Scheelite combined collecting agent and preparation method and application thereof

Abstract

The invention discloses a scheelite combined collecting agent and a preparation method and application thereof, and belongs to the technical field of mineral processing. The combined collecting agent comprises the following components in percentage by mass: 2%-5% of sucrose laurate, 85%-92% of C16-C18 fatty acid salt and 6%-10% of hexamethyldisiloxane. The combined collecting agent is applied to flotation of scheelite, and efficient recovery of scheelite can be achieved through closed-loop flotation of one-time roughing, three-time refining and two-time sweeping. According to the combined collecting agent, the problem that a traditional fatty acid collecting agent is poor in solubility is solved, the combined collecting agent is simple in preparation process, good in collecting performance and selectivity, good in dispersity and solubility and good in environmental protection property, and the grade and the recovery rate of scheelite concentrate can be remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, specifically to a combined collector for scheelite, its preparation method, and its application. Background Technology

[0002] Scheelite is a major tungsten-bearing mineral in nature. Scheelite deposits typically have low-grade, complex mineral compositions and fine-grained distribution of valuable minerals. Flotation is commonly used to recover scheelite, and the performance of the collector is crucial to the flotation effect. Developing scheelite collectors with both strong collecting ability and high selectivity has been a key research focus. Furthermore, as a calcium-bearing mineral, scheelite often coexists with calcium-bearing gangue minerals such as fluorite and calcite. These minerals share similar solution and surface chemistry in the pulp solution and possess the same surface calcium ion active sites. Therefore, achieving efficient separation of scheelite from calcium-bearing gangue minerals has long been a challenge and problem in the mineral processing field.

[0003] Currently, the most commonly used collectors for scheelite flotation in industry are anionic collectors, fatty acid collectors, and hydroxamic acid collectors. Traditional fatty acid collectors face the following drawbacks: First, they have poor selectivity, as the polar carboxyl groups in their molecular structure can indiscriminately adsorb onto the active sites of calcium ions on the surface of scheelite and calcium-bearing gangue minerals. Second, these collectors are easily affected by unavoidable ions in the pulp solution; fatty acid ions will pre-form fatty acid salts with calcium and magnesium ions in the pulp solution, thus consuming the collector. Finally, and most importantly, these collectors have poor solubility and are sensitive to temperature. At low temperatures, the solubility and dispersibility of fatty acid collectors deteriorate sharply, resulting in high foam viscosity. The collectors will form micelles or agglomerates in the pulp solution, failing to efficiently adsorb onto the mineral surface to perform a collecting effect, thus greatly affecting the mineral flotation.

[0004] Therefore, developing a highly efficient flotation collector is of great significance for the recovery of scheelite. Summary of the Invention

[0005] To address the problems of conventional collectors such as poor solubility in slurry, significant temperature dependence, poor dispersibility in slurry solutions, and weak collecting ability, the present invention aims to provide a combined collector for scheelite. The combined collector and the mass percentage of its components are as follows: 2%-5% sucrose laurate, C... 16 -C 18 Fatty acid salts 85%-92%, hexamethyldisiloxane 6%-10%, wherein the total mass of all components of the combined collector is 100% by mass percentage; the C 16 -C 18 The fatty acid salt is sodium palmitate or sodium oleate.

[0006] Another object of the present invention is to provide a method for preparing a combined collector for scheelite, specifically including the following steps: (1) Dissolve sucrose laurate in water and stir until homogeneous to obtain sucrose laurate solution.

[0007] (2) Add C to the sucrose laurate solution 16 -C 18 Fatty acid salts and hexamethyldisiloxane are heated and stirred until homogeneous to obtain a combined collector solution.

[0008] Preferably, the conditions for uniform mixing in step (1) of the present invention are: stirring at 800-1200 rpm for 2-6 minutes.

[0009] Preferably, the conditions for heating, stirring and mixing uniformly in step (2) of the present invention are: stirring for 5-8 minutes at 50℃-65℃ and 800-1200rpm.

[0010] Preferably, in step (2) of the present invention, the combined collector solution contains sucrose laurate and C 16 -C 18 The total mass percentage concentration of fatty acid salts and hexamethyldisiloxane is 5%-10%.

[0011] Another object of the present invention is to provide an application of a combined collector in the flotation of scheelite, specifically including the following steps: (1) Grind and adjust the raw scheelite ore to obtain slurry.

[0012] (2) Add a mixture of inhibitor and combined collector to the slurry, and separate it by one roughing, three cleaning and two scavenging flotation to obtain scheelite concentrate and scheelite tailings.

[0013] Preferably, in step (1) of the present invention, grinding to -0.074 mm accounts for 65% to 80%.

[0014] Preferably, the slurry preparation in step (1) of the present invention specifically involves: adding water to adjust the slurry concentration to 20%~35%, and using one or both of sodium hydroxide and sodium carbonate to adjust the slurry pH to 8.5~11.5.

[0015] Preferably, the inhibitor in step (2) of the present invention is water glass or acidified water glass, and the water glass modulus is 2.5-3.

[0016] Preferably, in step (2) of the present invention, the amount of inhibitor used in the roughing process is 600-1200 g / t, and the amount of the combined collector mixed solution is 200-600 g / t based on the total amount of solute in the combined collector mixed solution.

[0017] Preferably, no combined collector is added during the three selection processes in step (2) of the present invention. The amount of inhibitor used in selection I is 300-600 g / t, the amount of inhibitor used in selection II is 150-300 g / t, and the amount of inhibitor used in selection III is 75-150 g / t.

[0018] Preferably, no inhibitors are added during the two scavenging processes in step (2) of the present invention. The amount of the combined collector mixed solution used in scavenging operation I is 100-300 g / t based on the total solute in the combined collector mixed solution; the amount of the combined collector mixed solution used in scavenging operation II is 50-150 g / t based on the total solute in the combined collector mixed solution.

[0019] This invention provides a combined collector for scheelite, its preparation method, and its application, which has the following beneficial effects: (1) This invention is the first to propose the use of sucrose laurate and C 16 -C 18 Fatty acid salts and hexamethyldisiloxane are combined in a certain proportion to form a collector for the flotation of scheelite. Under the synergistic effect of this collector system, efficient flotation separation of scheelite and calcium-bearing gangue minerals is achieved, which can obtain high-grade scheelite concentrate and reduce the amount of reagents used.

[0020] (2) The combined collector of the present invention overcomes the shortcomings of traditional fatty acid collectors, such as poor solubility, poor dispersibility, poor resistance to low temperatures, and poor selectivity. Sucrose laurate and hexamethyldisiloxane are similar to C 16 -C 18 The synergistic effect of fatty acid salts compensates for the shortcomings of single fatty acid collectors and enhances the collection efficiency of scheelite.

[0021] (3) The components of the combined collector in this invention are widely available, easy to obtain, easy to preserve and store, have good environmental protection properties, the preparation process is relatively simple and convenient, and it is also easy to add during the flotation reagent addition process. It is a highly efficient combined collector for scheelite flotation. Attached Figure Description

[0022] Figure 1 This is a process flow diagram of Embodiment 1 and Comparative Examples 1-3 of the present invention.

[0023] Figure 2 These are process flow diagrams for Embodiments 2-3 and Comparative Examples 4-6 of the present invention. Detailed Implementation

[0024] 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.

[0025] Example 1 In the tailings of a certain polymetallic sulfide ore, tungsten is mainly found in the form of scheelite. The main gangue minerals in this sulfide ore are calcium-bearing gangues, primarily fluorite and calcite, with a CaF2 grade of 34.36% and a CaO grade of 12.43%. This embodiment uses a combined collector for flotation, with the following mass percentage composition: 2% sucrose laurate, 92% sodium oleate, and 6% hexamethyldisiloxane. Water glass with a modulus of 2.5 is used as the depressant. The flotation feed is the aforementioned tailings, with a WO3 grade of approximately 0.18% and a high calcium-bearing gangue content (CaF2 34.36%, CaO 12.43%). The flotation process is as follows: Figure 1 As shown, the specific preparation and flotation steps of the combined collector are as follows: (1) Dissolve sucrose laurate in water and stir at 800 rpm for 6 minutes to mix evenly to obtain sucrose laurate solution.

[0026] (2) Add sodium oleate and hexamethyldisiloxane to the sucrose laurate solution and stir for 8 minutes at 50°C and 800 rpm to obtain a combined collector solution (the total mass percentage concentration of sucrose laurate, sodium oleate and hexamethyldisiloxane in the combined collector solution is 5%).

[0027] (3) Grind the raw scheelite ore to 75% of the size of -0.074 mm, add water to adjust the slurry concentration to 30%, and adjust the pH of the slurry to 8.5 with sodium carbonate. Stir for 1.5 minutes to obtain the slurry.

[0028] (4) Add water glass (1000 g / t) to the slurry as a depressant, stir for 3 minutes, then add a mixed solution of combined collectors (500 g / t based on the total solute content of the combined collectors), stir for 3 minutes, and then ventilate for roughing for 4 minutes to obtain roughing concentrate and roughing tailings; perform two scavenging processes on the roughing tailings, without adding depressant during the two scavenging processes. In scavenging operation I, add a mixed solution of combined collectors (250 g / t based on the total solute content of the combined collectors), stir for 2.5 minutes, and then float for 3 minutes; in scavenging operation II... Add a combined collector solution (the amount of the combined collector solution is 125 g / t based on the total solute in the combined collector solution), stir for 2.5 minutes, and float for 2 minutes to obtain scheelite tailings; perform three cleaning processes on the roughing concentrate, without adding the combined collector solution during the three cleaning processes. In cleaning process I, add water glass (500 g / t), stir for 2.5 minutes, and float for 3 minutes; in cleaning process II, add water glass (250 g / t), stir for 2.5 minutes, and float for 3 minutes; in cleaning process III, add water glass (125 g / t), stir for 2 minutes, and float for 2 minutes to obtain scheelite concentrate.

[0029] The closed-circuit flotation results of this embodiment are shown in Table 1.

[0030] Example 2 The main gangue minerals in a certain scheelite ore are fluorite and calcite. The ore contains 0.62% WO3. Tungsten mainly exists in the form of scheelite. The gangue minerals mainly include fluorite, calcite, and quartz, with fluorite content at 30.16% and calcite content at 28.41%. This embodiment uses a combined collector for flotation, with the following mass percentage composition: 3% sucrose laurate, 90% sodium palmitate, and 7% hexamethyldisiloxane. The depressant is acidified water glass with a modulus of 2.8. The flotation feed is the aforementioned scheelite ore with a WO3 grade of 0.62%. The flotation process is as follows: Figure 2 As shown, the specific preparation and flotation steps of the combined collector are as follows: (1) Dissolve sucrose laurate in water and stir at 1000 rpm for 2 minutes to mix evenly to obtain sucrose laurate solution.

[0031] (2) Add sodium palmitate and hexamethyldisiloxane to the sucrose laurate solution and stir for 5 minutes at 55°C and 1000 rpm to obtain a combined collector solution (the total mass percentage concentration of sucrose laurate, sodium oleate and hexamethyldisiloxane in the combined collector solution is 8%).

[0032] (3) Grind the raw scheelite to 80% of the size of -0.074 mm, add water to adjust the slurry concentration to 25%, and adjust the pH of the slurry to 9.5 with sodium hydroxide. Stir for 2 minutes to obtain the slurry.

[0033] (4) Add water glass (1200 g / t) to the slurry as a depressant, stir for 3 minutes, then add a mixed solution of combined collectors (600 g / t based on the total solute content of the combined collectors), stir for 3 minutes, and then perform roughing for 3 minutes to obtain roughing concentrate and roughing tailings; perform two scavenging processes on the roughing tailings, without adding depressant during the two scavenging processes. In scavenging process I, add a mixed solution of combined collectors (300 g / t based on the total solute content of the combined collectors), stir for 3 minutes, and then perform flotation for 3 minutes; in scavenging process II... In the process, a combined collector solution is added (the amount of the combined collector solution is 150 g / t based on the total solute in the combined collector solution), stirred for 3 minutes, and floated for 2 minutes to obtain scheelite tailings. The roughing concentrate is then subjected to three cleaning processes without the addition of the combined collector solution. In cleaning process I, water glass (600 g / t) is added, stirred for 3 minutes, and floated for 3 minutes. In cleaning process II, water glass (300 g / t) is added, stirred for 3 minutes, and floated for 3 minutes. In cleaning process III, water glass (150 g / t) is added, stirred for 3 minutes, and floated for 2 minutes to obtain scheelite concentrate.

[0034] The closed-circuit flotation results of this embodiment are shown in Table 1.

[0035] Example 3 The main gangue minerals in a certain scheelite ore are fluorite and calcite. The ore contains 0.62% WO3. Tungsten mainly exists in the form of scheelite. The gangue minerals mainly include fluorite, calcite, and quartz, with fluorite content at 30.16% and calcite content at 28.41%. This embodiment uses a combined collector for flotation, with the following mass percentage composition: 5% sucrose laurate, 85% sodium palmitate, and 10% hexamethyldisiloxane. The depressant is acidified water glass with a modulus of 3.0. The flotation feed is the aforementioned scheelite ore with a WO3 grade of 0.62%. The flotation process is as follows: Figure 2 As shown, the specific preparation and flotation steps of the combined collector are as follows: (1) Dissolve sucrose laurate in water and stir at 1200 rpm for 4 minutes to mix evenly to obtain sucrose laurate solution.

[0036] (2) Add sodium palmitate and hexamethyldisiloxane to the sucrose laurate solution and stir for 6 minutes at 65°C and 1200 rpm to mix evenly to obtain a combined collector solution (the total mass percentage concentration of sucrose laurate, sodium oleate and hexamethyldisiloxane in the combined collector solution is 10%).

[0037] (3) Grind the raw scheelite ore to 65% of the size of -0.074 mm, add water to adjust the slurry concentration to 20%, and adjust the pH of the slurry to 11.5 with sodium hydroxide and sodium carbonate (sodium hydroxide and sodium carbonate mass ratio of 1:1). Stir for 2 minutes to obtain the slurry.

[0038] (4) Add water glass (600 g / t) as a depressant to the slurry, stir for 3 minutes, then add a mixed solution of combined collectors (200 g / t based on the total solute content of the combined collectors), stir for 3 minutes, and then perform roughing for 3 minutes to obtain roughing concentrate and roughing tailings; perform two scavenging processes on the roughing tailings, without adding depressant during the two scavenging processes. In scavenging operation I, add a mixed solution of combined collectors (100 g / t based on the total solute content of the combined collectors), stir for 3 minutes, and then perform flotation for 3 minutes; scavenging In operation II, a combined collector solution is added (the amount of the combined collector solution is 50 g / t based on the total solute in the combined collector solution), stirred for 3 minutes, and floated for 2 minutes to obtain scheelite tailings. The roughing concentrate is then subjected to three cleaning processes without the addition of the combined collector solution. In cleaning operation I, water glass (300 g / t) is added, stirred for 3 minutes, and floated for 3 minutes. In cleaning operation II, water glass (150 g / t) is added, stirred for 3 minutes, and floated for 3 minutes. In cleaning operation III, water glass (75 g / t) is added, stirred for 3 minutes, and floated for 2 minutes to obtain scheelite concentrate.

[0039] The closed-circuit flotation results of this embodiment are shown in Table 1.

[0040] Comparative Example 1 The difference between this comparative example and Example 1 is that the collector used is a single sodium oleate. The amount of sodium oleate in the roughing process is 400 g / t, the amount of sodium oleate in scavenging I is 200 g / t, and the amount of sodium oleate in scavenging II is 100 g / t. The remaining steps are the same as in Example 1. The closed-circuit flotation results are shown in Table 1.

[0041] Comparative Example 2 The difference between this comparative example and Example 1 is that the collector used is sodium oleate alone. The amount of sodium oleate in the roughing process is 500 g / t, the amount of sodium oleate in scavenging I is 250 g / t, and the amount of sodium oleate in scavenging II is 125 g / t. The remaining steps are the same as in Example 1. The closed-circuit flotation results are shown in Table 1.

[0042] Comparative Example 3 The difference between this comparative example and Example 1 is that the collector used is a single sodium oleate. The amount of sodium oleate in the roughing process is 600 g / t, the amount of sodium oleate in scavenging I is 300 g / t, and the amount of sodium oleate in scavenging II is 150 g / t. The remaining steps are the same as in Example 1. The closed-circuit flotation results are shown in Table 1.

[0043] Comparative Example 4 The difference between this comparative example and Example 2 is that the collector used is sodium palmitate alone. The amount of sodium palmitate in the roughing process is 400 g / t, the amount of sodium palmitate in scavenging I is 200 g / t, and the amount of sodium palmitate in scavenging II is 100 g / t. The remaining steps are the same as in Example 2. The closed-circuit flotation results are shown in Table 1.

[0044] Comparative Example 5 The difference between this comparative example and Example 2 is that the collector used is sodium palmitate alone. The amount of sodium palmitate in the roughing process is 600 g / t, the amount of sodium palmitate in scavenging I is 300 g / t, and the amount of sodium palmitate in scavenging II is 150 g / t. The remaining steps are the same as in Example 2. The closed-circuit flotation results are shown in Table 1.

[0045] Comparative Example 6 The difference between this comparative example and Example 2 is that the collector used is sodium palmitate alone. The amount of sodium palmitate in the roughing process is 800 g / t, the amount of sodium palmitate in scavenging I is 400 g / t, and the amount of sodium palmitate in scavenging II is 200 g / t. The remaining steps are the same as in Example 2. The closed-circuit flotation results are shown in Table 1.

[0046] Table 1 As shown in Examples 1 and Comparative Examples 1-3, under the same flotation process, flotation depressant, flotation pulp concentration, and flotation pH, compared with the single flotation collector sodium oleate, the combined collector (sucrose laurate, sodium oleate, and hexamethyldisiloxane) can achieve higher WO3 grade and WO3 recovery rate. Compared with the test indicators of sodium oleate alone at the same dosage, it can be shown that the combined collector has better collecting performance and selectivity than the single collector, and can more effectively separate scheelite from gangue minerals, reducing impurities entering the concentrate. The tailings grade of Example 1 is lower, the resource loss is minimal, and resource waste is reduced.

[0047] As shown in Examples 2-3 and Comparative Examples 4-6, under the same flotation process, flotation depressant, flotation pulp concentration, and flotation pH, compared with the single flotation collector sodium palmitate, the combined collector (mass ratio of sucrose laurate, sodium palmitate, and hexamethyldisiloxane) can achieve higher WO3 grade and WO3 recovery rate. When using the single depressant sodium palmitate, as the amount of reagent increases, its effect still cannot reach the level of the combined collector at a low dosage (Example 2). This indicates that the combined collector has better collecting performance and selectivity than the single collector, and achieves better indicators with lower total reagent consumption, thereby reducing reagent costs and having economic benefits.

[0048] The combined harvester used in this invention (sucrose laurate, C 16 -C 18 Through the synergistic effect of fatty acid salts and hexamethyldisiloxane, this combined collector achieves both high selectivity and high collecting power, ensuring high grade while obtaining high recovery rate. Moreover, this combined collector has good environmental properties, is more convenient to prepare and store, and has lower dosage and cost. This combined collector is a highly efficient flotation collector for scheelite.

[0049] 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 combined collector for scheelite, characterized in that, The combined collector and the mass percentage of its components are as follows: sucrose laurate 2%-5%, C 16 -C 18 Fatty acid salts 85%-92%, hexamethyldisiloxane 6%-10%, wherein the total mass of all components of the combined collector is 100% by mass percentage; the C 16 -C 18 The fatty acid salt is sodium palmitate or sodium oleate.

2. The method for preparing the combined collector according to claim 1, characterized in that, Specifically, the following steps are included: (1) Dissolve sucrose laurate in water and stir until homogeneous to obtain a sucrose laurate solution; (2) Add C to the sucrose laurate solution 16 -C 18 Fatty acid salts and hexamethyldisiloxane are heated and stirred until homogeneous to obtain a combined collector solution.

3. The method for preparing the combined collector according to claim 2, characterized in that, The conditions for uniform mixing in step (1) are: stirring at 800-1200 rpm for 2-6 minutes.

4. The method for preparing the combined collector according to claim 2, characterized in that, The conditions for heating, stirring, and mixing in step (2) are: stirring at 50℃-65℃ and 800-1200rpm for 5-8 minutes; the combined collector solution contains sucrose laurate, C 16 -C 18 The total mass percentage concentration of fatty acid salts and hexamethyldisiloxane is 5%-10%.

5. The application of the combined collector according to claim 1 in the flotation separation of scheelite and calcium-bearing gangue minerals, characterized in that, Specifically, the following steps are included: (1) Grind and prepare the raw scheelite ore to obtain a slurry; (2) Add a mixture of inhibitor and combined collector to the slurry, and separate it by one roughing, three cleaning and two scavenging flotation to obtain scheelite concentrate and scheelite tailings.

6. The application of the combined collector according to claim 5 in the flotation separation of scheelite and calcium-bearing gangue minerals, characterized in that, In step (1), grinding to -0.074 mm accounts for 65%-80%; the slurry preparation specifically involves adding water to adjust the slurry concentration to 20%-35%, and using one or two of sodium hydroxide and sodium carbonate to adjust the slurry pH to 8.5-11.

5.

7. The application of the combined collector according to claim 5 in the flotation separation of scheelite and calcium-bearing gangue minerals, characterized in that, The inhibitor mentioned in step (2) is water glass or acidified water glass, and the modulus of the water glass is 2.5-3.

8. The application of the combined collector according to claim 5 in the flotation separation of scheelite and calcium-bearing gangue minerals, characterized in that, In step (2), the amount of inhibitor used in the roughing process is 600-1200 g / t, and the amount of the combined collector mixed solution is 200-600 g / t based on the total amount of solute in the combined collector mixed solution.

9. The application of the combined collector according to claim 5 in the flotation separation of scheelite and calcium-bearing gangue minerals, characterized in that, No combined collectors are added during the three selection processes described in step (2). The amount of inhibitor used in selection I is 300-600 g / t, the amount of inhibitor used in selection II is 150-300 g / t, and the amount of inhibitor used in selection III is 75-150 g / t.

10. The application of the combined collector according to claim 5 in the flotation separation of scheelite and calcium-bearing gangue minerals, characterized in that, No inhibitors are added during the two scavenging processes described in step (2). The amount of the combined collector mixed solution used in scavenging operation I is 100-300 g / t based on the total solute in the combined collector mixed solution. In the scavenging II operation, the dosage of the combined collector solution is 50-150 g / t, calculated based on the total solute content of the combined collector solution.

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