Collecting agent, preparation method of collecting agent and application of collecting agent in metal ore flotation

Abstract

The invention belongs to the field of mineral flotation, and particularly discloses a novel collecting agent and application thereof in metal ore flotation. The collecting agent of a brand new structure is provided, flotation enrichment and recovery of ores such as copper, tin, titanium, tungsten, iron and rare earth can be effectively enhanced on the basis of the synergistic effect of a molecular internal structure, and the flotation recovery rate and selectivity of valuable metal minerals are improved.

Description

Technical Field

[0001] This invention relates to the field of metal beneficiation, and more specifically to the field of flotation collectors. Technical Background

[0002] Flotation is a crucial method for mineral recovery. By adding collectors to the slurry, the hydrophobicity of the target mineral's surface is improved, thereby achieving effective separation of the target mineral from gangue minerals. Oxime molecules, due to the abundance of lone pairs of electrons in their nitrogen and oxygen atoms, readily undergo chelation reactions with metal ions, forming cyclic coordination structures. They exhibit excellent chelating ability and selectivity, and are widely used as flotation collectors for oxide ores such as malachite, ilmenite, cassiterite, wolframite, scheelite, and rare earth elements. In recent years, with the increasing severity of low-grade, fine-grained, and complex metal mineral resources, efficient separation of target minerals from gangue minerals has become increasingly difficult. Therefore, developing novel, highly efficient flotation collectors to improve mineral particle separation is of great significance for enhancing the overall recovery rate of metal minerals.

[0003] Zheng Jie's research indicates that 5-nonyl salicylaldehyde oxime is a high-performance flotation collector for copper oxide ores, capable of selectively separating malachite, calcite, and quartz (Zheng J., Luo A., Jin Y., Feng B., Chen J., Zhang X. Interface adsorption mechanism of 5-nonyl salicylaldehyde oxime onmalachite surface and its flotation separation performance with calcite and quartz [J], Separation and Purification Technology, 2024, 125758); Xu Jinqiu and Zhu Jianguang's research found that the combined use of salicylaldehyde oxime and lead nitrate can selectively separate wolframite and calcite (Xu Jinqiu, Zhu Jianguang. Study on the collecting performance and mechanism of salicylaldehyde oxime for wolframite [J]. Nonferrous Metals, 1989 (02)); Chinese patent CN108456153A discloses a phenylpropenyl hydroxamic acid, its preparation method and its application in tungsten ore flotation, showing that under neutral conditions, the flotation recovery rate of phenylpropenyl hydroxamic acid for wolframite is higher than that of salicyl hydroxamic acid and benzyl hydroxamic acid; Chinese patent CN115228617A discloses a 3-allyl salicyl hydroxamic acid compound, its preparation and its application in metal ore flotation, suggesting that the introduction of the propenyl group can improve the flotation performance of salicyl hydroxamic acid for cassiterite; Chinese patent CN111841896A discloses a heterocyclic hydroxamic acid collector, its preparation method and application, showing that this type of compound has excellent flotation performance for bastnaesite. Although existing oxime collectors such as benzyl hydroxamic acid or salicylaldehyde oxime have advantages such as good selectivity and simple preparation process, their poor hydrophobicity makes it difficult to meet the urgent need for collectors in the efficient separation of complex ores. Therefore, it is of great significance to optimize and adjust their molecular structure to endow oxime collectors with good collecting ability and selectivity. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the first objective of the present invention is to provide a collector with a novel structure, which aims to improve the enrichment efficiency of valuable metal minerals and their selective separation effect from gangue minerals.

[0005] A second objective of this invention is to provide a method for preparing a novel collector.

[0006] A third object of the present invention is to provide the collector for flotation applications of metallic minerals.

[0007] A collector, wherein the collector is a compound of formula 1;

[0008] Formula 1

[0009] In Equation 1, R1 is C1~C 12 Alkyl or C2~C 12 Alkoxyalkyl, R2 is H, C1~C 12 Alkyl or C2~C 12 alkoxyalkyl, where R3 is a hydroxyl or H atom;

[0010] R4 is or M is H + Na + K + or NH4 + .

[0011] This invention provides a collector with a novel structure, which can enhance the flotation recovery and selectivity of metallic ores such as malachite, cassiterite, and tungsten ore based on the synergy between intramolecular structures.

[0012] In this invention, as an optional solution, R3 is located adjacent to R4; Interposition or opposite position located in R4.

[0013] For example, the collector described in this invention may specifically be a compound having the structure shown in formula (I) or formula (II);

[0014] Formula (I)

[0015] Equation (II)

[0016] Where R1 is C1~C 12 Alkyl or C2~C 12 Alkoxyalkyl groups, where R2 is H, C1~C1 respectively. 12 Alkyl or C2~C 12 alkoxyalkyl, R3 is a hydroxyl or H atom, M is H + Na + K + or NH4 + .

[0017] R1 and R2 are individually C1 to C4 alkyl groups.

[0018] The present invention also provides the aforementioned collector, obtained by reacting according to formulas 2 and 3;

[0019] Formula 2

[0020] NH2OH (Formula 3);

[0021] In Equation 2, the selection ranges of R1, R2, and R3 are the same as in Equation 1, and R5 is... or ;

[0022] The R6 is a C1-C6 alkyl group.

[0023] For example, in this invention, the alkylamino-substituted aromatic aldehyde of formula (III) can be oximated with formula 3 to obtain the collector of formula (I). Alternatively, the substituted aromatic ester of formula (IV) can be oximated with formula 3 to obtain the collector of formula (II).

[0024] Equation (III)

[0025] or Formula (IV)

[0026] The solvent for the reaction includes at least one of methanol, ethanol, isopropanol, and diethyl ether. The amount of solvent used is 100~1000 mL / mol (Formula 2).

[0027] Preferably, the solvent is at least one of methanol or ethanol, and the solvent used can be recycled.

[0028] Preferably, the molar ratio of Formula 2 and Formula 3 is 1:1~2; more preferably, it is 1.0:1.0~1.5.

[0029] The oxime reaction temperature is 10 ~ 80°C, and the reaction time is 1 ~ 10 h.

[0030] The present invention also provides an application of the aforementioned collector, using it as a collector for the flotation of target metallic ores.

[0031] Furthermore, the target metal ore is at least one of copper, iron, tin, tungsten, titanium, rare earth, and fluorite.

[0032] Furthermore, the target metallic mineral includes at least one of malachite, cassiterite, scheelite, rare earth elements, and fluorite.

[0033] In this invention, the collector is used as a collector for selectively flotating metallic minerals from a mixture of minerals (minerals to be processed) containing gangue minerals and the target metallic mineral.

[0034] Preferably, the gangue mineral includes at least one of calcite, quartz, pyrophyllite, sericite, and chlorite.

[0035] In this invention, the weight of the ore used for flotation is used as the calculation standard. The amount of the novel collector added is 10~4000 g / t. Considering the cost, it can be further 200~3000 g / t; and even further 500~2600 g / t.

[0036] In this invention, the pH during the flotation process is 6 to 12; more preferably, the pH during the flotation process is 6 to 10.

[0037] In this invention, apart from using the collector described herein, all other flotation operations can be known or reasonably controlled based on known principles.

[0038] For example, pH adjusters, frothers, activators, inhibitors and other components are also allowed in the flotation process.

[0039] For example, the optional flotation process of the present invention includes the following steps:

[0040] Step (1): The metal ore is ground, crushed, stirred and mixed to obtain a slurry;

[0041] Step (2): Add flotation reagents to the slurry from step (1) for flotation and collect the concentrate; the flotation reagents include the collector of Formula 1.

[0042] Beneficial effects of the present invention

[0043] This invention is the first to discover that it provides a novel type 1 collector, which can enhance the flotation recovery and selectivity of metallic ores such as malachite, cassiterite, and scheelite based on the synergistic effect between molecular structures.

[0044] Furthermore, the present invention also provides a one-pot synthesis method for the collector, which is simple to operate and has good reaction effect; the solvent can be recycled during the synthesis process. Attached Figure Description

[0045] Figure 1 For Equation 1A 1 H NMR spectrum;

[0046] Figure 2 For Equation 1B 1 H NMR spectrum;

[0047] Figure 3 For Equation 1C 1 H NMR spectrum. Detailed Implementation

[0048] The following examples are intended to further illustrate the present invention, but not to limit the scope of protection of the present invention. All parts and percentages in the examples refer to mass unless otherwise specified.

[0049] Synthesis Example 1:

[0050] Weigh 7.0 parts of hydroxylamine hydrochloride (Formula 3) and 50 parts of methanol (99% purity) into a three-necked flask, stir at 10°C for 10 minutes, then add 8 parts of sodium hydroxide (96% purity) and stir the reaction at 10°C for 30 minutes. Next, add 18.3 parts of methanol (Formula 2A) (98% purity) to the reaction flask. The temperature was raised to 50°C and the reaction was carried out for 4 hours. After the reaction was complete, the solvent was removed by vacuum distillation to obtain the sodium salt of formula 1A ( The reaction yield based on Formula 2A was 89.28%. The crude sodium salt of Formula 1A obtained can be directly used for metal ore flotation. The sodium salt of Formula 1A can be purified by acidification and recrystallization to obtain Formula 1A (…). ),That 1 H NMR such as Figure 1 As shown.

[0051] Synthesis Example 2:

[0052] Weigh 7.0 parts of hydroxylamine hydrochloride and 50 parts of 99% pure methanol into a three-necked flask, stir at 10°C for 10 minutes, then add 8 parts of 96% pure sodium hydroxide, and stir the reaction at 10°C for 30 minutes. Next, add 18.3 parts of 98% pure formula 2B (… The temperature was raised to 50°C and the reaction was carried out for 4 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain sodium salt of formula 1B ( The reaction yield based on Formula 2B was 91.45%. The crude sodium salt of Formula 1B obtained can be directly used for metal ore flotation. The sodium salt of Formula 1B can be purified by acidification and recrystallization to obtain Formula 1B(…). ),That 1 H NMR such as Figure 2 As shown.

[0053] Synthesis Example 3:

[0054] Weigh 7.0 parts of hydroxylamine hydrochloride (99% purity) and 50 parts of methanol (99% purity) into a three-necked flask, stir at 10°C for 10 minutes, then add 8 parts of sodium hydroxide (96% purity) and stir the reaction at 10°C for 30 minutes. Next, add 19.3 parts of formula 2C (98% purity) to the reaction flask. The temperature was raised to 45°C and the reaction was carried out for 6 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain a brown sodium salt of formula 1C ( The reaction yield based on formula 2C was 92.6%. The resulting crude sodium salt of formula 1C can be directly used for metal ore flotation. The sodium salt of formula 1C can be purified by acidification to obtain formula 1C(…). ),That 1 The H NMR spectra are as follows: Figure 3 As shown.

[0055] All material usage amounts in the above synthesis process refer to parts by weight. The specific amount can be adjusted reasonably according to the preparation scale. For example, one part in laboratory scale can be 1~50 g.

[0056] Following the approach of preparation examples 1-3, the raw materials of formula 2 were adjusted, and the following structure of the collector was obtained through further synthesis;

[0057] Sodium salt of formula 1D.

[0058] Sodium salt of Formula 1E.

[0059] The M in the collector of formula (I) or (II) is affected by the pH during the flotation process. For example, when the flotation pH is alkaline, M is mainly salt type, and when the flotation pH is acidic, M is mainly H type.

[0060] As examples, in the following cases, unless otherwise stated, the original collectors of formula (I) or (II) are of type H.

[0061] Application Example 1: Single Mineral Flotation Experiment

[0062] At a collector concentration of 5 × 10 -5 The slurry concentration was 1.5 × 10⁻⁶ mol / L, the pulp pH was 8.0, and the frother (MIBC) concentration was 1.5 × 10⁻⁶. -4 At a flow rate of 200 mL / min and mol / L N2, cassiterite, scheelite, malachite, calcite, or quartz with a particle size of -0.076 mm to +0.038 mm were floated for 3 minutes. The flotation recovery rates of different collectors for different minerals are shown in Table 1.

[0063]

[0064] Note: All collectors used are sodium salt type collectors.

[0065] As can be seen from Equations 1B and 1D, replacing the benzene ring with highly branched R1R2N- is expected to further enhance the recovery rate and selectivity of the target ore.

[0066] Application Example 2: Actual Ore Flotation Experiment

[0067] The SnO2 content in the tailings of a cassiterite shaking table in Hunan Province was 0.56%. The experiment employed a single roughing process, with a soda ash dosage of 2500 g / t, pH 8.0, a collector dosage of 500 g / t, and frother #2 oil at 15 g / t. The flotation results are shown in Table 2. The results indicate that, compared with benzoyl hydroxamic acid, salicylic acid, and octyl hydroxamic acid, formulas 1A, 1B, and 1C significantly improved the flotation recovery rate of SnO2 in the cassiterite shaking table tailings.

[0068]

[0069] Note: All collectors used are sodium salt type collectors.

[0070] Through comparison of the examples and comparative reagents, it is evident that introducing alkylamino groups onto the benzene ring can significantly improve the collector's ability and selectivity for collecting metal minerals. Furthermore, unexpectedly, the novel Formula 1 collector exhibits superior flotation performance compared to long-chain oximes such as octyl hydroxamic acid and 4-tert-butylbenzohydroxyxamic acid or 4-tert-butylsalicylaldehyde oxime. This indicates that the collector described in this invention, based on intramolecular synergy of its structure, can achieve better collecting performance and has promising application prospects.

Claims

1. A collector, characterized in that, The collector is a compound with the structure of Formula 1; Formula 1 In Equation 1, R1 is C1~C 12 Alkyl or C2~C 12 Alkoxyalkyl, R2 is H, C1~C 12 Alkyl or C2~C 12 alkoxyalkyl, where R3 is a hydroxyl or H atom; R4 is or M is H + Na + K + or NH4 + .

2. The collector as described in claim 1, characterized in that, R3 is adjacent to R4; Intermediate or contralateral position located on R4; Preferably, R1 and R2 are individually C1 to C4 alkyl groups.

3. A collector according to claim 1 or 2, characterized in that, It is obtained by reacting according to Equations 2 and 3; Formula 2 NH2OH (Formula 3); In Equation 2, the selection ranges of R1, R2, and R3 are the same as in Equation 1, and R5 is... or ; The R6 is a C1-C6 alkyl group.

4. The collector as described in claim 3, characterized in that, The molar ratio of Equation 2 and Equation 3 is 1:1~2; Preferably, the solvent for the reaction includes at least one of methanol, ethanol, isopropanol, and diethyl ether; Preferably, the reaction temperature is 10°C to 80°C and the reaction time is 1 to 10 hours.

5. The application of the collector according to claim 1 or 2, characterized in that, It is used as a collector for the flotation of target metallic ores.

6. The application of the collector as described in claim 5, characterized in that, The target metal ore is at least one of copper, tin, titanium, tungsten, iron, rare earth, and fluorite.

7. The application of the collector as described in claim 6, characterized in that, The target metallic minerals include at least one of malachite, cassiterite, scheelite, rare earth elements, and fluorite.

8. The application of the collector as described in claim 6 or 7, characterized in that, It is used as a collector for the selective flotation of target metal minerals from mixed minerals containing gangue minerals and target metal minerals; Preferably, the gangue mineral includes at least one of calcite, quartz, pyrophyllite, sericite, and chlorite.

9. The application of the collector according to any one of claims 5 to 8, characterized in that, The dosage of the collector is 10~4000g / t.

10. The application of the collector according to any one of claims 5 to 8, characterized in that, The pH during the flotation process is 6-12, preferably 6-10.

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