CN116213128A - Flotation separation method for refractory scheelite - Google Patents

Abstract

The invention belongs to the technical field of ore dressing, and particularly relates to a flotation separation method for refractory scheelite, which adopts polyglutamic acid as an inhibitor, wherein polyglutamic acid can be adsorbed on the surface of calcite mineral, and the hydrophilicity of the calcite mineral is improved, so that the selective inhibition effect on the calcite is generated.

Description

A method for flotation separation of refractory scheelite

technical field

The invention belongs to the technical field of ore dressing, in particular to a method for flotation separation of refractory scheelite.

Background technique

Tungsten has good thermal conductivity, high hardness, and stable chemical properties. Because of its unique physical properties and excellent physical and chemical properties, it is widely used in the field of high-tech product manufacturing and is an irreplaceable strategic metal for industrial development. China is known as the "Kingdom of Tungsten", with large reserves of tungsten ore resources. Among the many tungsten-containing minerals, only wolframite and scheelite have good mining value and industrial utilization value, but with the increasing tungsten ore resources Mining, high-quality wolframite has been exhausted, the comprehensive utilization of low-grade scheelite with complex associated components has become the mainstream, and scheelite is a calcium-containing mineral, and it often closely coexists with calcium-containing gangue minerals such as calcite in the deposit. As a result, the separation of scheelite and calcite has become a recognized technical problem in the field of mineral processing. Researchers at home and abroad have conducted a lot of research on the separation of such ores.

Due to the generally low grade of scheelite in my country, uneven particle size distribution and complex associated components, flotation has become the most commonly used method to recover scheelite, and fatty acid collectors are usually added to improve flotation. Scheelite is buoyant, while calcite and scheelite have the same Ca active sites, and their physical and chemical properties are very similar. At the same time, calcite has good natural buoyancy, which makes the flotation separation of scheelite and calcite extremely difficult. . Therefore, it is very important to selectively reduce the buoyancy of calcite by adding inhibitors. However, the existing inhibitors not only use a large amount of chemicals, but the effect of inhibiting calcite is poor. The separation efficiency of ore and calcite is low, which is not conducive to the efficient utilization of scheelite resources.

Contents of the invention

In order to solve the problems existing in the prior art, the main purpose of the present invention is to propose a method for flotation separation of refractory scheelite, to develop an inhibitor with high selectivity and excellent inhibitory effect on scheelite, and to realize the separation of scheelite and calcite The high-efficiency flotation separation of scheelite is of great significance to realize the efficient and comprehensive utilization of scheelite.

In order to solve the above technical problems, according to one aspect of the present invention, the present invention provides the following technical solutions:

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

S2. adjust the pH value of the slurry and stir;

S3. Add polyglutamic acid to the pulp and stir for 3 to 5 minutes; the method of adding polyglutamic acid is: polyglutamic acid is configured into a solution with a concentration of 0.1 to 1.0 wt%, and the amount of the solution is 10 to 60 mg/L;

S4. Continue to add sodium oleate and stir, and finally inflate flotation to obtain foam products and products in the tank, the foam product is scheelite, and the product in the tank is calcite.

As a preferred scheme of the method for flotation separation of refractory scheelite according to the present invention, wherein: in the step S1, the raw material of refractory scheelite is ground, and the ground mineral raw material is added to flotation In the flotation tank of the machine, add water to the flotation tank and stir to obtain a uniform pulp.

As a preferred solution of the method for flotation separation of refractory scheelite in the present invention, wherein: in the step S1, the raw material of refractory scheelite is ground to a particle size of 38-74 μm.

As a preferred solution of the method for the flotation separation of refractory scheelite in the present invention, wherein: in the step S1, the solid-to-liquid ratio of the mineral raw material to water is 1:10-30 g/mL.

As a preferred solution of the method for flotation and separation of refractory scheelite in the present invention, wherein: in the step S1, the rotational speed of the flotation machine is 1800-2000r/min.

As a preferred solution of the method for flotation and separation of refractory scheelite in the present invention, wherein: in the step S2, the stirring time is 3-5 minutes.

As a preferred solution of the method for flotation separation of refractory scheelite in the present invention, wherein: in the step S2, the pH value of the pulp is adjusted with a pH regulator, and the pH regulator is hydrochloric acid or sodium hydroxide.

As a preferred solution of the method for flotation and separation of refractory scheelite in the present invention, wherein: in the step S2, the pH value of the slurry is adjusted to 7-11.

As a preferred solution of the method for flotation separation of refractory scheelite in the present invention, wherein: in the step S4, the stirring time is 3-5 minutes.

As a preferred scheme of the method for the flotation separation of refractory scheelite in the present invention, wherein: in the step S4, the method of adding sodium oleate is: sodium oleate is configured to a concentration of 0.2 to 1.0 wt%. Solution, the solution dosage is 20-50mg/L.

The beneficial effects of the present invention are as follows:

The invention proposes a method for flotation separation of refractory scheelite, using polyglutamic acid as an inhibitor, polyglutamic acid can be adsorbed on the surface of calcite minerals, improving the hydrophilicity of calcite minerals, thereby producing selectivity to calcite Inhibition, compared with the traditional flotation process, a very small amount of inhibitors and collectors can be used to achieve good flotation separation of scheelite and calcite. At the same time, polyglutamic acid is non-toxic, has a wide range of sources, low cost and economical Significant benefits.

Detailed ways

A clear and complete description will be made below in conjunction with the technical solutions in the embodiments. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

The main purpose of the present invention is to propose a method for flotation separation of refractory scheelite, to develop inhibitors with high selectivity and excellent inhibitory effect on scheelite, to realize efficient flotation separation of scheelite and calcite, and to realize scheelite The efficient and comprehensive utilization of tungsten ore is of great significance.

According to one aspect of the present invention, the present invention provides following technical scheme:

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

S2. adjust the pH value of the slurry and stir;

S3. Add polyglutamic acid to the pulp and stir for 3 to 5 minutes; the method of adding polyglutamic acid is: polyglutamic acid is configured into a solution with a concentration of 0.1 to 1.0 wt%, and the amount of the solution is 10 to 60 mg/L; If the concentration of polyglutamic acid is too high, the dissolution of polyglutamic acid will be more difficult, and the error caused by the dosing operation will be larger; if the concentration of polyglutamic acid is too low, the medicament of polyglutamic acid required If the volume is too large, it is easy to cause a sudden change in the flotation concentration before and after dosing.

S4. Continue to add sodium oleate and stir, and finally inflate flotation to obtain foam products and products in the tank, the foam product is scheelite, and the product in the tank is calcite.

Preferably, in the step S1, the refractory scheelite raw material is ground, and the ground mineral raw material is added to the flotation cell of the flotation machine, and water is added to the flotation cell for stirring to obtain a uniform slurry. Further preferably, the refractory scheelite raw material is ground to a particle size of 38-74 μm; the solid-to-liquid ratio of the mineral raw material to water is 1:10-30 g/mL; the rotational speed of the flotation machine is 1800-2000 r/min. Specifically, the solid-to-liquid ratio of mineral raw materials and water can be, for example but not limited to, 1:10g/mL, 1:12g/mL, 1:15g/mL, 1:18g/mL, 1:20g/mL, 1:23g Any one in /mL, 1:25g/mL, 1:27g/mL, 1:30g/mL or the range between any two; the rotating speed of flotation machine can be for example but not limited to 1800r/min, 1850r Any one of /min, 1900r/min, 1950r/min, 2000r/min or the range between any two;

Preferably, in the step S2, the pH of the pulp is adjusted to 7-11 with a pH regulator, the pH regulator is hydrochloric acid or sodium hydroxide, and the stirring time is 3-5 minutes. Specifically, the pH value can be, for example, but not limited to, any one of 7, 8, 9, 10, 11 or a range between any two; the stirring time is, for example, but not limited to 3min, 3min30s, 4min, 4min30s, 5min Any one of them or the range between any two of them;

Preferably, in the step S3, the method of adding polyglutamic acid is: polyglutamic acid is configured into a solution with a concentration of 0.1-1.0 wt%, and the amount of the solution is 10-60 mg/L; specifically, the concentration of the solution can be For example but not limited to any one or any The range between the two; the amount of solution can be, for example but not limited to, 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L, 35mg/L, 40mg/L, 45mg/L, 50mg/L , 55mg/L, 60mg/L, any one or the range between any two; the stirring time is for example but not limited to 3min, 3min30s, 4min, 4min30s, 5min any one or between any two scope;

Preferably, in the step S4, the method of adding sodium oleate is as follows: sodium oleate is configured into a solution with a concentration of 0.2-1 wt%, and the amount of the solution is 20-50 mg/L;

The stirring time is 3 to 5 minutes. Specifically, the solution concentration can be, for example but not limited to, any one of 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt% or any range between the two; the solution dosage can be, for example but not limited to, any one of 20mg/L, 25mg/L, 30mg/L, 35mg/L, 40mg/L, 45mg/L, 50mg/L Or any range between the two; the stirring time is, for example but not limited to, any one of 3min, 3min30s, 4min, 4min30s, 5min or a range between any two.

The technical solutions of the present invention will be further described below in conjunction with specific embodiments.

Example 1

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

Grind the refractory scheelite to 38-74μm, take 2g of the ground mineral raw material and add it to the flotation cell of the hanging cell flotation machine, set the speed of the flotation machine to 1900r/min, add 40mL of water and stir to obtain Uniform slurry;

S2. adding sodium hydroxide to adjust the pH value of the slurry to 9 and stirring for 3 minutes;

S3. Adding 20 mg/L concentration of 0.5 wt% polyglutamic acid to the pulp and stirring for 5 min;

S4. continue to add 20mg/L concentration and be the sodium oleate of 0.5wt% and stir 3min, finally aeration flotation obtains foam product and the product in the tank, and the foam product is scheelite, and the product in the tank is calcite; The foam product and the tank The internal products were dried, weighed, and tested; the mineral processing results are shown in Table 1.

Table 1 embodiment 1 beneficiation result

Example 2

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

Grind the refractory scheelite to 38-74μm, take 2g of the ground mineral raw material and add it to the flotation cell of the hanging cell flotation machine, set the speed of the flotation machine to 1900r/min, add 40mL of water and stir to obtain Uniform slurry;

S2. adding hydrochloric acid to adjust the pH value of the slurry to 8 and stirring for 3 minutes;

S3. Adding 20mg/L concentration of 1.0wt% polyglutamic acid to the pulp and stirring for 3min;

S4. continue to add 30mg/L concentration and be the sodium oleate of 0.5wt% and stir 3min, finally aeration flotation obtains foam product and the product in the tank, and the foam product is scheelite, and the product in the tank is calcite; The foam product and the tank The domestic product was dried, weighed, and tested; the mineral processing results are shown in Table 2.

Table 2 embodiment 2 beneficiation result

Example 3

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

Grind the refractory scheelite to 38-74μm, take 2g of the ground mineral raw material and add it to the flotation cell of the hanging cell flotation machine, set the speed of the flotation machine to 1900r/min, add 40mL of water and stir to obtain Uniform slurry;

S2. adding sodium hydroxide to adjust the pH value of the slurry to 10 and stirring for 5 minutes;

S3. Adding 50 mg/L concentration of 0.5 wt% polyglutamic acid to the pulp and stirring for 5 min;

S4. continue to add 40mg/L concentration and be the sodium oleate of 1.0wt% and stir 3min, finally aeration flotation obtains foam product and the product in the tank, and the foam product is scheelite, and the product in the tank is calcite; The foam product and the tank The internal products were dried, weighed, and tested; the mineral processing results are shown in Table 3.

Table 3 embodiment 3 beneficiation result

Comparative example 1

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

Grind the refractory scheelite to 38-74μm, take 2g of the ground mineral raw material and add it to the flotation cell of the hanging cell flotation machine, set the speed of the flotation machine to 1900r/min, add 40mL of water and stir to obtain Uniform slurry;

S2. adding hydrochloric acid to adjust the pH value of the slurry to 8 and stirring for 5 minutes;

S3. adding 150mg/L concentration to the slurry is water glass of 0.5wt% and stirred for 5min;

S4. continue to add 80mg/L concentration and be the sodium oleate of 0.5wt% and stir 3min, finally aeration flotation obtains foam product and the product in the tank, and the foam product is scheelite, and the product in the tank is calcite; The foam product and the tank The domestic products were dried, weighed, and assayed; the beneficiation results are shown in Table 4.

Table 4 Comparative Example 1 Mineral Processing Results

Comparative example 2

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

Grind the refractory scheelite to 38-74μm, take 2g of the ground mineral raw material and add it to the flotation cell of the hanging cell flotation machine, set the speed of the flotation machine to 1900r/min, add 40mL of water and stir to obtain Uniform slurry;

S2. adding sodium hydroxide to adjust the pH value of the slurry to 9 and stirring for 3 minutes;

S3. Adding 90 mg/L concentration of 0.3 wt% polyaspartic acid to the pulp and stirring for 5 min;

S4. continue to add 50mg/L concentration and be the sodium oleate of 0.4wt% and stir 3min, finally aeration flotation obtains foam product and the product in the tank, and the foam product is scheelite, and the product in the tank is calcite; The foam product and the tank The domestic products were dried, weighed, and tested; the mineral processing results are shown in Table 5.

Table 4 Comparative Example 2 Mineral Processing Results

Comparative example 3

A method for flotation separation of refractory scheelite, comprising the steps of:

S1. Refractory scheelite pulping to obtain pulp;

Grind the refractory scheelite to 38-74μm, take 2g of the ground mineral raw material and add it to the flotation cell of the hanging cell flotation machine, set the speed of the flotation machine to 1900r/min, add 40mL of water and stir to obtain Uniform slurry;

S2. adding sodium hydroxide to adjust the pH value of the slurry to 9 and stirring for 3 minutes;

S3. adding 100mg/L concentration to the pulp is carboxymethyl cellulose of 0.2wt% and stirred for 5min;

S4. continue to add 70mg/L concentration and be the sodium oleate of 0.5wt% and stir 3min, finally aeration flotation obtains foam product and the product in the tank, and the foam product is scheelite, and the product in the tank is calcite; The foam product and the tank The domestic products were dried, weighed, and assayed; the beneficiation results are shown in Table 6.

Table 6 Comparative Example 3 Mineral Processing Results

As can be seen from Examples 1-3 of the present invention and comparative examples 1-3, the present invention adopts polyglutamic acid as inhibitor, and polyglutamic acid can be adsorbed on the calcite mineral surface, improves the hydrophilicity of calcite mineral, thereby the calcite mineral Selective inhibitory effect is produced, and as can be seen from Comparative Example 2, even if adopting the polyammonium aspartate that belongs to amino acid equally, even if adding more amount, also can't obtain the effect of polyglutamic acid of the present invention; The present invention compares The traditional flotation process can achieve good flotation separation of scheelite and calcite with a very small amount of inhibitors and collectors. At the same time, polyglutamic acid is non-toxic, has a wide range of sources, low cost, and significant economic benefits.

The above is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. Under the inventive concept of the present invention, the equivalent structure transformation made by using the content of the description of the present invention, or directly/indirectly used in other related All technical fields are included in the patent protection scope of the present invention.

Claims (10)

1. A method for refractory scheelite flotation separation, characterized in that, comprises the steps: S1. Refractory scheelite pulping to obtain pulp; S2. adjust the pH value of the slurry and stir; S3. Add polyglutamic acid to the pulp and stir for 3 to 5 minutes; the method of adding polyglutamic acid is: polyglutamic acid is configured into a solution with a concentration of 0.1 to 1.0 wt%, and the amount of the solution is 10 to 60 mg/L; S4. Continue to add sodium oleate and stir, and finally inflate flotation to obtain foam products and products in the tank, the foam product is scheelite, and the product in the tank is calcite. 2. The method according to claim 1, characterized in that, in the step S1, the refractory scheelite raw material is ground, and the ground mineral material is added to the flotation cell of the flotation machine, and the flotation Add water to the selection tank and stir to obtain a uniform slurry. 3. The method according to claim 2, characterized in that, in the step S1, the refractory scheelite raw material is ground to a particle size of 38-74 μm. 4. The method according to claim 2, characterized in that, in the step S1, the solid-to-liquid ratio of the mineral raw material to water is 1:10-30 g/mL. 5. The method according to claim 2, characterized in that, in the step S1, the rotational speed of the flotation machine is 1800-2000 r/min. 6. The method according to claim 1, characterized in that, in the step S2, the stirring time is 3-5 minutes. 7. The method according to claim 1, characterized in that, in the step S2, a pH regulator is used to adjust the pH value of the pulp, and the pH regulator is hydrochloric acid or sodium hydroxide. 8. The method according to claim 1, characterized in that, in the step S2, the pH of the pulp is adjusted to 7-11. 9. The method according to claim 1, characterized in that, in the step S4, the stirring time is 3-5 minutes. 10. The method according to claim 1, characterized in that, in the step S4, the method of adding sodium oleate is: sodium oleate is configured into a solution with a concentration of 0.2-1.0 wt%, and the amount of the solution is 20-50 mg/ L.