Short flow step-by-step separation method of sulfur-oxygen mixed zinc ore

Abstract

The present application relates to a kind of short process step-by-step separation method of sulfur oxygen mixed zinc ore, belong to mineral processing technical field.The present application sulfur oxygen mixed zinc ore is finely treated, adds multi-metal activator to target activation of zinc sulfide mineral in ore, then the activated zinc sulfide mineral is preferentially recovered by flotation machine, and zinc sulfide concentrate is obtained;In zinc sulfide flotation tailings, add combination regulator and combination collector to carry out synergistic slurry conditioning and bubble control, then adopt flotation column to carry out rapid and efficient recovery of zinc oxide mineral in ore, and high-quality zinc oxide concentrate can be obtained by using only once roughing.The present application is based on the occurrence characteristics of zinc mineral in ore to formulate target reagent system, by using flotation machine and flotation column in combination, realize the short process step-by-step recovery of zinc sulfide and oxide in sulfur oxygen mixed zinc ore, solve the technical problem that zinc sulfide and oxide in sulfur oxygen mixed zinc ore are difficult to be efficiently recovered when coexisting in ore, improve the comprehensive utilization rate of complex and difficult to handle zinc ore resources.

Description

Technical Field

[0001] This invention relates to a short-process step-by-step separation method for sulfur-oxygen mixed zinc ore, belonging to the field of mineral processing technology. Background Technology

[0002] Flotation is the main method for recovering zinc ore resources, and the selective control of mineral interface wettability by flotation reagents is a key factor in mineral flotation separation. Zinc sulfide ores are mainly pre-activated with copper sulfate, followed by the addition of mercapto-based collectors for recovery. However, copper sulfate, as an activator, has poor selectivity; it not only activates zinc sulfide minerals in the ore but also gangue minerals such as pyrite, severely affecting the ore separation effect. Simultaneously, copper sulfate alone has limited adsorption capacity on the surface of zinc sulfide minerals, failing to ensure sufficient activation of the zinc minerals in the ore. This results in some zinc sulfide minerals not being effectively hydrophobically controlled by the collector, thus being lost in the tailings.

[0003] Zinc oxide ore is primarily pre-enriched using amine sulfide flotation. However, this technology is highly susceptible to the unavoidable slime in the pulp, making normal production impossible. While pre-desliming can improve the flotation process, the zinc oxide minerals in the removed slime cannot be recovered, resulting in significant zinc metal loss. Furthermore, slime adhering to amines can also attach to the mineralized flotation foam, effectively "armoring" the flotation foam with both slime and amine collectors. This leads to a long lifespan and high stability of the flotation foam, which not only increases the amount of middlings recycled but also severely impairs the fluidity of the ore-laden foam, making it difficult to eliminate and causing severe "fountain run-off." Ultimately, this makes the flotation process difficult to control and production impossible.

[0004] When zinc minerals in ores do not exist as single zinc sulfide or zinc oxide minerals, the significant differences in crystal structure and surface properties between these two types of zinc minerals make it impossible for existing flotation technologies to simultaneously collect them, resulting in severe losses of zinc minerals during beneficiation. Therefore, there is an urgent need to develop new and efficient flotation reagents and separation processes to achieve efficient recovery of mixed sulfur and oxygen zinc ores in a short process, thereby improving the technological advancement of complex and difficult-to-beneficiate zinc ore resources. Summary of the Invention

[0005] This invention addresses the shortcomings of existing technologies by providing a short-process, stepped separation method for sulfur-oxygen mixed zinc ore. After crushing, grinding, and pulp conditioning, a multi-metal activator is added to target and activate the zinc sulfide minerals in the ore. The activated zinc sulfide minerals are then preferentially recovered using a flotation machine to obtain zinc sulfide concentrate. A combination modifier and a combination collector are added to the zinc sulfide flotation tailings for synergistic pulp conditioning and foam control. Finally, a flotation column is used to rapidly and efficiently recover zinc oxide minerals from the ore. High-quality zinc oxide concentrate can be obtained with only one roughing stage.

[0006] A short-process, multi-stage separation method for sulfur-oxygen mixed zinc ore, comprising the following specific steps:

[0007] (1) Crush and grind the sulfur-oxygen mixed zinc ore until the zinc minerals are fully liberated, and add water to adjust the slurry to a slurry mass percentage concentration of 26-38%;

[0008] (2) Add polymetallic activator, isoamyl xanthate and pine oil to the slurry obtained in step (1) in sequence, and carry out a first zinc sulfide roughing operation in the flotation machine to obtain a first zinc sulfide roughing concentrate and a first zinc sulfide roughing tailings.

[0009] (3) In step (2), polymetallic activator, isoamyl xanthate and pine oil are added sequentially to the primary zinc sulfide roughing tailings, and secondary zinc sulfide roughing operation is carried out in the flotation machine to obtain secondary zinc sulfide roughing concentrate and secondary zinc sulfide roughing tailings.

[0010] (4) The primary zinc sulfide rough concentrate obtained in step (2) and the secondary zinc sulfide rough concentrate obtained in step (3) are combined and then isoamyl xanthate and pine oil are added in sequence. The zinc sulfide is then treated in a flotation machine to obtain zinc sulfide concentrate and flotation tailings I.

[0011] (5) Add combined modifier and combined collector to the secondary zinc sulfide roughing tailings obtained in step (3) and carry out zinc oxide roughing operation in the flotation column to obtain zinc oxide concentrate and flotation tailings II;

[0012] (6) The zinc sulfide concentrate obtained in step (4) and the zinc oxide concentrate obtained in step (5) are zinc concentrate products. The flotation tailings I obtained in step (4) and the flotation tailings II obtained in step (5) are combined to obtain flotation tailings.

[0013] The multi-metal activator is a mixture of copper nitrate, lead nitrate and silver nitrate; the combined modifier is a mixture of sodium sulfide, acidified water glass and disodium malonate; and the combined collector is a mixture of laurylamine acetate, ammonium dodecyl sulfate and Pingpingjia O-25.

[0014] Preferably, the zinc content in the sulfur-oxygen mixed zinc ore in step (1) is 4.4~7.8% by mass.

[0015] Preferably, per ton of mixed zinc sulfide ore, 140-280g of polymetallic activator, 180-320g of isoamyl xanthate and 20-40g of pine oil are added to the slurry of the first zinc sulfide roughing operation in step (2).

[0016] Preferably, per ton of sulfur-oxygen mixed zinc ore, 40-80g of polymetallic activator, 60-100g of isoamyl xanthate and 10-20g of pine oil are added to the slurry of the secondary zinc sulfide roughing operation in step (3).

[0017] Preferably, for every ton of mixed zinc sulfide ore, 20-40g of isopentyl xanthate and 5-10g of pine oil are added to the slurry of the zinc sulfide beneficiation operation in step (4).

[0018] Preferably, for every ton of sulfur-oxygen mixed zinc ore, 4000~6000g of combined modifier and 220~340g of combined collector are added to the slurry of the zinc oxide roughing operation in step (5).

[0019] Preferably, based on a mass fraction of 100% for the multi-metal activator, the multi-metal activator contains 50-60% copper nitrate, 39-48% lead nitrate, and 1-3% silver nitrate.

[0020] Preferably, based on a mass fraction of 100% for the combined modifier, sodium sulfide accounts for 80-90%, acidified water glass accounts for 5-10%, and disodium malonate accounts for 5-10%.

[0021] Preferably, based on a mass fraction of 100% for the combined collector, laurylamine acetate accounts for 45-55%, ammonium dodecyl sulfate accounts for 30-40%, and phenacetin O-25 accounts for 10-20%.

[0022] The beneficial effects of this invention are:

[0023] (1) Based on the occurrence characteristics of zinc minerals in the ore, this invention formulates a new strategy of multi-metal ion targeted activation of zinc sulfide minerals and combined reagents to synergistically enhance the flotation of zinc oxide minerals. By using flotation machines and flotation columns in combination, the high separation accuracy of flotation columns is fully utilized to achieve short-process cascade recovery of zinc sulfides and oxides in sulfur-oxygen mixed zinc ores. This solves the technical problem of difficult efficient recovery when sulfur-oxygen mixed zinc minerals coexist in the ore, and improves the comprehensive utilization rate of complex and difficult-to-process zinc ore resources.

[0024] (2) This invention utilizes the fact that copper ions, lead ions and silver ions have a stronger reactivity with mercapto collectors than zinc ions in zinc sulfide minerals. This not only enhances the reactivity of the surface of zinc sulfide minerals in the ore, but also the combined use of the three highly active metal ions can make up for the lack of active sites when a single metal ion is activated, thus achieving full activation of the target minerals and strengthening hydrophobicity. This promotes the preferential recovery of zinc sulfide minerals in mixed zinc sulfide and oxide minerals without interfering with the recovery process of zinc oxide minerals.

[0025] (3) In this invention, a combination modifier is added to the zinc sulfide flotation tailings. Through chemical reactions, hydrogen bonds or electrostatic interactions, it selectively covers the active sites on the surface of gangue minerals, blocks the adsorption of collectors on the surface of gangue minerals, and uses the steric hindrance effect to prevent gangue minerals from floating. At the same time, it fully disperses the fine mineral particles in the ore, avoids the sludge covering the surface of zinc oxide minerals, and optimizes the flotation kinetics conditions by means of dispersion, creating conditions for the targeted adsorption of collectors.

[0026] (4) This invention precisely controls the stability, fluidity and viscosity of the flotation foam layer of zinc oxide ore by developing a combination of collectors, thereby changing the thickness of the liquid film. This makes the foam of zinc oxide concentrate easy to break and dissipate, enhancing the enrichment effect and separation efficiency of zinc oxide minerals. Moreover, the use of flotation columns can achieve rapid and efficient recovery of zinc oxide minerals in the ore. High-quality zinc oxide concentrate can be obtained with only one roughing process, without involving the return of middlings. This avoids the accumulation and circulation of slime in the flotation system, solves the problems of foam control and slime suppression in the flotation process, and opens up a new way for the efficient separation of sulfur-oxygen mixed zinc ore. Attached Figure Description

[0027] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described.

[0029] In the following embodiments of the present invention, the multi-metal activator is a mixture of copper nitrate, lead nitrate and silver nitrate, the combined modifier is a mixture of sodium sulfide, acidified water glass and disodium malonate, and the combined collector is a mixture of laurylamine acetate, ammonium dodecyl sulfate and Pingpingjia O-25.

[0030] Example 1: In this example, the multi-metal activator has a mass fraction of 100%, with copper nitrate accounting for 50%, lead nitrate for 48%, and silver nitrate for 2%; the combined modifier has a mass fraction of 100%, with sodium sulfide for 80%, acidified water glass for 10%, and disodium malonate for 10%; the combined collector has a mass fraction of 100%, with laurylamine acetate for 45%, ammonium dodecyl sulfate for 35%, and 20% of phenoxymethyl sulfoxide (PMS) for 25%.

[0031] like Figure 1 As shown, a short-process cascade separation method for sulfur-oxygen mixed zinc ore includes the following specific steps:

[0032] (1) The sulfur-oxygen mixed zinc ore is crushed and ground until the zinc minerals are fully liberated, and water is added to adjust the slurry to a slurry mass percentage concentration of 26%; wherein the zinc mass percentage content in the sulfur-oxygen mixed zinc ore is 4.4%;

[0033] (2) In step (1), polymetallic activator, isoamyl xanthate and pine oil are added to the slurry in sequence, and a first zinc sulfide roughing operation is carried out in the flotation machine to obtain a first zinc sulfide roughing concentrate and a first zinc sulfide roughing tailings; per ton of sulfur-oxygen mixed zinc ore, 140g of polymetallic activator, 180g of isoamyl xanthate and 20g of pine oil are added to the slurry of the first zinc sulfide roughing operation.

[0034] (3) In step (2), polymetallic activator, isoamyl xanthate and pine oil are added to the primary zinc sulfide roughing tailings in sequence, and secondary zinc sulfide roughing operation is carried out in the flotation machine to obtain secondary zinc sulfide roughing concentrate and secondary zinc sulfide roughing tailings; based on each ton of sulfur-oxygen mixed zinc ore, 40g of polymetallic activator, 60g of isoamyl xanthate and 10g of pine oil are added to the slurry of the secondary zinc sulfide roughing operation.

[0035] (4) The primary zinc sulfide rough concentrate obtained in step (2) and the secondary zinc sulfide rough concentrate obtained in step (3) are combined and then isoamyl xanthate and pine oil are added in sequence. The zinc sulfide refining operation is carried out in the flotation machine to obtain zinc sulfide concentrate and flotation tailings I. Based on each ton of sulfur-oxygen mixed zinc ore, 20g of isoamyl xanthate and 5g of pine oil are added to the slurry of the zinc sulfide refining operation.

[0036] (5) The combined modifier and combined collector are added sequentially to the secondary zinc sulfide roughing tailings obtained in step (3), and zinc oxide roughing operation is carried out in the flotation column to obtain zinc oxide concentrate and flotation tailings II; based on each ton of sulfur-oxygen mixed zinc ore, 4000g of combined modifier and 220g of combined collector are added to the slurry of the zinc oxide roughing operation.

[0037] (6) The zinc sulfide concentrate obtained in step (4) and the zinc oxide concentrate obtained in step (5) are zinc concentrate products. The flotation tailings I obtained in step (4) and the flotation tailings II obtained in step (5) are combined to obtain flotation tailings.

[0038] In this embodiment, the zinc flotation recovery rate was 85.3%.

[0039] Example 2: In this example, based on a 100% mass fraction of the multi-metal activator, copper nitrate accounts for 55%, lead nitrate for 42%, and silver nitrate for 3%; based on a 100% mass fraction of the combined modifier, sodium sulfide accounts for 85%, acidified water glass for 5%, and disodium malonate for 10%; based on a 100% mass fraction of the combined collector, laurylamine acetate accounts for 50%, ammonium dodecyl sulfate for 40%, and phenazine O-25 for 10%.

[0040] like Figure 1 As shown, a short-process cascade separation method for sulfur-oxygen mixed zinc ore includes the following specific steps:

[0041] (1) The sulfur-oxygen mixed zinc ore is crushed and ground until the zinc minerals are fully liberated, and water is added to adjust the slurry to a slurry mass percentage concentration of 32%; wherein the zinc mass percentage content in the sulfur-oxygen mixed zinc ore is 6.1%;

[0042] (2) In step (1), polymetallic activator, isoamyl xanthate and pine oil are added to the slurry in sequence, and a first zinc sulfide roughing operation is carried out in the flotation machine to obtain a first zinc sulfide roughing concentrate and a first zinc sulfide roughing tailings; per ton of sulfur-oxygen mixed zinc ore, 210g of polymetallic activator, 250g of isoamyl xanthate and 30g of pine oil are added to the slurry of the first zinc sulfide roughing operation.

[0043] (3) In step (2), polymetallic activator, isoamyl xanthate and pine oil are added sequentially to the primary zinc sulfide roughing tailings, and secondary zinc sulfide roughing operation is carried out in the flotation machine to obtain secondary zinc sulfide roughing concentrate and secondary zinc sulfide roughing tailings; based on each ton of sulfur-oxygen mixed zinc ore, 60g of polymetallic activator, 80g of isoamyl xanthate and 15g of pine oil are added to the slurry of the secondary zinc sulfide roughing operation;

[0044] (4) The primary zinc sulfide roughing concentrate obtained in step (2) and the secondary zinc sulfide roughing concentrate obtained in step (3) are combined and then isoamyl xanthate and pine oil are added in sequence. The zinc sulfide refining operation is carried out in the flotation machine to obtain zinc sulfide concentrate and flotation tailings I. Based on each ton of sulfur-oxygen mixed zinc ore, 30g of isoamyl xanthate and 7.5g of pine oil are added to the slurry of the zinc sulfide refining operation.

[0045] (5) The combined modifier and combined collector are added sequentially to the secondary zinc sulfide roughing tailings obtained in step (3), and zinc oxide roughing operation is carried out in the flotation column to obtain zinc oxide concentrate and flotation tailings II; based on each ton of sulfur-oxygen mixed zinc ore, 5000g of combined modifier and 280g of combined collector are added to the slurry of the zinc oxide roughing operation.

[0046] (6) The zinc sulfide concentrate obtained in step (4) and the zinc oxide concentrate obtained in step (5) are used to obtain zinc concentrate products. The flotation tailings I obtained in step (4) and the flotation tailings II obtained in step (5) are combined to obtain flotation tailings.

[0047] In this embodiment, the zinc flotation recovery rate was 87.1%.

[0048] Example 3: In this example, based on a 100% mass fraction of the multi-metal activator, copper nitrate accounts for 60%, lead nitrate for 39%, and silver nitrate for 1%; based on a 100% mass fraction of the combined modifier, sodium sulfide accounts for 90%, acidified water glass for 5%, and disodium malonate for 5%; based on a 100% mass fraction of the combined collector, laurylamine acetate accounts for 55%, ammonium dodecyl sulfate for 30%, and phenazine O-25 for 15%.

[0049] like Figure 1 As shown, a short-process cascade separation method for sulfur-oxygen mixed zinc ore includes the following specific steps:

[0050] (1) The sulfur-oxygen mixed zinc ore is crushed and ground until the zinc minerals are fully liberated, and water is added to adjust the slurry to a slurry mass percentage concentration of 38%; wherein the zinc mass percentage content in the sulfur-oxygen mixed zinc ore is 7.8%;

[0051] (2) In step (1), polymetallic activator, isoamyl xanthate and pine oil are added to the slurry in sequence, and a first zinc sulfide roughing operation is carried out in the flotation machine to obtain a first zinc sulfide roughing concentrate and a first zinc sulfide roughing tailings; per ton of sulfur-oxygen mixed zinc ore, 280g of polymetallic activator, 320g of isoamyl xanthate and 40g of pine oil are added to the slurry of the first zinc sulfide roughing operation.

[0052] (3) In step (2), polymetallic activator, isoamyl xanthate and pine oil are added to the primary zinc sulfide roughing tailings in sequence, and secondary zinc sulfide roughing operation is carried out in the flotation machine to obtain secondary zinc sulfide roughing concentrate and secondary zinc sulfide roughing tailings; based on each ton of sulfur-oxygen mixed zinc ore, 80g of polymetallic activator, 100g of isoamyl xanthate and 20g of pine oil are added to the slurry of the secondary zinc sulfide roughing operation.

[0053] (4) The primary zinc sulfide rough concentrate obtained in step (2) and the secondary zinc sulfide rough concentrate obtained in step (3) are combined and then isoamyl xanthate and pine oil are added in sequence. The zinc sulfide is then treated in a flotation machine to obtain zinc sulfide concentrate and flotation tailings I. Based on each ton of sulfur-oxygen mixed zinc ore, 40g of isoamyl xanthate and 10g of pine oil are added to the slurry of the zinc sulfide treatment operation.

[0054] (5) The combined modifier and combined collector are added sequentially to the secondary zinc sulfide roughing tailings obtained in step (3), and zinc oxide roughing operation is carried out in the flotation column to obtain zinc oxide concentrate and flotation tailings II; based on each ton of sulfur-oxygen mixed zinc ore, 6000g of combined modifier and 340g of combined collector are added to the slurry of the zinc oxide roughing operation.

[0055] (6) The zinc sulfide concentrate obtained in step (4) and the zinc oxide concentrate obtained in step (5) are zinc concentrate products. The flotation tailings I obtained in step (4) and the flotation tailings II obtained in step (5) are combined to obtain flotation tailings.

[0056] In this embodiment, the zinc flotation recovery rate was 88.5%.

[0057] The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A short-process, stepped separation method for sulfur-oxygen mixed zinc ore, characterized in that, The specific steps are as follows: (1) Crush and grind the sulfur-oxygen mixed zinc ore until the zinc minerals are fully liberated, and add water to adjust the slurry to a slurry mass percentage concentration of 26-38%; (2) Add polymetallic activator, isoamyl xanthate and pine oil to the slurry obtained in step (1) in sequence, and carry out a first zinc sulfide roughing operation in the flotation machine to obtain a first zinc sulfide roughing concentrate and a first zinc sulfide roughing tailings. (3) In step (2), polymetallic activator, isoamyl xanthate and pine oil are added sequentially to the primary zinc sulfide roughing tailings, and secondary zinc sulfide roughing operation is carried out in the flotation machine to obtain secondary zinc sulfide roughing concentrate and secondary zinc sulfide roughing tailings. (4) The primary zinc sulfide rough concentrate obtained in step (2) and the secondary zinc sulfide rough concentrate obtained in step (3) are combined and then isoamyl xanthate and pine oil are added in sequence. The zinc sulfide is then treated in a flotation machine to obtain zinc sulfide concentrate and flotation tailings I. (5) Add combined modifier and combined collector to the secondary zinc sulfide roughing tailings obtained in step (3) and carry out zinc oxide roughing operation in the flotation column to obtain zinc oxide concentrate and flotation tailings II; (6) The zinc sulfide concentrate obtained in step (4) and the zinc oxide concentrate obtained in step (5) are zinc concentrate products. The flotation tailings I obtained in step (4) and the flotation tailings II obtained in step (5) are combined to obtain flotation tailings. The multi-metal activator is a mixture of copper nitrate, lead nitrate and silver nitrate; the combined modifier is a mixture of sodium sulfide, acidified water glass and disodium malonate; and the combined collector is a mixture of laurylamine acetate, ammonium dodecyl sulfate and Pingpingjia O-25.

2. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: Step (1) The zinc content in the sulfur-oxygen mixed zinc ore is 4.4~7.8% by mass.

3. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: For each ton of sulfur-oxygen mixed zinc ore, 140-280g of polymetallic activator, 180-320g of isoamyl xanthate and 20-40g of pine oil are added to the slurry of the first zinc sulfide roughing operation in step (2).

4. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: For each ton of sulfur-oxygen mixed zinc ore, 40-80g of polymetallic activator, 60-100g of isoamyl xanthate and 10-20g of pine oil are added to the slurry of the secondary zinc sulfide roughing operation in step (3).

5. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: For every ton of sulfur-oxygen mixed zinc ore, 20-40g of isoamyl xanthate and 5-10g of pine oil are added to the slurry of the zinc sulfide beneficiation operation in step (4).

6. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: For every ton of sulfur-oxygen mixed zinc ore, 4000~6000g of combined modifier and 220~340g of combined collector are added to the slurry of the zinc oxide roughing operation in step (5).

7. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: Based on a mass fraction of 100% for the multi-metal activator, the multi-metal activator contains 50-60% copper nitrate, 39-48% lead nitrate, and 1-3% silver nitrate.

8. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: Based on a mass fraction of 100% for the combined modifier, the combined modifier contains 80-90% sodium sulfide, 5-10% acidified water glass, and 5-10% disodium malonate.

9. The short-process cascade separation method for sulfur-oxygen mixed zinc ore according to claim 1, characterized in that: Based on a mass fraction of 100% for the combined collector, laurylamine acetate accounts for 45-55%, ammonium dodecyl sulfate accounts for 30-40%, and phenacetin O-25 accounts for 10-20%.

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