A method for recovering tungsten from tungsten mine tailings

Abstract

This invention relates to a method for recovering tungsten from tungsten ore tailings, belonging to the field of mineral flotation technology. The method for recovering tungsten from tungsten ore tailings using this invention can obtain tungsten with high grade and recovery rate. Because the collector used in this invention contains quaternary ammonium salts, double bonds, hydroxyl groups, and carboxyl groups, the quaternary ammonium salts can improve the dispersion stability of the collector and its affinity for the mineral surface. The double bonds can bind to the mineral surface through π-π interactions, increasing the adsorption capacity and stability of the collector on the mineral surface, improving the stability of the froth, and enhancing the flotation efficiency and grade of tungsten. The hydroxyl and carboxyl groups can mutually adsorb with the mineral surface through electrostatic attraction, hydrogen bonding, and complexation, increasing the interaction force with the mineral surface. The four alkane substituents connected to the quaternary ammonium nitrogen atom can effectively improve the hydrophobicity of the mineral surface, thereby improving its collecting performance and the selectivity for tungsten collection.

Description

Technical Field

[0001] This invention relates to a method for recovering tungsten from tungsten ore tailings, belonging to the field of mineral flotation technology. Background Technology

[0002] Tungsten, known as "industrial MSG," is widely used in cutting tools, drill bits, armor-piercing projectiles, and electronic devices. Its alloy products have advantages such as high melting point, high density, and high hardness, making them an indispensable material in modern industry. Tungsten compounds are also used in catalysis, energy, and environmental protection.

[0003] In recent years, tungsten resources have become increasingly scarce and complex, leading to a large amount of tungsten tailings generated during the production of tungsten concentrate. Besides tungsten, tungsten tailings also contain other valuable elements and have significant utilization value. However, the current utilization rate of tungsten tailings is low; the particles are fine and severely muddy, and they are mainly stockpiled in tailings ponds or used for mine backfilling. This results in the ineffective utilization of residual tungsten, leading to resource waste. Furthermore, tungsten tailings ponds occupy large amounts of land, limiting land resource utilization efficiency, and also face the risks of collapse and leakage, posing significant safety hazards.

[0004] Currently, research on the comprehensive utilization of tungsten tailings mainly focuses on the recovery of valuable components and the preparation of materials, such as cement, microcrystalline glass, ceramics, and geopolymers. However, this approach leads to the ineffective utilization of residual tungsten, resulting in resource waste. Therefore, there is an urgent need to develop a method for recovering tungsten from tungsten mine tailings. Summary of the Invention

[0005] The purpose of this invention is to provide a method for recovering tungsten from tungsten mine tailings, so as to solve the problem that tungsten elements in tungsten mine tailings cannot be effectively recovered and utilized.

[0006] This invention provides a method for recovering tungsten from tungsten ore tailings, comprising the following steps: roughing the tungsten ore tailings to obtain a rougher concentrate and a rougher tailings slurry; then performing three cleaning processes on the rougher concentrate and two scavenging processes on the rougher tailings slurry to complete the recovery of tungsten from the tungsten ore tailings; the inhibitors used in the roughing, three cleaning processes, and two scavenging processes consist of sodium hexametaphosphate, ferric chloride, citric acid, and pentene edible acid in a mass ratio of 3~4:2~3:4~5:1~2; the chemical structures of the collectors used in the roughing and two scavenging processes are as follows:

[0007] , , .

[0008] Preferably, the method for roughing tungsten tailings is as follows: the tungsten tailings raw material and water are stirred and mixed to obtain a slurry with a mass concentration of 35-40%, then a pH adjuster is added to adjust the pH of the slurry to 8-9, then an inhibitor is added and stirred for 2-5 minutes, then a collector is added and stirred for 2-5 minutes, and finally the mixture is sent to a flotation machine for roughing to obtain a rough concentrate and a rough tailings slurry.

[0009] Preferably, when roughing tungsten tailings, the dosage of inhibitor is 250-300 g / t and the dosage of collector is 350-400 g / t.

[0010] Preferably, the method for performing three cleaning processes on the roughing concentrate is as follows: the roughing concentrate is first cleaned to obtain a first-cleaned concentrate and a first-cleaned tailings slurry; then the first-cleaned concentrate is cleaned a second time to obtain a second-cleaned concentrate and a second-cleaned tailings slurry; finally, the second-cleaned concentrate is cleaned a third time to obtain a third-cleaned concentrate and a third-cleaned tailings slurry.

[0011] Preferably, the method for first cleaning of the roughing concentrate is as follows: the first cleaning concentrate is mixed with water to obtain a slurry with a mass concentration of 20-25%, then an inhibitor is added, the mixture is stirred for 2-5 minutes, and then sent to a flotation machine for second cleaning to obtain the second cleaning concentrate and the second cleaning tailings slurry; the amount of inhibitor used is 25-30 g / t.

[0012] Preferably, the method for performing a second cleaning of the first-cleaned concentrate is as follows: the first-cleaned concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 20-25%, then an inhibitor is added, stirred for 2-5 minutes, and sent to a flotation machine for a second cleaning to obtain a second-cleaned concentrate and a second-cleaned tailings slurry; the amount of inhibitor used is 25-30 g / t.

[0013] Preferably, the method for the third cleaning of the second-cleaned concentrate is as follows: the second-cleaned concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 15~20%, then an inhibitor is added, stirred for 2~5 minutes, and sent to a flotation machine for the third cleaning to obtain the third-cleaned concentrate and the third-cleaned tailings slurry; the amount of inhibitor used is 12~15g / t.

[0014] Preferably, the method for performing two scavenging processes on the roughing tailings slurry is as follows: an inhibitor is added to the roughing tailings slurry and stirred for 2-5 minutes, then a collector is added and stirred for 2-5 minutes, and then the slurry is sent to a flotation machine for the first scavenging process to obtain the first scavenged concentrate and the first scavenged slurry; then an inhibitor is added to the first scavenged slurry and stirred for 2-5 minutes, then a collector is added and stirred for 2-5 minutes, and then the scavenging machine is sent to a flotation machine for the second scavenging process to obtain the second scavenged concentrate and the second scavenged tailings.

[0015] Preferably, the amount of inhibitor used in the first scavenging is 120~150g / t; the amount of inhibitor used in the second scavenging is 50~70g / t; the amount of collector used in the first scavenging is 150~180g / t; and the amount of collector used in the second scavenging is 70~90g / t.

[0016] Preferably, the tungsten ore tailings are tungsten ore gravity separation tailings.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: The method of the present invention for recovering tungsten from tungsten tailings can obtain tungsten with higher grade and recovery rate, effectively improve the recovery effect of tungsten in tailings, and the tungsten content in tailings is low, which can effectively avoid the waste of tungsten resources. This is because the collector used in this invention contains quaternary ammonium salt, double bond, hydroxyl, and carboxyl structures. Quaternary ammonium salt can improve the dispersion stability of the collector and its affinity for the mineral surface. Double bonds can bind to the mineral surface through π-π interactions, thereby increasing the adsorption amount and stability of the collector on the mineral surface. Moreover, double bonds can form stable complexes with tungsten on the mineral surface, promoting foam generation, improving foam stability, and increasing the flotation efficiency and grade of tungsten. Hydroxyl and carboxyl groups can mutually adsorb with the mineral surface through electrostatic attraction, hydrogen bonding, and complexation, increasing the interaction force with the mineral surface. The four alkane substituents connected to the quaternary ammonium nitrogen atom have good hydrophobicity. When the collector is adsorbed onto the mineral surface, it can effectively improve the hydrophobicity of the mineral surface. Furthermore, the branched structure at the ends of the alkane substituents can increase the hydrophobic surface area, further improving hydrophobicity, thereby improving its collecting performance and the collecting selectivity for tungsten. Attached Figure Description

[0018] Figure 1 The image shows the 1H NMR spectrum of the collector prepared in Example 1 of this invention. Detailed Implementation

[0019] The following examples are intended to further illustrate the content of the present invention, rather than to limit the scope of protection of the present invention.

[0020] The tungsten tailings used in the following examples and comparative examples are gravity separation tailings from a tungsten mine. Their main gangue minerals include siliceous gangues such as quartz and mica, calcium-bearing gangues such as calcite and fluorite, and carbonaceous gangues such as graphite. The main chemical composition of the tailings is as follows: WO3 0.352wt%, MO 0.081wt%, Cu 0.031wt%, Zn 0.027wt%, Pb 0.022wt%, Sn 0.029wt%, As 0.051wt%, S 0.521wt%, C 0.437wt%, CaF2 2.374wt%, P2O5 0.318wt%, Fe2O3 5.265wt%, SiO2 65.131wt%, MgO 1.136wt%, CaO 8.143wt%, Al2O3 12.308wt%, K2O 1.241wt%, Na2O The chemical composition of tungsten in the tailings is as follows: WO3 content is 0.311 wt% in scheelite, 0.036 wt% in wolframite, and 0.005 wt% in tungsten smelting. In the tailings, the distribution rate of WO3 in the +0.074 mm particle size is 1.15%, and the distribution rate in the -0.03 mm particle size is 91.12%. Example 1

[0021] The method for recovering tungsten from tungsten ore tailings in this embodiment includes the following steps:

[0022] (1) Tungsten tailings raw material and water were mixed to obtain a slurry with a mass concentration of 38%. Then, a pH adjuster was added to adjust the pH of the slurry to 8.5, followed by the addition of an inhibitor. The mixture was stirred for 3 minutes, then a collector was added and stirred for 4 minutes. Finally, the mixture was sent to a flotation machine for roughing to obtain a roughing concentrate and a roughing tailings slurry. The pH adjuster was sodium carbonate, and the inhibitor was composed of sodium hexametaphosphate, ferric chloride, citric acid, and pentene edible acid in a mass ratio of 3:3:5:1. The amount of inhibitor used was... The collector dosage is 380 g / t, and the amount of collector used is 270 g / t. The preparation method of the collector is as follows: A primary amine compound, a primary olefin compound, triethylamine, and anhydrous tetrahydrofuran are added to a reaction vessel, heated to 68°C, and stirred under reflux for 6 hours. The solvent and triethylamine are removed by vacuum distillation to obtain a secondary amine product. Then, the secondary amine product, an epoxide compound, a boron trifluoride ether complex, and butanone are added to the reaction vessel, heated to 72°C, and stirred for 5 hours. The solvent and boron trifluoride ether complex are removed by vacuum distillation. An ether complex was formed to yield an alkanolamine compound. Finally, the alkanolamine compound, bromoalkane, and toluene were added to a reaction vessel, nitrogen gas was introduced into the vessel, and the mixture was heated to 85°C and stirred for 6 hours. The solvent toluene and excess bromoalkane were removed by vacuum distillation to obtain a collector. The molar ratio of the primary amine compound, the olefin compound, the epoxide compound, and the bromoalkane was 1:1:1:1.2. The mass of triethylamine was 0.4% of the sum of the masses of the primary amine compound and the olefin compound. Anhydrous tetrahydroquinone... The mass of furan is 5 times the sum of the masses of the primary amine and the olefin; the mass of the boron trifluoride diethyl ether complex is 0.6% of the mass of the epoxide; the mass of butanone is 6 times the sum of the masses of the secondary amine and the epoxide; and the mass of toluene is 9 times the sum of the masses of the alkanolamine and the bromoalkane. The primary amine is isononylamine, the olefin is isoheptene, the epoxide is 2-isobutylethylene oxide, and the bromoalkane is 4-bromocrotonic acid. The 1H NMR spectrum of the collector is shown below. Figure 1 As shown, the chemical structure is as follows:

[0023] ;

[0024] (2) Mix the rough concentrate and water to obtain a slurry with a mass concentration of 28%. Then add the inhibitor, stir for 3 minutes, and send it to the flotation machine for the first cleaning to obtain the first clean concentrate and the first clean tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor is 55g / t.

[0025] Then, the first-selected concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 22%. Then, an inhibitor is added, stirred for 3 minutes, and sent to a flotation machine for a second-selection process to obtain a second-selected concentrate and a second-selected tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor used is 28 g / t.

[0026] The second-selected concentrate and water are then mixed to obtain a slurry with a mass concentration of 18%. Then, an inhibitor is added, and the mixture is stirred for 3 minutes. The mixture is then sent to a flotation machine for a third-selection process to obtain a third-selected concentrate and a third-selected tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor used is 13 g / t.

[0027] Finally, add inhibitor to the roughing tailings slurry, stir for 3 minutes, then add collector, stir for 4 minutes, and then send it to the flotation machine for the first scavenging to obtain the first scavenged concentrate and the first scavenged slurry; then add inhibitor to the first scavenged slurry, stir for 4 minutes, then add collector, stir for 3 minutes, and then send it to the flotation machine for the second scavenging to obtain the second scavenged concentrate and the second scavenged tailings; the inhibitor used in the first scavenging is the same as the inhibitor in step (1), and the amount of inhibitor is 130 g / t; the inhibitor used in the second scavenging is the same as the inhibitor in step (1), and the amount of inhibitor is 60 g / t; the collector used in the first and second scavenging is the same as the collector in step (1), the amount of collector used in the first scavenging is 160 g / t, and the amount of collector used in the second scavenging is 80 g / t. Example 2

[0028] The method for recovering tungsten from tungsten ore tailings in this embodiment includes the following steps:

[0029] (1) Tungsten tailings raw material and water are mixed to obtain a slurry with a mass concentration of 35%. Then, a pH adjuster is added to adjust the pH of the slurry to 8, and then an inhibitor is added. The mixture is stirred for 2 minutes, then a collector is added and stirred for 2 minutes. Finally, the mixture is sent to a flotation machine for roughing to obtain a roughing concentrate and a roughing tailings slurry. The pH adjuster is sodium carbonate, and the inhibitor is composed of sodium hexametaphosphate, ferric chloride, citric acid and pentene edible acid in a mass ratio of 3:2:4:1. The amount of inhibitor used is 25. The collector dosage is 350 g / t, and the preparation method of the collector is as follows: A primary amine compound, a primary olefin compound, triethylamine, and anhydrous tetrahydrofuran are added to a reaction vessel, heated to 65°C, and stirred under reflux for 5 hours. The solvent and triethylamine are removed by vacuum distillation to obtain a secondary amine product. Then, the secondary amine product, an epoxide compound, a boron trifluoride diethyl ether complex, and butanone are added to the reaction vessel, heated to 70°C, and stirred for 4 hours. The solvent and boron trifluoride diethyl ether are removed by vacuum distillation. The complex was obtained to yield an alkanolamine compound; finally, the alkanolamine compound, bromoalkane, and toluene were added to a reaction vessel, nitrogen gas was introduced into the reaction vessel, the mixture was heated to 80°C, and the reaction was stirred for 5 hours. The solvent toluene and excess bromoalkane were removed by vacuum distillation to obtain a collector; wherein the molar ratio of the monobasic primary amine compound, monobasic olefin compound, epoxide compound, and bromoalkane was 1:1:1:1.2, the mass of triethylamine was 0.3% of the sum of the masses of the monobasic primary amine compound and the monobasic olefin compound, and anhydrous tetrahydrofuran was used. The mass of uranium is 5 times the sum of the masses of the primary amine compound and the olefin compound; the mass of the boron trifluoride diethyl ether complex is 0.5% of the mass of the epoxy compound; the mass of butanone is 6 times the sum of the masses of the secondary amine product and the epoxy compound; and the mass of toluene is 8 times the sum of the masses of the alkanolamine compound and the bromoalkane. The primary amine compound is isononylamine, the olefin compound is isoheptene, the epoxy compound is 2-isobutylethylene oxide, and the bromoalkane is 4-bromocrotonic acid. The chemical structure of the collector is as follows:

[0030] ;

[0031] (2) Mix the rough concentrate and water to obtain a slurry with a mass concentration of 25%. Then add the inhibitor, stir for 2 minutes, and send it to the flotation machine for the first cleaning to obtain the first clean concentrate and the first clean tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor is 50g / t.

[0032] Then, the first-selected concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 20%. Then, an inhibitor is added, stirred for 2 minutes, and sent to a flotation machine for a second-selection process to obtain a second-selected concentrate and a second-selected tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor used is 25 g / t.

[0033] The second-selected concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 15%. Then, an inhibitor is added, and the mixture is stirred for 2 minutes. The mixture is then sent to a flotation machine for a third-selection process to obtain a third-selected concentrate and a third-selected tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor used is 12 g / t.

[0034] Finally, add inhibitor to the roughing tailings slurry, stir for 2 minutes, then add collector, stir for 2 minutes, and then send it to the flotation machine for the first scavenging to obtain the first scavenged concentrate and the first scavenged slurry; then add inhibitor to the first scavenged slurry, stir for 2 minutes, then add collector, stir for 2 minutes, and then send it to the flotation machine for the second scavenging to obtain the second scavenged concentrate and the second scavenged tailings; the inhibitor used in the first scavenging is the same as the inhibitor in step (1), and the amount of inhibitor is 120 g / t; the inhibitor used in the second scavenging is the same as the inhibitor in step (1), and the amount of inhibitor is 50 g / t; the collector used in the first and second scavenging is the same as the collector in step (1), the amount of collector used in the first scavenging is 150 g / t, and the amount of collector used in the second scavenging is 70 g / t. Example 3

[0035] The method for recovering tungsten from tungsten ore tailings in this embodiment includes the following steps:

[0036] (1) Tungsten tailings raw material and water are mixed to obtain a slurry with a mass concentration of 40%. Then, a pH adjuster is added to adjust the pH of the slurry to 9, and then an inhibitor is added. The mixture is stirred for 5 minutes, then a collector is added and stirred for 5 minutes. Finally, the mixture is sent to a flotation machine for roughing to obtain a roughing concentrate and a roughing tailings slurry. The pH adjuster is sodium carbonate, and the inhibitor is composed of sodium hexametaphosphate, ferric chloride, citric acid and pentene edible acid in a mass ratio of 4:3:5:2. The amount of inhibitor used is 30. The collector dosage is 400 g / t, and the preparation method of the collector is as follows: A primary amine compound, a primary olefin compound, triethylamine, and anhydrous tetrahydrofuran are added to a reaction vessel, heated to 70°C, and stirred under reflux for 7 hours. The solvent and triethylamine are removed by vacuum distillation to obtain a secondary amine product. Then, the secondary amine product, an epoxide compound, a boron trifluoride ether complex, and butanone are added to the reaction vessel, heated to 75°C, and stirred for 6 hours. The solvent and boron trifluoride ether complex are removed by vacuum distillation. The reaction mixture was subjected to reactants to obtain an alcoholic amine compound. Finally, the alcoholic amine compound, bromoalkane, and toluene were added to a reaction vessel, nitrogen gas was introduced into the vessel, and the mixture was heated to 90°C and stirred for 7 hours. The solvent toluene and excess bromoalkane were removed by vacuum distillation to obtain a collector. The molar ratio of the primary amine compound, the olefin compound, the epoxide compound, and the bromoalkane was 1:1:1:1.3. The mass of triethylamine was 0.5% of the sum of the masses of the primary amine compound and the olefin compound. Anhydrous tetrahydrofuran was also used. The mass of the collector is 6 times the sum of the masses of the primary amine compound and the olefin compound; the mass of the boron trifluoride diethyl ether complex is 0.7% of the mass of the epoxy compound; the mass of butanone is 7 times the sum of the masses of the secondary amine product and the epoxy compound; and the mass of toluene is 10 times the sum of the masses of the alkanolamine compound and the bromoalkane. The primary amine compound is isononylamine, the olefin compound is isoheptene, the epoxy compound is 2-isobutylethylene oxide, and the bromoalkane is 4-bromocrotonic acid. The chemical structure of the collector is as follows:

[0037] ;

[0038] (2) Mix the rough concentrate and water to obtain a slurry with a mass concentration of 30%. Then add the inhibitor, stir for 5 minutes, and send it to the flotation machine for the first cleaning to obtain the first clean concentrate and the first clean tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor is 60g / t.

[0039] Then, the first-selected concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 25%. Then, an inhibitor is added, stirred for 5 minutes, and sent to a flotation machine for a second-selection process to obtain a second-selected concentrate and a second-selected tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor used is 30g / t.

[0040] The second-selected concentrate and water are then mixed to obtain a slurry with a mass concentration of 20%. Then, an inhibitor is added, and the mixture is stirred for 5 minutes. The mixture is then sent to a flotation machine for a third-selection process to obtain a third-selected concentrate and a third-selected tailings slurry. The inhibitor is the same as the inhibitor in step (1), and the amount of inhibitor used is 15 g / t.

[0041] Finally, add inhibitor to the roughing tailings slurry, stir for 5 minutes, then add collector, stir for 5 minutes, and then send it to the flotation machine for the first scavenging to obtain the first scavenging concentrate and the first scavenging slurry; then add inhibitor to the first scavenging slurry, stir for 5 minutes, then add collector, stir for 5 minutes, and then send it to the flotation machine for the second scavenging to obtain the second scavenging concentrate and the second scavenging tailings; the inhibitor used in the first scavenging is the same as the inhibitor in step (1), and the amount of inhibitor is 150 g / t; the inhibitor used in the second scavenging is the same as the inhibitor in step (1), and the amount of inhibitor is 70 g / t; the collector used in the first and second scavenging is the same as the collector in step (1), the amount of collector used in the first scavenging is 180 g / t, and the amount of collector used in the second scavenging is 90 g / t. Example 4

[0042] The method for recovering tungsten from tungsten ore tailings in this embodiment differs from the method for recovering tungsten from tungsten ore tailings in Example 1 only in that the collector used in the method for recovering tungsten from tungsten ore tailings in this embodiment is isooctene, and the chemical structure of the collector is as follows:

[0043] . Example 5

[0044] The method for recovering tungsten from tungsten ore tailings in this embodiment differs from the method for recovering tungsten from tungsten ore tailings in Example 1 only in that the collector used in the method for recovering tungsten from tungsten ore tailings in this embodiment is a 7-methyl-1-octene monoolefin compound prepared in the form of the collector. The chemical structure of the collector is as follows:

[0045] .

[0046] Comparative Example 1

[0047] The only difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is that the collector used in the method for recovering tungsten from tungsten ore tailings in this comparative example is prepared using a mono-olefin compound of 2-methyl-2-butene, and the chemical structure of the collector is as follows:

[0048] .

[0049] Comparative Example 2

[0050] The only difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is that the collector used in the method for recovering tungsten from tungsten ore tailings in this comparative example is prepared using a mono-olefin compound of 2-methyl-1-nonene, and the chemical structure of the collector is as follows:

[0051] .

[0052] Comparative Example 3

[0053] The only difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is that the collector used in the method for recovering tungsten from tungsten ore tailings in this comparative example is n-heptene, a mono-olefin compound prepared in preparation. The chemical structure of the collector is as follows:

[0054] .

[0055] Comparative Example 4

[0056] The difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is only that the collector used in the method for recovering tungsten from tungsten ore tailings in this comparative example is prepared with isopropyl ethylene oxide as the epoxy compound. The chemical structure of the collector is as follows:

[0057] .

[0058] Comparative Example 5

[0059] The difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is only that the collector used in the method for recovering tungsten from tungsten ore tailings in this comparative example is prepared with butyl ethylene oxide as the epoxy compound. The chemical structure of the collector is as follows:

[0060] .

[0061] Comparative Example 6

[0062] The only difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is that the collector used in this comparative example has 4-bromobutyric acid as the bromine hydrocarbon during preparation. The chemical structure of the collector is as follows:

[0063] .

[0064] Comparative Example 7

[0065] The only difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is that the collector used in the method for recovering tungsten from tungsten ore tailings in this comparative example is isooctylamine, and the chemical structure of the collector is as follows:

[0066] .

[0067] Comparative Example 8

[0068] The only difference between the method for recovering tungsten from tungsten ore tailings in this comparative example and the method for recovering tungsten from tungsten ore tailings in Example 1 is that the collector used in the method for recovering tungsten from tungsten ore tailings in this comparative example is nonylamine, a monobasic primary amine compound prepared in preparation. The chemical structure of the collector is as follows:

[0069] .

[0070] Comparative Example 9

[0071] The only difference between the method for recovering tungsten from tungsten tailings in this comparative example and the method for recovering tungsten from tungsten tailings in Example 1 is that the inhibitors in steps (1) and (2) of the method for recovering tungsten from tungsten tailings in this comparative example are composed of sodium hexametaphosphate, ferric chloride and citric acid in a mass ratio of 3.3:3.3:5.4.

[0072] Comparative Example 10

[0073] The only difference between the method for recovering tungsten from tungsten tailings in this comparative example and the method for recovering tungsten from tungsten tailings in Example 1 is that the inhibitors in steps (1) and (2) of the method for recovering tungsten from tungsten tailings in this comparative example are composed of sodium hexametaphosphate, ferric chloride and pentenoic acid in a mass ratio of 5.1:5.1:1.8.

[0074] Comparative Example 11

[0075] The only difference between the method for recovering tungsten from tungsten tailings in this comparative example and the method for recovering tungsten from tungsten tailings in Example 1 is that the inhibitors in steps (1) and (2) of the method for recovering tungsten from tungsten tailings in this comparative example are composed of sodium hexametaphosphate, citric acid and pentenoic acid in a mass ratio of 4:6.7:1.3.

[0076] Comparative Example 12

[0077] The only difference between the method for recovering tungsten from tungsten tailings in this comparative example and the method for recovering tungsten from tungsten tailings in Example 1 is that the inhibitors in steps (1) and (2) of the method for recovering tungsten from tungsten tailings in this comparative example are composed of ferric chloride, citric acid and pentenoic acid in a mass ratio of 4:6.7:1.3.

[0078] Experimental Example

[0079] To evaluate the tungsten recovery efficiency of the methods for recovering tungsten from tungsten ore tailings in each embodiment and comparative example, the WO3 grade and recovery rate of the third-stage concentrate and the WO3 grade and recovery rate of the second-stage scavenging tailings obtained by the methods for recovering tungsten from tungsten ore tailings in each embodiment and comparative example were tested and calculated. The recovery rate refers to the ratio of the total mass of WO3 in the third-stage concentrate or the second-stage scavenging tailings to the total mass of WO3 in the tungsten ore tailings raw material. The tungsten recovery efficiency of the methods for recovering tungsten from tungsten ore tailings in each embodiment and comparative example is shown in Table 1.

[0080] Table 1. WO3 grade and recovery rate of the third-stage beneficiation concentrate and the second-stage scavenging tailings

[0081]

[0082] As shown in Table 1, the method for recovering tungsten from tungsten tailings of the present invention can obtain tungsten with high grade and recovery rate, effectively improving the recovery effect of tungsten in tailings. Moreover, the tungsten content in the tailings is low, which can effectively avoid the waste of tungsten resources. This is because the collector used in this invention contains quaternary ammonium salt, double bond, hydroxyl, and carboxyl structures. Quaternary ammonium salt can improve the dispersion stability of the collector and its affinity for the mineral surface. Double bonds can bind to the mineral surface through π-π interactions, thereby increasing the adsorption amount and stability of the collector on the mineral surface. Moreover, double bonds can form stable complexes with tungsten on the mineral surface, promoting foam generation, improving foam stability, and increasing the flotation efficiency and grade of tungsten. Hydroxyl and carboxyl groups can mutually adsorb with the mineral surface through electrostatic attraction, hydrogen bonding, and complexation, increasing the interaction force with the mineral surface. The four alkane substituents connected to the quaternary ammonium nitrogen atom have good hydrophobicity. When the collector is adsorbed onto the mineral surface, it can effectively improve the hydrophobicity of the mineral surface. Furthermore, the branched structure at the ends of the alkane substituents can increase the hydrophobic surface area, further improving hydrophobicity, thereby improving its collecting performance and the collecting selectivity for tungsten.

[0083] As can be seen from Example 1 and Comparative Examples 1-8, when the structure of the collector is changed by adjusting the type of raw materials used in its preparation, the structure of the collector has a significant impact on the tungsten recovery effect. When the length of the hydrocarbon carbon chain in the collector is too long or too short, the collection effect of the collector will be reduced due to decreased solubility or reduced hydrophobicity. When the degree of branching at the end of the hydrocarbon group in the collector decreases, the area of ​​the hydrophobic branch chain decreases, resulting in poorer collection performance. When the degree of branching in the middle of the hydrocarbon group increases, the steric hindrance between the hydroxyl and carboxyl groups and the mineral surface increases, resulting in reduced adsorption. When the hydrocarbon group lacks double bonds, the binding ability between the collector and the mineral surface becomes poor, foam generation and stability decrease, which in turn leads to a decrease in the flotation efficiency and grade of tungsten.

[0084] As can be seen from Example 1 and Comparative Examples 9-12, the combination of four inhibitors, namely sodium hexametaphosphate, ferric chloride, citric acid and pentene, has the best inhibitory effect. It can effectively inhibit the flotation of quartz, mica, calcite, fluorite and graphite, and achieve selective separation of tungsten in tailings by adjusting the charge state and wettability of the mineral surface.

Claims

1. A method of recovering tungsten from a tungsten mine tailings, characterized by, The method comprises the following steps: The tungsten ore tailings are coarsely selected to obtain coarse concentrate and coarse tailings slurry; the coarse concentrate is then three times selected, and the coarse tailings slurry is two times scavenged to complete the recovery of tungsten from the tungsten ore tailings; the depressor used in the coarse selection, the three times selection and the two times scavenging is composed of sodium hexametaphosphate, ferric chloride, citric acid and glutaric acid with a mass ratio of 3-4:2-3:4-5:1-2; the chemical structure of the collector used in the coarse selection and the two times scavenging is as follows: ， ， 。 2. The method of recovering tungsten from tungsten mine tailings of claim 1, wherein, The method for coarsely selecting the tungsten ore tailings is as follows: the tungsten ore tailings raw material and water are stirred and mixed to obtain a slurry with a mass concentration of 35-40%, then a pH adjusting agent is added until the pH of the slurry is 8-9, then a depressor is added, stirred for 2-5 min, then a collector is added, stirred for 2-5 min, and finally sent into a flotation machine for coarse selection to obtain coarse concentrate and coarse tailings slurry.

3. The method of recovering tungsten from tungsten mine tailings of claim 2, wherein, When the tungsten ore tailings are coarsely selected, the amount of the depressor is 250-300 g / t, and the amount of the collector is 350-400 g / t.

4. The method of recovering tungsten from tungsten mine tailings according to any one of claims 1 to 3, wherein The method for three times selecting the coarse concentrate is as follows: the coarse concentrate is first selected once to obtain first selection concentrate and first selection tailings slurry; then the first selection concentrate is selected twice to obtain second selection concentrate and second selection tailings slurry; finally the second selection concentrate is selected three times to obtain third selection concentrate and third selection tailings slurry.

5. The method of recovering tungsten from tungsten mine tailings of claim 4, wherein, The method for first selecting the coarse concentrate is as follows: the first selection concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 20-25%, then a depressor is added, stirred for 2-5 min, and sent into a flotation machine for second selection to obtain second selection concentrate and second selection tailings slurry; the amount of the depressor is 25-30 g / t.

6. The method of recovering tungsten from tungsten mine tailings of claim 4, wherein, The method for second selecting the first selection concentrate is as follows: the first selection concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 20-25%, then a depressor is added, stirred for 2-5 min, and sent into a flotation machine for second selection to obtain second selection concentrate and second selection tailings slurry; the amount of the depressor is 25-30 g / t.

7. The method of recovering tungsten from tungsten mine tailings of claim 4, wherein, The method for third selecting the second selection concentrate is as follows: the second selection concentrate and water are stirred and mixed to obtain a slurry with a mass concentration of 15-20%, then a depressor is added, stirred for 2-5 min, and sent into a flotation machine for third selection to obtain third selection concentrate and third selection tailings slurry; the amount of the depressor is 12-15 g / t.

8. The method of recovering tungsten from tungsten mine tailings of any one of claims 1-3, wherein, The method for two times scavenging the coarse tailings slurry is as follows: a depressor is added to the coarse tailings slurry, stirred for 2-5 min, then a collector is added, stirred for 2-5 min, and sent into a flotation machine for first selection to obtain first selection concentrate and first selection slurry; then a depressor is added to the first selection slurry, stirred for 2-5 min, then a collector is added, stirred for 2-5 min, and sent into a flotation machine for second selection to obtain second selection concentrate and second selection tailings.

9. The method of recovering tungsten from tungsten mine tailings of claim 8, wherein, The amount of the depressant is 120-150 g / t in the first scavenging, and 50-70 g / t in the second scavenging; the amount of the collector is 150-180 g / t in the first scavenging, and 70-90 g / t in the second scavenging.

10. The method of recovering tungsten from tungsten mine tailings of any one of claims 1-3, wherein, The tungsten ore tailings are tungsten ore gravity separation tailings.

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