Application of a sulfur-nitrogen-phosphonate flotation collector

Abstract

The invention discloses an application of a sulfur-nitrogen-phosphonate flotation collector. The application method comprises the following steps: applying a sulfur-nitrogen-phosphonate compound having a structure of formula (1) to at least one ore containing rare earth, niobium, scandium, copper, silver or gold minerals, and flotation recovering valuable metals; #imgabs0# formula (1), wherein R1 and R2 are one or two selected from hydrogen atoms, alkyl groups, cycloalkyl groups, aryl groups, polymer skeletons and heterocycles; R3 is an alkylene group, an alkenylene group, R1, R2, N or an alkoxy ether group having a structure of formula (2); R4 is an alkyl group having 4 to 8 carbon atoms; R-O-formula (2), wherein R is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a polymer skeleton or a heterocycle.

Description

Technical Field

[0001] The invention belongs to the field of metal beneficiation, and in particular relates to the application of a sulfur-nitrogen-phosphonate flotation collector. Background Art

[0002] Sulfur nitrogen-phosphonate compounds have biological activity and chelating properties. First, phosphonate compounds have stable structures and can react with metal ions to form chelates. They are widely used in biomedicine, mineral processing, corrosion protection, extraction and other fields in the agricultural field. Secondly, because phosphate compounds have strong chelating ability, they are often used as metal corrosion inhibitors and extractants. Thirdly, sulfur nitrogen (dithiocarbamate / ester) compounds are widely used in the fields of petroleum industry, environmental protection, rubber industry, plastic industry, agriculture, medicine and mineral processing. Its capture ability and sorting effect are better than xanthate, and it has strong chelating ability with metal ions. Therefore, it is widely used in the field of mineral processing. Among them, sulfur nitrogen-phosphonate compounds can be used as multidentate ligands to chelate rare earth, niobium, copper, lead, silver, nickel, mercury and other ions because they contain P and S heteroatoms with strong coordination ability. They can be used in the fields of metal corrosion protection, extraction and mineral processing.

[0003] There are many methods for synthesizing sulfur-nitrogen-phosphonate compounds, among which the synthetic route of di-n-ethylsulfonitrile propenylphosphonic acid butyl ester is as follows:

[0004]

[0005] The method synthesizes di-n-ethylthiocarbamate butyl ester compounds through four steps. First, the thiocarbamate compounds are prepared at low temperature, and then the thiocarbamate compounds are reacted with phosphorus pentachloride and alcohol, and then hydrolyzed to prepare di-n-ethylthiocarbamate butyl ester (S. Liu, G. Liu, H. Zhong, X. Yang, The role of HABTC's hydroxamate and dithiocarbamate groups in chalcopyrite flotation [J], Journal of Industrial and Engineering Chemistry, 2017, (52): 359-368; Kaihua Huang, Xiaoping Huang, Yun Jia, Shuai Wang, Zhanfang Cao, Hong Zhong. A novel surfactant styryl phosphonate mono-iso-octyl ester with improved adsorption capacity and hydrophobicity for cassiterite flotation. Minerals Engineering, 2019, 142: 105895).

[0006] Zheng et al. found that 1-hydroxyoctyl diphosphonic acid was chemically adsorbed on the surface of niobite through its -P=O and -PO- groups (Zheng XP, Misra M, Smith RW, et al. Fersmite flotation with diphosphonicacid and other collectors [J]. Minerals Engineering, 2015, 9 (3): 331-341). Chen reported the flotation study of niobite and dolomite with 1-hydroxyoctyl diphosphonic acid. The study found that at the same dosage, 1-hydroxyoctyl diphosphonic acid had a higher recovery rate than benzyl arsenic acid, styrene phosphonic acid and diisobutyl sulfosuccinate, and had better selectivity than C7-C9 alkyl hydroxamic acid (Chen GL, Tao D, Ren H, et al. An investigation of niobite flotation 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 by heptyl phosphate monoester. The results showed that heptyl phosphate monoester had a strong collection ability for cassiterite, and the recovery rate could reach about 80% (Zhang BR, Zhang L, Li FT, et al. Testing the formation of Ca-phosphonateprecipitates and evaluating the anionic polymers as Ca-phosphonateprecipitates 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 DM. Process development for treatment of complex perovskite, ilmenite and rutile ores [J]. Minerals Engineering, 1999, 12 (12): 1407-1417). 12 -C16 The combination of phosphate and sulfonated paraffin soap can have a stronger capture ability for ilmenite, which is better than C 12 -C 16 The effect of phosphate ester when used alone, and the use of compound agents can significantly reduce C 12 -C 16 Compared with tall oil and oleic acid, C 12 -C 16 Phosphates have stronger capture ability for perovskites.

[0007] Fabrizio found that sulfur and nitrogen compounds have better resistance and separation effect than xanthate, especially for oxidized minerals (Fabrizio Carta, Mayank Aggarwal, Alfonso, et al. Dithiocarbamates: a new class of carbonnic anhydrase inhibiors. Crystallographic and kinetic investigations [J]. Chemical Communications, 2012, 48: 1868-1870)

[0008] Many researchers are committed to developing and researching new multi-functional collectors, introducing different functional groups into the same molecular structure, so that the collector has the properties of multi-functional groups and improves the interaction ability with minerals (Duan H, Liu W, Wang X, et al. Investigation on flotation separation of bastnaesite from calcite and barite with a novel surfactant: Octylamino-bis-(butanohydroxamic acid)[J]. Separation and Purification Technology, 2021, 256: 117792; Xiao J, Liu G, Zhong H. The adsorption mechanism of N-butoxypropyl-S-[2-(hydroxyimino)propyl]dithiocarbamate ester to copper minerals flotation[J]. International Journal of Mineral Processing, 2017, 166: 53-61; Liu S, Liu G, Zhong H, et al. The role of HABTC's hydroxamate and dithiocarbamate groups inchalcopyrite flotation[J].Journal of Industrial and Engineering Chemistry,2017,52:359-368).

[0009] At present, there is no report on using di-n-ethylsulfonylphosphonate compounds as flotation collectors. Summary of the invention

[0010] In view of the above problems, the present invention provides an application of a sulfur-nitrogen-phosphonate flotation collector, which can effectively improve the enrichment and recovery efficiency of valuable metals in ores containing rare earth, niobium, scandium, copper, silver or gold minerals.

[0011] In order to achieve the above-mentioned object, the present invention provides an application of a sulfur-nitrogen-phosphonate flotation collector, and the specific method is: applying a sulfur-nitrogen-phosphonate compound having a structure of formula (1) to at least one ore containing rare earth, niobium, scandium, copper, silver or gold minerals, and flotation recovering valuable metals;

[0012]

[0013] Wherein, R1, R2 are one or two selected from hydrogen atom, alkyl, cycloalkyl, aryl, polymer skeleton and heterocycle; R3 is alkylene, alkenylene, R1, R2, N or alkoxy ether group having the structure of formula (2); R4 is alkyl group having 4 to 8 carbon atoms;

[0014] RO-

[0015] Formula (2)

[0016] Wherein, R is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a polymer skeleton or a heterocycle.

[0017] The sulfur-nitrogen-phosphonate compounds of the present invention can be prepared by reacting the corresponding dithiocarbamate with allyl chloride at low temperature (<20° C.) to obtain mercaptopropylene, which is then reacted with phosphorus pentachloride at high temperature (>40° C.), and the obtained product is further reacted with the corresponding alcohol such as n-butanol and hydrolyzed to obtain the obtained product.

[0018] Preferably, R1 is propyl, butyl or hexyl, R3 is heptyl, nonyl or propenyl, and R4 is butyl, hexyl or octyl.

[0019] Specifically, the application method comprises the following steps:

[0020] S1. An ore containing at least one of rare earth, niobium, scandium, copper, silver and gold is crushed and slurried to obtain a slurry;

[0021] S2. Adding a flotation agent to the ore pulp obtained in step S1 to perform flotation, and collecting the flotation concentrate.

[0022] Preferably, the pH of the slurry is 4-12.

[0023] Preferably, based on the slurry volume, the dosage of the flotation collector is 1×10 -5 mol / L.

[0024] Through the above technical solution, the present invention achieves the following beneficial effects:

[0025] The present invention applies sulfur-nitrogen-phosphonate compounds to the flotation capture of valuable metals in minerals for the first time, and is particularly suitable for the enrichment and recovery of valuable metals in ores containing rare earth, niobium, copper, silver or gold minerals, and can improve the recovery rate of valuable metals compared with existing commonly used collectors. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The effect of slurry pH on the recovery rate of bastnaesite in Example 1 of the present invention;

[0027] Figure 2The effect of slurry pH on malachite recovery in Example 2 of the present invention;

[0028] Figure 3 This is the infrared spectrum of butyl di-n-ethylthiocyanate;

[0029] Figure 4 Butyl di-n-ethylthiocyanate 1 H NMR spectra;

[0030] Figure 5 Butyl di-n-ethylthiocyanate 31 P NMR spectrum. DETAILED DESCRIPTION

[0031] The specific implementation of the present invention is described in detail below in conjunction with the examples. It should be understood that the specific implementation described herein is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0032] All parts and percentages in the examples are by mass unless otherwise specified. The flotation collection process of the minerals in the examples is a conventional process, except that the di-n-ethylthiocyanate propenylphosphonate compound of the present invention is used to replace the conventional collector.

[0033] Example 1

[0034] The fluorocarbon cerium ore was crushed to a particle size of -0.076 mm to +0.038 mm, and the pH of the slurry was adjusted to about 5.5, about 6, about 7, about 8, about 9, about 10, and about 11, respectively. Di-n-ethylthiocyanate butyl phosphonate (its infrared spectrum, 1 H NMR and 31 P NMR Figure 3-Figure 5 As shown), at a concentration of 1×10 -5 mol / L, the concentration of methyl isobutyl carbinol (MIBC) was 15 mg / L, and the N2 gas flow rate was 200 mL / min. The pulp was floated for 3 minutes. The results are as follows Figure 1 As shown, when the pH value of the slurry is about 7, the flotation recovery rate of bastnaesite reaches 92.62%.

[0035] Example 2

[0036] The malachite was crushed to a particle size of -0.076 mm to +0.038 mm, and the pH of the slurry was adjusted to about 5, about 6, about 7, about 8, about 9, about 10, and about 11, respectively. Di-n-ethylthiocyanate was added to the butyl propenylphosphonate at a concentration of 1×10 -5mol / L, the concentration of methyl isobutyl carbinol (MIBC) was 15 mg / L, and the N2 gas flow rate was 200 mL / min. The pulp was floated for 3 minutes. The results are as follows Figure 2 As shown, when the pH value of the slurry is about 7.5, the flotation recovery rate of bastnaesite reaches 85.23%.

[0037] The preferred implementation modes of the present invention are described in detail above in combination with the embodiments; however, the present invention is not limited to the specific details in the above implementation modes. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical scheme of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0038] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0039] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. An application of a sulfur-nitrogen-phosphonate flotation collector, characterized in that: Applying a sulfur-nitrogen-phosphonate compound having a structure of formula (1) to at least one ore containing rare earth, niobium, scandium, copper, silver or gold minerals to flotation and recover the valuable metals; Formula (1) Wherein, R1, R2 are one or two selected from hydrogen atom, alkyl, cycloalkyl, aryl, polymer skeleton and heterocycle; R3 is alkylene, alkenylene, R1, R2, N or alkoxy ether group having the structure of formula (2); R4 is alkyl group having 4 to 8 carbon atoms; Formula (2) Wherein, R is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a polymer skeleton or a heterocycle.

2. The use of the sulfur-nitrogen-phosphonate flotation collector according to claim 1, characterized in that: R1 is propyl, butyl or hexyl, R3 is heptyl or nonyl, and R4 is butyl, hexyl or octyl.

3. The use of the sulfur-nitrogen-phosphonate flotation collector according to claim 1 or 2, characterized in that: The following steps are involved: S1. An ore containing at least one of rare earth, niobium, scandium, copper, silver and gold is crushed and slurried to obtain a slurry; S2. Adding a flotation collector to the ore pulp obtained in step S1 to perform flotation, and collecting the flotation concentrate.

4. The use of the sulfur-nitrogen-phosphonate flotation collector according to claim 3, characterized in that: In step S1, the pH of the slurry is 4-12.

5. The use of the sulfur-nitrogen-phosphonate flotation collector according to claim 3, characterized in that: In step S2, based on the slurry volume, the dosage of the flotation collector is 1×10 -5 mol / L.

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