Preparation method and application of fine-grained copper sulfide ore collector

Abstract

The application provides a preparation method and application of a micro-fine particle sulfide copper ore collector, which uses styrene and allyl thiourea as main reaction monomer raw materials, and synthesizes a high molecular polymer through free radical initiation catalysis, has a certain flocculation effect on micro-fine particle minerals; meanwhile, the thiourea group (-NHCSNH2) existing on the molecular chain has selective adsorption effect on micro-fine particle sulfide copper ore, and can realize high-efficiency recovery of the micro-fine particle sulfide copper ore. The aforementioned micro-fine particle sulfide copper ore collector has strong collecting capacity on sulfide ores, and meanwhile, has a synergistic collecting effect when used together with a conventional sulfide copper collector, so that the micro-fine particle sulfide copper ore flotation recovery rate can be significantly improved. In addition, the micro-fine particle sulfide copper ore collector has cheap and easily obtained raw materials, a simple preparation method, is suitable for continuous large-scale production, and has high popularization and application value.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, specifically to a method for preparing and applying a fine-grained copper sulfide ore collector. Background Technology

[0002] Copper is one of my country's strategic minerals. As a major metallic mineral product for the national economy and people's livelihood, it can be used in many fields of industrial and agricultural production. China's copper consumption accounts for nearly 50% of the world's total, making it the world's largest importer of copper resources.

[0003] Copper resources are most widely distributed in nature as copper sulfide minerals, accounting for about 70%, and currently, copper sulfide minerals account for about four-fifths of mined copper resources. With the continuous exploitation of copper resources, copper ore resources are becoming increasingly scarce, fine-grained, and complex. High-grade, easily beneficiated copper ore is very limited, while the proportion of low-grade, fine-grained copper resources is increasing. Statistics show that approximately one-sixth of global copper resources are lost in tailings each year due to their fine particle size, making flotation impossible. Because fine-grained copper sulfide minerals have small particle sizes (<15μm) and large specific surface areas, conventional copper sulfide mineral collectors, such as xanthates, dioxins, sulfur-nitrogen compounds, and sulfur-amino esters, generally suffer from low flotation recovery rates. Therefore, developing a novel flotation collector for fine-grained copper sulfide minerals to achieve efficient recovery is of great significance and value for the efficient utilization of copper resources. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a method for preparing and applying a fine-particle copper sulfide ore collector.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A fine-particle copper sulfide ore collector having the structure shown in Formula I:

[0007]

[0008] The present invention also provides a method for preparing the above-mentioned fine-particle copper sulfide ore collector, comprising the following steps:

[0009] S1. Styrene, surfactant and deionized water are mixed and reacted under nitrogen atmosphere and temperature of 60°C.

[0010] S2. Add catalyst and deionized water, and continue stirring the reaction at 60°C; then add styrene and allyl thiourea in batches, and continue stirring the reaction at 60-70°C. The light blue emulsion obtained after the reaction is complete is the fine-particle copper sulfide ore collector.

[0011] The equations for the above synthesis process are as follows:

[0012]

[0013] Furthermore, in step S1, the weight ratio of styrene to surfactant is 5:1, the volume ratio of deionized water to the total mass of styrene and surfactant is 150 mL / g, and the stirring reaction time is 0.5 h.

[0014] Further, in step S1, the surfactant is at least one of sodium dodecyl sulfonate and sodium dodecylbenzene sulfonate.

[0015] Further, in step S2, the catalyst is at least one of potassium persulfate, sodium persulfate, and azobisisobutyronitrile.

[0016] Furthermore, the weight ratio of styrene, catalyst and allyl thiourea added in step S2 is 1:0.02-0.045:0.08-0.34; the mass ratio of styrene added in step S1 to styrene added in step S2 is 1:9.

[0017] Furthermore, the peak molecular weight (MP) of the fine-particle copper sulfide ore collector is 30317, and the average molecular weight (Mn) is 14247.

[0018] The fine-grained copper sulfide ore collector described in this invention can be applied to the flotation of fine-grained copper ores. Furthermore, the fine-grained copper sulfide ore collector and the butyl xanthate collector are used in combination.

[0019] The beneficial effects of this invention are as follows:

[0020] (1) This invention provides a method for preparing and applying a collector for fine-grained copper sulfide ore. This type of collector has a strong ability to collect sulfide ore. At the same time, it has a synergistic collecting effect when used with conventional copper sulfide collectors, which can significantly improve the flotation recovery rate of fine-grained copper sulfide ore.

[0021] (2) The fine-particle copper sulfide ore collector provided by the present invention uses styrene and allyl thiourea as the main reactant monomer raw materials, and synthesizes a high molecular polymer through free radical initiation catalysis, which has a certain flocculation effect on fine-particle minerals; at the same time, there are thiourea groups (-NHCSNH2) on the molecular chain, which have selective adsorption effect on fine-particle copper sulfide ore, and can realize the efficient recovery of fine-particle copper sulfide ore.

[0022] (3) The raw materials of the fine-particle copper sulfide ore collector of the present invention are inexpensive and readily available, the preparation method is simple, it is suitable for continuous large-scale production, and it has high promotion and application value. Attached Figure Description

[0023] Figure 1The infrared spectrum is shown for the fine-particle copper sulfide ore collector prepared in Example 1 of this invention.

[0024] Figure 2 This is a molecular weight distribution diagram of the fine-particle copper sulfide ore collector prepared in Example 1 of the present invention. Detailed Implementation

[0025] The present invention will be further described below with reference to the accompanying drawings. It should be noted that this embodiment is based on the present technical solution and provides detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to this embodiment.

[0026] Example 1

[0027] Add 0.5g styrene, 0.1g sodium dodecyl sulfonate, and 90mL deionized water to a 250mL three-necked flask, and simultaneously purge with nitrogen gas and stir at 60℃ for 0.5h. Then add 0.1g potassium persulfate and 10mL deionized water and continue stirring at 60℃ for another 0.5h. Next, add 4.5g styrene and 1.5g allyl thiourea in batches and stir at 70℃ for 20h. The resulting pale blue emulsion is the collector for fine-grained copper sulfide ore.

[0028] Figure 1 The image shown is the infrared spectrum of the fine-particle copper sulfide ore collector prepared in this embodiment. Figure 1 It can be seen that the wavelength is 3460cm -1 The broad and strong absorption peak appearing at 2910 cm⁻¹ is the -NH stretching vibration absorption peak, with a wavelength of 2910 cm⁻¹. -1 The absorption peak appearing at this point is the absorption peak of the -CH2 stretching vibration, with a wavelength of 1650 cm⁻¹. -1 1600cm -1 The absorption peak appearing at 1108 cm⁻¹ is the absorption peak of the C=C stretching vibration of the benzene ring skeleton, with a wavelength of 1108 cm⁻¹. -1 The absorption peak appearing at [location] is an absorption peak of the -C=S stretching vibration. The infrared spectrum indicates that the compound contains functional groups such as amine, benzene ring, alkyl, and -C=S, which are consistent with the characteristic functional groups of the target compound's absorption peaks.

[0029] Figure 2 The figure shown is a molecular weight distribution diagram of the fine-particle copper sulfide ore collector prepared in this embodiment. From... Figure 2 It can be seen that the peak molecular weight MP of the fine-particle copper sulfide ore collector is 30317, and the average molecular weight Mn is 14247.

[0030] Example 2

[0031] Add 0.5g styrene, 0.1g sodium dodecylbenzenesulfonate, and 90mL deionized water to a 250mL three-necked flask, and simultaneously purge with nitrogen gas and stir at 60℃ for 0.5h. Then add 0.2g sodium persulfate and 10mL deionized water and stir at 60℃ for 0.5h. Next, add 4.5g styrene and 0.4g allyl sulfide in batches and stir at 70℃ for 12h. The light blue emulsion obtained after the reaction is complete is the collector for fine-grained copper sulfide ore.

[0032] Example 3

[0033] Add 0.5g styrene, 0.1g sodium dodecylbenzenesulfonate, and 90mL deionized water to a 250mL three-necked flask, and simultaneously purge with nitrogen gas and stir at 60℃ for 0.5h. Then add 0.15g potassium persulfate and 10mL deionized water and stir at 60℃ for 0.5h. Next, add 4.5g styrene and 1.0g allyl thiourea in batches and stir at 60℃ for 24h. The light blue emulsion obtained after the reaction is complete is the collector for fine-grained copper sulfide ore.

[0034] Example 4

[0035] For pure chalcopyrite minerals, with a grinding fineness of P80@3.56μm, a roughing test was conducted using the fine-grained copper sulfide ore collector from Example 1, compared with that of butyl xanthate collector. The results are shown in Table 1. Except for the type of collector, all other test conditions were the same. The test results in Table 1 show that, compared with butyl xanthate collector, the copper recovery rate of pure chalcopyrite minerals obtained by flotation using the fine-grained copper sulfide ore collector from Example 1 is slightly higher. Furthermore, when combined with butyl xanthate collector at a mass ratio of 1:1, the copper flotation recovery rate increased by 20.71 percentage points. This indicates that the fine-grained copper sulfide ore collector has a synergistic collecting effect with conventional copper sulfide collectors (butyl xanthate), which can significantly improve the flotation recovery rate of fine-grained chalcopyrite.

[0036] Table 1

[0037]

[0038] Example 5

[0039] A synthetic ore mixture was prepared by combining pure chalcopyrite minerals and gangue minerals (silica) at a mass ratio of 1:8.5. The grinding fineness was P80@3.50μm. Roughing flotation tests were conducted using the fine-grained copper sulfide ore collectors from Examples 1-3, combined with butyl xanthate collectors at a mass ratio of 1:1. The results, compared with those using butyl xanthate collectors alone, are shown in Table 2. Except for the type of collector, all other test conditions were the same. The test results in Table 2 indicate that the fine-grained copper sulfide ore collectors from Examples 1-3 have a synergistic collecting effect with butyl xanthate, which can significantly improve the flotation recovery rate of fine-grained chalcopyrite.

[0040] Table 2

[0041]

[0042] For those skilled in the art, various corresponding changes and modifications can be made based on the above technical solutions and concepts, and all such changes and modifications should be included within the protection scope of the claims of this invention.

Claims

1. The application of a fine-grained copper sulfide ore collector in the flotation of fine-grained copper sulfide ore, characterized in that, A combination of fine-grained copper sulfide ore collector and butyl xanthate collector; The fine-particle copper sulfide ore collector is prepared by the following steps: S1. Styrene, surfactant and deionized water are mixed and reacted under nitrogen atmosphere and temperature of 60°C. S2. Add catalyst and deionized water, and continue stirring the reaction at 60°C; then add styrene and allyl thiourea in batches, and continue stirring the reaction at 60-70°C. The light blue emulsion obtained after the reaction is completed is the fine-particle copper sulfide ore collector. Fine-grained copper sulfide ore collectors have the structure shown in Formula I: ； Formula I.

2. The application according to claim 1, characterized in that, In step S1, the weight ratio of styrene to surfactant is 5:1, the volume ratio of deionized water to the total mass of styrene and surfactant is 150 mL / g, and the stirring reaction time is 0.5 h.

3. The application according to claim 1, characterized in that, The surfactant mentioned in step S1 is at least one of sodium dodecyl sulfonate and sodium dodecylbenzene sulfonate.

4. The application according to claim 1, characterized in that, The catalyst mentioned in step S2 is at least one of potassium persulfate, sodium persulfate, and azobisisobutyronitrile.

5. The application according to claim 1, characterized in that, The weight ratio of styrene, catalyst and allyl thiourea added in step S2 is 1:0.02-0.045:0.08-0.34; the mass ratio of styrene added in step S1 to styrene added in step S2 is 1:

9.

6. The application according to claim 1, characterized in that, The peak molecular weight (MP) of the fine-grained copper sulfide ore collector is 30317, and the average molecular weight (Mn) is 14247.

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