Combined collecting agent for flotation of zinc oxide ore in sulfide flotation tailings and application of combined collecting agent

Abstract

The invention relates to the technical field of beneficiation reagents, in particular to a combined collecting agent for flotation of zinc oxide ore in sulfide flotation tailings and application of the combined collecting agent. The invention aims to provide the combined collecting agent aiming at zinc oxide ore with few surface active sites in sulfide flotation tailings, the combined collecting agent is applied to actual flotation production, through the flotation process of two times of roughing, one time of scavenging and one time of concentration, the combined collecting agent is added according to a specific amount in the two times of roughing and one time of scavenging, and the flotation efficiency is improved. And the active sites on the surface of the zinc oxide ore are preferentially adsorbed, so that the zinc ore can be adsorbed and enriched, the zinc grade of the zinc concentrate is improved, and the zinc recovery rate is increased.

Description

Technical Field

[0001] The present invention relates to the technical field of beneficiation reagents, and particularly relates to a combined collector for flotation of zinc oxide ore in sulfide flotation tailings and its application. Background Art

[0002] Zinc oxide ore is an important source of zinc metal, and zinc is widely used in fields such as metallurgy, chemical industry, and batteries. Sulfide flotation tailings often contain low-grade and highly oxidized zinc oxide minerals, which have a dense crystal structure and few surface active sites, making it difficult for collectors to adsorb. Recovering zinc from it through flotation can improve the comprehensive utilization rate of mineral resources and extend the service life of the mine.

[0003] In the prior art, a combined collector has been proposed for flotation of zinc oxide ore. This combined collector includes 60 - 95 wt.% of fatty acid type, 0 - 10 wt.% of hydroxamic acid type, and 5 - 35 wt.% of mercaptobenzothiazole. However, the proportion of fatty acid type in this combined collector is relatively large, and its non-polar hydrocarbon chain structure is prone to physical adsorption with carbonate or silicate gangue minerals in the ore. When the zinc grade of the raw ore is low (<3%) and the zinc oxidation rate is high, the physical adsorption will be aggravated, reducing the adsorption ability for zinc oxide ore with few surface active sites; therefore, when collecting zinc oxide ore with few surface active sites, the collecting ability of this combined collector is insufficient, resulting in a decrease in the enrichment ratio of zinc concentrate and a significant decrease in zinc recovery rate.

[0004] Therefore, for zinc oxide ore with few surface active sites in sulfide flotation tailings, focusing on low-grade and highly oxidized zinc oxide resources and developing corresponding flotation collectors to improve the zinc grade of zinc concentrate and the zinc recovery rate is a powerful measure to ensure the zinc resource advantage in China.

[0005] The above content is only used to assist in understanding the technical solution of the present invention and does not represent an admission that the above content is prior art. Summary of the Invention

[0006] The present invention aims at zinc oxide ore with few surface active sites in sulfide flotation tailings, proposes a combined collector, and applies the combined collector to actual production. Through a flotation process of two rough selections - one scavenging - one cleaning, the combined collector is added in a specific amount during the two rough selections and one scavenging to synergistically enhance the surface hydrophobicity of minerals, preferentially adsorb the surface active sites of zinc oxide ore, so that zinc minerals can be adsorbed and enriched, thereby improving the zinc grade of zinc concentrate and the zinc recovery rate.

[0007] To achieve the above object, on the one hand, the present invention provides a combined collector for flotation of zinc oxide ore in sulfide flotation tailings, and the combined collector includes collector A and collector B; Collector A is any one of butyl xanthate and fatty acid salts; The collector B is any one or any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate.

[0008] Optionally, the mass ratio of the collector A to the collector B is (2:1)-(5:2).

[0009] Optionally, when the collector B is composed of any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate, the mass ratio of the two components is (2:3)-(1:1).

[0010] Optionally, the fatty acid salt is sodium oleate.

[0011] On the other hand, a flotation method for zinc oxide ore in sulfide flotation tailings is provided. The flotation method includes the following steps: S1, grinding the zinc oxide ore to obtain a ground pulp with a mass concentration of 15%-20%; The zinc oxide ore is sulfide flotation tailings; S2, rough selection I: adding an activator, a regulator, the above-mentioned combined collector, and a frother to the ground pulp obtained in S1 in sequence and then performing flotation to obtain a rough selection I concentrate and a rough selection I tailings; S3, rough selection II: adding the above-mentioned combined collector and a frother to the rough selection I concentrate obtained in S2 in sequence and then performing flotation to obtain a rough selection II concentrate and a rough selection II tailings; S4, cleaning I: mixing the rough selection I concentrate obtained in S3 and the rough selection II concentrate obtained in S4 and then performing flotation to obtain a final zinc concentrate and a cleaning I tailings; The cleaning I tailings are returned to S3 for rough selection I again; S5, scavenging I: adding the above-mentioned combined collector and a frother to the rough selection II tailings obtained in S4 in sequence and then performing flotation to obtain a scavenging I concentrate and a scavenging I tailings; The scavenging I tailings are the final tailings; The activator is sodium sulfide; the regulator is sodium silicate; the frother is pine oil.

[0012] Optionally, based on the mass of the original ore, the addition amount of the activator in S2 is 900 g / t, the addition amount of the regulator is 200 g / t, the addition amount of the combined collector is 60 g / t, and the addition amount of the frother is 10 g / t.

[0013] Optionally, based on the mass of the original ore, the addition amount of the combined collector in S3 is 30 g / t, and the addition amount of the frother is 5 g / t.

[0014] Optionally, based on the mass of the original ore, the addition amount of the combined collector in S5 is 10 g / t, and the addition amount of the frother is 5 g / t.

[0015] On the other hand, an application of the combined collector as described above in the flotation of zinc oxide ore in sulfide flotation tailings is proposed.

[0016] Principle of the invention: In the process of flotation of zinc oxide ore in sulfide flotation tailings, the combined action of collector A (sodium butyl xanthate, fatty acid salts) and collector B (sodium ethyl xanthate, amyl xanthate, isoamyl xanthate) is mainly reflected in two aspects: synergistically enhancing the hydrophobicity of the mineral surface and preferentially adsorbing active sites, thereby improving the collecting ability of the combined collector.

[0017] Synergistically enhancing the hydrophobicity of the mineral surface: The fatty acid salt (such as oleate) in collector A undergoes chemisorption with metal ions (such as Zn²⁺) on the surface of zinc oxide minerals through carboxylic acid groups to form a stable metal soap layer, while xanthates (sodium butyl xanthate) will undergo chemical reactions with metal ions (such as Cu²⁺, Pb²⁺, Zn²⁺, etc.) on the mineral surface to form insoluble metal xanthates. These salts are adsorbed on the mineral surface, making the mineral hydrophobic. At the same time, due to their longer carbon chain structures, sodium ethyl xanthate and amyl / isoamyl xanthate in collector B can form a dense double-layer adsorption structure on the mineral surface, filling the adsorption gaps of collector A and significantly enhancing the overall hydrophobic effect.

[0018] Preferentially adsorbing active sites: Due to the stronger steric hindrance effect of the branched-chain structure, amyl / isoamyl xanthate in collector B can preferentially adsorb on the active sites of zinc oxide minerals, inhibiting the collection of gangue minerals (such as calcite, dolomite). Therefore, high-oxidation-rate zinc oxide ores containing calcite and dolomite can also be efficiently collected, broadening the range of minerals on which it acts.

[0019] The embodiments of the present invention provide a combined collector for the flotation of zinc oxide ore in sulfide flotation tailings and its application, which at least have the following beneficial effects: 1. The combined collector for the flotation of zinc oxide ore in sulfide flotation tailings and its application provided by this application propose a combined collector and apply it to actual production. Through a flotation process of two rough selections - one scavenging - one cleaning, the combined collector is added in a specific amount during the two rough selections and one scavenging, synergistically enhancing the hydrophobicity of the mineral surface and preferentially adsorbing the active sites on the surface of zinc oxide ore, enabling zinc minerals to be adsorbed and enriched. This method not only improves the zinc grade of zinc concentrate but also improves the zinc recovery rate.

[0020] 2. In the flotation stage, by precisely controlling the flotation time, while taking into account the flotation efficiency, this application avoids the decrease in zinc grade and zinc recovery rate caused by too long flotation time.

[0021] 3. By adding the regulator sodium silicate, the adhesion between mineral particles and bubbles is enhanced, the characteristics and stability of the flotation foam are adjusted, and the zinc recovery rate is increased.

[0022] 4. The flotation of zinc oxide ore in sulfide flotation tailings can be achieved by the flotation process of two rough selections - one scavenging - one cleaning in this application. The process is simple and suitable for large-scale industrial production. Brief Description of the Drawings

[0023] Figure 1 It is a schematic flow chart of the present invention.

[0024] The realization, functional characteristics and advantages of the object of the present invention will be further described with reference to the embodiments and the accompanying drawings. Detailed Embodiments

[0025] To better understand the above technical solutions, the exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. Although the exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided so that the present disclosure can be more thoroughly understood and the scope of the present disclosure can be fully conveyed to those skilled in the art.

[0026] Based on the above description, an embodiment of a combined collector for the flotation of zinc oxide ore in sulfide flotation tailings and its application is proposed.

[0027] First Embodiment Prepare a combined collector: Collector A is any one of butyl xanthate and fatty acid salts; Collector B is any one or any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate; The mass ratio of Collector A to Collector B is (2:1)-(5:2); When Collector B is composed of any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate, the mass ratio of the two components is (2:3)-(1:1).

[0028] Second Embodiment After the flotation separation of sulfide ore in a certain oxygen-sulfur mixed lead-zinc ore in Yunnan, the resulting tailings are zinc oxide ore with low grade and high oxidation rate. The present invention explores with this zinc oxide ore as the raw ore, where the Zn grade is 0.9%-2.5%, the zinc oxidation rate is 15%-20%, and the mass percentage of smithsonite and willemite in zinc oxide minerals is greater than 60%. The specific flotation process includes the following steps: S1. Prepare a combined collector: Collector A is any one of butyl xanthate and fatty acid salts; Collector B is any one or any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate; The mass ratio of collector A to collector B is (2:1)-(5:2); When collector B is composed of any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate, the mass ratio of the two components is (2:3)-(1:1); The fatty acid salt is sodium oleate; S2, Grind the zinc oxide ore to obtain a ground pulp with a mass concentration of 15%-25%; S3, Rough selection I: Add an activator, a regulator, a combined collector, and a frother to the ground pulp obtained in S2 in sequence, and obtain a rough selection I concentrate and a rough selection I tailing; The specific steps include: Add the activator sodium sulfide to the ground pulp obtained in S2. The addition amount is 900 g / t based on the mass of the original ore, and carry out pulp conditioning for 3 minutes to obtain pulp A; add the regulator sodium silicate to the obtained pulp A. The addition amount is 200 g / t based on the mass of the original ore, and carry out pulp conditioning for 3 minutes to obtain pulp B; add the combined collector to the obtained pulp B. The addition amount is 60 g / t based on the mass of the original ore, and carry out pulp conditioning for 3 minutes to obtain pulp C; add the frother pine oil to the obtained pulp C. The addition amount is 10 g / t based on the mass of the original ore, and carry out pulp conditioning for 1 minute to obtain pulp D; inflate the pulp D and carry out flotation scraping to obtain a rough selection I concentrate and a rough selection I tailing; S4, Rough selection II: Add a combined collector and a frother to the rough selection I concentrate obtained in S3 in sequence and then carry out flotation to obtain a rough selection II concentrate and a rough selection II tailing; The specific steps include: Add the combined collector to the rough selection I concentrate obtained in S3. The addition amount is 30 g / t based on the mass of the original ore, and carry out pulp conditioning for 3 minutes, then add the frother pine oil. The addition amount is 5 g / t based on the mass of the original ore, and carry out pulp conditioning for 1 minute, and then carry out inflating flotation scraping to obtain a rough selection II concentrate and a rough selection II tailing; S5, Scavenging I: Mix the rough selection I concentrate obtained in S3 and the rough selection II concentrate obtained in S4 and then carry out flotation to obtain the final zinc concentrate and a scavenging I tailing; The scavenging I tailing is returned to S3 for rough selection I again; S6, Scavenging II: Add a combined collector and a frother to the rough selection II tailing obtained in S4 in sequence and then carry out flotation to obtain a scavenging II concentrate and a scavenging II tailing; The specific steps include: Add the combined collector to the rough selection II tailing obtained in S4. The addition amount is 10 g / t based on the mass of the original ore, and carry out pulp conditioning for 3 minutes, then add the frother pine oil. The addition amount is 5 g / t based on the mass of the original ore, and carry out pulp conditioning for 1 minute, and then carry out inflating flotation scraping to obtain a scavenging II concentrate and a scavenging II tailing; The scavenging II tailing is the final tailing.

[0029] In the above steps, during flotation and foam scraping, the rotational speed is 1600 - 2000 r / min; during aeration, the aeration rate is 1200 - 4000 L / h.

[0030] The third embodiment Compared with the second embodiment, all other conditions remain completely unchanged. Only the collector A and collector B are fixed reagents and fixed ratios, and zinc oxide ores (feed ores) with different grades are subjected to flotation. The test schemes and test results are as follows in the table.

[0031] Scheme 1: In the feed ore, the Zn grade is 1.65%, collector A is butyl xanthate, collector B is isoamyl xanthate, and the mass ratio of collector A to collector B is 2:1; Scheme 2: In the feed ore, the Zn grade is 1.80%, collector A is butyl xanthate, collector B is isoamyl xanthate, and the mass ratio of collector A to collector B is 4:3; Scheme 3: In the feed ore, the Zn grade is 0.90%, collector A is butyl xanthate, collector B is isoamyl xanthate, and the mass ratio of collector A to collector B is 5:2; Scheme 4: In the feed ore, the Zn grade is 1.86%, collector A is sodium oleate, collector B is isoamyl xanthate, and the mass ratio of collector A to collector B is 5:2; Scheme 5: In the feed ore, the Zn grade is 1.77%, collector A is sodium oleate, collector B is isoamyl xanthate, and the mass ratio of collector A to collector B is 3:2; Scheme 6: In the feed ore, the Zn grade is 1.43%, collector A is butyl xanthate, collector B is a reagent obtained by mixing isoamyl xanthate and sodium ethyl xanthate in a ratio of 2:1, and the mass ratio of collector A to collector B is 2:1; Scheme 7: In the feed ore, the Zn grade is 1.35%, collector A is butyl xanthate, collector B is a reagent obtained by mixing isoamyl xanthate and sodium ethyl xanthate in a ratio of 2:3, and the mass ratio of collector A to collector B is 2:1; Table 1 The yields, Zn grades and recovery rates of concentrate and tailings in different schemes The first comparative example The test purpose of this comparative example is to study the synergistic collecting ability of collector A and collector B; Compared with Scheme 1 in the third embodiment, all other conditions remain completely unchanged. In the combined collector, only collector A is added, and collector B is no longer added; Scheme 1: Collector A is butyl xanthate, collector B is isoamyl xanthate, the mass ratio of collector A to collector B is 2:1, and the addition amount of the combined collector is 60 g / t.

[0032] In this experiment: The collector A is butyl xanthate, and the addition amount of collector A is 60 g / t.

[0033] Table 2 Yields of concentrate and tailings, grades and recovery rates of Zn in different schemes Conclusion: According to the results analysis of Scheme 1 and Comparative Example 1 in the above table, the grade of zinc in the zinc oxide concentrate of Scheme 1 is 5.95 percentage points higher than that of Comparative Example 1, and the zinc metal recovery rate is 10 percentage points higher. Therefore, compared with the single butyl xanthate collector and the combined collector of butyl xanthate and isoamyl xanthate, the combined collector has stronger collecting ability. The use of the combined collector can enhance the collecting effect on the target minerals and improve the flotation performance.

[0034] Second Comparative Example The purpose of this comparative example experiment is to study the synergistic collecting ability of collector A and collector B; Compared with Scheme 1 in the third embodiment, with all other conditions remaining completely unchanged, only collector B is added to the combined collector, and collector A is no longer added; Scheme 1: The collector A is butyl xanthate, the collector B is isoamyl xanthate, the mass ratio of collector A to collector B is 2:1, and the addition amount of the combined collector is 60 g / t.

[0035] In this experiment: The collector B is isoamyl xanthate, and the addition amount of collector B is 60 g / t.

[0036] Table 3 Yields of concentrate and tailings, grades and recovery rates of Zn in different schemes Conclusion: According to the results analysis of Scheme 1 and Comparative Example 2 in the above table, the grade of zinc in the zinc oxide concentrate of Scheme 1 is 4 percentage points higher than that of Comparative Example 2, and the zinc metal recovery rate is 4 percentage points higher. Therefore, compared with the single isoamyl xanthate collector and the combined collector of butyl xanthate and isoamyl xanthate, the combined collector has stronger collecting ability. The use of the combined collector can enhance the collecting effect on the target minerals and improve the flotation performance.

[0037] Third Comparative Example This comparative example is an optimization ratio experiment.

[0038] The purpose of this comparative example experiment is to study the mass ratio of collector A to collector B and optimize the best ratio; Compared with Scheme 1 in the third embodiment, with all other conditions remaining completely unchanged, only the mass ratio of collector A to collector B is changed, and the test results are as follows; Table 4 Yields of concentrate and tailings, grades and recovery rates of Zn in different schemes Conclusion: From the comparative test analysis of the mass ratio of collector A and collector B in the above table, the flotation effects of the two collectors with different mass ratios on the target minerals are different. When the dosage of collector A is higher than that of collector B, the flotation effect is the best. The optimal mass ratio of collector A to collector B is (2:1)-(5:2).

[0039] Fourth Comparative Example This comparative example is an optimization ratio experiment. When collector B is composed of any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate, the mass ratio of the two components is (2:3)-(1:1).

[0040] Scheme 6: In the feed ore, the Zn grade is 1.43%, collector A is butyl xanthate, collector B is a reagent obtained by mixing isoamyl xanthate and sodium ethyl xanthate in a ratio of 2:1, and the mass ratio of collector A to collector B is 2:1; Compared with Scheme 6 in the third embodiment, with all other conditions remaining completely unchanged, only the mass ratio of collector B is changed. The test results are as follows; Table 5 Yields, Zn grades, and recovery rates of concentrate and tailings in different schemes Conclusion: From the analysis of Scheme 6 and the comparative example in the above table, it can be seen that changing the mass ratio of collector B has different flotation effects on the target zinc minerals. When the mass ratio of collector B is (2:3)-(1:1), the recovery rate of the target zinc minerals is greater than 60%. From the comparison of the grades and recovery rates of zinc oxide concentrate, this mass ratio is the optimal collector mass ratio.

[0041] It should be noted that although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications once they know the basic creative concept. Therefore, the appended claims are intended to be construed as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.

[0042] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims

1. A combined collector for flotation of zinc oxide ore in sulfide flotation tailings, characterized in that, The combined collector includes collector A and collector B; The collector A is any one of butyl xanthate and fatty acid salts; The collector B is any one or any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate.

2. The combined collector according to claim 1, characterized in that, The mass ratio of the collector A to the collector B is (2:1)-(5:2).

3. The combined collector according to claim 1 or 2, characterized in that, When the collector B is composed of any two of sodium ethyl xanthate, amyl xanthate, and isoamyl xanthate, the mass ratio of the two components is (2:3)-(1:1).

4. The combined collector according to claim 1, characterized in that, The fatty acid salt is sodium oleate.

5. A flotation method for zinc oxide ore in sulfide flotation tailings, characterized in that, The flotation method includes the following steps: S1. Grind the zinc oxide ore to obtain a ground ore pulp with a mass concentration of 15%-20%; The zinc oxide ore is a sulfide flotation tailing; S2. Rough selection I: Add an activator, a regulator, the combined collector as claimed in claim 1, and a foaming agent to the ground ore pulp obtained in S1 in sequence, and then perform flotation to obtain a rough selection I concentrate and a rough selection I tailing; S3. Rough selection II: Add the combined collector and a foaming agent to the rough selection I concentrate obtained in S2 in sequence, and then perform flotation to obtain a rough selection II concentrate and a rough selection II tailing; S4. Fine selection I: Mix the rough selection I concentrate obtained in S3 and the rough selection II concentrate obtained in S4, and then perform flotation to obtain a final zinc concentrate and a fine selection I tailing; The fine selection I tailing is returned to S3 for rough selection I again; S5. Scavenging I: Add the combined collector and a foaming agent to the rough selection II tailing obtained in S4 in sequence, and then perform flotation to obtain a scavenging I concentrate and a scavenging I tailing; The scavenging I tailing is the final tailing; The activator is sodium sulfide; the regulator is water glass; the foaming agent is pine oil.

6. The flotation method according to claim 5, characterized in that, Based on the mass of the original ore, the addition amount of the activator in S2 is 900 g / t, the addition amount of the regulator is 200 g / t, the addition amount of the combined collector is 60 g / t, and the addition amount of the foaming agent is 10 g / t.

7. The flotation method according to claim 5, wherein Based on the mass of the original ore, the addition amount of the combined collector in S3 is 30 g / t, and the addition amount of the foaming agent is 5 g / t.

8. The flotation method according to claim 5, characterized in that Based on the mass of the original ore, the addition amount of the combined collector in S5 is 10 g / t, and the addition amount of the foaming agent is 5 g / t.

9. Application of the combined collector as claimed in claim 1 in the flotation of zinc oxide ore in sulfide flotation tailings.

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