CN116637726A - Combined inhibitor of lead zinc oxide ore in lead zinc sulfur sulfide tailings and application thereof - Google Patents

Abstract

The invention relates to a combined inhibitor for lead zinc oxide ores in lead zinc sulfide tailings and application thereof, and belongs to the technical field of lead zinc oxide ore dressing. The combined inhibitor and the reverse flotation process adopted by the invention realize synchronous recovery of lead oxide and zinc oxide on the basis of ensuring the flotation recovery effect, and have the advantages of simple flow, less equipment investment and the like.

Description

A combined inhibitor of lead-zinc oxide in lead-zinc-sulfur sulfide tailings and its application

technical field

The invention belongs to the technical field of mineral processing of lead-zinc oxide ore, and in particular relates to a combined inhibitor of lead-zinc oxide in lead-zinc-sulfur sulfide tailings and its application.

Background technique

Sulfide-oxidation mixed lead-zinc ore is an important class of lead-zinc ore resources. The hydrophobicity of sulfide minerals is stronger than that of oxide minerals, so the recovery of sulfide minerals is relatively simple, so the key to the utilization of such ore resources lies in the recovery of oxide minerals.

When recycling mineral resources in sulfide-oxidation mixed lead-zinc ores, the process of first flotation of sulfide minerals and then flotation of oxide minerals is usually adopted. The recovery of lead and zinc oxide minerals usually adopts the sulfidation flotation process of lead first and then zinc, that is, the sulfide-xanthate method is used to recover lead oxide first, and then the sulfide-fatty amine method is used to recover zinc oxide minerals from the lead oxide tailings. However, the aforementioned methods have obvious disadvantages: (1) It is difficult to vulcanize oxidized minerals at room temperature; (2) The application of aliphatic amines has higher requirements on the slurry environment. (3) The oxidized minerals are brittle in nature, and the particle size of the embedded distribution is fine; if the conventional flotation process is adopted, the fine oxidized minerals are easily lost in the tailings. To sum up, the use of conventional inhibitors and flotation processes has the problems of high recovery cost, poor recovery effect and relatively complicated process.

Therefore, it is necessary to provide a high separation efficiency combined inhibitor of lead-zinc oxide in lead-zinc-sulfur sulfur tailings and its application. By simplifying the process flow, the recovery cost can be reduced, and at the same time, the flotation rate of complex refractory lead-zinc ore in my country can be improved. selection level and comprehensive utilization of resources.

Contents of the invention

In order to overcome the problems existing in the background technology, the present invention provides a combined inhibitor of lead-zinc oxide in lead-zinc sulfur sulfide tailings and its application. By using the combined inhibitor of high separation efficiency and the reverse flotation process, Simplify the process flow, reduce the recovery cost, realize the simultaneous suppression and recovery of low-grade refractory lead-zinc oxide minerals, and improve the flotation level and comprehensive resource utilization of complex refractory lead-zinc ores.

To achieve the above object, the present invention is achieved through the following technical solutions:

The combined inhibitor includes sodium fluorosilicate, sodium sulfide, and sodium humate, and the mass ratio of the sodium fluorosilicate, sodium sulfide, and sodium humate is 2:5:1.

The combined inhibitor is applied to the reverse flotation recovery process of lead-zinc oxide in lead-zinc-sulfur sulfide tailings.

Preferably, the lead oxide ore is plumberite, and the zinc oxide ore is sautzite or zincite.

Preferably, the gangue minerals contained in the lead-zinc-sulfur sulfide tailings are mainly calcite and dolomite.

As preferably, the specific steps of the reverse flotation recovery process are as follows:

S1: Grinding the lead-zinc-sulfur sulfide tailings to obtain a slurry with a grinding fineness of -200 mesh accounting for 90%;

S2: Add sodium fluorosilicate, sodium sulfide, and sodium humate sequentially to the pulp obtained in S1 as combined inhibitors, then add collectors, and then carry out reverse flotation operations, and get roughed concentrate after a rough selection ore and rougher tailings, the rougher concentrate is mainly lead-zinc oxide minerals, and the rougher tailings are mainly gangue minerals;

S3: Add collectors to the rougher concentrate obtained in S2, and then perform two sweeping operations, the second sweeping is blank sweeping, the rougher tailings obtained in S2 and the flotation obtained by sweeping Select the foam and combine it to remove the tailings.

Preferably, the collector includes oleic acid and oxidized paraffin soap, and the mass ratio of oleic acid and oxidized paraffin soap is 3:1.

As a preference, in S2, 6000g/t of combined inhibitors are input per ton of raw ore, including 1500g/t of ammonium fluorosilicate, 3750g/t of sodium sulfide, and 750g/t of sodium humate.

As a preference, in S2, 300g/t of collector is input per ton of raw ore.

As a preference, in S3, 100g/t of collector is input per ton of raw ore.

The combined inhibitor ammonium fluorosilicate, sodium sulfide and sodium humate of the present invention can realize the flotation and separation of lead-zinc oxide ore from lead-zinc-sulfur sulfide tailings, mainly relying on the synergistic and strengthening effects of the three agents. Ammonium fluorosilicate mainly exerts its erosion and cleaning effect on minerals. The pretreatment of fluorosilicic acid can increase the relative content of lead and zinc atoms on the surface of lead-zinc oxide ore, especially for zinc oxide minerals such as silicon-containing hemimorphite. In addition, because lead-zinc-sulfur sulfidation tailings usually contain a large amount of gangue minerals such as calcite and dolomite, and ammonium fluorosilicate has a certain acidity, it has a cleaning effect on calcium and magnesium ions precipitated on the surface of lead-zinc oxide ore, thus exposing fresh surface. Sodium sulfide mainly exerts its sulfidation effect on the target mineral. Sodium sulfide undergoes redox reaction with lead and zinc atoms on the surface of lead-zinc oxide ore, and then forms lead sulfide and zinc sulfide films similar to lead-zinc sulfide ore. Pretreatment with ammonium fluorosilicate further facilitated the action of sodium sulfide. The addition of sodium humate will react with the lead sulfide and zinc sulfide films produced after the action of sodium sulfide, and physical and chemical adsorption will occur on the surface to further form a covering layer of macromolecular organic matter, thereby increasing the lead-zinc oxide under the fatty acid system. Difference in buoyancy with gangue minerals such as calcite.

The flotation of lead-zinc oxide minerals in traditional lead-zinc-sulfur sulfidation tailings uses the sulfuration-direct flotation process of lead first and then zinc, that is, the lead oxide minerals are first floated by the sulfuration-xanthate method, and then the sulfuration-fatty amine method is used to float the lead oxide minerals. Recovering zinc oxide minerals from lead oxide tailings, adding corresponding inhibitors to inhibit the floating of gangue minerals during the sorting process, due to the type of collector and other factors in the positive flotation process, there will be adverse effects such as more flotation foam, which has a negative impact on The flotation recovery effect has a greater impact. The reverse flotation process of the present invention inhibits the floating of lead-zinc oxide minerals by combining inhibitors, and floats gangue minerals through collectors, which is opposite to the traditional positive flotation process for floating and inhibiting floating substances, so it is called reverse flotation craft. The invention improves the sorting effect by applying the combined inhibitor in the reverse flotation process, especially the flotation effect of low-grade lead-zinc oxide minerals has a favorable effect.

Beneficial effects of the present invention:

1. Compared with the traditional flotation process of lead-zinc oxide minerals, the reverse flotation process adopted by the method of the present invention has the advantages of simple process and less equipment investment. The traditional flotation process of lead-zinc oxide minerals generally adopts the sulfide-xanthate method to recover lead oxide first, and then adopts the sulfide-fatty amine method to further recover zinc oxide. The reverse flotation process in the invention can realize the synchronous recovery of lead oxide and zinc oxide.

2. The present invention adopts a combined inhibitor with high separation efficiency and strong adaptability to ore property fluctuations to ensure the flotation recovery effect of lead-zinc oxide minerals.

3. The combined inhibitor and reverse flotation process used in the present invention realize the simultaneous recovery of lead oxide and zinc oxide, which has great theoretical value and economical value for improving the flotation level and comprehensive resource utilization of complex lead-zinc mines in my country. value.

Description of drawings

Fig. 1 is a process flow diagram of the present invention

Figure 2 is a flow chart of the flotation process for traditional lead-zinc oxide ore

Detailed ways

In order to make the purpose, technical solutions and beneficial effects of the present invention more clear, the preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, so as to facilitate the understanding of technical personnel.

The raw ore of the present invention is the lead-zinc-sulfur sulfide tailings of a certain unit in Yunnan area. The raw ore contains 0.64% Pb and 1.52% Zn. The lead oxide minerals are mainly white lead ore and lead alum, and the zinc oxide minerals are mainly zinc-iron spinel ore , The gangue mineral content is relatively high, mainly calcite, dolomite and so on.

Example 1

The present invention adopts reverse flotation process and ammonium fluorosilicate, sodium sulfide, sodium humate as combined inhibitor of lead-zinc oxide minerals, wherein the mass ratio of ammonium fluorosilicate, sodium sulfide, and sodium humate is 2:5 :1.

Firstly, the lead-zinc-sulfur sulfur sulfide tailings are ground to obtain a pulp with a grinding fineness of -200 mesh, accounting for 90%; In terms of raw ore per ton, the total amount is 6000g/t, calculated according to the mass ratio of 2:5:1, ammonium fluorosilicate is 1500g/t, sodium sulfide is 3750g/t, sodium humate is 750g/t, and then added Collector, the total amount of collector added is calculated per ton of raw ore, the total amount added is 300g/t, calculated according to the mass ratio of 3:1, the amount of oleic acid added is 225g/t, and the amount of oxidized paraffin wax soap added is 75g/t t, follow-up reverse flotation operation, after a rough selection to obtain gangue mineral roughing tailings and lead-zinc oxide mineral roughing concentrate, and then in the obtained lead-zinc oxide mineral roughing concentrate, the raw ore per ton Then add 100g/t collector, calculate according to the proportion, the addition amount of oleic acid is 75g/t, the addition amount of oxidized paraffin wax soap is 25g/t, then carry out two sweeps, wherein the second time is a blank sweep, After the sweeping, the roughing tailings and the flotation foam generated by the sweeping were combined to remove the tailings, and finally the mixed concentrate of lead oxide and zinc was obtained. The yield and grade were detected during the experiment. The results are shown in Table 1 shown.

According to the experimental results in Table 1, it can be seen that the present invention can effectively realize the comprehensive recovery of lead-zinc oxide ore in lead-zinc sulfur sulfidation tailings, the grade of lead in the lead-zinc oxide mixed concentrate is 3.61%, and the grade of zinc is 12.04% , the enrichment ratio of lead is 5.64, and the enrichment ratio of zinc is 7.92, indicating that the combination inhibitor of the present invention can effectively realize the separation of gangue minerals such as lead-zinc oxide minerals and calcite, and ensure the flotation effect of lead-zinc oxide minerals.

Comparative example 1

In Comparative Example 1, the traditional positive flotation process and traditional inhibitors were used to carry out the flotation experiment of lead-zinc-sulfur sulfide tailings raw ore in Yunnan. The raw ore contained 0.64% Pb, 1.52% Zn, and lead oxide minerals Mainly white lead ore, lead alum, zinc oxide minerals are mainly zinc iron spinel ore, gangue mineral content is relatively high, mainly calcite, dolomite and so on.

Firstly, the lead-zinc-sulfur sulfide tailings are ground to obtain a pulp with a grinding fineness of -200 mesh, which accounts for 90%; then sodium sulfide is added to the pulp as an activator of lead oxide, and the amount added is calculated per ton of raw ore. The amount is 1000g/t, and then add collector butyl yellow, the amount added is calculated per ton of raw ore, the amount of lead oxide is 75g/t for rough selection, the amount of lead oxide sweep is 25 g/t, and then foaming agent No. 2 is added Oil, the amount added is calculated per ton of raw ore, the rough selection of lead oxide is 20 g/t, the selection of lead oxide is 5 g/t, and the lead oxide concentrate and lead oxide tailings are obtained after one roughing and one sweeping operation ore; add sodium sulfide to the obtained lead oxide tailings as an activator of zinc oxide to separate the zinc oxide ore, the addition amount is calculated as 5000 g/t per ton of raw ore, and sodium hexametaphosphate is added as the activator of gangue minerals Inhibitor, the addition amount is 1200 g/t per ton of raw ore; then add collector stearylamine, the addition is based on each ton of raw ore, the rough selection of zinc oxide is 100 g/t, and the selection of zinc oxide sweeping is 50 g/t, zinc oxide concentrate and total tailings were obtained after one roughing and one sweeping operation, the results are shown in Table 2.

According to the experimental results in Table 2, it can be seen that the comprehensive recovery effect of lead-zinc oxide minerals is poor by using the traditional positive flotation process and the traditional depressant. The grade of lead in the lead oxide concentrate is 3.11%, which is 0.50% lower than the grade of lead in the present invention; the grade of zinc in the zinc oxide concentrate is 6.74%, which is 5.30% lower than the grade of zinc in the present invention; The recovery rate in the present invention is respectively high 3.21% and 6.22% compared with the present invention, and the recovery rate of lead and zinc in the total tailings is high, indicating that the loss rate of lead-zinc oxide minerals is large. On the other hand, the sum of lead-zinc oxide concentrate yields in comparative example 1 is 21.85%, which is 12.48% higher than that in the present invention. The high yield shows that the separation effect of lead-zinc oxide minerals and gangue minerals is poor, and also increases the cost of subsequent transportation and smelting process. . Finally, the traditional positive flotation process and the traditional depressant require more roughing and sweeping times, and the process is relatively cumbersome.

Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention rather than limit them. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that it can be described in terms of form and Various changes may be made in the details without departing from the scope of the invention defined by the claims.

Claims (9)

1. A combined inhibitor of lead-zinc oxide in lead-zinc-sulfur sulfide tailings, characterized in that: said combined inhibitor comprises sodium fluorosilicate, sodium sulfide, sodium humate, and said sodium fluorosilicate , sodium sulfide, and sodium humate in a mass ratio of 2:5:1. 2. The combination inhibitor according to claim 1 is applied to the reverse flotation recovery process of lead-zinc oxide ore in lead-zinc-sulfur sulfide tailings. 3. The reverse flotation recovery process of lead-zinc oxide ore in a kind of lead-zinc-sulfur sulfide tailings according to claim 2, characterized in that: said lead oxide ore is lead alum, and said zinc oxide ore is zinc Iron spinel or zincite. 4. The reverse flotation recovery process of lead-zinc-sulfur sulfide tailings in lead-zinc-sulfur sulfide tailings according to claim 2, characterized in that: the gangue minerals contained in the lead-zinc-sulfur sulfide tailings are mainly calcite and dolomite. 5. The reverse flotation recovery process of lead-zinc-sulfur sulfide tailings in a kind of lead-zinc-sulfur sulfide tailings according to claim 2, characterized in that: the specific steps of the reverse flotation recovery process are as follows: S1: Grinding the lead-zinc-sulfur sulfide tailings to obtain a slurry with a grinding fineness of -200 mesh accounting for 90%; S2: Add sodium fluorosilicate, sodium sulfide, and sodium humate sequentially to the pulp obtained in S1 as combined inhibitors, then add collectors, and then carry out reverse flotation operations, and get roughed concentrate after a rough selection ore and rougher tailings, the rougher concentrate is mainly lead-zinc oxide minerals, and the rougher tailings are mainly gangue minerals; S3: Add collectors to the rougher concentrate obtained in S2, and then perform two sweeping operations, the second sweeping is blank sweeping, the rougher tailings obtained in S2 and the flotation obtained by sweeping Select the foam and combine it to remove the tailings. 6. The reverse flotation recovery process of lead-zinc oxide in lead-zinc-sulfur sulfide tailings according to claim 5, characterized in that: the collector includes oleic acid, oxidized paraffin wax soap, and the oleic acid The mass ratio to oxidized paraffin soap is 3:1. 7. The reverse flotation recovery process of lead-zinc-sulfur sulfide tailings in a kind of lead-zinc-sulfur sulfide tailings according to claim 5, characterized in that: in S2, 6000g/t of combination inhibitors are input per ton of raw ore, wherein fluorine silicon Ammonium acid 1500g/t, sodium sulfide 3750g/t, sodium humate 750g/t. 8. The reverse flotation recovery process of lead-zinc-sulfur sulfide tailings in lead-zinc-sulfur sulfide tailings according to claim 5, characterized in that: in S2, 300 g/t of collector is put in per ton of raw ore. 9. The reverse flotation recovery process of lead-zinc-sulfur sulfide tailings in lead-zinc-sulfur sulfide tailings according to claim 5, characterized in that: in S3, 100 g/t of collector is put into each ton of raw ore.