CN115254436A - Flotation separation method of molybdenite based on emulsifier and preparation method of emulsifier - Google Patents

Abstract

The invention discloses a flotation separation method of molybdenite based on an emulsifier, which adopts the emulsifier for molybdenite flotation, and the emulsifier is mixed with a diesel oil collecting agent according to a proportion and then used; the method is implemented by the following steps: taking a certain amount of active ingredient A and an active ingredient B, uniformly mixing, then loading into a reaction vessel, catalyzing by concentrated sulfuric acid at a certain temperature, reacting for a certain time, and then separating and purifying to obtain the emulsifier; the emulsifier is used for improving the dispersivity of the diesel oil collecting agent in water in the flotation separation process, so that the molybdenite flotation effect is improved.

Description

Flotation separation method of molybdenite based on emulsifier and preparation method of emulsifier

technical field

The invention belongs to the technical field of mineral processing and relates to a method for flotation and separation of molybdenite based on an emulsifier.

The invention also relates to a method for preparing an emulsifier for molybdenite flotation.

Background technique

Molybdenite is an important rare metal and strategic reserve resource, which plays an extremely important role in the fields of steel, machinery, chemical industry, aerospace and nuclear industry. At present, 99% of the world's molybdenum production comes from molybdenite acquired. In the process of flotation molybdenite, hydrocarbon oils are usually used as collectors, such as kerosene and diesel oil, etc., which can enhance the hydrophobicity of the surface after being adsorbed on the surface of molybdenite, and then be separated from other minerals.

With the development and utilization of molybdenite resources, the shortcomings of hydrocarbon oil collectors gradually appear. The dispersibility of hydrocarbon oil in water is poor, and it is generally dispersed into small oil droplets into the pulp by strong stirring of the flotation machine. However, the particle size of the oil droplets dispersed in water is very limited, and the dispersed phase is very unstable. After the mechanical stirring is stopped, the small oil droplets will coagulate quickly, so it is difficult to further improve the return flotation yield of molybdenite. The smaller the particle size of the oil droplet, the greater the probability of its collision with the molybdenite particles, which is more conducive to the flotation of the molybdenite. Therefore, it is very important to develop an emulsifier to emulsify hydrocarbon oil in water to obtain an emulsion with smaller dispersion particle size and more stable dispersion performance, which is very important for improving the recovery rate of molybdenite flotation.

Contents of the invention

The object of the present invention is to provide a method for flotation separation of molybdenite based on emulsifier, which is used to improve the dispersibility of diesel collector in water, thereby improving the flotation effect of molybdenite.

Another object of the present invention is to provide a method for preparing an emulsifier for molybdenite flotation.

The technical solution adopted in the present invention is, the flotation separation method of the molybdenite based on emulsifier adopts a kind of emulsifier for flotation of molybdenite, after the described emulsifier is mixed with the diesel oil collector in proportion Use, the weight ratio is 5:105-5:85, preferably, the weight ratio of emulsifier to diesel collector is 5:100-5:95.

The present invention is also characterized in that:

Wherein the dosage of the mixed agent after mixing the emulsifier and the diesel collector is 15-40 mg/L, preferably, the dosage of the mixed agent is 20-30 mg/L;

In the flotation separation method, the rotational speed of the flotation machine is 1650-1800 rpm; the flotation temperature is 15-30° C.; the particle size of the flotation feed material is -200 mesh and the content is 60%-65%.

The second technical solution adopted in the present invention is the preparation method of the emulsifier used for molybdenite flotation, the emulsifier includes active ingredient A with formula (1) and active ingredient B with formula (2), Specifically, it is implemented according to the following steps: take a certain amount of active ingredient A and active ingredient B, mix them evenly, put them into a reaction container, catalyze them with concentrated sulfuric acid at a certain temperature, react for a certain period of time, and then obtain an emulsifier after separation and purification;

R`-CH ₂ -OH (2)

In the formula, R is an alkyl group of C8, C12 and C14, and R' is any one of a C1-C3 alkyl group, a phenyl group or a hydrogen atom, and the above-mentioned alkyl group is a linear structure.

The second technical solution of the present invention is characterized in that:

Wherein the weight ratios of C12 to C8 and C14 in the active ingredient A are 5-6:1 and 2-3:1 respectively;

Wherein the weight ratio of active ingredient A to active ingredient B is 1:3 to 5, preferably, the weight ratio of active ingredient A to active ingredient B is 1:3 to 4;

Wherein the weight ratio of active ingredient A to concentrated sulfuric acid is 5:1～2, preferably, the weight ratio of active ingredient A to concentrated sulfuric acid is 5:1.5～2;

Wherein the reaction temperature in the catalytic process is 80-110°C, preferably, the reaction temperature is 85-100°C; the reaction time is 0.5-2h, preferably, the reaction time is 1.5-2h;

In the purification process, the reaction product is first moved to a separatory funnel, then sodium carbonate solution is added to remove excess acid, the water layer is removed after stratification, and then deionized water is added for washing, and the water layer is removed after stratification. , then add anhydrous sodium sulfate to dry, and finally filter through filter paper to obtain a yellow liquid that is the emulsifier.

The beneficial effects of the present invention are:

The molybdenite emulsifier prepared by the method for preparing the emulsifier for molybdenite flotation of the present invention can effectively improve the dispersibility of hydrocarbon oil in water, significantly reduce the dispersion particle size of hydrocarbon oil in water, and is equivalent to the concentrate grade In the case of using the emulsifier provided by the present invention, the recovery rate of molybdenum is significantly improved compared with when no emulsifier is used. In addition, after using the emulsifier provided by the present invention, it can be realized under the condition of reducing the amount of hydrocarbon oil collector. Efficient separation of molybdenite.

Description of drawings

Fig. 1 is the flotation flow chart of Examples 1-4 in the flotation separation method of molybdenite based on emulsifier in the present invention.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.

The invention provides a preparation method of an emulsifier for molybdenite flotation, adding the active ingredient A and active ingredient B into a flask in proportion and continuously stirring, raising the temperature to 80-110°C, and slowly adding concentrated sulfuric acid dropwise The reaction product was obtained after 0.5-2 hours of reaction;

After the reaction product was washed 3 times with sodium carbonate solution and deionized water, the water layer was removed, dried with anhydrous sodium sulfate, and filtered to obtain an emulsifier;

The present invention also provides a method for flotation and separation of molybdenite based on an emulsifier. The emulsifier and diesel oil are mixed according to a certain ratio and then used directly, and the diesel oil is emulsified in the flotation pulping stage;

In the flotation process, the molybdenite powder is first slurried, aerated and stirred for 5 minutes, and then the required amount of emulsified collector is added for flotation, and the flotation time is 3 minutes;

The heating equipment adopted in the embodiment of the present invention is a heat-collecting magnetic stirrer, and the stirring speed is 300r/min;

The fineness of the molybdenite mineral material used in the embodiments of the present invention is controlled at less than 0.074mm and the content accounts for 65% of the total material;

Example 1

Raw materials: 9.5g of diesel oil, 20.0g of active ingredient A (wherein R is C8 and C12, the content ratio is 1:5), 60.0g of active ingredient B (R` is C1), 8.0g of concentrated sulfuric acid.

Preparation method: mix the active ingredient A and active ingredient B and put them into a three-necked flask, then add concentrated sulfuric acid dropwise and continue to stir, react at 85°C for 2 hours, wash the reaction product three times with sodium carbonate solution, and then use deionized Wash with water for 3 times, after each washing, it needs to stand still to remove the water layer, and finally add anhydrous sodium sulfate to dry, and the liquid obtained after filtering through filter paper is the emulsifier; after mixing the emulsifier and diesel oil in a ratio of 5:95 ready to use;

Flotation process: Add 500g of molybdenite into a 1.5L flotation tank, add an appropriate amount of water, stir for 5 minutes to make it slurry, add the mixed agent described in Example 1, stir and inflate for 5 minutes, and scrape off the molybdenum that floats together with the foam For the concentrate, the scraping time is 3 minutes. The concentrate, medium ore, and tailings are dried and weighed separately. The calculated recovery rate is shown in Table 1. The flotation process is shown in Figure 1.

Example 2

Raw materials: 9.5g of diesel oil, 20.0g of active ingredient A (wherein R is C8 and C12, the content ratio is 1:5), 80.0g of active ingredient B (R` is C3), 8.0g of concentrated sulfuric acid.

Preparation method: mix active ingredient A and active ingredient B and put them into a three-necked flask, slowly add concentrated sulfuric acid dropwise and continue to stir, react at 90°C for 1.5h, wash the reaction product 3 times with sodium carbonate solution, and then use Wash with ionic water for 3 times, let it stand to remove the water layer after each washing, and finally add anhydrous sodium sulfate to dry, and the liquid obtained after filtering through filter paper is the emulsifier; the emulsifier and diesel oil can be used after mixing evenly at a ratio of 5:95 ;

Flotation process: Add 500g of molybdenite into a 1.5L flotation tank, add an appropriate amount of water, stir for 5 minutes to make it slurry, add the mixed agent described in Example 2, stir and inflate for 5 minutes, and scrape off the molybdenum that floats together with the foam For the concentrate, the scraping time is 3 minutes. The concentrate, medium ore, and tailings are dried and weighed separately. The calculated recovery rate is shown in Table 1. The flotation process is shown in Figure 1.

Example 3

Raw materials: diesel oil 10.0g g, active ingredient A (wherein R is C12 and C14, content ratio is 2.5:1) 20.0g, active ingredient B (R` is phenyl) 60.0g, concentrated sulfuric acid 6.0g.

Preparation method: mix active ingredient A and active ingredient B into a three-necked flask, slowly add 6.0 g of concentrated sulfuric acid dropwise, react at 100°C for 1.8 hours, wash the reaction product three times with sodium carbonate solution, and then use Wash with ionic water for 3 times. After each washing, you need to stand still to remove the water layer. Finally, add anhydrous sodium sulfate to dry. be usable;

Flotation process: Add 500g of molybdenite into a 1.5L flotation tank, add appropriate amount of water, stir for 5 minutes to make it slurry, add the mixed agent described in Example 3, stir and inflate for 5 minutes, and then scrape the molybdenite that floats together with the foam For the concentrate, the scraping time is 3 minutes. The concentrate, medium ore, and tailings are dried and weighed separately. The calculated recovery rate is shown in Table 1. The flotation process is shown in Figure 1.

Example 4

Raw materials: 10.0g of diesel oil, 20.0g of active ingredient A (wherein R is C12 and C14, the content ratio is 2.5:1), 75.0g of active ingredient B (R` is a hydrogen atom), 6.0g of concentrated sulfuric acid.

Preparation method: mix active ingredient A and active ingredient B into a three-necked flask, slowly add 6.0 g of concentrated sulfuric acid dropwise, react at 90°C for 1.0 h, wash the product obtained by the reaction with sodium carbonate solution for 3 times, and then use Wash with ionic water for 3 times. After each washing, you need to stand still to remove the water layer. Finally, add anhydrous sodium sulfate to dry. be usable;

Flotation process: Add 500g of molybdenite into a 1.5L flotation tank, add appropriate amount of water, stir for 5 minutes to make it slurry, add the mixed agent described in Example 4, stir and inflate for 5 minutes, and then scrape the molybdenite that floats together with the foam For the concentrate, the scraping time is 3 minutes. The concentrate, medium ore, and tailings are dried and weighed separately. The calculated recovery rate is shown in Table 1. The flotation process is shown in Figure 1.

In order to verify the advantages of the present invention, diesel oil (comparative example) and emulsifiers of four embodiments of the present invention are selected to carry out flotation to the same batch of molybdenite samples, and the best flotation results are shown in Table 1.

Table 1

It can be seen from the table that when diesel oil is used for flotation, the optimum molybdenum recovery rate of the concentrate is 83.4%, and the amount of diesel oil is 40mg/L. After using the emulsifier prepared by the present invention, the flotation recovery rate in Examples 1 to 4 was significantly improved, and the amount of flotation agents was reduced by more than 25% compared with the comparative example, which can effectively reduce costs and increase benefits; 1. In embodiment 3, when the molybdenum grade of the concentrate is slightly reduced, the molybdenum recovery rate of the concentrate can be improved by 2.2% and 3.4%; The recovery rate of molybdenum was increased by 3.2%. It can be seen that the emulsifier of the present invention has a very significant effect on improving the flotation recovery rate of molybdenite. In addition, the emulsifier of the present invention can be used directly after being mixed with diesel oil, or can be added separately, and the diesel oil can be emulsified through the mixing and stirring process without adding water in advance to prepare the emulsified diesel oil. This method can simplify the operation process.

Claims (9)

1. The flotation separation method of molybdenite based on the emulsifier is characterized in that the emulsifier used for molybdenite flotation is adopted, the emulsifier is mixed with a diesel oil collecting agent according to a proportion and then used, the weight ratio is 5.

2. The method for flotation separation of molybdenite based on emulsifier according to claim 1, wherein the amount of mixed agent after mixing the emulsifier with the diesel oil collector is 15-40 mg/L, preferably 20-30 mg/L.

3. The method for flotation separation of molybdenite based on emulsifier according to claim 1, wherein the rotation speed of the flotation machine in the method for flotation separation is 1650-1800 rpm; the flotation temperature is 15-30 ℃; the flotation feed granularity is 60-65% of-200 meshes.

4. The preparation method of the emulsifier for molybdenite flotation is characterized in that the emulsifier comprises an active ingredient A with a structural formula of formula (1) and an active ingredient B with a structural formula of formula (2);

the method is implemented by the following steps: taking a certain amount of active ingredient A and an active ingredient B, uniformly mixing, then loading into a reaction vessel, catalyzing by concentrated sulfuric acid at a certain temperature, reacting for a certain time, and then separating and purifying to obtain the emulsifier;

R`-CH₂-OH (2)

wherein R is C8, C12 and C14 alkyl, R' is any one of C1-C3 alkyl, phenyl or hydrogen atom, and the alkyl is a straight chain structure.

5. The method for preparing an emulsifier for molybdenite flotation according to claim 4, wherein the weight ratio of C12 to C8, C14 in the active ingredient A is 5-6 and 2-3.

6. The method for preparing an emulsifier for molybdenite flotation according to claim 4, wherein the weight ratio of the active ingredient A to the active ingredient B is 1.

7. The method for preparing an emulsifier for molybdenite flotation according to claim 4, wherein the weight ratio of the active ingredient A to the concentrated sulfuric acid is 5.

8. The method for preparing an emulsifier for molybdenite flotation according to claim 4, wherein the reaction temperature in the catalytic process is 80-110 ℃, preferably 85-100 ℃; the reaction time is 0.5 to 2 hours, preferably 1.5 to 2 hours.

9. The method for preparing the emulsifier for molybdenite flotation according to claim 4, wherein in the purification process, the reaction product is transferred to a separating funnel, then a sodium carbonate solution is added to remove excess acid, the mixture is allowed to stand for layering and then an aqueous layer is removed, then deionized water is added for washing, the mixture is allowed to stand for layering and then an aqueous layer is removed, then anhydrous sodium sulfate is added for drying, and finally, the yellow liquid obtained by filtering through filter paper is the emulsifier.

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