Process for floating sulfur from tungsten calcium-containing polymetallic ore

Abstract

The application provides a tungsten calcium-containing polymetallic ore sulfur flotation process and relates to the field of metal ore sulfur flotation. The tungsten calcium-containing polymetallic ore sulfur flotation process comprises the following steps: S1, after the raw ore is ground by a grinding system, the ore pulp is delivered to a sulfide ore flotation stage; S2, the pH is adjusted to 9.8-10.0, and sodium carbonate is added; S3, an activator is added, and 45 g / t of sodium citrate and 45 g / t of copper sulfate are added during the flotation; S4, a collector is added, and 40 g / t of sodium butyl xanthate is added; and S5, a foaming agent is added, and pine oil is added. The process flotation is used to adjust the pH to 9.8-10.0 by adding sodium carbonate, to add 45 g / t of sodium citrate and 45 g / t of copper sulfate (the ratio of sodium citrate to copper sulfate is 1:1) as the activator, to add 40 g / t of the collector sodium butyl xanthate, and to add 20 g / t of the foaming agent pine oil. After one roughing, a sulfur concentrate with a sulfur grade of 1.66% and a recovery rate of 81.68% is obtained, the sulfur floating efficiency is greatly improved, and the problem of poor sulfur flotation efficiency of the tungsten calcium-containing polymetallic ore at pH 9.0-10.0 is effectively solved.

Description

Technical Field

[0001] This invention relates to the field of sulfur flotation technology for metal ores, specifically a sulfur flotation process for tungsten-calcium polymetallic ores. Background Technology

[0002] Flotation is a widely used mineral processing method in mineral processing. It refers to the mineral processing process in which solid minerals are floated out of a suspension (slurry) in water based on the differences in the physical and chemical properties of the mineral surface. Flotation has been widely used in the mineral processing industry and is most suitable for separating disseminated ores with low grade and fine particles.

[0003] Before flotation, the ore must be ground to the particle size required for flotation, ensuring that the valuable minerals are essentially liberated for separation. Flotation reagents are then added. During flotation, air is introduced into the pulp, creating numerous air bubbles. Particles that are not easily wetted by water, commonly referred to as hydrophobic minerals, adhere to these bubbles and rise to the surface of the pulp, forming a mineralized froth layer. Particles that are easily wetted by water, commonly referred to as hydrophilic minerals, do not adhere to the bubbles and remain in the pulp. The mineralized froth is then removed, thus achieving the separation process.

[0004] In existing methods for flotating sulfide tungsten-bearing polymetallic ores containing calcium, copper sulfate is used as an activator and sodium ethyl xanthate or sodium butyl xanthate as a collector under acidic or neutral pH conditions. This method is less effective for semi-oxidized sulfide minerals, especially when the ore contains calcium carbonate and is intended for tungsten flotation, requiring a pH adjustment to 9.0-10.0. Summary of the Invention

[0005] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a sulfur flotation process for tungsten-calcium polymetallic ores, which solves the problem of poor sulfur flotation efficiency in tungsten-calcium polymetallic ores at pH 9.0-10.0 in existing technologies.

[0006] (II) Technical Solution To achieve the above objectives, the present invention provides a sulfur flotation process for tungsten-calcium polymetallic ore, comprising the following steps: S1. After the raw ore is ground by the grinding system, the slurry is transported to the sulfide ore flotation stage. S2, pH adjusted to 9.8-10.0, sodium carbonate and inhibitor added; S3. Add activator: add 45g / t sodium citrate and 45g / t copper sulfate during flotation. S4. Add a collector, add 40g / t of sodium butyl xanthate; S5. Add foaming agent and pine oil.

[0007] Preferably, when sodium carbonate is added in S2 to adjust the pH to 9.8-10.0, calcium ions will form calcium hydroxyl ions (Ca[OH]-) and adsorb onto the sulfur surface, preventing the adsorption of copper sulfate and sodium butyl xanthate.

[0008] Preferably, the ratio of sodium citrate to copper sulfate in S3 is 1:1.

[0009] Preferably, sodium citrate and copper sulfate are used together in S3. After adding sodium citrate, it can react with calcium hydroxyl ions (Ca[OH]-) adsorbed on the sulfur surface to form calcium citrate chelate which dissolves in the aqueous solution, thereby eliminating the adsorption of calcium hydroxyl ions on the pyrite surface. This facilitates the adsorption of copper sulfate and sodium butyl xanthate on the pyrite surface and improves the sulfur flotation efficiency.

[0010] Preferably, the best sulfur flotation effect can be achieved when the amount of frother pine oil in S5 is 20g / t, while having no negative impact on subsequent tungsten flotation.

[0011] Preferably, in S1, the raw ore is ground by water milling. The specific grinding steps are as follows: weigh 1000g of feed ore, add 500ml of water, and grind the ore to -200 mesh to achieve 75%-78% density. A 1.5L flotation machine is used.

[0012] Preferably, after the grinding step, the ore is disposed of by a heavy medium cyclone. The heavy mineral concentrate product after disposal is mixed with the -0.5mm product, and the raw ore is processed by a two-stage closed-circuit process.

[0013] Preferably, the raw ore is ground using a semi-autogenous mill and then vertically screened to obtain two materials, one above the screen and one below the screen.

[0014] Preferably, in addition to adding a carbonate, S2 can also be adjusted by any one of lime, sulfur dioxide, or caustic soda.

[0015] Preferably, the inhibitor in S2 is any one of sodium sulfide, zinc sulfate, sodium cyanide, potassium dichromate, water glass, lime, ferrous sulfate, tannin, starch (dextrin), carboxymethyl cellulose, etc., with sodium sulfide being the most preferred. When sodium sulfide is added to the slurry, the slurry becomes alkaline, causing a hydrophilic hydroxide film to form on the surface of the sulfide minerals, thus inhibiting the growth of sulfide minerals.

[0016] (III) Beneficial Effects This invention provides a process for sulfur flotation in tungsten-calcium polymetallic ore. It has the following beneficial effects: When using the traditional process, with a sulfur content of 0.2% in the feed ore, a single roughing stage yields a sulfur concentrate with a sulfur grade of 2.96% and a recovery rate of 38.74%, indicating poor sulfur flotation efficiency. However, by adding sodium carbonate to adjust the pH to 9.8-10.0 during the flotation process, and adding 45g / t of sodium citrate and 45g / t of copper sulfate (sodium citrate to copper sulfate ratio 1:1) as activators, along with 40g / t of sodium butyl xanthate as a collector and 20g / t of pine oil as a frother, a single roughing stage yields a sulfur concentrate with a sulfur grade of 1.66% and a recovery rate of 81.68%. This significantly improves sulfur flotation efficiency and effectively solves the problem of poor sulfur flotation efficiency in tungsten-calcium polymetallic ores at pH 9.0-10.0. Furthermore, industrial practice has shown that the sulfur recovery rate in the sulfide ore flotation stage of the concentrator is 84.23%, demonstrating excellent operational performance. Attached Figure Description

[0017] Figure 1 This is a flotation flow chart of a sulfur flotation process for tungsten-calcium polymetallic ore proposed in this invention. Detailed Implementation

[0018] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1: like Figure 1 As shown, this embodiment of the invention provides a sulfur flotation process for tungsten-calcium polymetallic ore, comprising the following steps: S1. After the raw ore is ground by the grinding system, the slurry is transported to the sulfide ore flotation stage. S2, pH adjusted to 9.8-10.0, sodium carbonate and inhibitor added; S3. Add activator: add 45g / t sodium citrate and 45g / t copper sulfate during flotation. S4. Add a collector, add 40g / t of sodium butyl xanthate; S5. Add foaming agent and pine oil.

[0020] In S2, when sodium carbonate is added to adjust the pH to 9.8-10.0, calcium ions will form calcium hydroxyl ions (Ca[OH]-) and adsorb onto the sulfur surface, preventing the adsorption of copper sulfate and sodium butyl xanthate.

[0021] In S3, the ratio of sodium citrate to copper sulfate is 1:1.

[0022] In S3, sodium citrate is used in combination with copper sulfate. After adding sodium citrate, it can react with calcium hydroxyl ions (Ca[OH]-) adsorbed on the sulfur surface to form calcium citrate chelate which dissolves in the aqueous solution. This eliminates the adsorption of calcium hydroxyl ions on the pyrite surface, which is beneficial for copper sulfate and sodium butyl xanthate to adsorb on the pyrite surface and improve the sulfur flotation efficiency.

[0023] When the dosage of pine oil frother in S5 is 20 g / t, the best sulfur flotation effect can be achieved without negatively affecting the subsequent tungsten flotation.

[0024] In S1, the raw ore is ground using water milling. The specific grinding steps are as follows: Weigh 1000g of feed ore, add 500ml of water, and grind the ore to -200 mesh (75%-78%). A 1.5L flotation machine is used. The feed ore contains 0.2% sulfur. After one roughing process, a sulfur concentrate with a sulfur grade of 2.96% and a recovery rate of 38.74% is obtained.

[0025] After the grinding step, the ore is disposed of by a heavy medium cyclone. The heavy mineral concentrate product is then mixed with the -0.5mm product, and the raw ore is processed using a two-stage, two-closed-circuit process.

[0026] The raw ore is ground using a semi-autogenous mill and then vertically screened to obtain two materials, one above the screen and one below. The semi-autogenous mill is a wet autogenous mill with a diameter of 5.5m and a length of 1.8m.

[0027] In addition to adding a carbonate, S2 can also be adjusted by any one of lime, sulfur dioxide, or caustic soda. Meanwhile, the inhibitor in S2 can be any one of sodium sulfide, zinc sulfate, sodium cyanide, potassium dichromate, water glass, lime, ferrous sulfate, tannin, starch (dextrin), or carboxymethyl cellulose. Sodium sulfide is the most preferred choice. When sodium sulfide is added to the slurry, the slurry becomes alkaline, which causes a hydrophilic hydroxide film to form on the surface of the sulfide minerals, thus inhibiting the growth of sulfide minerals. Among these, sodium sulfide is the most preferred inhibitor.

[0028] The specific working principle is as follows: First, 1000g of feed containing 0.2% sulfur is weighed and then coarsely ground in a water mill to a fineness of less than 74 micrometers (70%), resulting in a sulfur concentrate with a sulfur grade of 2.96% and a recovery rate of 38.74%. The slurry is then transported to the sulfide ore flotation stage. Then, sodium carbonate is added to adjust the pH to 9.8-10.0, followed by the addition of 45g / t of sodium citrate and 45g / t of copper sulfate (sodium citrate to copper sulfate in a 1:1 ratio), and then the addition of 40g / t of sodium butyl xanthate as a collector. The best sulfur flotation effect can be achieved when the dosage of 20g / t of pine oil as a foaming agent is 20g / t. When sodium carbonate is added to adjust the pH to 9.8-10.0, calcium ions form calcium hydroxyl ions (Ca[OH]-) which are adsorbed on the sulfur surface, preventing the adsorption of copper sulfate and sodium butyl xanthate. Using sodium citrate in conjunction with copper sulfate allows the sodium citrate to react with the calcium hydroxyl ions (Ca[OH]-) adsorbed on the sulfur (i.e., pyrite) surface, forming a calcium citrate chelate that dissolves in the aqueous solution. This eliminates the adsorption of calcium hydroxyl ions on the pyrite surface, thereby facilitating the adsorption of copper sulfate and sodium butyl xanthate on the pyrite surface and improving the sulfur flotation efficiency.

[0029] The test results showed that the sulfur recovery rate in the flotation stage of sulfide ore was 84.23%.

[0030] Example 2: Based on the sulfur flotation process for tungsten-calcium polymetallic ore provided in the first embodiment of this application, the second embodiment of this application proposes another sulfur flotation process for tungsten-calcium polymetallic ore. The second embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the separate implementation of the first embodiment.

[0031] Specifically, the difference in the tungsten-calcium polymetallic ore sulfur flotation process provided in the second embodiment of this application is as follows: S1. After the raw ore is ground by the grinding system, the slurry is transported to the sulfide ore flotation stage. The raw ore is ground by water grinding. The specific grinding steps are as follows: Weigh 1000g of feed ore, add 500ml of water, and grind the ore to -200 mesh (75%-78%). The flotation machine used is 1.5L. After the grinding step, the ore is discarded by a heavy medium hydrocyclone. The heavy mineral concentrate product after discarding the waste is mixed with the -0.5mm product. The raw ore is processed by a two-stage closed-circuit process. The feed ore contains 0.2% sulfur. After one roughing process, a sulfur concentrate with a sulfur grade of 2.96% and a recovery rate of 38.74% is obtained. S2, pH adjusted to 9.8-10.0, sodium carbonate and inhibitor added. When the pH is adjusted to 9.8-10.0 by adding sodium carbonate, calcium ions will form calcium hydroxide ions (Ca[OH]-) and adsorb on the sulfur surface, preventing the adsorption of copper sulfate and sodium butyl xanthate. In addition to adding carbonate, it can also be adjusted by lime, sulfur dioxide, caustic soda, etc. At the same time, the inhibitor can be any one of sodium sulfide, zinc sulfate, sodium cyanide, potassium dichromate, water glass, lime, ferrous sulfate, tannin, starch (dextrin), carboxymethyl cellulose, etc. Sodium sulfide is the most preferred choice. When sodium sulfide is added to the slurry, the slurry is alkaline, which causes a hydrophilic hydroxide film to form on the surface of the sulfide minerals, making them hydrophilic and inhibiting the sulfide minerals. Among these, sodium sulfide is the most preferred inhibitor. S3. Add activator: Add 40g / t of sodium citrate and 40g / t of copper sulfate during flotation. The ratio of sodium citrate to copper sulfate is 1:1. Sodium citrate and copper sulfate are used together. After adding sodium citrate, it can react with calcium hydroxyl ions (Ca[OH]-) adsorbed on the sulfur surface to form calcium citrate chelate which dissolves in the aqueous solution. This eliminates the adsorption of calcium hydroxyl ions on the pyrite surface, which is beneficial for copper sulfate and sodium butyl xanthate to adsorb on the pyrite surface and improve the sulfur flotation efficiency. S4. Add a collector, add 35g / t of sodium butyl xanthate; S5. Adding a frother and pine oil, with a frother and pine oil dosage of 20g / t, can achieve the best sulfur flotation effect, while having no negative impact on subsequent tungsten flotation.

[0032] When using the process flotation, sodium carbonate is added to adjust the pH to 9.8-10.0, and 40g / t of sodium citrate and 40g / t of copper sulfate (sodium citrate to copper sulfate ratio of 1:1) are added as activators. Sodium butyl xanthate collector is added at a rate of 35g / t, and pine oil frother is added at a rate of 20g / t. After one roughing stage, a sulfur concentrate with a sulfur grade of 1.60% and a recovery rate of 81.50% can be obtained. The sulfur flotation efficiency is greatly improved, effectively solving the problem of poor sulfur flotation efficiency in tungsten-calcium polymetallic ores at pH 9.0-10.0.

[0033] The test results showed that the sulfur recovery rate in the flotation stage of sulfide ore was 83.10%.

[0034] Example 3: Based on the sulfur flotation process for tungsten-calcium polymetallic ore provided in the first embodiment of this application, the third embodiment of this application proposes another sulfur flotation process for tungsten-calcium polymetallic ore. The third embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the third embodiment will not affect the separate implementation of the first embodiment.

[0035] Specifically, the difference in the tungsten-calcium polymetallic ore sulfur flotation process provided in the third embodiment of this application lies in: S1. After the raw ore is ground by the grinding system, the slurry is transported to the sulfide ore flotation stage. The raw ore is ground by water grinding. The specific grinding steps are as follows: Weigh 1000g of feed ore, add 500ml of water, and grind the ore to -200 mesh (75%-78%). The flotation machine used is 1.5L. After the grinding step, the ore is discarded by a heavy medium hydrocyclone. The heavy mineral concentrate product after discarding the waste is mixed with the -0.5mm product. The raw ore is processed by a two-stage closed-circuit process. The feed ore contains 0.2% sulfur. After one roughing process, a sulfur concentrate with a sulfur grade of 2.96% and a recovery rate of 38.74% is obtained. S2, pH adjusted to 9.8-10.0, sodium carbonate and inhibitor added. When the pH is adjusted to 9.8-10.0 by adding sodium carbonate, calcium ions will form calcium hydroxide ions (Ca[OH]-) and adsorb on the sulfur surface, preventing the adsorption of copper sulfate and sodium butyl xanthate. In addition to adding carbonate, it can also be adjusted by lime, sulfur dioxide, caustic soda, etc. At the same time, the inhibitor can be any one of sodium sulfide, zinc sulfate, sodium cyanide, potassium dichromate, water glass, lime, ferrous sulfate, tannin, starch (dextrin), carboxymethyl cellulose, etc. Sodium sulfide is the most preferred choice. When sodium sulfide is added to the slurry, the slurry is alkaline, which causes a hydrophilic hydroxide film to form on the surface of the sulfide minerals, making them hydrophilic and inhibiting the sulfide minerals. Among these, sodium sulfide is the most preferred inhibitor. S3. Add activator: Add 50g / t of sodium citrate and 50g / t of copper sulfate during flotation. The ratio of sodium citrate to copper sulfate is 1:1. Sodium citrate and copper sulfate are used together. After adding sodium citrate, it can react with calcium hydroxyl ions (Ca[OH]-) adsorbed on the sulfur surface to form calcium citrate chelate which dissolves in the aqueous solution. This eliminates the adsorption of calcium hydroxyl ions on the pyrite surface, which is beneficial for copper sulfate and sodium butyl xanthate to adsorb on the pyrite surface and improve the sulfur flotation efficiency. S4. Add a collector, add 45g / t of sodium butyl xanthate; S5. Adding a frother and pine oil, with a frother and pine oil dosage of 20g / t, can achieve the best sulfur flotation effect, while having no negative impact on subsequent tungsten flotation.

[0036] When using the process flotation, sodium carbonate is added to adjust the pH to 9.8-10.0, and 50g / t of sodium citrate and 50g / t of copper sulfate (sodium citrate to copper sulfate ratio of 1:1) are added as activators. 45g / t of sodium butyl xanthate is added as a collector, and 20g / t of pine oil is added as a frother. After one roughing stage, a sulfur concentrate with a sulfur grade of 1.80% and a recovery rate of 81.95% can be obtained. The sulfur flotation efficiency is greatly improved, effectively solving the problem of poor sulfur flotation efficiency in tungsten-calcium polymetallic ores at pH 9.0-10.0.

[0037] The test results showed that the sulfur recovery rate in the flotation stage of sulfide ore was 82.18%.

[0038] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A process for sulfur flotation in tungsten-calcium polymetallic ore, characterized in that, Includes the following steps: S1. The raw ore is ground through the grinding system to a fineness of less than 74 micrometers (70%), and the slurry is then transported to the sulfide ore flotation stage. S2, pH adjusted to 9.8-10.0, sodium carbonate and inhibitor added; S3. Add activator: add 45g / t sodium citrate and 45g / t copper sulfate during flotation. S4. Add a collector, add 40g / t of sodium butyl xanthate; S5. Add foaming agent and pine oil.

2. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 1, characterized in that: In S2, when sodium carbonate is added to adjust the pH to 9.8-10.0, calcium ions will form calcium hydroxyl ions (Ca[OH]-) and adsorb onto the sulfur surface, preventing the adsorption of copper sulfate and sodium butyl xanthate.

3. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 1, characterized in that: In S3, the ratio of sodium citrate to copper sulfate is 1:

1.

4. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 1, characterized in that: In S3, sodium citrate is used in combination with copper sulfate. After adding sodium citrate, it can react with calcium hydroxyl ions (Ca[OH]-) adsorbed on the sulfur surface to form calcium citrate chelate which dissolves in the aqueous solution. This eliminates the adsorption of calcium hydroxyl ions on the pyrite surface, which is beneficial for copper sulfate and sodium butyl xanthate to adsorb on the pyrite surface and improve the sulfur flotation efficiency.

5. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 1, characterized in that: When the dosage of pine oil frother in S5 is 20 g / t, the best sulfur flotation effect can be achieved without negatively affecting the subsequent tungsten flotation.

6. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 1, characterized in that: In S1, the raw ore is ground using water milling. The specific grinding steps are as follows: Weigh 1000g of feed ore, add 500ml of water, and grind the ore to -200 mesh (75%-78%). A 1.5L flotation machine is used. The feed ore contains 0.2% sulfur. After one roughing process, a sulfur concentrate with a sulfur grade of 2.96% and a recovery rate of 38.74% is obtained.

7. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 6, characterized in that: After the grinding step, the ore is disposed of by a heavy medium cyclone. The heavy mineral concentrate product is then mixed with the -0.5mm product, and the raw ore is processed using a two-stage, two-closed-circuit process.

8. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 1, characterized in that: The raw ore is ground using a semi-autogenous mill and then vertically screened to obtain two materials, one above the screen and one below. The semi-autogenous mill is a wet autogenous mill with a diameter of 5.5m and a length of 1.8m.

9. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 1, characterized in that: The inhibitors mentioned in S2 are any one of sodium sulfide, zinc sulfate, sodium cyanide, potassium dichromate, water glass, lime, ferrous sulfate, tannin, or carboxymethyl cellulose, with adjustments made.

10. The sulfur flotation process for tungsten-calcium polymetallic ore according to claim 9, characterized in that: The inhibitor is sodium sulfide. When sodium sulfide is added to the slurry, the slurry becomes alkaline, causing a hydrophilic hydroxide film to form on the surface of the sulfide minerals, thus inhibiting the growth of sulfide minerals.

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