A magnetic-float combined tungsten-tin separation beneficiation method

Abstract

The invention discloses a tungsten-tin diversion beneficiation method combining magnetic and flotation. The method comprises the following steps: subjecting tungsten-tin polymetallic ore to crushing, grinding, iron removal and magnetic separation in sequence to obtain a non-magnetic product and a magnetic product; after desulfurization, the non-magnetic product is subjected to tungsten flotation using a metal ion complex with relatively weak hydrophobicity as a collector, salinized water glass as a depressant, and No. 2 oil as a frother to obtain a tungsten concentrate; and the magnetic product is subjected to tin flotation using a metal ion complex with relatively strong hydrophobicity as a collector, and sodium fluorosilicate as a depressant to obtain a tin concentrate. The method can achieve a WO3 recovery rate of more than 85% and a Sn recovery rate of more than 60%, and has the characteristics of a short process, convenient operation, low labor intensity, low energy consumption, environmental protection and high efficiency. It not only significantly improves the utilization efficiency of tungsten and tin resources, but also greatly reduces beneficiation costs and expands the production capacity of the mine.

Description

Technical Field

[0001] The present invention relates to a tungsten-tin polymetallic ore beneficiation method, in particular to a magnetic-flotation combined tungsten-tin diversion beneficiation method, belonging to the technical field of ore beneficiation. Background Art

[0002] Tungsten and tin are important strategic mineral resources, and their security is related to the long-term stable development of the national economy and national security. At present, the rich tungsten and tin mineral resources are becoming increasingly scarce, and a large amount of tungsten and tin minerals are difficult to effectively sort and recycle, resulting in a large amount of tungsten and tin resources being wasted. The existing reserves of high-quality single tungsten or single tin ores are very few. Therefore, it is necessary to increase the development of complex and difficult-to-select tungsten-tin polymetallic ores. The resources of tungsten-tin polymetallic mines are characterized by their high number of valuable components, complex co-existing relationships, and fine embedded particle size. As a result, the current tungsten and tin beneficiation recovery rates in such mines are low (especially tin), resulting in serious waste of resources. It is of great significance to improve the recovery and utilization rate of tungsten, tin and polymetallic resources to ensure the sustainable development of my country's tungsten and tin industries.

[0003] Currently, the raw tungsten-tin polymetallic ores in my country have low tungsten grades, making efficient tungsten recovery difficult through flotation alone, leading to resource loss. High levels of gangue minerals such as diopside, hedgmannite, andradite in the raw ore affect the grade of the tungsten concentrate. Furthermore, tungsten is primarily concentrated in the Earth's crust as tungstates within granite contact metamorphic zones. In many tungsten deposits, tungsten is associated with tin-bearing minerals to varying degrees, particularly in porphyry tungsten deposits. These polymetallic sulfide ores often contain tin-bearing minerals such as cassiterite. For example, the Shizhuyuan tungsten polymetallic ore body contains 460,000 tons of associated tin, but the grade of the raw ore is only 0.10-0.12%. 60% of this associated tin is colloidal, with poor floatability, making comprehensive utilization difficult. As a result, 1,500 tons of tin is discharged into tailings ponds annually. Currently, there is no effective means of recovering this tin. Existing beneficiation processes for treating this type of tungsten-tin polymetallic resource primarily utilize chelating and fatty acid-based collectors. In fact, regardless of which process is currently used, tungsten recovery is the primary focus, with a small amount of tin being recovered and incorporated into the tungsten concentrate. The remainder is lost in the tailings, resulting in a significant waste of tin resources.

[0004] Since cassiterite cannot be effectively enriched in tungsten concentrate, is it possible to recover tin from tungsten tailings? In fact, because cassiterite in tailings is interfered with by a large amount of reagents, its floatability is very poor, making it difficult to effectively recover tungsten and tin using flotation processes. For example, using the fatty acid method, cassiterite ultimately ends up in tungsten rougher tailings and scheelite heated flotation tailings. There, it is inhibited by a large amount of water glass, significantly reducing its floatability and resulting in extremely poor flotation results.

[0005] The most recently reported beneficiation methods for tungsten-tin polymetallic minerals, such as the Chinese patent application (publication number CN115555124A), disclose a tungsten-tin asynchronous flotation method. This method involves sequentially crushing, grinding, de-ironizing, and desulfurizing the tungsten-tin ore to produce a tungsten-tin mixed ore pulp. This tungsten-tin mixed ore pulp is first flotated under weakly alkaline conditions using a metal ion complex as a collector to produce a tungsten concentrate. This slurry is then flotated under strongly alkaline conditions using a metal ion complex as a collector to produce a tungsten-tin mixed concentrate. This method achieves a WO3 recovery rate exceeding 80% and a Sn recovery rate exceeding 50% from the tungsten-tin ore. However, the tin is primarily recovered as the tungsten-tin mixed concentrate, and the yield of high-grade tungsten concentrate is relatively low. Summary of the Invention

[0006] In view of the problems in the current actual production of tungsten-tin polymetallic ores, such as low grade of selected tungsten-tin ore and high gangue content, which lead to low tungsten-tin recovery rate and difficulty in separation from garnet in traditional mineral processing processes, the purpose of the present invention is to provide a method with short process, low energy consumption and low cost, which can realize the diversion and efficient enrichment of tungsten-tin minerals.

[0007] In order to achieve the above technical objectives, the present invention provides a magnetic-levitation combined tungsten-tin separation method, which comprises the following steps:

[0008] 1) The tungsten-tin polymetallic ore is sequentially crushed, ground, iron removed, and magnetically separated to obtain non-magnetic products and magnetic products;

[0009] 2) After desulfurization, the non-magnetic product is subjected to tungsten flotation using metal ion complex I as a collector, salted water glass as a depressant, and No. 2 oil as a frother to obtain tungsten concentrate;

[0010] 3) The magnetic product is subjected to tin flotation using the metal ion complex II as a collector and sodium fluorosilicate as a depressant to obtain a tin concentrate;

[0011] The metal ion complex I is composed of a divalent or trivalent metal ion and a ligand of formula 1;

[0012]

[0013]

[0014] The metal ion complex II is composed of a divalent or trivalent metal ion and a ligand of formula 2;

[0015]

[0016] in,

[0017] Ar is an aryl group;

[0018] R is a C6-C8 alkyl group;

[0019] Divalent or trivalent metal ions are Fe 3+ 、Fe 2+ , Pb 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、Mn 2+ 、Ni 2+ or Ca 2+ .

[0020] The key to the technical solution of the present invention is the use of magnetic separation to pre-separate tungsten-tin polymetallic ore into magnetic and non-magnetic products. Scheelite, being non-magnetic, enters the non-magnetic product during magnetic separation. This non-magnetic product then enters the tungsten flotation process. This significantly improves tungsten flotation efficiency, increases the yield of high-grade tungsten concentrate, reduces subsequent flotation feedstock, improves feed grade, reduces beneficiation reagent costs, and increases production capacity, thereby improving the economic benefits of mineral processing. Although pure cassiterite is non-magnetic, research has shown that cassiterite in tungsten-tin polymetallic ores exhibits a certain degree of weak magnetism due to the presence of iron. Since tin is a siderophile element, the cassiterite formed in tungsten-tin polymetallic ore bodies during geochemical mineralization is mostly iron-rich, thus exhibiting a certain degree of weak magnetism. Furthermore, a considerable portion of cassiterite is primarily associated with garnet. Therefore, high-intensity magnetic separation can be used to enrich cassiterite in the magnetic product, followed by subsequent tin recovery using a separate flotation system. Tungsten ore and cassiterite differ significantly in their natural floatability and flotation behavior, making co-enrichment of tungsten and tin impossible using a single flotation system. The technical solution of the present invention uses strong magnetic pre-selection to divert the beneficiation of tungsten-tin polymetallic ore into two branch flotation processes, which recover tungsten minerals and tin minerals separately. It not only improves the selected grades of tungsten flotation and tin separation, but also avoids the interaction between the two flotation reagent systems of tungsten and tin minerals, purifies the flotation environment, improves the efficiency of the flotation process, and simultaneously and efficiently recovers both tungsten and tin resources.

[0021] As a preferred solution, the tungsten-tin polymetallic ore is ground to a particle size that satisfies the -200 mesh particle size, with a mass percentage content greater than 65%. Grinding to an appropriate particle size can ensure that the degree of dissociation of the tungsten-tin mineral monomer is greater than 90%.

[0022] As a preferred option, the magnetic separator used in the magnetic separation is a vertical ring high-gradient magnetic separator with a magnetic field strength of 0.6 to 1.2 T. During the magnetic separation process, the ring is rotated vertically, the concentrate is recoiled, and a high-frequency vibration mechanism is used. At the optimal magnetic field strength, minerals primarily containing tin ore and garnet can be subjected to magnetic separation concentrate. The magnetic product yield is ≥30%, of which the recovery rate of tungsten minerals lost in the magnetic product is ≤5%, and the recovery rate of cassiterite lost in the non-magnetic product is ≤15%.

[0023] As a preferred embodiment, Ar in the ligand is a phenyl group or a substituted phenyl group; the substituted phenyl group is a phenyl group containing at least one of a C1-C5 methyl group, a halogen substituent (e.g., fluorine, chlorine, etc.), a carboxyl group, and a hydroxyl group. When Ar is a phenyl group or a substituted phenyl group, the metal ion complex I exhibits high selectivity for scheelite, thereby facilitating the flotation separation of tungsten ore and achieving efficient enrichment. In the non-magnetic product of the present invention, tungsten ore primarily coexists with other calcium-containing minerals, making separation of the two relatively difficult. Therefore, an arylhydroxamic acid is selected, which has relatively weak hydrophobicity (weak capture ability) but strong selectivity, thus improving the concentrate grade.

[0024] As a preferred embodiment, in the metal ion complex II of the present invention, when R is a C6-C8 alkyl group, the alkyl group can be a straight-chain alkyl group or a branched alkyl group, preferably a straight-chain alkyl group. The metal ion complex II has a long saturated fatty chain, which has a strong capture ability for cassiterite, thereby improving the recovery efficiency of cassiterite. In the magnetic product of the present invention, the separation of cassiterite and garnet is relatively simple. Therefore, the use of hydroxamic acid with a long saturated fatty chain has slightly poor selectivity, but is highly hydrophobic (strong capture ability), which helps to improve the recovery rate of cassiterite.

[0025] As a preferred embodiment, the coordination molar ratio of the divalent or trivalent metal ion to the ligand of Formula 1 in the metal ion complex I is 1:2 to 16. As a preferred embodiment, the coordination molar ratio of the divalent or trivalent metal ion to the ligand of Formula 2 in the metal ion complex II is 1:2 to 16. The coordination molar ratio of the divalent or trivalent metal ion to the ligand of Formula 1 or Formula 2 is more preferably 1:2, 1:4, 1:8 or 1:16.

[0026] As a preferred solution, the tungsten flotation includes 1 roughing selection, 2 to 4 cleaning selections and 2 to 3 scavenging selections.

[0027] As a more preferred solution, the scanning is a blank scanning without adding drugs.

[0028] As a preferred solution, the pH during the roughing process is 7.5-8.5, the amount of metal ion complex I added to the tungsten-tin polymetallic ore is 300-500 g / t, and the amount of 2# oil added to the tungsten-tin polymetallic ore is 20-50 g / t. A weakly alkaline slurry environment facilitates the flotation of tungsten ore. Furthermore, the combination of metal ion complex I, which has a highly selective capture effect on tungsten ore, as a collector and salted water glass, which has a strong inhibitory effect on calcium-containing gangue minerals, allows for efficient flotation and enrichment of tungsten ore from calcium-containing gangue minerals. During the tungsten flotation process, the metal ion complex I used has high selectivity but poor capture and foaming properties, so 2# oil is added as a frother.

[0029] As a preferred embodiment, the amount of salted water glass added to the tungsten-tin polymetallic ore during the concentrating process is 100-300 g / t. As a preferred embodiment, the salted water glass comprises Al2(SO4)3 or Pb(NO3)2 and water glass, and the mass ratio of Al2(SO4)3 and / or Pb(NO3)2 to water glass is 1:2-8; a further preferred mass ratio is 1:2-4.

[0030] As a preferred solution, the tin flotation comprises 1 roughing, 2 to 4 cleaning and 2 to 3 scavenging.

[0031] As a more preferred solution, the scanning is a blank scanning without adding drugs.

[0032] As a preferred solution, the pH during the roughing process is 9.0-9.5, and the amount of Metal Ion Complex II added to the tungsten-tin polymetallic ore is 500-800 g / t. The strongly alkaline slurry environment favors cassiterite flotation. The combination of Metal Ion Complex II, which has a highly selective capture effect on cassiterite, as a collector and sodium fluorosilicate, which has a strong hydrophilic modification on garnet surfaces, as an inhibitor, enables efficient flotation and enrichment of cassiterite. During the tin flotation process, the use of Metal Ion Complex Collector II provides strong capture and foaming properties, eliminating the need for an additional frother.

[0033] As a preferred solution, the amount of sodium fluorosilicate added to the tungsten-tin polymetallic ore during the concentration process is 200-300 g / t. Sodium fluorosilicate can selectively adsorb on the surface of garnet, making it hydrophilic and dispersible, thereby preventing the inclusion of fine mud gangue.

[0034] The tungsten-tin polymetallic ore involved in the present invention has a WO3 content of greater than 0.10% by mass and a Sn content of greater than 0.07% by mass, wherein the tungsten-containing mineral is scheelite, the tin mineral is cassiterite, and the gangue minerals are mainly garnet (>30%), quartz, feldspar, calcite, fluorite and a small amount of other silicate minerals.

[0035] After de-ironization, the tungsten-tin polymetallic ore of the present invention has a magnetic iron content of less than 10%. Because magnetite has strong magnetism, weak magnetic de-ironization is generally used. The magnetic separation de-ironization process of tungsten-tin polymetallic ore is a common process in the art.

[0036] The desulfurization process involved in the present invention adopts conventional flotation desulfurization in the art, with butyl xanthate and butylamine black medicine as collectors.

[0037] The magnetic-levitation combined tungsten-tin separation beneficiation method provided by the present invention comprises the following specific steps:

[0038] 1) The tungsten-tin polymetallic ore is crushed and ground in sequence, and the grinding particle size satisfies the mass percentage of the -200 mesh particle size greater than 65%, ensuring that the dissociation degree of the tungsten-tin mineral monomer is greater than 90%. After grinding, the ore is subjected to weak magnetic iron removal, and the weak magnetic separation adopts a drum-type wet magnetic separator with a magnetic field strength of 0.25 to 0.45T; the tailings after weak magnetic iron removal are subjected to high-intensity magnetic separation, and the high-intensity magnetic separation adopts a vertical ring high-gradient magnetic separator with a magnetic field strength of 0.6 to 1.2T. At the same time, a rotating ring is used for vertical rotation and recoil concentrate, and a high-frequency vibration mechanism is provided to obtain non-magnetic products and magnetic products;

[0039] 2) The non-magnetic product is first desulfurized using conventional sulfide ore flotation collectors, copper sulfate (100-300 g / t) as an activator, butyl xanthate (50-150 g / t) and ethylthiocyanate (20-60 g / t) as collectors, and 2# oil (20-50 g / t) as a frother. After desulfurization, tungsten flotation is performed using metal ion complex I as a collector, salted water glass as a depressant, and 2# oil as a frother. Tungsten flotation includes 1 roughing, 2-4 cleaning, and 2-3 scavenging. During the roughing process, the pulp pH is 7.5. ~8.5, the addition amount of metal ion complex I relative to tungsten-tin polymetallic ore is 300-500g / t, and the addition amount of 2# oil relative to tungsten-tin polymetallic ore is 20-50g / t; during the concentration process, the addition amount of salted water glass relative to the tungsten-tin polymetallic ore is 100-300g / t, and the salted water glass comprises Al2(SO4)3 or Pb(NO3)2 and water glass, and the mass ratio of Al2(SO4)3 and / or Pb(NO3)2 to water glass is 1:2-8, the final foam product is tungsten concentrate, and the scavenging is blank scavenging;

[0040] The metal ion complex I is composed of a divalent or trivalent metal ion and a ligand of formula 1;

[0041]

[0042] Ar is an aryl group; more specifically, Ar is a phenyl group or a substituted phenyl group; the substituted phenyl group is a phenyl group containing at least one substituent selected from the group consisting of a C1 to C5 methyl group, a halogen substituent, a carboxyl group, and a hydroxyl group; the divalent or trivalent metal ion is Fe 3+ 、Fe 2+ , Pb 2+ 、Cu 2 + 、Zn 2+ 、Al 3+ 、Mn 2+ 、Ni 2+ or Ca 2+ , the coordination molar ratio of the divalent or trivalent metal ion to the ligand of formula 1 is 1:2 to 16;

[0043] 3) The magnetic product uses metal ion complex II as a collector and sodium fluorosilicate as a depressant to carry out tin flotation, and the tin flotation includes 1 roughing, 2 to 4 cleaning and 2 to 3 scavenging; during the roughing process, the pH is 9.0 to 9.5, and the amount of metal ion complex II added relative to the tungsten-tin polymetallic ore is 500 to 800 g / t; during the cleaning process, the amount of sodium fluorosilicate added relative to the tungsten-tin polymetallic ore is 200 to 300 g / t, the scavenging is blank scavenging, and the final foam product is tin concentrate;

[0044] The metal ion complex II is composed of a divalent or trivalent metal ion and a ligand of formula 2;

[0045]

[0046] Wherein, R is a C6-C8 alkyl group; the divalent or trivalent metal ion is Fe 3+ 、Fe 2+ , Pb 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、Mn 2 + 、Ni 2+ or Ca 2+ ; The coordination molar ratio of the divalent or trivalent metal ion to the ligand of formula 2 is 1:2 to 16.

[0047] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0048] 1. The technical solution of the present invention uses a strong magnetic method to achieve the diversion of tungsten and tin, while improving the selection grade of the tungsten flotation process and the tin flotation process, greatly improving the selectivity of the ore, and can reduce the mineral processing cost and improve the economic benefits of mineral processing.

[0049] 2. The present invention combines magnetic separation with flotation to give full play to the differences in magnetism, floatability, flotation rate, etc. between scheelite, cassiterite and gangue minerals, thereby greatly improving the recovery rate of tungsten and tin.

[0050] 3. The garnet resources in the tin flotation tailings of the present invention have the potential to be partially commercialized or repurposed, which can alleviate the pressure on the tailings pond;

[0051] 4. The technical solution of the present invention has a short process, is easy to operate, has low labor intensity, and is environmentally friendly and efficient. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is a process flow chart of the magnetic-levitation combined tungsten-tin diversion beneficiation process of the present invention.

[0053] Figure 2 This is the flow chart of tungsten-tin flotation in comparative example 1.

[0054] Figure 3 For comparison with the mineral phase diagram of the magnetic product obtained by strong magnetic separation in Example 1, it can be seen that, in addition to cassiterite, the main gangue mineral in the magnetic product is garnet, and a large amount of cassiterite and garnet are co-produced. Therefore, it is necessary not only to suppress the garnet gangue mineral, but also to carry out regrinding to increase the monomer dissociation degree of cassiterite.

[0055] Figure 4 This is a flow chart of the mineral processing process test in Example 2. DETAILED DESCRIPTION

[0056] The following examples are provided to further illustrate the present invention, but are not intended to limit the scope of protection of the claims of the present invention.

[0057] Example 1

[0058] Add 0.125 mol of lead nitrate to 1 L of 1.0 mol / L benzohydroxamic acid solution under stirring, and react for 3 minutes to obtain the metal ion complex collector I;

[0059] 0.025 mol of ferric sulfate was added to 1 L of 0.5 mol / L n-decylhydroxamic acid solution under stirring, and the mixture was reacted for 3 minutes to obtain the metal ion complex collector II.

[0060] This process was used to treat a certain associated tungsten-tin polymetallic ore in Hunan. After crushing and grinding, the particle size met the mass percentage of 72% of the -200 mesh size. Subsequently, a drum wet magnetic separator (magnetic field strength 0.4T) was used for weak magnetic iron removal. After the weak magnetic iron removal, the tailings were separated by 1.0T strong magnetic separation, and the non-magnetic product 200g / t copper sulfate was used as an activator, 80g / t butyl xanthate and 40g / t ethylsulfoxide were used as collectors, and 30g / t 2# oil was used as a frother for desulfurization flotation. The desulfurized tailings were first adjusted to a pH of 9.0 by sodium carbonate, and 380 g / t of metal ion complex collector I and 30 g / t of 2# oil were added as a foaming agent. After aeration and slurry stirring for 5 minutes, the pH was adjusted to 7.8. Tungsten roughing and two blank sweeps were carried out. The total amount of Al-SBL (1:2) was 200 g / t. After four rounds of selection, tungsten concentrate WO3 40.99% and Sn grade 1.32% were obtained.

[0061] The magnetic product enters the tin flotation system, and the pH is adjusted to 10.3 by sodium carbonate. 600g / t of metal ion complex collector II is added. After aeration and slurry stirring for 5 minutes, the pH reaches 9.1. Tin roughing is carried out, and the total amount of sodium fluorosilicate used for selection is 250g / t. After four rounds of selection, a tin concentrate with a Sn grade of 15.38% and a WO3 grade of 1.90% is obtained. The overall WO3 recovery rate is 87.17%, and the overall Sn recovery rate is 68.77%.

[0062] Table 1 Beneficiation test results of a certain associated tungsten-tin polymetallic ore in Hunan

[0063]

[0064] Comparative Example 1:

[0065] Comparative Example 1 is used for comparison with Example 1. The crushing, grinding, weak magnetic separation, desulfurization and other processes in Comparative Example 1 are consistent with those in Example 1. The difference is that the strong magnetic diversion process is not set in this process. The process is as follows Figure 2 As shown, the desulfurized tailings were first adjusted to a pH of 9.4 with sodium carbonate. 480 g / t of the same metal ion complex collector I as in Example 1 was added. After aeration and stirring for 5 minutes, the pH reached 7.8. 30 g / t of 2# oil was used as a frother. Tungsten roughing and two blank sweeps were performed. The total amount of Al-SBL (1:2) used for the concentrator was 200 g / t. After two rounds of concentrating, a tungsten concentrate with a WO3 content of 30.12% and a Sn content of 3.66% was obtained. The overall WO3 recovery was 74.25%, and the Sn recovery was 18.93%. The results of Example 1 show that conventional tungsten-tin mixed flotation methods struggle to achieve satisfactory beneficiation performance, with a Sn recovery of only 18.93%.

[0066] Table 2 Comparative experimental results of a certain associated tungsten-tin polymetallic ore in Hunan

[0067]

[0068] Example 2

[0069] 0.125 mol of lead nitrate was added to 1 L of a 1.0 mol / L salicylic hydroxamic acid solution under stirring, and the mixture was reacted for 3 minutes to obtain the metal ion complex collector I;

[0070] 0.025 mol of lead nitrate was added to 1 L of a 0.5 mol / L naphthylhydroxamic acid solution under stirring, and the mixture was reacted for 3 minutes to obtain the metal ion complex collector II.

[0071] The process was used to treat the Hunan Huangshaping tungsten-tin polymetallic ore. After crushing and grinding, the particle size met the mass percentage of 75% of the -200 mesh size. Subsequently, a drum wet magnetic separator (magnetic field strength 0.3T) was used for weak magnetic iron removal. After the weak magnetic iron removal, the tailings were separated by 1.2T strong magnetic separation. The non-magnetic product 230g / t copper sulfate was used as an activator, 100g / t butyl xanthate and 60g / t ethyl thiocyanate were used as collectors, and 40g / t 2# oil was used as a frother for desulfurization flotation. The MLA test results of the magnetic product were as follows: Figure 3As shown in Figure 2, a large amount of cassiterite and garnet coexist. Therefore, when designing the process, coarse concentrate was added to the tin flotation system for regrinding. The overall experimental process is as follows: Figure 4 shown.

[0072] The magnetic product was adjusted to a pH of 10.3 using sodium carbonate. 630 g / t of metal ion complex collector II was added, and after aeration and stirring for 5 minutes, the pH reached 9.1. This was then used for tin roughing. The rough concentrate was then regrinded for 3 minutes before being refined. A total of 200 g / t of sodium fluorosilicate was used for the refinery. After four refinery passes, a tin concentrate with a Sn grade of 25.54% and a WO3 grade of 0.99% was obtained. The non-magnetic product was desulfurized, and then the pH was adjusted to 8.8 using sodium carbonate. 420 g / t of metal ion complex collector I and 40 g / t of 2# oil were added. After aeration and stirring for 5 minutes, the pH reached 7.5. This was then used for tungsten roughing. A total of 300 g / t of Al-SBL (1:2) was used for the refinery. After four refinery passes, a tungsten concentrate with a WO3 grade of 30.99% and a Sn grade of 0.92% was obtained. (Both the tungsten and tin scavenging processes were blank, with no reagents added.) The final indicators are that the overall recovery rate of WO3 is 84.75%, and the overall recovery rate of Sn is 67.41%.

[0073] Table 3 Beneficiation test results of Hunan Huangshaping polymetallic ore

[0074]

[0075]

Claims

1. A magnetic-levitation combined tungsten-tin separation method, characterized by: The following steps are involved: 1) The tungsten-tin polymetallic ore is sequentially crushed, ground, iron removed, and magnetically separated to obtain non-magnetic products and magnetic products; 2) After desulfurization, the non-magnetic product is subjected to tungsten flotation using metal ion complex I as a collector, salted water glass as a depressant, and No. 2 oil as a frother to obtain tungsten concentrate; 3) The magnetic product is subjected to tin flotation using the metal ion complex II as a collector and sodium fluorosilicate as a depressant to obtain a tin concentrate; The metal ion complex I is composed of a divalent or trivalent metal ion and a ligand of formula 1; The metal ion complex II is composed of a divalent or trivalent metal ion and a ligand of formula 2; in, Ar is an aryl group; R is a C6-C8 alkyl group; Divalent or trivalent metal ions are Fe 3+ 、Fe 2+ , Pb 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、Mn 2+ 、Ni 2+ or Ca 2+ .

2. The magnetic-levitation combined tungsten-tin separation method according to claim 1 is characterized in that: The mass percentage of the tungsten-tin polymetallic ore grinding to a particle size of -200 mesh is greater than 65%.

3. The magnetic-levitation combined tungsten-tin separation method according to claim 1 is characterized in that: The magnetic separator used in the magnetic separation is a vertical ring high gradient magnetic separator with a magnetic field strength of 0.6 to 1.2T.

4. The magnetic-levitation combined tungsten-tin separation method according to claim 1 is characterized in that: Ar in the ligand is a phenyl group or a substituted phenyl group; the substituted phenyl group is a phenyl group containing at least one substituent selected from the group consisting of a C1 to C5 methyl group, a halogen substituent, a carboxyl group, and a hydroxyl group.

5. The magnetic-levitation combined tungsten-tin separation method according to claim 1 is characterized in that: The coordination molar ratio of the divalent or trivalent metal ion to the ligand of formula 1 in the metal ion complex I is 1:2 to 16; The coordination molar ratio of the divalent or trivalent metal ion to the ligand of formula 2 in the metal ion complex II is 1:2-16.

6. A magnetic-levitation combined tungsten-tin separation method according to any one of claims 1 to 5, characterized in that: The tungsten flotation comprises 1 roughing, 2 to 4 cleaning and 2 to 3 scavenging.

7. The magnetic-levitation combined tungsten-tin separation method according to claim 6 is characterized in that: During the roughing process, the pH value is 7.5 to 8.5, the amount of metal ion complex I added to the tungsten-tin polymetallic ore is 300 to 500 g / t; the amount of 2# oil added to the tungsten-tin polymetallic ore is 20 to 50 g / t; In the concentration process, the amount of salted water glass added relative to the tungsten-tin polymetallic ore is 100-300 g / t.

8. The magnetic-levitation combined tungsten-tin separation method according to claim 7 is characterized in that: The salted water glass comprises Al2(SO4)3 or Pb(NO3)2 and water glass, and the mass ratio of Al2(SO4)3 and / or Pb(NO3)2 to water glass is 1:2-8.

9. The magnetic-levitation combined tungsten-tin separation method according to any one of claims 1 to 5, characterized in that: The tin flotation comprises 1 roughing selection, 2 to 4 cleaning selections and 2 to 3 scavenging selections.

10. The magnetic-levitation combined tungsten-tin separation method according to claim 7, characterized in that: During the roughing process, the pH is 9.0-9.5, and the amount of the metal ion complex II added to the tungsten-tin polymetallic ore is 500-800 g / t; In the concentration process, the amount of sodium fluorosilicate added relative to the tungsten-tin polymetallic ore is 200-300 g / t.

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