Low-grade zinc oxide ore amine sulfide process defoaming agent and application thereof

Abstract

The invention discloses a low-grade zinc oxide ore amine sulfide process defoaming agent and application thereof.The low-grade zinc oxide ore amine sulfide process defoaming agent is characterized in that firstly, ore is crushed and ground to achieve monomer dissociation between minerals, and meanwhile, a small amount of sodium carbonate and sodium sulfide are added into a grinding machine to serve as regulators; lS-X1 is used as a selective defoaming agent for amine sulfide flotation of smithsonite, and zinc sulfide concentrate is obtained after a section of roughing operation; and sodium sulfide and sodium carbonate are added into the zinc sulfide tailings for activation, and zinc oxide concentrate and tailings are obtained after the one-roughing, one-refining and one-scavenging flotation process. The efficient flotation defoaming agent LS-X1 has high selective defoaming capacity, has high defoaming capacity on amine collecting agents, does not affect the flotation performance of the amine collecting agents, and can greatly reduce the foam stability of the amine collecting agents, so that flotation closed cycle can be carried out; the method has the advantages of high feasibility, wide application range, high product index and the like.

Description

Technical Field

[0001] The invention relates to a low-grade zinc oxide ore sulfidation amine method defoamer and application thereof, and particularly relates to the technical field of mineral separation. Background Art

[0002] Zinc, as an important nonferrous metal raw material, possesses excellent electrical conductivity, corrosion resistance, ductility, heat resistance, and mechanical properties. It is widely used in the automotive, electrical, electronics, machinery manufacturing, chemical metallurgy, and steel industries. Zinc sulfide minerals are the primary source of zinc, and conventional flotation techniques can easily separate sulfide minerals from gangue. However, with the increasing depletion of sulfide ores, the flotation of zinc oxide ores has become increasingly important in recent years.

[0003] Zinc oxide ore flotation is primarily categorized into direct flotation and sulfidation flotation. Direct flotation involves the direct application of a collector to the target mineral; sulfidation flotation involves first adding a sulfiding agent to the target mineral for sulfidation, followed by the addition of a collector. Direct flotation of zinc oxide ore is limited by the poor selectivity of fatty acid collectors and their high water quality requirements, making it difficult to flot low-grade zinc oxide. The sulfidation amine method offers high flotation performance for low-grade zinc oxide ores, but due to the inherent properties of amine collectors, it suffers from severe flotation foam accumulation, making closed-loop operation unsuitable, hindering its application. Adding a defoamer can effectively alleviate the foam accumulation problem in zinc oxide ore flotation using the sulfidation amine method. Currently, silicones, polyethers, alcohols, and mineral oils are commonly used defoamers in flotation. However, these conventional defoamers all have drawbacks, primarily due to their chemical incompatibility with the multiphase interface of mineral flotation. Therefore, developing a defoamer with chemical properties compatible with the multiphase interface of zinc oxide ore flotation is crucial. Summary of the Invention

[0004] To solve the above problems, one of the objectives of the present invention is to provide a low-grade zinc oxide ore sulfide amine method defoamer, the defoamer is LS-X1, and the preparation method of LS-X1 is: 2-phosphonopropionic acid triethyl ester is combined with trimethylsiloxane and kerosene in a ratio of 2-2.5:1:1, and the mixture is added as an emulsion.

[0005] The second object of the present invention is to provide an application of the defoamer in the flotation of low-grade zinc oxide ore using a sulfide amine method, a flotation method for low-grade zinc oxide ore using a sulfide amine method, wherein the defoamer is LS-X1 during the flotation process, and the specific steps are as follows: (1) When grinding low-grade zinc oxide ore, add 1000-1200g / t sodium carbonate and 1000-1200g / t sodium sulfide to obtain ore pulp; (2) adding 200-300 g / t of collector I prepared by mixing amyl xanthate and ethyl thiocyanate in a mass ratio of 1-1.2:1 to the slurry obtained in step (1), and adding 15-20 g / t of No. 2 oil as a frother, and performing a zinc sulfide flotation operation to obtain zinc sulfide concentrate and zinc sulfide tailings; (3) Sodium sulfide is added to the zinc sulfide tailings obtained in step (2) as an activator, wherein the amount of sodium sulfide is 6000-7000 g / t; then a combined inhibitor of water glass and sodium hexametaphosphate with a mass ratio of 1-1.2:1 is added, and the amount is 400-500 g / t; 400-500 g / t of collector I and collector II octadecylamine and 100-140 g / t of defoamer LS-X1 are added, and 15-20 g / t of foaming agent No. 2 oil is added to obtain zinc oxide concentrate and tailings under the conditions of one coarse, one fine and one sweep, wherein the amount of sweeping collector I added is 300-40 g / t, and the amount of collector II added is 300-400 g / t, and the selected unmedicated middlings are returned in sequence.

[0006] Preferably, in the slurry of the present invention, minerals with a fineness of less than 200 mesh account for 85-90%, thereby achieving relative dissociation between useful minerals and between useful minerals and gangue minerals.

[0007] Preferably, the zinc sulfide flotation operation time in step (2) is 10 minutes.

[0008] Preferably, in step (3), the defoamer LS-X1 is used as a selective defoamer for zinc oxide sulfide amine flotation, and the preparation method is as follows: the defoamer LS-X1 is prepared as an emulsion and added, and the ratio of triethyl 2-phosphonopropionate, trimethylsiloxane and kerosene is 2-2.5:1:1.

[0009] Preferably, in step (3), the roughing operation time is 5 minutes, the sweeping operation time is 5 minutes, and the fine selection operation time is 10 minutes.

[0010] Preferably, in step (2), the foaming agent is No. 2 oil, and the addition ratio is 15-20 g / t.

[0011] The zinc oxide ore of the present invention is a low-grade zinc oxide ore, the main zinc mineral is smithsonite, and the main gangue minerals are calcite and dolomite.

[0012] The LS-X1 of the present invention has good defoaming ability and a selective defoaming mechanism, while ensuring the recovery rate of zinc oxide; the cumulative effect of the defoaming agent in the subsequent closed-loop circulation is not significantly affected.

[0013] The principles of the present invention are as follows: LS-X1 has the following effects on the defoaming flotation of low-grade zinc oxide ore by sulfidation amine method: (1) Using LS-X1 as a defoamer can reduce the stability of octadecylamine foam and shorten the existence time of foam while ensuring the recovery rate of zinc in zinc oxide concentrate.

[0014] (2) Triethyl 2-phosphonopropionate and trimethylsiloxane in LS-X1 have the effect of reducing the surface tension of the octadecylamine foam film. They also reduce the polarity of octadecylamine and promote its association to form a thin film layer. This substance will cause the liquid with higher surface tension to flow to the area with lower surface tension. Due to the traction of the high surface tension film layer and the imbalance of internal forces, the bubble wall will rupture.

[0015] (3) Triethyl 2-phosphonopropionate itself has a certain collection capacity, which can improve the recovery rate reduced by trimethylsiloxane defoaming. At the same time, triethyl 2-phosphonopropionate and trimethylsiloxane reduce the surface tension of the pulp, which greatly shortens the foam life of octadecylamine but does not cause octadecylamine to lose its selective collection ability for zinc oxide minerals. Kerosene can form hydrophobic aggregates after octadecylamine combines with mineral particles, thereby ensuring the recovery rate of the concentrate.

[0016] The beneficial effects of the present invention are as follows: (1) The high-efficiency defoaming agent used in the present invention has a strong defoaming ability and can effectively achieve selective defoaming of octadecylamine.

[0017] (2) Compared with the conventional defoaming method using tributyl phosphonate, the high-efficiency octadecylamine defoamer LS-X1 used in the present invention can eliminate the octadecylamine foam while ensuring the recovery rate of zinc.

[0018] (3) The present invention uses a defoaming flotation method of low-grade zinc oxide ore using sulfidation amine, which can efficiently recover the difficult-to-select zinc oxide ore stored in the mining process and solve the environmental problems caused by the storage of zinc oxide ore. It has the advantages of good defoaming effect, small dosage, strong adaptability, etc., and can bring higher economic benefits to enterprises. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a flotation process flow chart of Example 1 of the present invention.

[0020] Figure 2 This is the flotation foam diagram of Example 1 of the present invention.

[0021] Figure 3 This is the flotation foam diagram of Example 2 of the present invention.

[0022] Figure 4 This is the flotation foam diagram of Example 3 of the present invention.

[0023] Figure 5 This is the flotation foam diagram of Comparative Example 1 of the present invention.

[0024] Figure 6 This is the flotation foam diagram of Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0025] The present invention will be further described in detail below with reference to specific embodiments, but the protection scope of the present invention is not limited to the contents described above.

[0026] Example 1 Mineral raw materials The mineral used in Example 1 was derived from a low-grade zinc oxide ore in Lanping, Yunnan, with a total zinc grade of 5.22%, wherein the zinc mineral was mainly smithsonite. The dosage of the reagents was shown in Table 1.

[0027] Table 1 Dosage of Example 1 The specific steps are as follows: (1) When grinding low-grade zinc oxide ore, 1000 g / t sodium carbonate and 1000 g / t sodium sulfide are added to the ore and the ore is ground to obtain slurry; (2) adding a collector I of 200 g / t of amyl xanthate and ethyl sulfide nitrogen in a mass ratio of 1:1 to the slurry obtained in step (1), adding a foaming agent No. 2 oil, and performing a roughing process to obtain zinc sulfide concentrate and zinc sulfide tailings; (3) Sodium sulfide is added as an activator to the zinc sulfide tailings obtained in step (2), wherein the amount of sodium sulfide is 6000 g / t; then a combined inhibitor of water glass and sodium hexametaphosphate in a mass ratio of 1:1 is added, and the amount is 400 g / t; 400 g / t each of collector I and collector II octadecylamine and 100 g / t of defoamer LS-X1 are added, and 15 g / t of foaming agent No. 2 oil is added to obtain zinc oxide concentrate and tailings under the conditions of one coarse, one fine, and one sweep, and the middlings are returned in sequence.

[0028] See attached for foam effect Figure 2 .

[0029] Depend on Figure 2 The results show that when the present invention is used for the flotation of low-grade zinc oxide using the sulfide amine method, Example 1 produces a zinc oxide concentrate with a zinc grade of 21.78% and a zinc recovery of 75.65%, with virtually no foam accumulation. This demonstrates that the octadecylamine in Example 1 has a significant defoaming effect and produces a high-quality zinc oxide concentrate.

[0030] Example 2 Mineral raw materials The mineral used in Example 2 was sourced from Liangshan, Sichuan, with a total zinc grade of 5.98%. The dosage of the reagents is shown in Table 3.

[0031] Table 3 Dosage of Example 2 The operating steps are the same as in Example 1.

[0032] See attached for foam effect Figure 3 .

[0033] Product indicators are shown in Table 4.

[0034] Table 4 Flotation product indicators of Example 2 Depend on Figure 3 As shown in Table 4, when the present invention was used for flotation of low-grade zinc oxide using the sulfide amine method, Example 2 produced a zinc oxide concentrate with a zinc grade of 24.12% and a zinc recovery of 79.18%, with virtually no foam accumulation. This demonstrates that the octadecylamine in Example 2 has a significant defoaming effect and produces a high-quality zinc oxide concentrate.

[0035] Example 3 Mineral raw materials The mineral source used in Example 3 is slightly higher than that in Example 2, with a total zinc grade of 6.50%. The dosage of the reagents is shown in Table 5.

[0036] Table 5 Dosage of Example 1 The operating steps are the same as in Example 1.

[0037] See attached for foam effect Figure 4 .

[0038] Product indicators are shown in Table 6.

[0039] Table 6 Flotation product indicators of Example 1 Depend on Figure 4 As shown in Table 6, when the present invention was used for flotation of low-grade zinc oxide using the sulfide amine method, Example 3 produced a zinc oxide concentrate with a zinc grade of 26.18% and a zinc recovery of 83.09%, with virtually no foam accumulation. This demonstrates that the octadecylamine in Example 3 exhibited a significant defoaming effect and produced a high-quality zinc oxide concentrate.

[0040] Comparative Example 1 The mineral raw materials used in this embodiment are the same as those in Example 1, no defoaming agent is added, and the dosages of the other agents are the same as those in Example 1. The dosages of the agents are shown in Table 7. Table 7 Comparative Example 1 Dosage of the drug The specific steps are as follows: (1) When grinding low-grade zinc oxide ore, add 1000g / t sodium carbonate and 1000g / t sodium sulfide to grind the ore to obtain slurry; (2) adding a collector I of a mixture of amyl xanthate and ethyl sulfide nitrogen in a mass ratio of 1:1 to the slurry obtained in step (1) in an amount of 200 g / t, adding a foaming agent No. 2 oil, and performing a roughing process to obtain zinc sulfide concentrate and zinc sulfide tailings; (3) Sodium sulfide is added to the zinc sulfide tailings obtained in step (2) as an activator, wherein the amount of sodium sulfide is 6000 g / t; then a combined inhibitor of water glass and sodium hexametaphosphate in a mass ratio of 1:1 is added, and the amount is 400 g / t; 400 g / t of each of collector I and collector II octadecylamine is added, and a foaming agent No. 2 oil is added to obtain zinc oxide concentrate and tailings under the conditions of one coarse, one fine, and one sweep, and the middlings are returned in sequence.

[0041] Foam effect Figure 5 .

[0042] Product indicators are shown in Table 8.

[0043] Table 8 Flotation product indicators of comparative example 1 from Figure 5 As shown in the results of Table 8, when the low-grade zinc oxide ore was flotated by sulfidation amine method without using a defoamer, a zinc oxide concentrate with a zinc grade of 16.67% and a zinc recovery rate of 76.13% was obtained in Comparative Example 1; and the foam accumulation phenomenon was serious.

[0044] Comparative Example 2 The mineral raw materials used in this example are the same as those in Example 1, and conventional defoaming agent tributyl phosphate is added. The amounts of other agents used are the same as those in Example 1, as shown in Table 9. Table 9 Comparative Example 2 dosage Foam effect Figure 6 .

[0045] Product indicators are shown in Table 9.

[0046] Table 9 Flotation product indicators of comparative example 2 from Figure 6 As shown in the results of Table 9, when tributyl phosphate was used as a defoamer for the sulfidation amine flotation of low-grade zinc oxide ore, a zinc oxide concentrate with a zinc grade of 5.61% and a zinc recovery rate of 31.05% was obtained in Comparative Example 2; foam accumulation was not obvious, but the addition of tributyl phosphate caused the collector to lose its selective capture ability for the target mineral, resulting in a low separation efficiency.

[0047] Comparison of Example 1 with two comparative examples reveals that the sulfidation amine method exhibits significant drawbacks in treating low-grade zinc oxide ore when no defoamer is added and when the traditional defoamer, tributyl phosphate, is added. In Comparative Example 1, where no defoamer is used, the zinc oxide concentrate has a high recovery rate and grade, but severe foam accumulation occurs, making closed-loop circulation difficult. In Comparative Example 2, where tributyl phosphate is used as a defoamer, the foaming phenomenon is significantly reduced, but the grade of the zinc oxide concentrate and the recovery rate also decrease significantly. The results of Comparative Examples 1 and 2 demonstrate that conventional sulfidation flotation methods for zinc oxide ore have significant limitations when treating this type of zinc oxide ore and cannot achieve efficient recovery of zinc oxide ore. Compared to conventional sulfidation flotation methods for zinc oxide ore, the flotation method of the present invention effectively eliminates foam while also ensuring the grade and recovery rate of the zinc oxide concentrate, effectively achieving high-quality recovery of low-grade zinc oxide ore. Furthermore, the defoamer used provides excellent and stable defoaming flotation performance.

[0048] The above describes in detail the specific embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

1. A low-grade zinc oxide ore sulfide amine defoamer, characterized by: LS-X1 is used as a selective defoamer for zinc oxide sulfide amine flotation. The preparation method of LS-X1 is as follows: triethyl 2-phosphonopropionate, trimethylsiloxane and kerosene are prepared in a ratio of 2-2.5:1:1 and added as an emulsion.

2. The use of the defoamer according to claim 1 in the flotation of low-grade zinc oxide ore by sulfidation amine method, characterized in that: The specific steps are as follows: (1) When grinding low-grade zinc oxide ore, add 1000-1200g / t sodium carbonate and 1000-1200g / t sodium sulfide to obtain ore pulp; (2) adding a combined collector I of amyl xanthate and ethyl sulfide nitrogen in a mass ratio of 1-1.2:1 in an amount of 200-300 g / t to the slurry obtained in step (1), and adding a foaming agent No. 2 oil in an amount of 15-20 g / t, and performing a roughing process to obtain zinc sulfide concentrate and zinc sulfide tailings; (3) Sodium sulfide is added as an activator to the zinc sulfide tailings obtained in step (2), wherein the amount of sodium sulfide is 6000-7000 g / t; then a combined inhibitor of water glass and sodium hexametaphosphate is added in a mass ratio of 1-1.2:1, and the amount is 400-500 g / t; 400-500 g / t of combined collector I and collector II octadecylamine and 100-140 g / t of defoamer LS-X1 are added, and a foaming agent No. 2 oil is added to obtain zinc oxide concentrate and tailings in a process of one coarse, one fine, and one sweep, and the intermediate mineral products are returned in sequence.

3. The use of the defoamer according to claim 2 in the flotation of low-grade zinc oxide ore by sulfidation amine method, characterized in that: The grinding conditions in step (1) are: the fineness of -200 mesh in the ore pulp accounts for 85-90%, and the useful minerals are relatively dissociated from each other and from the gangue minerals.

4. The use of the defoamer according to claim 2 in the flotation of low-grade zinc oxide ore by sulfidation amine method, characterized in that: In step (3), the zinc oxide roughing operation time is 5 minutes, the zinc oxide scavenging operation time is 5 minutes, and the zinc oxide scavenging and cleaning operation time is 10 minutes; in the scavenging operation, the addition amount of collector I is 300-400 g / t, and the addition amount of collector II is 300-400 g / t.

Images