CN114653483A

CN114653483A - Inhibitor for talc in high-talc molybdenum ore and preparation method and application thereof

Info

Publication number: CN114653483A
Application number: CN202111673257.XA
Authority: CN
Inventors: 刘新; 刘启生; 吕伟栋; 梁中堂; 林威; 卢圣龙; 谭政; 王啸宇
Original assignee: Hunan Yunxuan Mining Technology Co ltd
Current assignee: Hunan Yunxuan Mining Technology Co ltd
Priority date: 2021-12-31
Filing date: 2021-12-31
Publication date: 2022-06-24

Abstract

The invention belongs to the field of mineral flotation, and particularly relates to a preparation method of a talc inhibitor, which comprises the steps of mixing a sulfuric acid solution with the concentration of 10-30 wt.% and a water glass solution with the concentration of 20-50 wt.%, then adding an additive, and uniformly stirring to obtain the talc inhibitor; the mass ratio of solutes in the sulfuric acid solution and the water glass solution is 1: 2-4; the additive comprises aluminum sulfate, zinc sulfate and polymeric ferrous sulfate in a mass ratio of 8-8.5: 1-1.5; the weight ratio of the additive to the solute in the water glass solution is 1:2 to 4. The inhibitor provided by the invention can effectively inhibit the flotation of the talc, and has an excellent effect.

Description

Inhibitor for talc in high-talc molybdenum ore and preparation method and application thereof

Technical Field

The invention relates to the technical field of mineral separation, in particular to a preparation method and application of a talc inhibitor in high-talc molybdenum ore.

Background

With the increasing depletion of molybdenum ore resources, the demand of molybdenum metal is increasing, and the molybdenum ore resources which are difficult to recover are developed and utilized, but according to the traditional direct ore dressing process which adopts kerosene as a collecting agent and water glass as an inhibitor, the molybdenum ore resources of high-sulfur high-talc cannot be effectively recovered, the recovery rate is 20-30%, the concentrate grade is about 20%, the recovery rate is low, and the produced concentrate cannot meet the requirement of molybdenum smelting.

The talc is mainly aqueous magnesium silicate with molecular formula of Mg3[ Si4O10] (OH) 2. Talc belongs to the monoclinic system. The crystals are in the form of pseudo-hexagonal or rhombohedral flakes, and occasionally are usually in the form of dense massive, foliate, radial, fibrous aggregates. Colorless and transparent or white, but light green, light yellow, light brown and even light red due to containing a small amount of impurities; the cleavage surface is pearl-like. 1 hardness and 2.7-2.8 specific gravity.

Talc has a lamellar crystal structure, is nonpolar on the surface, has strong hydrophobicity, is the softest mineral found, is an 'isosuperficial mineral' with molybdenite, has a tendency of being easily cracked into scales and has special lubricating property

From the characteristics of the talc, the talc is easy to argillize in the ore dressing and grinding processes, the floating performance of the talc is superior to that of molybdenite in the flotation process, and when a lipid collecting agent is adopted, the talc is easy to flocculate on the surface of the molybdenite, so that the separation of the molybdenite and the talc is extremely difficult, the flotation index is seriously influenced, and the talc is a great problem which puzzles the ore dressing industry all the time. Two methods which are feasible at present for high-talc minerals are available, the first method is a pre-desliming method, the pre-desliming method is to remove part of talc by a hydraulic cyclone or flotation equipment before molybdenum ore flotation, so that the talc content in the molybdenum ore flotation process is reduced, the talc content in the molybdenum ore beneficiation process can be reduced by the method, the concentrate grade in the molybdenum ore concentrate is favorably improved, and the recovery rate in the molybdenum ore flotation process is improved. The second method is an ore blending method, namely, high-talc molybdenum ore and low-talc molybdenum ore or talc-free easy-to-select molybdenum ore are mixed according to a certain proportion, the content of talc in the molybdenum ore is controlled from the source, the second method is theoretically feasible, but as the molybdenum ore resources are increasingly exhausted, the low-talc or talc-free easy-to-select molybdenum ore resources are increasingly reduced, the ore blending requirement cannot be met, and for large-scale industrial production, large ore blending sites and stacking sites are needed for ore blending, and the ore blending method is also a large burden for enterprises.

Therefore, in industrial processes, the simplest and economically beneficial method is to directly inhibit talc in industrial processes, but the current inhibition methods cannot achieve effective inhibition of talc in molybdenum ore with high talc content. During the production process, the ore concentrate grade is lower than 30.0 percent due to the large upward floating of the talc, the requirement of molybdenum ore smelting cannot be met, and meanwhile, the upward floating of the molybdenum ore is interfered by the large upward floating of the talc, the recovery rate of the molybdenum ore is greatly reduced, molybdenum metal loss is caused, and the loss can not be created but can be formed.

Disclosure of Invention

In order to solve the problems of the prior art, the invention aims to provide a preparation method of a talc inhibitor, aiming at improving the inhibiting effect of talc, particularly high-content talc.

The second purpose of the invention is to provide the talc inhibitor prepared by the preparation method.

The third purpose of the invention is to provide the application of the inhibitor prepared by the preparation method in the flotation of minerals with high talc content.

A preparation method of talc inhibitor comprises mixing 10-30 wt.% sulfuric acid solution and 20-50 wt.% water glass solution, adding additive, and stirring;

the mass ratio of solutes in the sulfuric acid solution and the water glass solution is 1: 2-4;

the additive is a mixture of aluminum sulfate, zinc sulfate and polymeric ferrous sulfate in a mass ratio of 8-8.5: 1-1.5;

the weight ratio of the additive to the solute in the water glass solution is 1:2 to 4.

The prior art has good inhibition effect on low content of talcum, but has limited inhibition effect on high content of talcum. In order to solve the problem, the industry has some solutions, wherein the combination of different inhibitors is a research direction, but the research of the inventor finds that the positive synergy is difficult to realize by combining the water glass and the sulfate, and the main difficulty is that the crystallization is easy to generate in the preparation process, and the synergy among the components is difficult to effectively exert. Aiming at the technical problem, the invention unexpectedly discovers, through intensive research, that the effective inhibition of talc, particularly talc with high content which is difficult to be effective in the industry, can be effectively and successfully realized by premixing the sulfuric acid solution with the concentration and the water glass solution and further matching the ternary additive and the combined control of the component proportion.

In the invention, the combined control of the concentration, the proportion, the ternary additive components, the proportion and the addition amount of the sulfuric acid solution and the water glass solution is the key for synergistically improving the performance of the inhibitor.

In the invention, the sulfuric acid solution is obtained by diluting industrial sulfuric acid;

preferably, the concentration of industrial sulfuric acid is greater than or equal to 95.0%.

In the invention, the water glass solution is obtained by diluting industrial water glass;

preferably, the industrial water glass is sodium-based and/or potassium-based water glass, the modulus is 2.4-3.0, and the pH is more than 8.

Preferably, the concentration of the diluted sulfuric acid solution is 10-15 wt.%. The concentration of the diluted water glass is 20-25 wt.%. Preferably, the talc-inhibiting effect can be further synergistically improved at a diluted concentration.

In the present invention, it is preferred to add the water glass solution to the sulfuric acid solution and to continue stirring during the addition to obtain a homogeneous clear solution. And then adding the ternary additive, and uniformly stirring to obtain the ternary additive.

The preferred preparation process of the invention comprises the following steps:

the method comprises the following steps: preparation of 10-30.0% concentration sulfuric acid solution

The sulfuric acid is industrial sulfuric acid, and the specific gravity of the sulfuric acid is between 1.80 and 1.85.

Before the preparation of the medicament, adding the calculated proportion of industrial sulfuric acid (the content is 95-98.5%) into a medicament preparation tank according to the weight proportion of the industrial sulfuric acid to the water glass of 1:2-4, wherein the weight proportion of the sulfuric acid to the water is 1: 10-20. The sulfuric acid is required to be prepared in a container with a stirrer, and the stirring speed is not lower than 60 r/min.

Step two: preparation of 20-50.0% concentration water glass solution

The modulus of the adopted water glass is 2.4-3.0, the weight of the water glass is 2-4 times of that of sulfuric acid, and the ratio of the water glass to water is 1: 1-4; the water glass is required to be configured in a container with stirring, and the stirring speed is not lower than 60 r/min; the water glass is industrial water glass, the modulus of the water glass is between 2.4 and 3.0, and the PH is more than 8.

Step three: mixing sulfuric acid with water glass

Because the process of dissolving the sulfuric acid in the water is exothermic reaction, when the sulfuric acid is fully dissolved in the reagent preparation tank, the dissolved and diluted water glass is dissolved and added into the diluted sulfuric acid solution through the delivery pump after the temperature is lower than 30 ℃, and in the adding process of the water glass, the stirrer in the reagent preparation tank continuously stirs to achieve the purpose of fully mixing the water glass and the sulfuric acid diluted solution. The adding speed of the water glass needs to be controlled during the mixing process, and crystallization and precipitation are not formed.

Step four: additive mixing

After the fully mixed solution of sulfuric acid and water glass is obtained through the three steps, an additive (GG for short) is added, wherein the additive comprises aluminum sulfate, zinc sulfate and polymeric ferrous sulfate in a mass ratio of 8:1: 1; the additive can be directly added into the solid, and the adding proportion is as follows according to the weight proportion: adding the mixture with water glass in a ratio of 1:2-4 at a constant speed in the adding process, stirring the mixed solution of sulfuric acid and water glass in the process, adding GG, and continuously stirring for 5-10min, thus completing the preparation of the novel efficient talc inhibitor with the chemical code of SG. The mixed solution of the water glass and the sulfuric acid is transparent or a small amount of turbid solution, the pH value is acidic, and the pH value is between 1.0 and 4.0. The mixed solution is white or light yellow solution, turbid solution without suspended matters or trace precipitates.

By the preparation method, the problems of easy crystallization and precipitation in the mixed solution of sulfuric acid and water glass can be effectively solved; the prepared inhibitor solution can effectively improve the inhibition selectivity of the talc, is particularly suitable for inhibiting the talc from floating in the separation process of the molybdenite of the high-sulfur high-talc, and also can be used for chemically cleaning the surface of the molybdenite, improving the adsorption capacity of the molybdenite surface and the molybdenite collecting agent, and improving the molybdenite recovery rate and the concentrate grade in the high-talc environment.

The invention also provides the talc inhibitor prepared by the preparation method.

The talc inhibitor is a transparent or slightly turbid solution, and the pH value is between 1.0 and 4.0;

preferably, its suspended particles are less than or equal to 2 wt.%.

The invention also provides application of the talc inhibitor prepared by the preparation method, and the talc inhibitor is added into a talc mineral-containing flotation reagent and is used for inhibiting talc flotation.

In the invention, the inhibitor can be used for inhibiting talc with different contents, and is particularly suitable for minerals with high talc content, which are difficult to effectively inhibit by means in the industry; the content of the talc is not less than 10.0%, preferably 10-60.0%; more preferably 45 to 60%.

The invention also provides a flotation method of the high-talc molybdenite, which comprises the steps of placing the high-talc molybdenite into a flotation reagent for flotation to obtain molybdenum concentrate and talc tailings;

the inhibitor is added into the flotation reagent.

In the high-talc molybdenite, the content of talc is not less than 10.0%, and preferably 10-60.0%;

preferably, in the high-talc molybdenite, the oxidation rate of the molybdenite is not less than 10.0%, and preferably 10-50.0%;

preferably, the high talc molybdenite contains 0.07-0.15% molybdenum and 1.5-4% sulfur.

Preferably, in the flotation stage, the dosage of the inhibitor is 1500-3500 g/t;

the flotation method for the high-talc molybdenite has the advantages that other flotation materials and means can be known except for the inhibitor.

For example, a collector is added into the flotation reagent, and the collector is at least one of kerosene and a collector GD;

preferably, the amount of collector used in the flotation stage is 50-350 g/t.

Compared with the prior art, the invention has the advantages that:

(1) the method can obviously inhibit the upward floating of the talc, particularly the high-content talc, and has the talc inhibition rate of more than or equal to 90 percent and the molybdenum loss rate of only about 10 percent in the rough concentration and pre-concentration processes in molybdenite containing more than or equal to 10 percent of talc in raw ore.

(2) The unit consumption of the reagent is reduced, the consumption of the novel talc inhibitor obtained by the new formula is calculated according to the solute concentration in the flotation operation process, the consumption of the inhibitor is 2000g/t and the consumption of the production inhibitor is saved, and the production cost is saved by 40%.

(3) The quality of the circulating water is improved, and because the tailing pulp generated in the mineral separation process is mainly conveyed to a tailing pond through a mortar pump, cleaner circulating water is obtained through the self-purification effect of the tailing pond. However, due to the tolerance of a tailing pond and production requirements, the solid content of the circulating water is usually 1-3%, and after the novel inhibitor is used, the solid content of the circulating water is less than or equal to 0.5%, so that the water quality of the circulating water is greatly improved. Is favorable for improving the production index.

(4) The temperature is not required in the medicament configuration process, the fluidity is better in the medicament adding process, the medicament pipeline blockage is not generated, the accurate control in the medicament adding process is facilitated, and the production stability is favorably maintained.

Drawings

FIG. 1 is a schematic diagram of the beneficiation process of high-talc molybdenum ore of the present invention.

Detailed Description

The invention will be further described with reference to the drawings and examples, but the scope of protection of the invention is not limited to the examples described

Preparation example 1:

preparation of inhibitor SG:

the method comprises the following steps: preparation of sulfuric acid solution

Industrial sulfuric acid with specific gravity of 1.80-1.85, H₂SO₄The content is 95-98.5%.

Mixing industrial sulfuric acid and water, and diluting the mixture under stirring to obtain 10 wt.% sulfuric acid diluent;

step two: preparation of water glass solution

The industrial water glass has the modulus of 2.9 and the PH of 8.5;

mixing the water glass and water, and diluting the mixture under stirring to obtain a water glass diluent with the concentration of 20 wt.%;

step three: mixing sulfuric acid with water glass

Adding the dissolved and diluted water glass solution into the diluted sulfuric acid solution through a delivery pump, and continuously stirring by using a stirrer in a medicament preparation tank in the water glass adding process to fully mix the water glass and the sulfuric acid diluted solution, wherein the ratio of sulfuric acid to water glass solute is 1: 2. The adding speed of the water glass needs to be controlled during the mixing process, and crystallization and precipitation are not formed.

Step four: additive mixing

Adding an additive (GG for short) into the mixed solution obtained in the third step, wherein the additive comprises aluminum sulfate, zinc sulfate and polymeric ferrous sulfate in a mass ratio of 8:1: 1; the ratio of GG to soluble glass is 1:2, the mixture is added at a constant speed in the process of adding, the mixed solution of sulfuric acid and soluble glass is in a stirring state in the process of adding, and stirring is continued for 5min after GG is added, so that the preparation of the novel high-efficiency talc inhibitor is finished, and the medicament code is SG 1. The mixed solution of the water glass and the sulfuric acid is transparent or a small amount of turbid solution, the pH value is acidic, and the pH value is between 3.0. The mixed solution is white or light yellow solution, turbid solution without suspended matters or trace precipitates.

Preparation example 2:

compared with the preparation example 1, the difference is only that the concentration of the diluted sulfuric acid in the step one is 30 percent; the concentration of the water glass diluted in the second step is 20 percent; in the third step, the weight ratio of the diluted sulfuric acid to the diluted water glass is 1: 4; in the fourth step, the weight ratio of GG to water glass is 1: 4. The other parameters were the same as in preparation example 1. The inhibitor SG2 was obtained.

Preparation example 3:

compared with the preparation example 1, the difference is only that the concentration of the diluted sulfuric acid in the step one is 10%; the concentration of the water glass diluted in the second step is 50 percent; in the third step, the weight ratio of the sulfuric acid to the water glass is 1: 3; in the fourth step, the weight ratio of GG to water glass is 1: 3. The other parameters were the same as in preparation example 1. The inhibitor SG3 was obtained.

Preparation example 4:

compared with the preparation example 1, the difference is only that the concentration of the diluted sulfuric acid in the step one is 15 percent; and the concentration of the water glass diluted in the second step is 25%. Other parameters were the same as in preparation example 1. The inhibitor SG4 was obtained.

Flotation research is carried out by adopting the inhibitor prepared in preparation examples 1-4, and the method comprises the following steps:

example 1:

inhibitor SG1 obtained in preparation example 1 was used as inhibitor SG. The method comprises the following steps:

the flotation process is schematically shown in figure 1, and the beneficiation process comprises ore crushing, ore grinding, rough concentration, scavenging, pre-concentration, concentrate regrinding, fine rough concentration, multiple concentration and fine scavenging. In the process, the molybdenite collecting agent is kerosene, and the using amount is 60 g/t; the foaming agent is MIBC (methyl isobutyl carbinol), and the dosage is 15 g/t; active carbon is used for grinding and removing the medicine, and the dosage is 20 g/t; the dosage of the synergistic inhibitor is 10g/t of GM (sodium carboxymethylcellulose),

in the flotation process, the raw material is high-talc high-sulfur molybdenite, the talc content is 54.66%, the molybdenum content is 0.12%, the molybdenum oxide content is 0.04%, the oxidation rate is 33.4%, and the sulfur content is 1.5%.

(1): the grinding parameters are that the content of the raw ore grinding ore of-200 meshes (0.074mm) is not less than 80 percent

The regrind concentrate has a content of 88.0-90% of 200 meshes.

(2): in the beneficiation process, the concentration of the ore pulp is 36 percent, and the pH value of the ore pulp is alkaline. The regrinding concentration of the concentrate is 8-10%.

And (3): stirring and size mixing before rough concentration are carried out by 3 stirring barrels, different medicaments are added into different stirring barrels, the rotating speed of the stirring barrels is 280r/min, and the total stirring time is 20 min. The two-stage rough concentration of the raw ore is respectively a first rough concentration and a second rough concentration; the four-section scavenging is scavenging one, scavenging two, scavenging three and scavenging four. The pre-concentration is at least two sections, namely a pre-concentration one and a pre-concentration two. The concentrate is reground, refined and roughly sorted into a first section, and the concentrate is sorted into a third section, namely a first concentrate, a second concentrate and a third concentrate; the fine scavenging is three sections, namely a first fine scavenging section, a second fine scavenging section and a third fine scavenging section. The flotation equipment adopted by the flotation can be a flotation machine or a flotation column.

(3): in the embodiment, the novel efficient talc inhibitor SG is added into a stirring barrel before rough concentration and fully mixed with ore pulp, the addition amount is 1600g/t, the stirring process is at least 15min, and the ore pulp enters the rough concentration after stirring.

(4): in the embodiment, the novel efficient talc inhibitor SG is also added in a scavenging process, the adding positions are scavenging one, fine sweeping three, pre-concentration one, pre-concentration two, concentration one, concentration two and concentration three, the adding amount is scavenging one 200g/t, fine sweeping one 50g/t, fine sweeping three 50g/t, pre-concentration one 100g/t, pre-concentration two 50g/t, concentration one 50g/t, concentration two 50g/t and concentration three 20g/t, and the adding positions of the agents can be directly in a middle box of a flotation machine or directly added into flotation equipment and can also play a role in inhibiting talc due to no stirring barrel.

(5): in the embodiment, the addition points of the novel efficient talc inhibitor SG are 1600g/t of addition amount into a pulp mixing stirring barrel before roughing or roughing, 200g/t of scavenging addition amount, 150g/t of addition amount into pre-concentration, 120g/t of addition amount into concentrate regrinding, fine roughing, 100g/t of addition amount into concentrate regrinding, 1970g/t of addition amount into full process SG, 20g/t of auxiliary inhibitor GM (sodium carboxymethylcellulose), and 200g/t of regulator GF (sodium polysulfide) in cooperation with collecting agent GD (ethyl-sulfur-nitrogen) + kerosene.

The pre-concentration product obtained in this example had a molybdenum grade of 15.6% and the pre-concentration concentrate had talc of 1.56%

The molybdenum content of the molybdenum concentrate product obtained in this example was 38.3%, and the talc content of the concentrate product was 0.75%.

In this example, the recovery rate of the roughing operation is about 70%, the molybdenum content of the middling product is less than or equal to 1.0%, and the recovery rate of the concentrating operation is greater than or equal to 90%. The overall recovery was 60.11%. From the data, the molybdenum resource in the ore can be effectively recycled, and benefits are created. The data are detailed in tables 1 and 2.

Example 2

Compared with example 1, the difference is only that the inhibitor SG2 prepared in preparation example 2 is used as the inhibitor SG. The other operations and parameters were the same as in example 1.

Example 3

Compared with example 1, the difference is only that the inhibitor SG3 prepared in preparation example 3 is used as the inhibitor SG. The other operations and parameters were the same as in example 1.

Example 4

Compared with example 1, the difference is only that the inhibitor SG4 prepared in preparation example 4 is used as the inhibitor SG. The other operations and parameters were the same as in example 1.

The flotation results of examples 1 to 4 are detailed in Table 1

TABLE 1 summary of the results of the various examples

Comparative example 1

Compared with example 1, the difference is only that water glass is used as an inhibitor (lacking sulfuric acid and GG) to replace the inhibitor SG1, and the flotation process and parameters are the same as those of example 1.

Comparative example 2

Compared with example 1, the difference is mainly that carboxymethyl cellulose is used as an inhibitor, instead of the inhibitor SG1, and the flotation process and parameters are the same as those in example 1.

Comparative example 3

Compared with example 1, the difference is mainly that guar gum is used as an inhibitor, instead of the inhibitor SG1, and the flotation process and parameters are the same as those in example 1.

Comparative example 4

Compared with the example 1, the difference is mainly that a mixture of water glass and GG is adopted as an inhibitor (SG1 lacks sulfuric acid) to replace the inhibitor SG1, and the flotation process and parameters are the same as those of the example 1.

Comparative example 5

Compared with the example 1, the difference is mainly that GG is adopted as an inhibitor (SG1 lacks sulfuric acid and water glass), the inhibitor SG1 is replaced, and the flotation process and parameters are the same as those of the example 1.

The data for example 1 and comparative examples 1 to 5 are detailed in table 2.

Table 2 results of comparing the effects of different inhibitors on high talc molybdenum ore recovery

In conclusion, the combined ingredients of the present invention can synergistically improve the inhibitory effect of talc.

Claims

1. A preparation method of a talc inhibitor is characterized in that a sulfuric acid solution with the concentration of 10-30 wt.% and a water glass solution with the concentration of 20-50 wt.% are mixed, then an additive is added, and the mixture is uniformly stirred to obtain the talc inhibitor;

the additive comprises aluminum sulfate, zinc sulfate and polymeric ferrous sulfate in a mass ratio of 8-8.5: 1-1.5;

2. The method for preparing a talc inhibitor according to claim 1, wherein said sulfuric acid solution is diluted with industrial sulfuric acid;

preferably, the concentration of industrial sulfuric acid is greater than or equal to 95 wt.%.

3. The method for preparing a talc inhibitor according to claim 1, wherein said water glass solution is diluted with industrial water glass;

4. A talc inhibitor obtained by the production method according to any one of claims 1 to 3.

5. The talc inhibitor prepared by the method of claim 4, wherein the talc inhibitor is a clear or slightly turbid solution having a pH of 1.0 to 4.0;

preferably, its suspended particles are less than or equal to 2 wt.%.

6. The use of the talc inhibitor prepared by the method of any one of claims 1 to 3 wherein said inhibitor is added to a talc mineral-containing flotation reagent to inhibit talc flotation therein.

7. The use according to claim 6, wherein the talc containing mineral is a high talc content mineral; the content of the talc is ≧ 10 wt.%, preferably 10-60 wt.%.

8. The flotation method of the high-talc molybdenite is characterized in that the high-talc molybdenite is placed in a flotation reagent for flotation to obtain molybdenum concentrate and talc tailings;

the flotation reagent is added with the inhibitor prepared by the preparation method of any one of claims 1 to 3.

9. The flotation method for high-talc molybdenite according to claim 8, wherein the content of talc in the high-talc molybdenite is not less than 10 wt.%, preferably 10 to 60 wt.%; further preferably 45-60%;

preferably, in the high-talc molybdenite, the oxidation rate of the molybdenite is not less than 10%, and preferably 10-50 wt%;

10. The flotation process for high-talc molybdenite according to claim 8 or 9, wherein,

in the flotation stage, the dosage of the inhibitor is 1500-3500 g/t;

preferably, a collector is added into the flotation reagent, and the collector is at least one of kerosene and GD;

preferably, in the flotation stage, the using amount of the collecting agent is 50-350 g/t.