A lead-zinc flotation composite collector and its flotation process and application

Abstract

The present invention relates to a lead-zinc flotation composite collector and a flotation process and application thereof, belonging to the technical field of lead-zinc ore flotation. The composite collector of the present invention comprises a collector A, a collector B and a collector C, wherein the collector A is any one of ethyl xanthate and butyl xanthate, the collector B is any one of ethylthiocarbamate, ethylthiocarbamate and butylamine black medicine or any two thereof, and the collector C is any one of diphenylthiourea and ethylthiourea or any two thereof. The process and application of the composite collector of the present invention in lead-zinc ore flotation realize the recovery of lead-zinc ore through roughing-scavenging-cleaning operations. The present invention increases the collector adsorption amount on the surface of the lead-zinc ore, and can collect not only single sphalerite but also galena.

Description

Technical Field

[0001] The present invention belongs to the technical field of lead-zinc ore flotation, and in particular relates to a lead-zinc flotation composite collector and a flotation process and application thereof. Background Art

[0002] Lead and zinc are two important nonferrous metals widely used in batteries, electronics, machinery, solder, and radiation protection. Lead and zinc are primarily derived from polymetallic lead-zinc sulfide ores. With the rapid development of industry, the consumption of lead and zinc is increasing. The production of polymetallic lead-zinc sulfide ores is crucial to the development of the national economy. Therefore, improving the recovery of lead and zinc resources is of great significance.

[0003] Traditional collectors for lead-zinc ore flotation primarily include xanthates, black powders, and esters. However, for complex and difficult-to-separate ores, these agents often struggle to achieve optimal results. Xiao Jun et al. conducted beneficiation trials on a polymetallic ore in Yunnan using butyl xanthate and ethyl xanthate, but the results were poor selectivity and resulted in low lead grades. Liu Liping also conducted beneficiation trials on a lead-zinc ore in Haicheng using butyl xanthate + butylamine black powder compared to butyl xanthate. However, the results were severe foam entrainment, resulting in low grade and recovery. As can be seen from the above, the development of new flotation agents is necessary to achieve efficient flotation recovery rates for lead-zinc ores. Summary of the Invention

[0004] In order to overcome the problems existing in the background technology, the present invention provides a lead-zinc flotation composite collector with strong collecting ability, high selectivity and non-toxicity, which can effectively recover lead-zinc ores in sulfur concentrate.

[0005] To achieve the above object, the present invention is implemented through the following technical solutions:

[0006] The lead-zinc flotation composite collector includes collector A, collector B and collector C, wherein the collector A is any one of ethyl xanthate and butyl xanthate, the collector B is any one of ethyl thiocarbamate, ethyl thiocarbamate and butylamine black medicine or any two thereof, and the collector C is any one of diphenylthiourea and ethylthiourea or any two thereof, and the mass ratio of collector A, collector B and collector C is 1:1:1 to 6:3:2.

[0007] Furthermore, when the collector B is composed of any two of ethylthiocarbamate, ethylthiocarbamate, and butylamine black medicine, the mass ratio of the two components is 1:1 to 1:2.

[0008] Furthermore, when the collector C is composed of diphenylthiourea and ethylthiourea, the mass ratio of the two components is 1:1 to 1:4.

[0009] Furthermore, when the collector C is composed of diphenylthiourea and ethylthiourea, the mass ratio of the two components is 1:1 to 1:4.

[0010] Another object of the present invention is to provide a process for flotation of lead-zinc ore using a lead-zinc flotation composite collector, comprising the following steps:

[0011] (1) grinding the sulfur concentrate and adjusting the pulp concentration, then adding lime as an inhibitor, copper sulfate as an activator, a lead-zinc flotation composite collector, and a frother to the pulp for roughing operation to obtain roughing concentrate and roughing tailings;

[0012] (2) scavenging the roughing tailings, wherein the reagents added in the scavenging operation are copper sulfate as an activator and lead-zinc flotation composite collector to obtain scavenging concentrate and scavenging tailings;

[0013] (3) The roughing concentrate is subjected to a beneficiation operation to obtain a beneficiated concentrate and beneficiated tailings. The beneficiated tailings are combined with the scavenging concentrate and then returned to the roughing operation to form a closed loop.

[0014] Furthermore, in step (1), the sulfur concentrate is ground to -0.074 mm, accounting for 80% to 90%, and the pulp concentration is 30% to 40%.

[0015] Furthermore, the roughing operation takes 3 to 7 minutes, the sweeping operation is performed 1 to 2 times, each sweeping operation takes 1 to 3 minutes, and the fine selection operation is performed 1 to 2 times, each fine selection operation takes 1 to 2 minutes.

[0016] Furthermore, in the roughing operation, per ton of raw ore, the amount of lime added to the slurry is 2000-6000 g / t, the amount of copper sulfate is 100-500 g / t, and the amount of lead-zinc flotation composite collector is 40-150 g / t; in the scavenging operation, the amount of copper sulfate is 0-200 g / t, and the amount of lead-zinc flotation composite collector is 20-40 g / t; no reagent is added in the cleaning operation.

[0017] Furthermore, the present invention provides an application of a lead-zinc flotation composite collector in the flotation of lead-zinc ores.

[0018] The present invention is characterized in that when collector C is either diphenylthiourea or ethylthiourea, or a combination of both, the thiourea group in collector C can form a complex with lead-zinc ions, which is adsorbed on the mineral surface, enhancing the hydrophobicity of the lead-zinc ore and causing it to float. The C=S double bond in the thiourea breaks, generating new Pb-SCN. The S atom coordinates with the lead-zinc ore. Furthermore, when collector C is used in combination with collectors A and B, the concentration of nitrogen atoms in the solution is increased, changing the flotation environment in the solution and enhancing the collection effect. This also enhances the selectivity of the composite collector, which has a relatively weak collection effect on pyrite, and can be used for the comprehensive recovery of lead-zinc ore.

[0019] Beneficial effects of the present invention:

[0020] 1. The present invention is a composite collector. Compared with a single collector, the composite collector can increase the adsorption amount of the collector on the surface of the lead-zinc ore, and can not only collect single sphalerite, but also collect galena.

[0021] 2. The composite collector of the present invention has a strong ability to capture fine-particle ores. Traditional collectors have poor capture performance for fine-particle ores. The combined collector can enhance the hydrophobicity of fine-particle ores to a greater extent, increase their floatability, and strengthen the capture effect of fine-particle ores.

[0022] 3. The composite collector of the present invention is safe and non-toxic, easy to add in actual production, convenient to use, and highly stable. It can effectively capture fine-grained lead-zinc ores, making the secondary utilization of resources better, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 1 is a schematic diagram of the process flow of Example 1 of the present invention;

[0024] Figure 2 1 is a schematic diagram of the process flow of Example 2 of the present invention;

[0025] Figure 3 1 is a schematic diagram of the process flow of Example 3 of the present invention. DETAILED DESCRIPTION

[0026] In order to make the objectives, technical solutions and beneficial effects of the present invention more clear, preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings to facilitate understanding by technicians.

[0027] Example 1

[0028] A composite collector for lead and zinc flotation includes collector A, collector B, and collector C. Collector A is butyl xanthate, collector B is ethylthiocarbamide, and collector C is a mixture of diphenylthiourea and ethylthiourea, with the mass ratio of the two components being 1:1. The mass ratio of collector A to collector B to collector C is 6:3:2. Before use, these components are mixed uniformly in a predetermined amount and added.

[0029] The above combined collector is used for the recovery of lead-zinc ore in sulfur concentrate:

[0030] In the sulfur concentrate processed in this embodiment, the Pb grade is 0.74%, the Zn grade is 1.24%, the lead-containing minerals are mainly galena, and the zinc-containing minerals are mainly sphalerite.

[0031] Flotation conditions: Grind the sulfur concentrate to a grinding fineness of -0.074mm accounting for 90%, adjust the pulp mass concentration to 40%, then add the inhibitor lime (5000g / t) and stir for 3min, activator copper sulfate (400g / t) and stir for 3min, lead-zinc flotation composite collector (77g / t, including 42g / t of butyl xanthate, 21g / t of ethylthiocyanate, 7g / t of diphenylthiourea and ethylthiourea) and foaming agent 2# oil (20g / t) to the pulp, stir for 3min and then carry out roughing operation. The selection time is 7 minutes to obtain rougher concentrate and rougher tailings. The rougher tailings are subjected to another scavenging operation (scavenging time is 3 minutes). 200g / t of copper sulfate and 35g / t of lead-zinc flotation composite collector are added to the scavenging to obtain scavenged concentrate and scavenged tailings. The rougher concentrate is subjected to a concentrating operation (concentrating time is 2 minutes). No reagent is added to the concentrating to obtain concentrating concentrate and concentrating tailings. The concentrating tailings are combined with the scavenging concentrate and returned to the roughing operation to form a closed loop. The concentrating concentrate is a lead-zinc mixed concentrate product. Its recovery rate and grade are shown in Table 1. The process flow chart is as follows: Figure 1 shown.

[0032] Example 2

[0033] A composite collector for lead-zinc ore flotation includes collector A, collector B, and collector C. Collector A is ethyl xanthate, collector B is butylamine black medicine, and collector C is a mixture of diphenylthiourea and ethylthiourea, with the mass ratio of the two in the mixture being 1:2. The mass ratio of collector A to collector B to collector C is 3:1:1. Before use, these are mixed uniformly in a predetermined amount and added.

[0034] The above combined collector is used for the recovery of lead-zinc ore in sulfur concentrate:

[0035] In the sulfur concentrate processed in this embodiment, the Pb grade is 0.36, the Zn grade is 2.73%, the lead-containing minerals are mainly galena, and the zinc-containing minerals are mainly sphalerite.

[0036] Flotation conditions: Grind the sulfur concentrate to a grinding fineness of -0.074mm, accounting for 80%, adjust the pulp mass concentration to 35%, and add the inhibitor lime (added amount 6000g / t) and stir for 3min, activator copper sulfate (added amount 500g / t) and stir for 3min, lead and zinc flotation composite collector (added amount 150g / t, including ethyl xanthate 90g / t, butylamine black medicine 30g / t, diphenylthiourea 10g / t and ethylthiourea 20g / t) and foaming agent 2# oil (added amount 30g / t) and stir for 3m After in, roughing operation is carried out, and the roughing time is 5 minutes to obtain roughing concentrate and roughing tailings. The roughing tailings are scavenged twice (scavenging time is 3 minutes and 2 minutes respectively). In the first scavenging, 200g / t of copper sulfate and 20g / t of lead-zinc flotation composite collector are added. In the second scavenging, 100g / t of copper sulfate and 10g / t of lead-zinc flotation composite collector are added. The roughing concentrate is cleaned twice (cleaning time is 2 minutes and 1 minute respectively) to obtain a lead-zinc mixed concentrate product. Its recovery rate and grade are shown in Table 1. The process flow chart is as follows: Figure 2 shown.

[0037] Example 3

[0038] A composite collector for lead-zinc ore includes collector A, collector B, and collector C. Collector A is butyl xanthate, collector B is ethylthiocarbamide and butylamine black medicine, and the mass ratio of the two is 1:1. Collector C is diphenylthiourea. The mass ratio of collector A, collector B, and collector C is 3:3:4. Before use, the collectors are mixed uniformly in a predetermined amount and added.

[0039] The above combined collector is used for the recovery of lead-zinc ore in sulfur concentrate:

[0040] In the sulfur concentrate processed in this embodiment, the Pb grade is 0.86, the Zn grade is 2.75%, the lead-containing minerals are mainly galena, and the zinc-containing minerals are mainly sphalerite.

[0041] Flotation conditions: Grind the sulfur concentrate to a grinding fineness of -0.074mm accounting for 85%, adjust the pulp mass concentration to 30%, and add the inhibitor lime (added amount 2000g / t) and stir for 3min, activator copper sulfate (added amount 100g / t) and stir for 3min, lead and zinc flotation composite collector (added amount 40g / t, including butyl xanthate 12g / t, ethylthiocyanate 6g / t, butylamine black medicine 6g / t and diphenylthiourea 16g / t) and starting Foaming agent 2# oil (added amount 20g / t), stirred for 3 minutes and then roughing operation was carried out. The roughing time was 3 minutes. After one roughing operation, roughing concentrate and roughing tailings were obtained. The roughing tailings were scavenged once (scavenging time was 3 minutes). After scavenging, 20g / t of lead-zinc flotation composite collector was added. The roughing concentrate was concentrating twice (concentrating time was 2 minutes and 1 minute respectively) to obtain lead-zinc mixed concentrate product. Its recovery rate and grade are shown in Table 1. The process flow chart is as follows: Figure 3 shown.

[0042] Example 4

[0043] This example is a comparison of Example 1. The processing conditions of this example are the same as those of Example 1, except that only collector A butyl xanthate is added, and collectors B and collector C are not added. The amount of butyl xanthate used is 42 g / t.

[0044] Example 5

[0045] This example is a comparison of Example 2. The processing conditions of this example are the same as those of Example 2, except that only collector A ethyl xanthate and collector B butylamine black medicine are added, and collector C is not added. The amount of ethyl xanthate is 90 g / t, and the amount of butylamine black medicine is 30 g / t.

[0046] Table 1 Test results of Examples 1-3

[0047]

[0048] Table 2 Comparative Example 4-5 Test Results

[0049]

[0050] As can be seen from Table 1, by adding the lead-zinc ore composite collector of the present invention during the flotation process of the sulfur concentrate, the lead and zinc grades in the lead-zinc mixed concentrates obtained in Examples 1-3 are improved, and the lead and zinc recovery rates are enhanced, thereby effectively realizing the recovery of lead and zinc metals in the sulfur concentrate.

[0051] The comparative data in Table 2 shows that using Collector A alone or in combination with Collector A and Collector B has a certain effect on the recovery of lead and zinc metals, but the effect is not strong, and the lead and zinc grade and recovery rate are not as high as when the same collector combination is used. Therefore, the combination of Collector A, Collector B, and Collector C can more effectively recover lead and zinc metals.

[0052] The collectors A and B of the present invention can adsorb on the surface of sulfide ore, thereby enhancing the hydrophobicity of the lead-zinc surface and increasing its floatability. At the same time, the collector C has a relatively weak adsorption capacity for pyrite, which reduces the adsorption of pyrite by collectors A and B. This allows the combined agent to selectively adsorb on the lead and zinc surfaces, enhancing the hydrophobicity of the lead-zinc surfaces without changing the surface properties of the pyrite. This enhances the recovery capacity of lead and zinc. The present invention also has the advantages of being safe, non-toxic, stable, and easy to configure and add, has broad application prospects, and effectively enhances the recovery capacity of lead-zinc ores.

[0053] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in form and details without departing from the scope defined by the claims of the present invention.

Claims

1. A composite collector for lead and zinc flotation, characterized by: The composite collector comprises collector A, collector B and collector C, and the mass ratio of collector A, collector B and collector C is 1:1:1 to 6:3:2; The collector A is any one of ethyl xanthate and butyl xanthate; The collector B is any one or any two of ethylthiocarbamate, ethylthiocarbamate, and butylamine black medicine; The collector C is composed of any one or any two of diphenylthiourea and ethylthiourea; When the collector C is composed of diphenylthiourea and ethylthiourea, the mass ratio of the two components is 1:1 to 1:

4.

2. The lead-zinc flotation composite collector according to claim 1, characterized in that: When the collector B is composed of any two of ethylthiocarbamate, ethylthiocarbamate, and butylamine black medicine, the mass ratio of the two components is 1:1 to 1:

2.

3. A process for flotation of lead-zinc ore using a lead-zinc flotation composite collector as claimed in any one of claims 1 to 2, characterized in that: The following steps are involved: (1) grinding the sulfur concentrate and adjusting the pulp concentration, then adding lime as an inhibitor, copper sulfate as an activator, a lead-zinc flotation composite collector, and a frother to the pulp for roughing operation to obtain roughing concentrate and roughing tailings; (2) scavenging the roughing tailings, wherein the reagents added in the scavenging operation are copper sulfate as an activator and lead-zinc flotation composite collector to obtain scavenging concentrate and scavenging tailings; (3) The roughing concentrate is subjected to a beneficiation operation to obtain a beneficiated concentrate and beneficiated tailings. The beneficiated tailings are combined with the scavenging concentrate and then returned to the roughing operation to form a closed loop.

4. The process for flotation of lead-zinc ore using a lead-zinc flotation composite collector according to claim 3, characterized in that: In step (1), the sulfur concentrate is ground to -0.074 mm, accounting for 80% to 90%, and the pulp concentration is 30% to 40%.

5. The process for flotation of lead-zinc ore using a lead-zinc flotation composite collector according to claim 3, characterized in that: The roughing operation takes 3 to 7 minutes, the sweeping operation is performed 1 to 2 times, each sweeping operation takes 1 to 3 minutes, and the fine selection operation is performed 1 to 2 times, each fine selection operation takes 1 to 2 minutes.

6. The process for flotation of lead-zinc ore using a lead-zinc flotation composite collector according to claim 3, characterized in that: In the roughing operation, per ton of raw ore, the amount of lime added to the slurry is 2000-6000 g / t, the amount of copper sulfate added is 100-500 g / t, and the amount of lead-zinc flotation composite collector added is 40-150 g / t. In the scavenging operation, the amount of copper sulfate added is 0-200 g / t, and the amount of lead-zinc flotation composite collector added is 20-40 g / t. No reagent is added in the cleaning operation.

7. Use of the composite collector according to any one of claims 1 to 2 in the flotation of lead-zinc ores.

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