsonite, and the smithsonite recovery rate was 91.9%.

[0035] Example 7 The flotation of smithsonite with 1,10-decanediaminodipropylhydroxamic acid follows these steps: (1) Crush smithsonite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,10-decanediaminodipropylhydroxamic acid to the slurry (the amount of 1,10-decanediaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0036] In this embodiment, 1,10-decanediaminodipropylhydroxamic acid was used as a collector for flotation of smithsonite, and the smithsonite recovery rate was 85.6%.

[0037] Example 8 The specific steps for flotation of scheelite with 1,12-dodecyldiaminodipropylhydroxamic acid are as follows: (1) The scheelite is crushed to a particle size of -200~+400 mesh, and the slurry is prepared (the pH of the slurry is 8.0). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0038] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of scheelite, and the scheelite recovery rate was 98.8%.

[0039] Example 9 The specific steps for flotation of scheelite with 1,10-decanediaminodipropylhydroxamic acid are as follows: (1) The scheelite is crushed to a particle size of -200~+400 mesh, and the slurry is prepared (the pH of the slurry is 8.0). (2) Add 1,10-decanediaminodipropylhydroxamic acid to the slurry (the amount of 1,10-decanediaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0040] In this embodiment, 1,10-decanediaminodipropylhydroxamic acid was used as a collector for flotation of scheelite, and the scheelite recovery rate was 90.3%.

[0041] Example 10 The flotation of wolframite with 1,12-dodecyldiaminodipropylhydroxamic acid follows these steps: (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). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0042] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of wolframite, and the wolframite recovery rate was 98.9%.

[0043] Example 11 The flotation of cerussite with 1,12-dodecyldiaminodipropylhydroxamic acid involves the following steps: (1) Crush cerussite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4(mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0044] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of cerussite, and the cerussite recovery rate was 98.6%.

[0045] Example 12 The flotation of rhodochrosite with 1,12-dodecyl diaminodipropyl hydroxamic acid follows these steps: (1) Crush rhodochrosite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add 1,12-dodecyldiaminodipropylhydroxamic acid to the slurry (the amount of 1,12-dodecyldiaminodipropylhydroxamic acid added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0046] In this embodiment, 1,12-dodecyldiaminodipropylhydroxamic acid was used as a collector for flotation of rhodochrosite, and the rhodochrosite recovery rate was 96.1%.

[0047] Comparative Example 1 The specific steps for flotation of ilmenite using sodium oleate are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add sodium oleate to the slurry (the amount of sodium oleate added to the slurry is 6×10). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0048] In this comparative example, sodium oleate was used as a collector for the flotation of ilmenite, and the ilmenite recovery rate was 77.1%.

[0049] Comparative Example 2 The specific steps for flotation of ilmenite using benzyl hydroxamic acid are as follows: (1) Pulverize ilmenite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add benzohydroxyxamic acid to the slurry (the amount of benzohydroxyxamic acid added to the slurry is 6×10). -4mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0050] In this comparative example, benzohydroxyxamic acid was used as a collector for the flotation of ilmenite, and the ilmenite recovery rate was 45.7%.

[0051] Comparative Examples 1, 2, and Examples 1-5 show that although the fatty acid collector (sodium oleate) in Comparative Example 1 has a certain degree of chemical adsorption, the resulting metal soap has generally low stability and readily reacts with Ca at pH=8.0. 2+ The reaction with impurity ions resulted in poor selectivity and low recovery rates. In Comparative Example 2, the chelate formed by a single hydroxamic acid group and metal ions was easily desorbed under mechanical stirring and fluid impact, failing to provide a stable and durable hydrophobic surface. In Examples 1-5, the two hydroxamic acid groups in 1,12-dodecyldiaminodipropylhydroxamic acid could simultaneously react with adjacent metal sites (Fe) on the ilmenite surface. 2+ Ti 4+ It forms a stable five-membered ring chelate, cross-linked adsorption with extremely high strength, and the long alkane chain provides strong hydrophobicity, resulting in a high mineral recovery rate.

[0052] Comparative Example 3 The specific steps for flotating dodecylamine onto smithsonite are as follows: (1) Crush smithsonite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add dodecylamine to the slurry (the amount of dodecylamine added to the slurry is 6 × 10⁻⁶). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0053] In this comparative example, dodecylamine was used as a collector to float smithsonite, and the smithsonite recovery rate was 80.6%.

[0054] Comparative Example 4 The specific steps for flotation of smithsonite with benzyl hydroxamic acid are as follows: (1) Crush smithsonite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add benzohydroxyxamic acid to the slurry (the amount of benzohydroxyxamic acid added to the slurry is 6×10). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4(mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0055] In this comparative example, benzohydroxyxamic acid was used as a collector for flotation of smithsonite, and the smithsonite recovery rate was 31.2%.

[0056] Examples 6, 7, Comparative Example 3, and Comparative Example 4 show that on the surface of smithsonite, a single hydroxamic acid group interacts with Zn. 2+ The chelating ability of zinc is relatively weak and cannot compete with the strong surface hydration energy, resulting in most mineral surfaces being non-hydrophobic and extremely low recovery rates. Dodecylamine mainly relies on electrostatic adsorption, is highly dependent on the negatively charged region of smithsonite surface, is easily interfered with by inevitable ions in the pulp, and has poor selectivity for gangue minerals (such as calcite). Carbonate mineral surfaces are easily hydrated and have complex surface properties. In Examples 6 and 7 of this invention, the dual action of chelation and electrostatic interaction of diamino-dihydroxyoxime acid effectively penetrates the hydration layer. The electrostatic adsorption of amino groups assists in the precise anchoring of Zn by hydroxyoxime acid. 2+ This enables efficient recycling.

[0057] Comparative Example 5 The specific steps for flotation of scheelite using benzyl hydroxamic acid are as follows: (1) The scheelite is crushed to a particle size of -200~+400 mesh, and the slurry is prepared (the pH of the slurry is 8.0). (2) Add benzohydroxyxamic acid to the slurry (the amount of benzohydroxyxamic acid added to the slurry is 6×10). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0058] In this comparative example, benzohydroxyxamic acid was used as a collector for the flotation of scheelite, and the scheelite recovery rate was 86.3%.

[0059] Comparative Example 6 The specific steps for flotation of wolframite with benzohydroxyoxime 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). (2) Add benzohydroxyxamic acid to the slurry (the amount of benzohydroxyxamic acid added to the slurry is 6×10). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0060] In this comparative example, benzohydroxyxamic acid was used as a collector for flotation of wolframite, and the wolframite recovery rate was 84.5%.

[0061] For tungsten ore, the Ca on the tungsten ore surface 2+ It is a preferred target for hydroxamic acid; the dihydroxamic acid groups in Examples 8-10 can achieve the capture of Ca. 2+ The multi-site, high-density coordination results in extremely strong adsorption and high recovery rate. In Comparative Examples 5 and 6, a single benzohydroxyoxime molecule interacts with Ca... 2+ The coordination of the minerals is insufficient to overcome the hydration layer on the mineral surface and resist desorption, resulting in a low recovery rate.

[0062] Comparative Example 7 The specific steps for flotation of cerussite using benzyl hydroxamic acid are as follows: (1) Crush cerussite to a particle size of -200~+400 mesh, adjust the slurry, and prepare the slurry (the pH of the slurry is 8.0). (2) Add benzohydroxyxamic acid to the slurry (the amount of benzohydroxyxamic acid added to the slurry is 6×10). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0063] In this comparative example, benzohydroxyxamic acid was used as a collector for flotation of cerussite, and the cerussite recovery rate was 74.5%.

[0064] In Example 11, the dihydroxamic acid group reacted with Pb in cerussite. 2+ It forms a super-strong chelate that can almost completely capture cerussite particles; although in Comparative Example 7, benzoxoxime acid has a strong effect on Pb 2+ It has some effect, but single-point adsorption is easily destroyed during the dynamic process of flotation, resulting in a low recovery rate.

[0065] Comparative Example 8 The specific steps for flotation of rhodochrosite with benzyl hydroxamic acid are as follows: (1) Crush rhodochrosite to a particle size of -200~+400 mesh, adjust the slurry, and prepare a slurry (the pH of the slurry is 8.0). (2) Add benzohydroxyxamic acid to the slurry (the amount of benzohydroxyxamic acid added to the slurry is 6×10). -4 mol / L) and MIBC (the amount of MIBC added to the pulp is 1×10 -4 (mol / L), and N2 was passed through for flotation for 3 minutes (N2 gas flow rate was 200 mL / min) to obtain the concentrate.

[0066] In this comparative example, benzohydroxyxamic acid was used as a collector for the flotation of rhodochrosite, and the recovery rate of rhodochrosite was 26.2%.

[0067] Mn 2+ 3D 5 Its electronic configuration results in an extremely high hydration energy, making it one of the most difficult metal ions to float. This invention (Example 12) utilizes the strong multi-site synergistic adsorption of diamino-dihydroxyxamic acid to provide an adsorption free energy sufficient to overcome the enormous hydration energy, achieving highly efficient flotation of rhodochrosite. Comparative Example 8 used benzyl hydroxamic acid to float rhodochrosite; a single hydroxamic acid group interacts with Mn... 2+ The chelation strength is much lower than that of Mn. 2+ The enormous hydration energy makes it impossible for the collector molecules to be stably adsorbed, and most of the minerals remain in the slurry, resulting in an extremely low recovery rate.

[0068] In summary, the flotation process of this invention is as follows: Figure 1 As shown, through molecular structure design, two amino groups and two hydroxamic acid groups are integrated into a single molecule, forming a unique two-site adsorption mechanism. The amino and hydroxamic acid groups produce a significant synergistic effect within the molecule, binding to the metal sites on the mineral surface through a multi-site coordination mechanism, greatly enhancing the interfacial adsorption strength and stability. This collector exhibits excellent and broad-spectrum collection performance for various metallic minerals such as ilmenite, scheelite, and difficult-to-flot rhodochrosite, providing an innovative solution for the efficient separation of complex metallic mineral resources.

[0069] 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. A diamino-dihydroxyoxime acid collector, characterized in that, The structural formula of the diamino-dihydroxyoxime acid collector is shown in formula (Ⅰ): Where R is C4-C 16 M is one of alkyl, phenyl, or cyclohexyl groups; M is one of sodium, potassium, ammonium, or hydrogen.

2. The application of the diamino-dihydroxyoxime acid collector according to claim 1 in the flotation of metal ores, characterized in that, Specifically, the following steps are included: (1) The metal ore is crushed, mixed into a slurry, and then a slurry is prepared. (2) Add collectors and frothers to the slurry, and then perform flotation to separate and obtain concentrate.

3. The application of the diamino-dihydroxyoxime acid collector according to claim 2 in the flotation of metal ores, characterized in that, The metal ore mentioned in step (1) is one of the following: ilmenite, zinc oxide ore, tungsten ore, cassiterite, copper oxide ore, copper sulfide ore, lead oxide ore, iron ore, bauxite, nickel ore, lithium ore, rhodochrosite, lead sulfide ore, and zinc sulfide ore.

4. The application of the diamino-dihydroxyoxime acid collector according to claim 2 in the flotation of metal ores, characterized in that, The pH of the slurry in step (1) is 4.0~12.

0.

5. The application of the diamino-dihydroxyoxime acid collector according to claim 2 in the flotation of metal ores, characterized in that, Step (2) The amount of collector added to the slurry is 1×10 -6 ~1×10 -2 mol / L.

6. The application of the diamino-dihydroxyoxime acid collector according to claim 2 in the flotation of metal ores, characterized in that, The foaming agent mentioned in step (2) is methyl isobutyl methanol, and the amount of foaming agent added is 0~1×10 -3 mol / L.

7. The application of the diamino-dihydroxyoxime acid collector according to claim 2 in the flotation of metal ores, characterized in that, The time for aeration flotation in step (2) is 2 to 5 minutes.

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