A copper flotation frother and its preparation method

Abstract

This invention discloses a copper flotation collector and frother, the composition of which, in parts by weight, is as follows: 100 parts of N,N-dibutyldithiocarbamate propionitrile; 25-32 parts of n-butylxanthoxycarbamate propionitrile; 17-23 parts of O-butyl-N-butylthiocarbamate; 30-40 parts of aviation kerosene; and 10-15 parts of fusel oil. The copper flotation collector and frother of this invention possesses multiple excellent properties, including strong collecting power, good selectivity, and excellent frother properties. It exhibits particularly strong collecting ability for copper mineral intergrowths, resulting in superior copper concentrate grade, recovery rate, and impurity content compared to other collectors, while also reducing reagent dosage.

Description

Technical Field

[0001] This invention belongs to the field of collectors, and particularly relates to a copper flotation collector foaming agent and its preparation method. Background Technology

[0002] Copper sulfide ores are an important source of copper extraction, and currently, copper resource enrichment is mainly achieved through flotation. The properties of the ore are the fundamental factor determining the flotation process. Since the mineral types, crystallinity, and distribution characteristics of copper ores, the types of associated elements in the ore, the types of gangue minerals, and the floatability of gangue minerals all affect flotation, the beneficiation process often varies significantly for different copper ores. Highly efficient beneficiation reagents are one of the essential conditions for achieving refined beneficiation processes.

[0003] Despite extensive research and optimization efforts by mineral processing scientists over the years, resulting in the development of numerous novel copper sulfide ore collectors, the development of novel, highly effective, low-toxicity, easily degradable, and environmentally friendly collecting and frothing agents has remained a hot topic in copper sulfide ore beneficiation reagent research in recent years. Especially with years of mining and utilization, the properties of copper sulfide ores have gradually become more complex, characterized by complex mineral composition, close intercalation, and dense intergrowth. This has led to previously effective copper sulfide ore collectors gradually showing signs of inadequacy, thus prompting the industry to place increasing emphasis on the research and development of highly efficient copper sulfide collectors.

[0004] Nonionic ester collectors have polar molecules, but they do not ionize in water and have low solubility in water. They are more stable than xanthates in acidic media and can be directly added to the slurry. They exhibit superior selectivity and collecting ability compared to traditional xanthates and can increase the flotation velocity of the target mineral, which is beneficial for improving the recovery rate of copper minerals. They are a good type of collector for sulfide minerals. In addition, long-term research and practice in the industry have shown that the combined effect of multiple mineral processing reagents with collecting and foaming properties is often better than single-reagent flotation. For example, Chinese patent document CN111298982B discloses a high-efficiency copper-gold collector for pyrometallurgical copper smelting slag, which is composed of multiple mineral processing reagents, including xanthic acid collectors, N,N-diethyldithiocarbamate propionitrile, and O-alkyl-N-alkylthiocarbamate.

[0005] In current copper sulfide flotation production practices, due to the increasingly complex properties of ores, the xanthic acid collectors (xanthates) commonly used in the past often exhibit insufficient selectivity for copper minerals, resulting in high impurity content in the produced copper sulfide concentrate. N,N-diethyldithiocarbamate propionitrile (ester-105) is currently widely used, but the collecting power of short-chain ethyl groups is still relatively weak, and it is also somewhat unsuitable for some mining enterprises. Summary of the Invention

[0006] The purpose of this invention is to provide a copper flotation frother that is adapted to improve the collection effect of copper sulfide minerals and its preparation method.

[0007] The technical solution adopted in this invention is as follows:

[0008] A copper flotation collector foaming agent comprises the following components: 100 parts by weight of N,N-dibutyldithiocarbamate propionitrile; 25-32 parts by weight of n-butyl xanthoxycarbamate propionitrile; 17-23 parts by weight of O-butyl-N-isobutylthiocarbamate; 30-40 parts by weight of kerosene; and 10-15 parts by weight of fusel oil.

[0009] The N,N-dibutyldithiocarbamate propionitrile synthesized in this invention enhances its collecting power by increasing the alkyl group length during molecular design, i.e., replacing the ethyl group with a long-chain butyl group. This strengthens the interchain van der Waals forces. In the slurry system, it overcomes the shortcomings of thiocarbamates prepared with short-chain alkyl groups, which have insufficient binding to some difficult-to-collect copper sulfide minerals and poor collecting effect. Simultaneously, it helps reduce reagent dosage and has a positive impact on the stability of production system indicators and the long-term recycling of production water. The other component of this invention, O-butyl-N-isobutylthiocarbamate, compared to the current O-isopropyl-N-ethylthiocarbamate, strengthens the steric hindrance effect of the collector functional groups by increasing the carbon chain length and branching structure, thus improving its selectivity, water solubility, and low-temperature resistance, facilitating its application in production. Butyl xanthate propionitrile is a sulfide mineral collector with foaming properties and good selectivity. During the invention process, it was found that as a compound component, it can be used to lower the overall freezing point of the agent, making it easier to apply in lower temperature environments, which is beneficial for the addition and use of the agent on the production site and for long-term storage.

[0010] A method for preparing a copper flotation collector includes the following steps:

[0011] S1: Add 100 parts by weight of N,N-dibutyldithiocarbamate propionitrile to a stirred reactor, and start stirring.

[0012] S2: During stirring, slowly add 25-32 parts by weight of n-butyl xanthate propionitrile, 17-23 parts by weight of O-butyl-N-isobutyl thiocarbamate, 30-40 parts by weight of aviation kerosene, and 10-15 parts by weight of fusel oil in sequence. The temperature inside the reactor should not exceed 40°C during the addition of materials.

[0013] S3: After feeding, keep the temperature within the range of 30-60℃ for 1 hour to obtain the copper flotation collector foaming agent.

[0014] A further technical solution involves N,N-dibutyldithiocarbamate propionitrile being obtained by a Michael addition reaction of dibutylamine, carbon disulfide, and acrylonitrile in a 1:1:1 molar ratio, stirred at 30-60°C for 1 hour. The reaction principle described in equation 1 is as follows. Figure 1 The structural formula of N,N-dibutyldithiocarbamate propionitrile is as follows: Figure 2 .

[0015] A further technical solution involves the direct synthesis of O-butyl-N-butylthiocarbamate from n-butyl xanthate and isobutylamine in a 1:1 molar ratio, using nickel sulfate as a catalyst at 60-90°C. The reaction principle described in equation 2 above is as follows: Figure 3 The structural formula of O-butyl-N-butylthiocarbamate is as follows: Figure 4 The structural formula of butyl xanthate propionitrile is shown below. Figure 5 .

[0016] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0017] 1. The raw material ratios used in this invention are more rational, and the synthesis process is relatively simple, significantly reducing operational safety risks and production costs. The use of intermediate products from the chemical and food industries, such as fusel oils, in the pharmaceutical preparation process facilitates the efficient utilization of resources and materials.

[0018] 2. The copper sulfide ore collector foaming agent prepared by the present invention contains N,N-dibutyldithiocarbamate propionitrile. Its long-chain (and branched) alkyl structure, compared with the traditional short-chain ethyl structure, binds more tightly to some copper sulfide minerals that are difficult to bind with polar agents, resulting in a more significant collecting effect. The combination of the two is more stable in the slurry system.

[0019] 3. The copper sulfide ore collector frothing agent prepared by this invention is a brownish-red oily liquid with a slight fishy smell. It is partially soluble in water, safe and environmentally friendly, easy to use, and readily applicable in industrial settings. It combines the advantages of strong collecting power and good selectivity, and also has frothing properties. It not only has a strong collecting ability for copper mineral intergrowths and good flotation technical indicators, but also effectively reduces the amount of reagent used in practical applications, which is beneficial for controlling production costs.

[0020] 4. The copper sulfide ore collector frother prepared by this invention can fully leverage the synergistic effect among various reagents during the flotation process. Especially considering the increasingly complex nature of copper sulfide ores and the higher requirements for collectors, it helps overcome the growing inadequacies of current collectors. The prepared copper sulfide ore collector frother possesses advantages such as good selectivity, strong collecting ability, and stable flotation froth, effectively reducing the impact of easily floatable gangue minerals such as serpentine and talc on copper mineral flotation, resulting in a good improvement and stabilization effect on beneficiation technical indicators. Comparative experimental studies on ore show that compared with the on-site reagent system, the copper grade and copper recovery rate in the copper concentrate of the prepared reagent scheme are improved, while the copper content in the tailings is reduced. Attached Figure Description

[0021] Figure 1 It is reaction formula 1;

[0022] Figure 2 It is the structural formula of N,N-dibutyldithiocarbamate propionitrile;

[0023] Figure 3 It is reaction formula 2;

[0024] Figure 4 It is the structural formula of O-butyl-N-butylthiocarbamate;

[0025] Figure 5 It is the structural formula of n-butyl xanthate propionitrile. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0027] like Figures 1-5 As shown;

[0028] Example 1:

[0029] A copper flotation collector foaming agent, the composition of which is expressed in parts by mass as follows: 100 parts of N,N-dibutyldithiocarbamate propionitrile; 32 parts of n-butyl xanthoxycarbamate propionitrile; 23 parts of O-butyl-N-isobutylthiocarbamate; 30 parts of aviation kerosene; 15 parts of fusel oil, and the compounding agent is represented as KY1.

[0030] Preparation method: Add 100 parts of N,N-dibutyldithiocarbamate propionitrile to a stirred reactor, start the stirrer and stir, then slowly add 32 parts of n-butyl xanthoxypropionitrile, 23 parts of O-butyl-N-isobutylthiocarbamate, 30 parts of aviation kerosene and 10 parts of fusel oil in sequence. The feeding temperature should not exceed 40℃. After the feeding is completed, keep the reaction at 30-60℃ for 1 hour to obtain the copper flotation collector foaming agent product.

[0031] Comparative mineral processing test: The copper beneficiation process in a certain copper mine consists of one roughing, three scavenging, and two cleaning processes. The collector is a mixture of ethyl xanthate and butyl xanthate, and the frother is 2... # The on-site copper concentrate beneficiation indicators fluctuate significantly, resulting in high reagent costs. Comparative tests based on comprehensive ore samples provided by the mine showed that the on-site reagent-based copper concentrate recovery rate was 87.75%. Replacing the on-site collector and frother with the synthesized collector and frother of this invention increased the copper grade of the resulting copper concentrate by 0.14% and the copper recovery rate by 0.94%. Therefore, for the copper ore from this mine, using the synthesized collector and frother of this invention as the copper flotation collector can significantly improve the copper recovery rate.

[0032] Table 1 Comparison of Experimental Results / %

[0033]

[0034] Example 2:

[0035] A copper flotation collector foaming agent, the composition of which is expressed in parts by mass as follows: 100 parts of N,N-dibutyldithiocarbamate propionitrile; 25 parts of n-butyl xanthoxycarbamate propionitrile; 17 parts of O-butyl-N-isobutylthiocarbamate; 40 parts of aviation kerosene; 10 parts of fusel oil, and the compounding agent is represented as KY2.

[0036] A method for preparing a copper flotation collector foaming agent involves adding 100 parts of N,N-dibutyldithiocarbamate propionitrile to a stirred reactor, stirring with a stirrer, and then slowly adding 25 parts of n-butyl xanthoxypropionitrile, 17 parts of O-butyl-N-isobutylthiocarbamate, 40 parts of aviation kerosene, and 10 parts of fusel oil in sequence. The addition temperature does not exceed 40°C. After the addition is completed, the mixture is kept at 30-60°C for 1 hour to obtain the copper flotation collector foaming agent product.

[0037] Comparative mineral processing test: A copper-lead-zinc mine used conventional collectors for copper flotation, but the flotation technical indicators were unsatisfactory. Therefore, a comparative test of copper flotation collectors was conducted. The results showed that the thiocarbamate Z-200 (O-isopropyl-N-ethylthiocarbamate) used on-site had a certain effect on copper collection, but the lead and zinc content in the copper concentrate was extremely high. In contrast, the collector-frothing agent scheme of this invention resulted in a concentrate with reduced lead and zinc content while maintaining the copper technical indicators. This indicates that the collector-frothing agent of this invention is suitable as a collector for this ore.

[0038] Table 2 Comparison of Experimental Results / %

[0039]

[0040] Example 3:

[0041] A copper flotation collector foaming agent, the composition of which is expressed in parts by mass as follows: 100 parts of N,N-dibutyldithiocarbamate propionitrile; 28 parts of n-butyl xanthoxycarbamate propionitrile; 21 parts of O-butyl-N-isobutylthiocarbamate; 34 parts of aviation kerosene; 12 parts of fusel oil, and the compounding agent is represented as KY3.

[0042] A method for preparing a copper flotation collector foaming agent involves adding 100 parts of N,N-dibutyldithiocarbamate propionitrile to a stirred reactor, stirring with a stirrer, and then slowly adding 28 parts of n-butyl xanthoxypropionitrile, 21 parts of O-butyl-N-isobutylthiocarbamate, 34 parts of aviation kerosene, and 12 parts of fusel oil in sequence. The addition temperature does not exceed 40°C. After the addition is completed, the reaction is maintained at 30-60°C for 1 hour to obtain the copper flotation collector foaming agent product.

[0043] Comparative mineral processing test: The copper flotation process of a certain copper mine consists of one roughing, three scavenging, and two cleaning stages. Ethylene sulfonate (N,N-diethyldithiocarbamate sodium salt) and 2... # Copper beneficiation was carried out on the oil. Experiments compared the flotation technical indicators of on-site reagent conditions, N,N-diethyldithiocarbamate propionitrile (ester-105), and the compound reagent KY3. The results showed that using the collector and frother of this invention as the copper mineral collector for this ore increased the copper grade in the copper concentrate by 0.64% and 0.47%, respectively, and increased the copper recovery rate by 2.19% and 1.11%, respectively, compared with the other two reagents. The experimental indicators of the compound reagent KY3 according to the invention were superior to other reagent schemes.

[0044] Table 3 Comparison of Experimental Results / %

[0045]

[0046] The present invention has been described in detail above, and the above description is only a preferred embodiment of the present invention.

Claims

1. A copper flotation collector frother characterized in that, The composition comprises the following components: 100 parts by mass of propyl nitrile N, N-dibutyl dithiocarbamate; 25-32 parts by mass of propyl nitrile n-butyl xanthate; 17-23 parts by mass of O-butyl-N-isobutyl thiuram disulfide; 30-40 parts by mass of kerosene; and 10-15 parts by mass of fusel oil.

2. A process for the preparation of a copper flotation collector, characterized by, The method comprises the following steps: S1: 100 parts by mass of propyl nitrile N, N-dibutyl dithiocarbamate is added into a stirring reaction kettle, and the stirring reaction kettle is started to stir. 3.S2: During the stirring process, 25-32 parts by mass of propyl nitrile n-butyl xanthate, 17-23 parts by mass of O-butyl-N-isobutyl thiuram disulfide, 30-40 parts by mass of aviation kerosene, and 10-15 parts by mass of fusel oil are slowly added in sequence, and the temperature in the stirring reaction kettle during the feeding process is not higher than 40℃, S3: After the feeding process is completed, the reaction is carried out at 30-60℃ for 1h, and a copper flotation collector and frother is obtained.

4. A process for the preparation of a copper flotation collector according to claim 2, characterized in that, The propyl nitrile N, N-dibutyl dithiocarbamate is obtained by Michael addition reaction of dibutylamine, carbon disulfide and propylene nitrile in a molar ratio of 1:1:1 at 30-60℃ for 1h.

5. A process for the preparation of a copper flotation collector according to claim 2, characterized in that, The propyl nitrile N, N-dibutyl dithiocarbamate is obtained by Michael addition reaction of dibutylamine, carbon disulfide and propylene nitrile in a molar ratio of 1:1:1 at 30-60℃ for 1h. The O-butyl-N-butyl thiuram disulfide is directly synthesized by using n-butyl xanthate and isobutylamine as raw materials, a molar ratio of 1:1, and nickel sulfate as a catalyst at 60-90℃.

6. A process for the preparation of a copper flotation collector according to claim 2, characterized in that, The propyl nitrile n-butyl xanthate is a transparent orange-yellow oil liquid, which is added as a finished product stock solution as one of the components.

Images