A process for the beneficiation of fine tungsten ore slimes

Abstract

The application belongs to the technical field of mineral processing, and particularly relates to a tungsten ore fine sludge separation process, which comprises the following steps: S1, obtaining tungsten ore fine sludge, and obtaining desulfurized concentrate by desulfurizing the tungsten ore fine sludge; S2, obtaining first flotation concentrate by first-time flotation of the desulfurized concentrate; S3, obtaining magnetic separation concentrate by magnetic separation of the first flotation concentrate; S4, obtaining gravity separation concentrate by table concentration of the magnetic separation concentrate; and S5, obtaining second-time flotation concentrate by second-time flotation of the gravity separation concentrate. The application solves the problem of recovery of -20 mu m micro-fine particles by coupling process of desulfurization, two-stage flotation, magnetic separation and table concentration, adopting a composite reagent system of phenylpropylene hydroxamic acid, octyl hydroxamic acid and sodium oleate, and using a cyclone micro-bubble flotation column and a high-speed shearing mixer, so as to improve the grade and recovery rate of tungsten concentrate, and the content of WO3 in the separated tungsten concentrate is greater than or equal to 11 wt%, the content of sulfur mineral impurities is less than or equal to 0.4 wt%, and the recovery rate of WO3 is greater than or equal to 90%.

Description

Technical Field

[0001] This application relates to the field of mineral processing technology, specifically, to a process for separating fine mud from tungsten ore. Background Technology

[0002] Wolframite is typically recovered using low-cost and relatively environmentally friendly gravity separation methods. The specific gravity separation method varies depending on the beneficiation equipment. While these methods offer advantages such as ease of operation, high throughput, and stable operation, they can sometimes suffer from insufficient enrichment and discontinuous operation. Although wolframite exhibits weak magnetism and can be recovered using magnetic separation, the grade of wolframite in my country is relatively low, containing numerous magnetic impurities, making complete removal of these impurities difficult using magnetic separation. Furthermore, wolframite has poor floatability, and Chinese wolframite contains many gangue minerals with similar active sites, thus making single flotation methods ineffective for recovery.

[0003] Scheelite has good floatability, so flotation is usually used for its recovery. However, most scheelite in my country is of low grade, has a fine particle size, and is associated with calcium-bearing gangue minerals such as calcite and fluorite, making flotation separation difficult.

[0004] Tungsten ore slime is even more difficult to recover due to the brittle nature of tungsten minerals and their fine particle size. Currently, most concentrators in my country have low recovery rates for tungsten ore slime, making it difficult to utilize this resource and resulting in resource waste and environmental pollution. Summary of the Invention

[0005] To solve the above-mentioned technical problems, this application provides a tungsten ore fine slime separation process, comprising the following steps: S1, obtaining tungsten ore fine slime, and desulfurizing the tungsten ore fine slime to obtain desulfurized concentrate; S2, performing a first flotation on the desulfurized concentrate to obtain a first flotation concentrate; S3, performing magnetic separation on the first flotation concentrate to obtain a magnetic concentrate; S4, performing shaking table cleaning on the magnetic concentrate to obtain a gravity concentrate; S5, performing a second flotation on the gravity concentrate to obtain a second flotation concentrate.

[0006] As a preferred embodiment of the tungsten ore fine slime separation process described in this application, in step S1, the proportion of -38μm particles in the tungsten ore fine slime is ≥85%, the proportion of -20μm micro-fine particles in the tungsten ore fine slime is ≥55%, the tungsten ore fine slime includes WO3, sulfur mineral impurities, magnetic impurities and gangue, the content of WO3 is 0.5-1.1wt%, the content of sulfur mineral impurities is ≥1.8wt%, the content of magnetic impurities is ≥2.5wt%, and the content of gangue is ≥15wt%. In step S5, the WO3 content of the second flotation concentrate is ≥11wt%, the content of sulfur mineral impurities in the second flotation concentrate is ≤0.4wt%, and the recovery rate of WO3 is ≥90%.

[0007] As a preferred embodiment of the tungsten ore fine mud separation process described in this application, in step S1, a desulfurization dispersant, a desulfurization activator, and a desulfurization collector are added during the desulfurization process. The desulfurization dispersant includes calcium carbonate, the desulfurization activator includes copper sulfate, and the desulfurization collector includes butyl yellow. The content of calcium carbonate is 400-500 g / t, the content of copper sulfate is 80-100 g / t, and the content of butyl yellow is 50-80 g / t. The desulfurization is carried out in a high-speed shear mixer and a cyclone microbubble flotation column. The desulfurization time is 10-15 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0008] As a preferred embodiment of the tungsten ore fine slime separation process described in this application, step S2 further includes: adding a first inhibitor, a first activator, and a first collector during the first flotation process. The first inhibitor includes water glass, the first activator includes lead sulfate, and the first collector includes benzohydroxyxamic acid. The content of the water glass is 2500-3500 g / t, the content of the lead sulfate is 220-250 g / t, and the content of the benzohydroxyxamic acid is 135-150 g / t. The first flotation time is 20-25 min, and the first flotation is carried out in a cyclone microbubble flotation column. The diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0009] As a preferred embodiment of the tungsten ore fine mud separation process described in this application, in step S3, the concentration of the slurry is controlled to be 22-24 wt% during the magnetic separation process, and the magnetic field strength of the magnetic separation is 1.0-1.1T; in step S4, the tilt angle of the shaking table for the shaking table separation is 4.0-5.5°.

[0010] As a preferred embodiment of the tungsten ore fine slime separation process described in this application, step S5 further includes: adding a second inhibitor, a second activator, and a second collector during the second flotation process. The second inhibitor includes water glass, the second activator includes lead sulfate, and the second collector includes phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate. The water glass content is 700-800 g / t, the lead sulfate content is 100-120 g / t, the phenylpropenyl hydroxamic acid content is 50-80 g / t, the octyl hydroxamic acid content is 12-20 g / t, and the sodium oleate content is 48-60 g / t. The second flotation time is 15-25 min, and the second flotation is carried out in a cyclone microbubble flotation column. The diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0011] As a preferred embodiment of the tungsten ore fine mud separation process described in this application, when the gangue in step S1 is calcite and the content of the calcite is 25-30 wt%, the content of the water glass in step S2 is 3200-3500 g / t.

[0012] As a preferred embodiment of the tungsten ore fine mud separation process described in this application, when the proportion of -20μm fine particles in the tungsten ore fine mud in step S1 is ≥70%, the gangue is mica, and the content of the mica is 15-25wt%, the desulfurization dispersant also includes sodium polyacrylate, and the content of the sodium polyacrylate is 200-280g / t.

[0013] As a preferred embodiment of the tungsten ore fine mud separation process described in this application, when the gangue in step S1 is fluorite and quartz, and the content of fluorite is 10-15 wt% and the content of quartz is 20-25 wt%, the first inhibitor in step S2 further includes sodium fluorosilicate, the content of sodium fluorosilicate is 150-220 g / t, and step S3 further includes: adding centrifugal gravity separation after magnetic separation, the rotation speed of the centrifugal gravity separation is 2000-2500 rpm.

[0014] As a preferred embodiment of the tungsten ore fine slime separation process described in this application, when the proportion of -20μm fine particles in the tungsten ore fine slime in step S1 is ≥80%, step S2 further includes adding pulsed microwave treatment before the first flotation, and step S5 further includes adding the pulsed microwave treatment before the second flotation. The power of the pulsed microwave treatment is 450-550W, the duration of the pulsed microwave treatment is 2-3min, and the content of phenylpropenyl hydroxamic acid in step S5 is 70-80g / t.

[0015] The beneficial effects of this application are as follows:

[0016] This application provides a fine tungsten ore separation process. This process combines desulfurization, two-stage flotation, magnetic separation, and shaking table cleaning. It employs a composite reagent system of phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate, and utilizes a cyclone microbubble flotation column and a high-speed shear mixer to solve the problem of recovering -20μm fine particles. This improves the grade and recovery rate of the tungsten concentrate. Using this separation method, the WO3 content of the separated tungsten concentrate is ≥11wt%, the sulfur mineral impurity content is ≤0.4wt%, and the WO3 recovery rate is ≥90%. Detailed Implementation

[0017] The technical solutions in the embodiments will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0018] This application provides a process for separating fine tungsten ore slime, including the following steps:

[0019] S1. Obtain tungsten ore fine mud, and desulfurize the tungsten ore fine mud to obtain desulfurized concentrate;

[0020] In step S1, the proportion of -38μm particles in the tungsten ore fine mud is ≥85%, the proportion of -20μm fine particles in the tungsten ore fine mud is ≥55%, and the tungsten ore fine mud includes WO3, sulfur mineral impurities, magnetic impurities, and gangue, wherein the content of WO3 is 0.5-1.1wt%, the content of sulfur mineral impurities is ≥1.8wt%, the content of magnetic impurities is ≥2.5wt%, and the content of gangue is ≥15wt%.

[0021] During the desulfurization process, a desulfurization dispersant, a desulfurization activator, and a desulfurization collector are added. The desulfurization dispersant includes calcium carbonate, the desulfurization activator includes copper sulfate, and the desulfurization collector includes butyl yellow. The content of calcium carbonate is 400-500 g / t, the content of copper sulfate is 80-100 g / t, and the content of butyl yellow is 50-80 g / t. The desulfurization is carried out in a high-speed shear mixer and a cyclone microbubble flotation column. The desulfurization time is 10-15 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0022] Specifically, the content of calcium carbonate is any one or a range between 400 g / t, 410 g / t, 420 g / t, 430 g / t, 440 g / t, 450 g / t, 460 g / t, 470 g / t, 480 g / t, 490 g / t, and 500 g / t; the content of copper sulfate is any one or a range between 80 g / t, 85 g / t, 90 g / t, 95 g / t, and 100 g / t; and the content of butyl yellow is any one or a range between 50 g / t, 55 g / t, 60 g / t, 65 g / t, 70 g / t, 75 g / t, and 80 g / t.

[0023] S2. Perform a first flotation on the desulfurized concentrate to obtain a first flotation concentrate;

[0024] Step S2 further includes: adding a first inhibitor, a first activator, and a first collector during the first flotation process. The first inhibitor includes water glass, the first activator includes lead sulfate, and the first collector includes benzohydroxyxamic acid. The content of the water glass is 2500-3500 g / t, the content of the lead sulfate is 220-250 g / t, and the content of the benzohydroxyxamic acid is 135-150 g / t. The first flotation time is 20-25 min. The first flotation is carried out in a cyclone microbubble flotation column, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0025] Specifically, the content of the water glass is any one or a range between two of the following: 2500 g / t, 2600 g / t, 2700 g / t, 2800 g / t, 2900 g / t, 3000 g / t, 3100 g / t, 3200 g / t, 3300 g / t, 3400 g / t, and 3500 g / t; the content of the lead sulfate is any one or a range between two of the following: 220 g / t, 225 g / t, 230 g / t, 235 g / t, 240 g / t, 245 g / t, and 250 g / t; and the content of the benzohydroxyxamic acid is any one or a range between two of the following: 135 g / t, 140 g / t, 145 g / t, and 150 g / t.

[0026] S3. The first flotation concentrate is subjected to magnetic separation to obtain a magnetically separated concentrate;

[0027] In step S3, the concentration of the slurry is controlled to be 22-24 wt% during the magnetic separation process, and the magnetic field strength of the magnetic separation is 1.0-1.1 T.

[0028] S4. The magnetic concentrate is further refined by shaking table to obtain gravity concentrate;

[0029] In step S4, the preferred tilt angle of the shaking table is 4.0-5.5°.

[0030] S5. The gravity concentrate is subjected to a second flotation to obtain a second flotation concentrate;

[0031] Step S5 further includes: adding a second inhibitor, a second activator, and a second collector during the second flotation process. The second inhibitor includes water glass, the second activator includes lead sulfate, and the second collector includes phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate. The content of water glass is 700-800 g / t, the content of lead sulfate is 100-120 g / t, the content of phenylpropenyl hydroxamic acid is 50-80 g / t, the content of octyl hydroxamic acid is 12-20 g / t, and the content of sodium oleate is 48-60 g / t. The second flotation time is 15-25 min, and the second flotation is carried out in a cyclone microbubble flotation column. The diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0032] The water glass content is any one or a range between 700 g / t, 710 g / t, 720 g / t, 730 g / t, 740 g / t, 750 g / t, 760 g / t, 770 g / t, 780 g / t, 790 g / t, and 800 g / t; the lead sulfate content is any one or a range between 100 g / t, 105 g / t, 110 g / t, 115 g / t, and 120 g / t; and the styrene-propenyl hydroxamic acid content is 50 g / t, 55 g / t, and 60 g / t. The content of octyl hydroxamic acid is within the range of any one or two of the following: g / t, 65 g / t, 70 g / t, 75 g / t, 80 g / t; the content of octyl hydroxamic acid is within the range of any one or two of the following: 12 g / t, 13 g / t, 14 g / t, 15 g / t, 16 g / t, 17 g / t, 18 g / t, 19 g / t, 20 g / t; and the content of sodium oleate is within the range of any one or two of the following: 48 g / t, 50 g / t, 52 g / t, 54 g / t, 56 g / t, 58 g / t, 60 g / t.

[0033] The technical solution of this application will be further described below with reference to specific embodiments.

[0034] Example 1

[0035] A process for separating fine tungsten ore slime includes the following steps:

[0036] Step S1: Obtain low-grade wolframite slime, wherein the proportion of -38μm particles in the tungsten ore slime is 85%, the proportion of -20μm fine particles is 55%, the content of WO3 is 0.5wt%, the content of sulfur mineral impurities is 1.8wt%, the content of magnetic impurities is 2.5wt%, and the content of gangue is 15wt%. Calcium carbonate, copper sulfate, and butyl yellow are added to the tungsten ore slime in a high-speed shear mixer and a cyclone microbubble flotation column to desulfurize and obtain a desulfurized concentrate, wherein the content of calcium carbonate is 400g / t, the content of copper sulfate is 80g / t, the content of butyl yellow is 50g / t, the desulfurization time is 10min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3mm.

[0037] Step S2: Water glass, lead sulfate, and benzoxime acid are added to a cyclone microbubble flotation column to perform the first flotation of the desulfurized concentrate to obtain the first flotation concentrate. The water glass content is 2500 g / t, the lead sulfate content is 220 g / t, and the benzoxime acid content is 135 g / t. The first flotation time is 20 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0038] Step S3: Magnetic separation is performed on the first flotation concentrate to obtain magnetic concentrate, wherein the concentration of the slurry is controlled at 22wt% and the magnetic field strength of the magnetic separation is 1.0T;

[0039] Step S4: After the magnetic concentrate is cleaned by shaking table, gravity concentrate is obtained, wherein the shaking table inclination angle of the shaking table is 4.0°.

[0040] Step S5: Water glass, lead sulfate, phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate are added to the cyclone microbubble flotation column to perform a second flotation on the gravity concentrate to obtain a second flotation concentrate. The water glass content is 700 g / t, the lead sulfate content is 100 g / t, the phenylpropenyl hydroxamic acid content is 50 g / t, the octyl hydroxamic acid content is 12 g / t, and the sodium oleate content is 48 g / t. The second flotation time is 15 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0041] The second flotation concentrate recovered in Example 1 was tested, and the results showed that the WO3 content was 11.3 wt% and the sulfur mineral impurity content was 0.3 wt%, with a WO3 recovery rate of 92.8%.

[0042] Example 2

[0043] A process for separating fine tungsten ore slime includes the following steps:

[0044] Step S1: Obtain high-sulfur scheelite slime, wherein the tungsten ore slime has a -38μm particle ratio of 90%, a -20μm micro-particle ratio of 60%, a WO3 content of 0.9wt%, a sulfur mineral impurity content of 3.0wt%, a magnetic impurity content of 3.0wt%, and a calcite content of 28wt%. Calcium carbonate, copper sulfate, and butyl yellow are added to a high-speed shear mixer and a cyclone microbubble flotation column to desulfurize the tungsten ore slime and obtain a desulfurized concentrate, wherein the calcium carbonate content is 450g / t, the copper sulfate content is 90g / t, the butyl yellow content is 65g / t, the desulfurization time is 13min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3mm.

[0045] Step S2: Water glass, lead sulfate, and benzoxime acid are added to a cyclone microbubble flotation column to perform the first flotation of the desulfurized concentrate to obtain the first flotation concentrate. The water glass content is 3400 g / t, the lead sulfate content is 235 g / t, and the benzoxime acid content is 145 g / t. The first flotation time is 22 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0046] Step S3: Magnetic separation is performed on the first flotation concentrate to obtain magnetic concentrate, wherein the concentration of the slurry is controlled at 23 wt% and the magnetic field strength of the magnetic separation is 1.05 T;

[0047] Step S4: After the magnetic concentrate is cleaned by shaking table, gravity concentrate is obtained, wherein the shaking table inclination angle of the shaking table is 5.0°.

[0048] Step S5: Water glass, lead sulfate, phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate are added to the cyclone microbubble flotation column to perform a second flotation on the gravity concentrate to obtain a second flotation concentrate. The water glass content is 750 g / t, the lead sulfate content is 110 g / t, the phenylpropenyl hydroxamic acid content is 55 g / t, the octyl hydroxamic acid content is 16 g / t, and the sodium oleate content is 54 g / t. The second flotation time is 20 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0049] The second flotation concentrate recovered in Example 2 was tested, and the results showed that the WO3 content was 12.1 wt% and the sulfur mineral impurity content was 0.2 wt%, with a WO3 recovery rate of 91.5%.

[0050] Example 3

[0051] A process for separating fine tungsten ore slime includes the following steps:

[0052] Step S1: Obtain ultrafine wolframite slime, wherein the proportion of -38μm particles in the tungsten slime is 90%, the proportion of -20μm micro-fine particles is 70%, the content of WO3 is 0.8wt%, the content of sulfur mineral impurities is 2.8wt%, the content of magnetic impurities is 3.2wt%, and the content of mica is 20wt%. Sodium polyacrylate, calcium carbonate, copper sulfate, and butyl yellow are added to a high-speed shear mixer and a cyclone microbubble flotation column to desulfurize the tungsten slime and obtain a desulfurized concentrate, wherein the content of sodium polyacrylate is 240g / t, the content of calcium carbonate is 450g / t, the content of copper sulfate is 90g / t, the content of butyl yellow is 70g / t, the desulfurization time is 13min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3mm.

[0053] Step S2: Water glass, lead sulfate, and benzoxime acid are added to a cyclone microbubble flotation column to perform the first flotation of the desulfurized concentrate to obtain the first flotation concentrate. The water glass content is 3500 g / t, the lead sulfate content is 240 g / t, and the benzoxime acid content is 143 g / t. The first flotation time is 23 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0054] Step S3: Magnetic separation is performed on the first flotation concentrate to obtain magnetic concentrate, wherein the concentration of the slurry is controlled at 24wt% and the magnetic field strength of the magnetic separation is 1.1T;

[0055] Step S4: After the magnetic concentrate is cleaned by shaking table, gravity concentrate is obtained, wherein the shaking table inclination angle of the shaking table is 5.5°.

[0056] Step S5: Water glass, lead sulfate, phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate are added to a cyclone microbubble flotation column to perform a second flotation on the gravity concentrate to obtain a second flotation concentrate. The diameter of the bubbles generated by the microbubble flotation column is 0.1-0.3 mm, the content of water glass is 755 g / t, the content of lead sulfate is 110 g / t, the content of phenylpropenyl hydroxamic acid is 58 g / t, the content of octyl hydroxamic acid is 17 g / t, and the content of sodium oleate is 55 g / t. The second flotation time is 19 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0057] The second flotation concentrate recovered in Example 3 was tested, and the results showed that the WO3 content was 11.0 wt% and the sulfur mineral impurity content was 0.3 wt%, with a WO3 recovery rate of 90.2%.

[0058] Example 4

[0059] A process for separating fine tungsten ore slime includes the following steps:

[0060] Step S1: Obtain complex symbiotic tungsten ore slime, wherein the ratio of wolframite to scheelite symbiotic slime is 1:1, the tungsten ore slime has a -38μm particle ratio of 88%, a -20μm micro-particle ratio of 58%, a WO3 content of 0.9wt%, a sulfur mineral impurity content of 3.6wt%, a magnetic impurity content of 3.0wt%, a fluorite content of 12wt%, and a quartz content of 23wt%. Calcium carbonate, copper sulfate, and butyl yellow are added to the tungsten ore slime in a high-speed shear mixer and a cyclone microbubble flotation column to desulfurize the tungsten ore slime and obtain a desulfurized concentrate, wherein the calcium carbonate content is 500g / t, the copper sulfate content is 100g / t, the butyl yellow content is 80g / t, the desulfurization time is 15min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3mm.

[0061] Step S2: Sodium fluorosilicate, water glass, lead sulfate, and benzoxime acid are added to a cyclone microbubble flotation column to perform the first flotation of the desulfurized concentrate to obtain the first flotation concentrate. The content of sodium fluorosilicate is 180 g / t, the content of water glass is 3500 g / t, the content of lead sulfate is 250 g / t, and the content of benzoxime acid is 150 g / t. The first flotation time is 25 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0062] Step S3: The first flotation concentrate is subjected to magnetic separation and centrifugal gravity separation to obtain magnetic concentrate, wherein the concentration of the slurry is controlled at 23wt%, the magnetic field strength of the magnetic separation is 1.1T, and the rotation speed of the centrifugal gravity separation is 2200rpm.

[0063] Step S4: After the magnetic concentrate is cleaned by shaking table, gravity concentrate is obtained, wherein the shaking table inclination angle of the shaking table is 5.5°.

[0064] Step S5: Water glass, lead sulfate, phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate are added to the cyclone microbubble flotation column to perform a second flotation on the gravity concentrate to obtain a second flotation concentrate. The water glass content is 800 g / t, the lead sulfate content is 120 g / t, the phenylpropenyl hydroxamic acid content is 60 g / t, the octyl hydroxamic acid content is 20 g / t, and the sodium oleate content is 60 g / t. The second flotation time is 25 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

[0065] The second flotation concentrate recovered in Example 4 was tested, and the results showed that the WO3 content was 11.6 wt% and the sulfur mineral impurity content was 0.2 wt%, with a WO3 recovery rate of 93.0%.

[0066] Example 5

[0067] A process for separating fine tungsten ore slime includes the following steps:

[0068] Step S1: Obtain extremely fine-grained tungsten tailings slime, wherein the tungsten ore slime contains 86% -38μm particles, 80% -20μm fine particles, 0.5wt% WO3, 2.0wt% sulfur mineral impurities, 2.8wt% magnetic impurities, and 15wt% gangue. Calcium carbonate, copper sulfate, and butyl yellow are added to a high-speed shear mixer and a cyclone microbubble flotation column to desulfurize the tungsten ore slime and obtain a desulfurized concentrate, wherein the calcium carbonate content is 500g / t, the copper sulfate content is 100g / t, the butyl yellow content is 60g / t, the desulfurization time is 15min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3mm.

[0069] Step S2: Water glass, lead sulfate, and benzoxime acid are added to a cyclone microbubble flotation column to perform the first flotation of the desulfurized concentrate to obtain the first flotation concentrate. Before the first flotation, pulse microwave treatment is performed with a power of 500W and a duration of 2 minutes. The content of water glass is 3000g / t, the content of lead sulfate is 250g / t, and the content of benzoxime acid is 150g / t. The first flotation time is 25 minutes, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3mm.

[0070] Step S3: Magnetic separation is performed on the first flotation concentrate to obtain magnetic concentrate, wherein the concentration of the slurry is controlled at 23 wt% and the magnetic field strength of the magnetic separation is 1.1 T;

[0071] Step S4: After the magnetic separation concentrate is further refined by shaking table, a gravity concentrate is obtained. The shaking table inclination angle for the shaking table refining is 5°.

[0072] Step S5: Water glass, lead sulfate, phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate are added to the cyclone microbubble flotation column to perform a second flotation of the gravity concentrate to obtain a second flotation concentrate. Before the second flotation, pulse microwave treatment is performed with a power of 500W for 2 minutes. The content of water glass is 800g / t, lead sulfate is 120g / t, phenylpropenyl hydroxamic acid is 80g / t, octyl hydroxamic acid is 20g / t, and sodium oleate is 60g / t. The second flotation time is 25 minutes. The diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3mm.

[0073] The second flotation concentrate recovered in Example 5 was tested, and the results showed that the WO3 content was 11.2 wt% and the sulfur mineral impurity content was 0.4 wt%, with the WO3 recovery rate being 90.0%.

[0074] Comparative Example 1

[0075] The difference between this comparative example and Example 1 is that this comparative example does not perform magnetic separation and a second flotation, while all other steps are the same as in Example 1.

[0076] The concentrate recovered in Comparative Example 1 was tested, and the results showed that the WO3 content was 4.5 wt% and the sulfur mineral impurity content was 1.1 wt%, with the WO3 recovery rate being 56.3%.

[0077] Comparative Example 2

[0078] The difference between this comparative example and Example 1 is that this comparative example does not undergo desulfurization, while all other steps are the same as in Example 1.

[0079] The concentrate recovered in Comparative Example 2 was tested, and the results showed that the WO3 content was 6.0 wt% and the sulfur mineral impurity content was 1.7 wt%, with the WO3 recovery rate being 70.1%.

[0080] Comparative Example 3

[0081] The difference between this comparative example and Example 1 is that the pulp concentration during magnetic separation in this comparative example is 30 wt%, while the other steps are the same as in Example 1.

[0082] The concentrate recovered in Comparative Example 3 was tested, and the results showed that the WO3 content was 7.2 wt% and the sulfur mineral impurity content was 1.2 wt%, with a WO3 recovery rate of 68.4%.

[0083] Comparative Example 4

[0084] The difference between this comparative example and Example 1 is that the second collector in the second flotation of this comparative example is sodium oleate, while the other steps are the same as in Example 1.

[0085] The concentrate recovered in Comparative Example 4 was tested, and the results showed that the WO3 content was 9.5 wt% and the sulfur mineral impurity content was 0.7 wt%, with the WO3 recovery rate being 85.2%.

[0086] Comparative Example 5

[0087] The difference between this comparative example and Example 1 is that this comparative example does not involve shaking for selection, while all other steps are the same as in Example 1.

[0088] The concentrate recovered from Comparative Example 5 was tested, and the results showed that the WO3 content was 8.9 wt% and the sulfur mineral impurity content was 0.9 wt%, with a WO3 recovery rate of 80.6%.

[0089] Comparative Example 6

[0090] The difference between this comparative example and Example 1 is that the phenylpropenyl hydroxamic acid in the second collector during the second flotation in Example 1 is replaced with phenylmethyl hydroxamic acid. All other steps are the same as in Example 1.

[0091] The concentrate recovered in Comparative Example 6 was tested, and the results showed that the WO3 content was 10.1 wt% and the sulfur mineral impurity content was 0.7 wt%, with the WO3 recovery rate being 87.5%.

[0092] Comparative Example 7

[0093] The difference between this comparative example and Example 1 is that the second collector in the second flotation of this comparative example is phenylpropenyl hydroxamic acid and octyl hydroxamic acid, without sodium oleate. All other steps are the same as in Example 1.

[0094] The concentrate recovered from Comparative Example 7 was tested, and the results showed that the WO3 content was 7.1 wt% and the sulfur mineral impurity content was 0.8 wt%, with the WO3 recovery rate being 65.2%.

[0095] As can be seen from the above examples and comparative examples, Example 1 combined with Example 2 shows that when the tungsten ore slime contains calcite, the amount of water glass used in the first flotation is increased to suppress calcite; Example 1 combined with Example 3 shows that when the tungsten ore slime contains mica and the proportion of -20μm fine particles in the tungsten ore slime is ≥70%, sodium polyacrylate is added during desulfurization to promote slime dispersion and improve the recovery rate of fine particles; Example 1 combined with Example 4 shows that when the tungsten ore slime contains fluorite and quartz, sodium fluorosilicate is added during the first flotation to selectively suppress fluorite, and a centrifugal concentrator is added after magnetic separation for pretreatment to remove light-density quartz; Example 1 combined with Example 5 shows that when the proportion of -20μm fine particles in the tungsten ore slime is ≥80%, the amount of phenylpropenyl hydroxamic acid used in the second flotation is increased to enhance the adsorption of fine particles, and pulsed microwave pretreatment is added before the first and second flotation to destroy the electrostatic adsorption between minerals and gangue, thereby improving the recovery rate of tungsten ore slime.

[0096] Example 1, in conjunction with Comparative Example 1, shows that omitting magnetic separation and the second flotation will result in the failure to remove magnetic impurities, and omitting the second flotation will lead to severe loss of fine particles. Example 1, in conjunction with Comparative Example 2, shows that omitting desulfurization will result in sulfides encapsulating tungsten minerals, wasting flotation reagents and thus reducing the recovery of tungsten ore slime. Example 1, in conjunction with Comparative Example 3, shows that excessively high pulp concentration will cause gangue to be entrained in magnetic separation, reducing flotation efficiency. Example 1, in conjunction with Comparative Example 4, shows that the absence of phenylpropenyl hydroxamic acid and octyl hydroxamic acid will lead to a decrease in the selectivity of wolframite. Example 1, in conjunction with Comparative Example 5, shows that omitting shaking table cleaning will result in the inclusion of intergrowths in the magnetic separation concentrate, affecting the final grade. Example 1, in conjunction with Comparative Example 6, shows that phenylpropenyl hydroxamic acid has a weaker adsorption capacity for Fe sites than phenylpropenyl hydroxamic acid, leading to a decrease in wolframite recovery. Example 1, in conjunction with Comparative Example 7, shows that the absence of sodium oleate as a collector will lead to a decrease in tungsten ore recovery, and the use of hydroxamic acids as collectors in the second flotation alone cannot achieve a high recovery rate of tungsten ore slime.

[0097] This application provides a fine tungsten ore separation process. This process combines desulfurization, two-stage flotation, magnetic separation, and shaking table cleaning. It employs a composite reagent system of phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate, and utilizes a cyclone microbubble flotation column and a high-speed shear mixer to solve the problem of recovering -20μm fine particles. This improves the grade and recovery rate of the tungsten concentrate. Using this separation method, the WO3 content of the separated tungsten concentrate is ≥11wt%, the sulfur mineral impurity content is ≤0.4wt%, and the WO3 recovery rate is ≥90%.

[0098] The above description is only a preferred embodiment of this application and does not limit the patent scope of this application. All equivalent structural transformations made using the content of this application's specification under the inventive concept of this application, or direct / indirect applications in other related technical fields, are included within the patent protection scope of this application.

Claims

1. A process for separating fine mud from tungsten ore, characterized in that, Includes the following steps: S1. Obtain tungsten ore fine mud, and desulfurize the tungsten ore fine mud to obtain desulfurized concentrate; S2. Perform a first flotation on the desulfurized concentrate to obtain a first flotation concentrate; S3. The first flotation concentrate is subjected to magnetic separation to obtain a magnetically separated concentrate; S4. The magnetic concentrate is further refined by shaking table to obtain gravity concentrate; S5. The gravity concentrate is subjected to a second flotation to obtain a second flotation concentrate; In step S1, a desulfurization dispersant, a desulfurization activator, and a desulfurization collector are added during the desulfurization process. The desulfurization dispersant includes calcium carbonate, the desulfurization activator includes copper sulfate, and the desulfurization collector includes butyl yellow. The content of calcium carbonate is 400-500 g / t, the content of copper sulfate is 80-100 g / t, and the content of butyl yellow is 50-80 g / t. The desulfurization is carried out in a high-speed shear mixer and a cyclone microbubble flotation column. The desulfurization time is 10-15 min, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm. Step S2 further includes: adding a first inhibitor, a first activator, and a first collector during the first flotation process. The first inhibitor includes water glass, the first activator includes lead sulfate, and the first collector includes benzohydroxyxamic acid. The content of the water glass is 2500-3500 g / t, the content of the lead sulfate is 220-250 g / t, and the content of the benzohydroxyxamic acid is 135-150 g / t. The first flotation time is 20-25 min. The first flotation is carried out in a cyclone microbubble flotation column, and the diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm. Step S5 further includes: adding a second inhibitor, a second activator, and a second collector during the second flotation process. The second inhibitor includes water glass, the second activator includes lead sulfate, and the second collector includes phenylpropenyl hydroxamic acid, octyl hydroxamic acid, and sodium oleate. The content of the water glass is 700-800 g / t, the content of the lead sulfate is 100-120 g / t, the content of the phenylpropenyl hydroxamic acid is 50-80 g / t, the content of the octyl hydroxamic acid is 12-20 g / t, and the content of the sodium oleate is 48-60 g / t. The second flotation takes 15-25 minutes and is carried out in a cyclone microbubble flotation column. The diameter of the bubbles generated by the cyclone microbubble flotation column is 0.1-0.3 mm.

2. The tungsten ore fine slime separation process according to claim 1, characterized in that, In step S1, the proportion of -38μm particles in the tungsten ore slime is ≥85%, the proportion of -20μm fine particles in the tungsten ore slime is ≥55%, the tungsten ore slime includes WO3, sulfur mineral impurities, magnetic impurities and gangue, the content of WO3 is 0.5-1.1wt%, the content of sulfur mineral impurities is ≥1.8wt%, the content of magnetic impurities is ≥2.5wt%, and the content of gangue is ≥15wt%. In step S5, the WO3 content of the second flotation concentrate is ≥11wt%, the content of sulfur mineral impurities in the second flotation concentrate is ≤0.4wt%, and the recovery rate of WO3 is ≥90%.

3. The tungsten ore fine slime separation process according to claim 1, characterized in that, In step S3, the concentration of the slurry is controlled to be 22-24 wt% during the magnetic separation process, and the magnetic field strength of the magnetic separation is 1.0-1.1T; in step S4, the tilt angle of the shaking table for the shaking table separation is 4.0-5.5°.

4. The tungsten ore fine slime separation process according to claim 2, characterized in that, When the gangue in step S1 is calcite and the content of calcite is 25-30 wt%, the content of water glass in step S2 is 3200-3500 g / t.

5. The tungsten ore fine slime separation process according to claim 2, characterized in that, When the proportion of -20μm fine particles in the tungsten ore slime in step S1 is ≥70%, the gangue is mica, and the content of mica is 15-25wt%, the desulfurization dispersant also includes sodium polyacrylate, and the content of sodium polyacrylate is 200-280g / t.

6. The tungsten ore fine slime separation process according to claim 2, characterized in that, When the gangue in step S1 is fluorite and quartz, and the content of fluorite is 10-15 wt% and the content of quartz is 20-25 wt%, the first inhibitor in step S2 further includes sodium fluorosilicate, the content of sodium fluorosilicate is 150-220 g / t, and step S3 further includes: adding centrifugal gravity separation after magnetic separation, the centrifugal gravity separation speed is 2000-2500 rpm.

7. The tungsten ore fine slime separation process according to claim 2, characterized in that, When the proportion of -20μm fine particles in the tungsten ore slime in step S1 is ≥80%, step S2 further includes adding pulsed microwave treatment before the first flotation, and step S5 further includes adding the pulsed microwave treatment before the second flotation. The power of the pulsed microwave treatment is 450-550W, the duration of the pulsed microwave treatment is 2-3min, and the content of phenylpropenyl hydroxamic acid in step S5 is 70-80g / t.