Flotation reagent and method for sulfur and arsenic mineral activating agent and tin concentrate reverse flotation desulfurization and dearsenification

Abstract

The invention discloses a flotation reagent and method for sulfur and arsenic mineral activating agent and tin concentrate reverse flotation desulfurization and dearsenification, and belongs to the technical field of mineral processing. The sulfur-arsenic mineral activating agent comprises thiosulfate, soluble lead salt and soluble copper salt, can activate arsenic-sulfur minerals such as arsenopyrite (FeAsS2), pyrite (FeS2) and pyrrhotite (Fe1-xS) in a high-selectivity mode, enhances the flotation performance of the arsenic-sulfur minerals, and is used in cooperation with a cassiterite inhibitor, a sulphide ore collecting agent and a foaming agent, so that the flotation efficiency of the arsenic-sulfur minerals is improved, and the flotation efficiency of the arsenic-sulfur minerals is improved. The method is particularly suitable for flotation removal of arsenic-sulfur minerals in the tin concentrate, the tin loss can be remarkably reduced while the tin concentrate desulfurization and dearsenification efficiency can be greatly improved, and the environmental protection pressure of subsequent smelting is effectively relieved.

Description

Technical Field

[0001] This invention relates to a sulfur-arsenic mineral activator, particularly to a sulfur-arsenic mineral activator used in the reverse flotation desulfurization and dearsenic removal process of tin concentrate, and also to a flotation reagent and method for reverse flotation desulfurization and dearsenic removal of tin concentrate, belonging to the field of mineral processing technology. Background Technology

[0002] Tin is widely used in electronic solders, tinplate, alloy manufacturing, and chemical industries. Tin concentrate, as the main raw material for tin smelting, directly affects the efficiency and environmental impact of subsequent metallurgical processes. However, tin ore often occurs in association with various sulfide minerals, especially arsenopyrite (FeAsS2), pyrite (FeS2), and pyrrhotite (Fe...). 1-x Arsenic and sulfur-containing minerals, such as sulfur dioxide (S), release toxic gases like sulfur dioxide and arsenic compounds during smelting, causing serious environmental pollution and increasing smelting costs. Therefore, efficiently removing sulfur and arsenic impurities from tin concentrate before it enters the smelting process is crucial for improving tin concentrate product quality and reducing environmental risks.

[0003] Currently, the main methods for desulfurization and arsenic removal from tin concentrate include oxidative roasting, alkaline leaching, and flotation separation. Among these, flotation is widely used due to its low cost and wide applicability. However, in traditional flotation processes, minerals such as arsenopyrite and pyrite have poor floatability and require activators to enhance their hydrophobicity for effective separation. In recent years, studies have shown that certain inorganic salts can enhance the flotation behavior of sulfide minerals. For example, Chinese patent application (CN119281499A) discloses the use of copper sulfate and oxalic acid as activators to achieve efficient desulfurization of tin crude concentrate; Chinese patent application (CN111974539A) discloses the use of sulfuric acid as an activator to achieve desulfurization of tin concentrate. However, these methods for desulfurizing tin concentrate still have technical problems such as large reagent consumption, complex processes, and difficulty in obtaining high-purity tin concentrate. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the first objective of this invention is to provide a sulfur-arsenic mineral activator that can selectively activate arsenopyrite (FeAsS2), pyrite (FeS2), and pyrrhotite (Fe... 1-x Arsenic and sulfur minerals such as S) enhance their flotation properties, making them particularly suitable for the flotation removal of arsenic and sulfur minerals from cassiterite.

[0005] The second objective of this invention is to provide a flotation reagent for desulfurization and dearsenic removal in reverse flotation of tin concentrate. This flotation reagent activates arsenic-sulfur minerals in the tin concentrate to enhance the hydrophobic effect of the collector on the surface of the arsenic-sulfur minerals, and works in conjunction with an inhibitor to suppress the flotation of cassiterite, thereby enhancing the difference in floatability between arsenic-sulfur minerals and cassiterite. This significantly improves the desulfurization and dearsenic removal efficiency of tin concentrate while significantly reducing tin loss.

[0006] The third objective of this invention is to provide a method for desulfurization and dearsenic removal from tin concentrate by reverse flotation. This method enhances the flotation separation effect between sulfur and arsenic minerals and cassiterite by using special combined flotation reagents, thereby improving the grade and recovery rate of tin concentrate. The process is simple, the reagent cost is low, and it is conducive to large-scale promotion and application.

[0007] To achieve the above-mentioned technical objectives, the present invention provides a sulfur-arsenic mineral activator comprising thiosulfate, soluble lead salt and soluble copper salt.

[0008] The main components of the sulfur-arsenic mineral activator of this invention are thiosulfate, soluble lead salt, and soluble copper salt. The thiosulfate mainly provides thiosulfate ions, while the soluble lead salt and soluble copper salt mainly provide lead ions and copper ions. The lead ions and copper ions can selectively act on the surface of sulfur-arsenic minerals such as arsenopyrite, pyrite, and pyrrhotite. The thiosulfate ions readily generate sulfide anions, thereby sulfiding the lead ions and copper ions adsorbed on the surface of sulfur-arsenic minerals and generating PbS and CuS similar to those in galena and chalcopyrite. This achieves hydrophobic modification of the surface of sulfur-arsenic minerals, which is beneficial to the collecting effect of sulfide mineral collectors on sulfur-arsenic minerals and enhances the collecting effect of sulfide mineral collectors on sulfur-arsenic minerals.

[0009] As a preferred embodiment, the thioarsenic mineral activator is composed of thiosulfate, soluble lead salt, and soluble copper salt in a mass ratio of (5~10):(0.8~1.2):(1~1.5). In this activator, sodium thiosulfate (Na2S2O3) primarily provides S2O3. 2- The S² produced by its decomposition in the slurry - It can remove Pb adsorbed on the surface of sulfur-arsenic minerals 2+ and Cu 2+ Sulfidation generates hydrophobic PbS and CuS films, thereby efficiently activating arsenic sulfide minerals; this process also removes the oxide film on the mineral surface, enhancing its floatability. Soluble lead and copper salts (such as Pb(NO3)2 and CuSO4) provide the crucial Pb content, respectively. 2+ and Cu 2+ Lead ions selectively adsorb and activate minerals such as arsenopyrite. The ratio is set at (5~10):(0.8~1.2):(1~1.5) to optimize the synergistic effect: insufficient thiosulfate leads to incomplete sulfidation, while excessive amounts are wasteful; excessive lead / copper salts may non-selectively activate other minerals and increase costs and environmental burden. Lead ions (Pb) 2+ With copper ions Cu 2+ The combined use of these two ions produced a significant synergistic effect. Its advantages are: firstly, the two ions are complementary in their selective adsorption and activation mechanisms; Pb 2+It exhibits stronger selectivity for arsenic-containing minerals (such as arsenopyrite), while Cu... 2+ It has superior activation ability for sulfides (such as pyrite), and the synergy of the two can cover a wider range of sulfur and arsenic mineral types; secondly, it can effectively avoid the limitations of a single ion system, which is not as effective when Cu is used alone. 2+ The removal effect on arsenic minerals is poor, and using Pb alone is ineffective. 2+ This may lead to insufficient sulfur removal and the introduction of excessive lead ions, increasing the environmental burden; third, by optimizing the ratio of the two, the total amount of reagents can be reduced while ensuring high-efficiency activation performance, improving the economics of the process, and enhancing the adaptability to tin concentrates with different mineral phase compositions.

[0010] As a preferred embodiment, the thiosulfate comprises sodium thiosulfate.

[0011] As a preferred embodiment, the soluble lead salt includes at least one of lead nitrate and lead acetate. The main function of the soluble lead salt is to provide lead ions. Theoretically, lead salts that readily ionize into lead ions in water meet the requirements, such as lead nitrate and lead acetate.

[0012] As a preferred embodiment, the soluble copper salt includes at least one of copper sulfate, copper nitrate, copper acetate, and copper chloride. Soluble lead salts primarily provide lead ions; theoretically, salts that readily ionize into lead ions in water meet the requirements. Soluble copper salts primarily provide copper ions; theoretically, copper salts that readily ionize into copper ions in water meet the requirements, such as copper sulfate, copper nitrate, and copper acetate.

[0013] The present invention also provides a flotation reagent for desulfurization and dearsenic removal in reverse flotation of tin concentrate, comprising the aforementioned sulfur and arsenic mineral activator, cassiterite inhibitor, sulfide mineral collector, and frother.

[0014] The flotation reagent of this invention contains a sulfur-arsenic mineral activator, a cassiterite inhibitor, a sulfide mineral collector, and a frother. The sulfur-arsenic mineral activator can selectively generate PbS and CuS, similar to galena and chalcopyrite, on the surface of sulfur-arsenic minerals such as arsenopyrite, pyrite, and pyrrhotite. This enhances the hydrophobic modification of the sulfur-arsenic mineral surface by the sulfide mineral collector. Combined with the inhibitory effect of the cassiterite inhibitor on cassiterite flotation, the difference in floatability between sulfur-arsenic minerals and cassiterite is increased. This significantly improves the desulfurization and dearsenic removal efficiency of tin concentrate while significantly reducing tin loss.

[0015] As a preferred embodiment, the cassiterite inhibitor comprises sodium carboxymethyl cellulose (CMC) and sodium silicate. CMC and sodium silicate, as cassiterite inhibitors, adsorb onto the surface of cassiterite, preventing the activation of cassiterite by lead and copper ions, while simultaneously enhancing the hydrophilicity of the cassiterite surface to strengthen its dispersion in water and inhibit its floating. As a more preferred embodiment, the cassiterite inhibitor is composed of sodium CMC and sodium silicate in a mass ratio of 1:(1.5~10). More preferably, the cassiterite inhibitor is composed of sodium CMC and sodium silicate in a mass ratio of 1:(1.5~2.5). Sodium CMC mainly inhibits cassiterite floating by adsorbing onto the surface to form a hydrophilic coating, while sodium silicate mainly enhances the inhibitory environment and prevents sludge interference by adjusting the slurry pH and dispersibility. The combination of the two in a mass ratio of 1:(1.5~2.5) ensures effective inhibition of cassiterite while avoiding excessive slurry viscosity due to excessive CMC, thus balancing the inhibitory effect with process stability.

[0016] As a preferred embodiment, the sulfide mineral collector includes at least one selected from ethyl xanthate, propyl xanthate, isopropyl xanthate, and butyl xanthate. Butyl xanthate is further preferred.

[0017] The present invention also provides a method for desulfurization and dearsenic removal of tin concentrate by reverse flotation. The method involves grinding and adjusting the tin concentrate to obtain a slurry; adding the flotation reagent to the slurry; and performing aeration flotation. The flotation concentrate is a sulfur-arsenic concentrate product, and the flotation tailings are a high-purity tin concentrate product.

[0018] As a preferred embodiment, the tin concentrate contains at least one of arsenopyrite, pyrite, and pyrrhotite.

[0019] As a preferred embodiment, the grinding process is performed to ensure that the particle size of the tin concentrate is 30% to 95% by mass of the -0.074mm particle size.

[0020] As a preferred embodiment, the flotation process includes a roughing process and a sweeping process.

[0021] As a preferred embodiment, both the roughing and scavenging processes involve the addition of a sulfur-arsenic mineral activator; in the roughing and scavenging processes, the total amount of the sulfur-arsenic mineral activator is 100-1000 g / t of ore, the total amount of the cassiterite inhibitor is 200-800 g / t of ore, the total amount of the sulfide mineral collector is 30-150 g / t of ore, and the total amount of the frother is 10-80 g / t of ore.

[0022] As a preferred embodiment, the sulfur arsenic activator, cassiterite inhibitor, sulfide ore collector and frother are added sequentially during the roughing process.

[0023] As a preferred embodiment, the foaming agent is methyl isobutyl methanol (MIBC) and / or pine oil. These are conventional foaming agents in this technical field.

[0024] The method for desulfurization and dearsenic removal from tin concentrate by reverse flotation of the present invention includes the following steps:

[0025] (1) Grinding: Grind the tin concentrate to a fineness of -0.074 mm with a particle size of 30%~95%.

[0026] (2) Slurry preparation: Transfer the slurry to the flotation cell and add sulfur and arsenic mineral activator (slurry preparation 1~10min), cassiterite inhibitor (slurry preparation 1~10min), sulfide mineral collector (slurry preparation 1~3min) and frother (slurry preparation 1min) in sequence.

[0027] (3) Aerated flotation, the concentrate is sulfur-arsenic concentrate and the tailings are high-purity tin concentrate.

[0028] Compared with existing technologies, the beneficial technical effects of the present invention are as follows:

[0029] The sulfur-arsenic mineral activator provided by this invention can generate PbS and CuS similar to galena and chalcopyrite on the surface of sulfur-arsenic minerals such as arsenopyrite, pyrite, and pyrrhotite, thereby achieving hydrophobic modification of the sulfur-arsenic mineral surface. This is beneficial to the collecting effect of sulfide mineral collectors on sulfur-arsenic minerals and enhances the collecting effect of sulfide mineral collectors on sulfur-arsenic minerals.

[0030] The sulfur and arsenic mineral activator in the flotation reagent provided by this invention can significantly improve the collection ability of sulfide mineral collectors for sulfur- and arsenic-containing minerals such as arsenopyrite, pyrite, and pyrrhotite. With the inhibitory effect of cassiterite depressant on cassiterite flotation, the recovery rate of arsenopyrite, pyrite, and pyrrhotite is significantly improved while minimizing cassiterite loss. This greatly reduces the sulfur and arsenic content in high-purity tin concentrate, which is beneficial to reducing subsequent smelting costs and reducing environmental burden.

[0031] The method for desulfurization and dearsenic removal of tin concentrate by reverse flotation provided by this invention can not only improve the grade and recovery rate of tin concentrate, but also has a simple process and low reagent cost, which is conducive to large-scale promotion and application. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the process for improving the flotation recovery rate of sulfur and arsenic minerals in tin concentrate using sulfur and arsenic mineral activators in Embodiment 3 of the present invention. Detailed Implementation

[0033] The technical solution of the present invention will be clearly and completely described below through specific embodiments, but the following specific embodiments are not limited to the scope of protection of the claims.

[0034] In the following examples, unless otherwise specified, all pharmaceutical agents used are commercially available products.

[0035] Ore raw material: a tin concentrate from a certain place in northwestern Guangxi. Its main components and grades are as follows: 46.7% tin, 9.36% sulfur, 1.52% arsenic, and the remaining main components are 3.73% silicon and 1.08% zinc.

[0036] Example 1

[0037] Tin concentrate was ground in a conical ball mill to achieve a product fineness of -200 mesh (80%). The pulp concentration was 54%. 200g of the resulting sample was placed in a 0.5L flotation cell and stirred for 1 minute at 1912 rpm. Then, 500g / t of Na₂S₂O₃ was added, followed by 3 minutes of pulp conditioning; 80g / t of Pb(NO₃)₂ was added, followed by 5 minutes of pulp conditioning; 100g / t of CuSO₄ was added, followed by 3 minutes of pulp conditioning; 50g / t of xanthate (SIBX) was added, followed by 3 minutes of pulp conditioning; and 20g / t of MIBC was added, followed by 1 minute of pulp conditioning. Roughing was then performed for 5 minutes. Finally, 40g / t of Pb(NO₃)₂ was added, followed by 3 minutes of pulp conditioning; 50g / t of CuSO₄ was added, followed by 3 minutes of pulp conditioning; 20g / t of SIBX was added, followed by 3 minutes of pulp conditioning; and MIBC was added. 20g / t, slurry conditioning for 1min, scavenging for 4min; filter, dry, and weigh the concentrate and tailings obtained from flotation, and calculate the recovery rate.

[0038] Table 1 shows that the addition of Na₂S₂O₃, Pb(NO₃)₂, and CuSO₄ significantly activated sulfur and arsenic minerals such as arsenopyrite, pyrite, and pyrrhotite in tin concentrate, thereby significantly improving the recovery rates of sulfur and arsenic in the tin concentrate. Compared with the absence of sulfur and arsenic mineral activators, the sulfur recovery rate increased from 41.79% to 72.01%, and the arsenic recovery rate increased from 38.99% to 90.29%. The tin recovery rate decreased slightly from 4.76% to 4.50%, indicating that the sulfur and arsenic mineral activators achieved highly efficient desulfurization and arsenic removal while having a very small impact on the tin loss rate.

[0039] Example 2

[0040] Example 1 has already demonstrated that the sulfur-arsenic mineral activator has a good effect on activating sulfur-arsenic minerals and improving the desulfurization and dearsenic removal effect. Example 2 is based on Example 1, further increasing the amount of Pb(NO3)2.

[0041] The raw mineral was ground in a conical ball mill, and the fineness of the ground product was controlled to be -200 mesh, accounting for 80%. The pulp concentration was 54%. 200g of the obtained sample was placed in a 0.5L flotation cell and stirred for 1 min at a speed of 1912 rpm. 500g / t of Na2S2O3 was added and the pulp was adjusted for 3 min, 100g / t of Pb(NO3)2 was added and the pulp was adjusted for 5 min, 100g / t of CuSO4 was added and the pulp was adjusted for 3 min, 50g / t of SIBX was added and the pulp was adjusted for 3 min, and 20g / t of MIBC was added and the pulp was adjusted for 1 min. Roughing was carried out for 5 min. Then, 50g / t of Pb(NO3)2 was added and the pulp was adjusted for 3 min, 50g / t of CuSO4 was added and the pulp was adjusted for 3 min, 1 min, 20g / t of SIBX was added and the pulp was adjusted for 3 min, and 20g / t of MIBC was added and the pulp was adjusted for 1 min. Scavenging was carried out for 4 min. The middlings and tailings of the concentrate obtained from flotation were filtered, dried, weighed, and the recovery rate was calculated.

[0042] As shown in Table 1, after adding 20 g / t Pb(NO3)2 to the method used in Example 1, the sulfur recovery rate increased from 41.79% to 72.95%, and the arsenic recovery rate increased from 38.99% to 91.95%. Compared to Example 1, the recovery rates of sulfur and arsenic increased slightly. The tin recovery rate further decreased to 4.17%. Example 2 demonstrates that a relatively small amount of Pb(NO3)2 in the activator can achieve highly efficient desulfurization and arsenic removal.

[0043] Example 3

[0044] Example 3 introduces two cassiterite inhibitors, sodium carboxymethyl cellulose (CMC) and sodium silicate (NaSi2O3), based on Example 2.

[0045] The raw ore was ground in a conical ball mill, and the fineness of the ground product was controlled to be -200 mesh, accounting for 80%; the pulp concentration was 54%. 200g of the obtained sample was placed in a 0.5L flotation cell and stirred for 1 min at 1912 rpm; 500g / t of Na2S2O3 was added, and the pulp was adjusted for 3 min; 100g / t of Pb(NO3)2 was added, and the pulp was adjusted for 5 min; CMC was added. 150 g / t NaSi2O3 300 g / t, slurry conditioning for 4 min; CuSO4 100 g / t, slurry conditioning for 3 min; SIBX 50 g / t, slurry conditioning for 3 min; MIBC 20 g / t, slurry conditioning for 1 min; roughing for 5 min; then sequentially add Pb(NO3)2 250 g / t, slurry conditioning for 3 min; CuSO4 50 g / t, slurry conditioning for 3 min; SIBX 20 g / t, slurry conditioning for 3 min; MIBC 20 g / t, slurry conditioning for 1 min; scavenging for 4 min; filter, dry, and weigh the concentrate and tailings obtained from flotation, and calculate the recovery rate.

[0046] As shown in Table 1, after adding 150g / t CMC and 300g / t NaSi₂O₃ to Example 2, the sulfur recovery rate increased from 41.79% to 84.33%, and the arsenic recovery rate increased from 38.99% to 94.03%. The sulfur and arsenic recovery rates further increased compared to Example 2. The tin recovery rate increased slightly to 5.07%. Example 3 demonstrates that, based on existing common cassiterite inhibitors, the addition of this series of sulfur and arsenic mineral activators can significantly reduce the sulfur and arsenic content while maintaining the tin recovery rate, with almost no effect on tin.

[0047] Example 4 (as a control)

[0048] Example 4 is based on Example 3, using only sodium thiosulfate (Na2S2O3) as the activator, omitting the addition of lead and copper salts. To clearly verify the synergistic effect among thiosulfate, soluble lead salt, and soluble copper salt in the thioarsenic mineral activator, all other flotation conditions and reagent formulations remained consistent with Example 3.

[0049] The raw mineral was ground in a conical ball mill, and the fineness of the ground product was controlled to be -200 mesh, accounting for 80%. The pulp concentration was 54%. 200g of the obtained sample was placed in a 0.5L flotation cell and stirred for 1 min at a speed of 1912 rpm. 500g / t of Na2S2O3 was added and the pulp was adjusted for 3 min. 50g / t of SIBX was added and the pulp was adjusted for 3 min. 20g / t of MIBC was added and the pulp was adjusted for 1 min. Roughing was carried out for 5 min. Then 20g / t of SIBX was added and the pulp was adjusted for 3 min. 20g / t of MIBC was added and the pulp was adjusted for 1 min. Scavenging was carried out for 4 min. The middlings and tailings of the concentrate obtained from flotation were filtered, dried, weighed, and the recovery rate was calculated.

[0050] As shown in Table 1, in Example 4, using only sodium thiosulfate as the activator, the sulfur recovery rate rapidly decreased from 84.33% to 41.66%, and the arsenic recovery rate rapidly decreased from 94.03% to 37.95%. These results clearly indicate that the lack of Pb... 2+ With Cu 2+ The synergistic effect of sodium thiosulfate alone on the activation effect of arsenic sulfide minerals is extremely limited, failing to achieve efficient removal. Simultaneously, the tin recovery rate only slightly increased to 5.20%. This indicates that when sodium thiosulfate is used alone, its activation effect lacks selectivity; it not only has a weak activation effect on arsenic sulfide minerals but may also slightly activate cassiterite or cause ore slime to float, resulting in fluctuations in tin concentrate grade and recovery rate. The comparison between this example and Example 3 strongly demonstrates the indispensable synergistic effect among the components of the activator of this invention. The main function of sodium thiosulfate is to provide sulfur for subsequent sulfidation reactions. 2- However, its use alone cannot effectively activate sulfur-arsenic minerals; while soluble lead and copper salts provide Pb 2+ and Cu2+ It can selectively adsorb onto the surface of sulfur-arsenic minerals and react with S. 2- The reaction generates hydrophobic PbS and CuS thin films, thereby achieving efficient and highly selective activation. All three components work synergistically and are indispensable. The absence of any component (whether lead salt, copper salt, or thiosulfate) will lead to a significant decrease in activation efficiency, failing to achieve the desired desulfurization and arsenic removal targets. This example, using only thiosulfate, fully demonstrates this conclusion.

[0051] Example 5 (as a control)

[0052] Example 5 is based on Example 3 without the addition of lead salt. To clearly verify the synergistic effect among thiosulfate, soluble lead salt, and soluble copper salt in the thioarsenic mineral activator, all other flotation conditions and reagent formulations remained consistent with Example 3.

[0053] The raw mineral was ground in a conical ball mill, and the fineness of the ground product was controlled to be -200 mesh, accounting for 80%. The pulp concentration was 54%. 200g of the obtained sample was placed in a 0.5L flotation cell and stirred for 1 min at a speed of 1912 rpm. 500g / t of Na2S2O3 was added and the pulp was adjusted for 3 min. 150g / t of CMC + 300g / t of NaSi2O3 were added and the pulp was adjusted for 4 min. 100g / t of CuSO4 was added and the pulp was adjusted for 3 min. 50g / t of SIBX was added and the pulp was adjusted for 3 min. 20g / t of MIBC was added and the pulp was adjusted for 1 min. Roughing was carried out for 5 min. Then, 50g / t of CuSO4, 20g / t of SIBX, and 20g / t of MIBC were added sequentially and the pulp was adjusted for 3 min. Scavenging was carried out for 4 min. The middlings and tailings of the concentrate obtained from flotation were filtered, dried, weighed, and the recovery rate was calculated.

[0054] As shown in Table 1, in Example 5, without the addition of lead salt, the sulfur recovery rate rapidly decreased from 84.33% to 62.49%, and the arsenic recovery rate rapidly decreased from 94.03% to 54.91%. This result indicates that although Cu... 2+ It has a certain activating ability for sulfur minerals, but in the absence of Pb 2+ In this case, the selective activation effect of copper salt on arsenic minerals (especially arsenopyrite) was significantly insufficient, leading to a substantial decrease in arsenic removal efficiency. Meanwhile, although the sulfur recovery rate was better than the system without activator, it was still far lower than the copper-lead synergistic system, indicating that a single copper salt is insufficient to achieve comprehensive and efficient activation of sulfur- and arsenic-containing minerals. Furthermore, the tin recovery rate fluctuated, further indicating that the selectivity of single copper ions is poor, and there may be slight activation of non-target minerals. These experimental results, in stark contrast to the copper-lead synergistic system, fully demonstrate the irreplaceable role of lead salt in the selective activation of arsenic-containing minerals, and that the synergistic use of copper and lead salts is key to achieving efficient and highly selective flotation removal of sulfur- and arsenic-containing minerals.

[0055] Example 6 (as a control)

[0056] Example 6 provides a blank control for obtaining the recovery rates of sulfur and arsenic under SIBX-only conditions.

[0057] The raw mineral was ground in a conical ball mill, and the fineness of the ground product was controlled to be -200 mesh, accounting for 80%. 200g of the obtained sample was placed in a 0.5L flotation cell and stirred for 1 min at a speed of 1912 rpm. 50 g / t of SIBX was added and the mixture was conditioned for 3 min, followed by 20 g / t of MIBC and conditioned for 1 min, and roughing was performed for 5 min. Then, 20 g / t of SIBX was added and conditioned for 3 min, followed by 20 g / t of MIBC and conditioned for 1 min, and scavenging was performed for 4 min. The middlings and tailings of the concentrate obtained from the flotation were filtered, dried, weighed, and the recovery rate was calculated.

[0058] As shown in Table 1, the recovery rate of sulfur was 41.79%, the recovery rate of arsenic was 38.99%, and the recovery rate of tin was 4.76% when only the collector was added.

[0059] Through five sets of comparative experiments, the sulfur-arsenic mineral activator disclosed in this invention has a good activation effect on sulfur-arsenic minerals in a tin concentrate in Southwest China, increasing the sulfur recovery rate by nearly 45 percentage points and the arsenic recovery rate by nearly 60 percentage points, while having almost no effect on the tin recovery rate. Comparing Example 1 with Example 2 shows that the sulfur-arsenic mineral activator can achieve ideal sulfur and arsenic recovery rates at lower dosages. Comparing Example 2 with Example 3 shows that the sulfur-arsenic mineral activator can achieve more ideal desulfurization and arsenic removal effects under the action of common cassiterite inhibitors. Comparing Example 3 with Example 4 shows that a single agent cannot achieve ideal sulfur and arsenic recovery rates; synergistic effects between agents are required, and any component is indispensable.

[0060]

[0061] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A sulpho-arsenical mineral activator, characterized in that: The thiosulfate salt, the soluble lead salt and the soluble copper salt are included.

2. The orpiment mineral activator according to claim 1, characterized by: The thiosulfate salt, the soluble lead salt and the soluble copper salt are composed according to the mass ratio (5-10):(0.8-1.2):(1-1.5). 3.The sulfide ore activator according to claim 1 or 2, characterized in that: The thiosulfate salt includes sodium thiosulfate; The soluble lead salt includes at least one of lead nitrate and lead acetate; The soluble copper salt includes at least one of copper sulfate, copper nitrate, copper acetate and copper chloride.

4. A flotation reagent for desulfurization and dearsenification of tin concentrate reverse flotation, characterized in that: The sulfide ore activator, the cassiterite inhibitor, the sulfide collector and the frother according to any one of claims 1-3 are included. 5.The flotation reagent for the reverse flotation of tin concentrate to remove sulfur and arsenic according to claim 4, characterized in that: The cassiterite inhibitor includes sodium carboxymethyl cellulose and sodium silicate; The sulfide collector includes at least one of ethyl xanthate, propyl xanthate, isopropyl xanthate and butyl xanthate.

6. The flotation reagent for desulfurization and dearsenification of tin concentrate reverse flotation according to claim 5, characterized in that: The cassiterite inhibitor is composed of sodium carboxymethyl cellulose and sodium silicate according to the mass ratio 1:(1.5-10).

7. A method for desulfurization and dearsenification of tin concentrate by reverse flotation, characterized by: The tin concentrate is ground and slurried to obtain a slurry; the flotation reagent according to any one of claims 4-6 is added to the slurry, and aeration flotation is performed, and a flotation concentrate is a sulfide concentrate product, and a flotation tailing is a high-purity tin concentrate product.

8. The method for desulfurization and dearsenification of tin concentrate by reverse flotation according to claim 7, characterized in that: The sulfide minerals included in the tin concentrate are at least one of arsenopyrite, pyrite and pyrrhotite. 9.The method for the reverse flotation of tin concentrate to remove sulfur and arsenic according to claim 7, characterized in that: The grinding is performed to meet the particle size of the tin concentrate: the mass ratio of the particle size of-0.074mm is 30%-95%. 10.The method for the reverse flotation of tin concentrate to remove sulfur and arsenic according to any one of claims 7-9, characterized in that: The flotation includes a once roughing and a once scavenging process; The sulfide ore activator is added to the roughing and the scavenging; In the roughing and the scavenging, the total amount of the sulfide ore activator is 100-1000g / t of ore, the total amount of the cassiterite inhibitor is 200-800g / t of ore, the total amount of the sulfide collector is 30-150g / t of ore, and the total amount of the frother is 10-80g / t of ore; The sulfide activator, the cassiterite inhibitor, the sulfide collector and the frother are sequentially added in the roughing process.

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