CN114054212A

CN114054212A - Composite inhibitor and application thereof

Info

Publication number: CN114054212A
Application number: CN202111224878.XA
Authority: CN
Inventors: 焦芬; 王旭; 覃文庆; 杨聪仁; 李卫; 张政权; 任满年; 宋灏
Original assignee: Luoyang North Industry & Trade Co ltd; Central South University
Current assignee: Luoyang North Industry & Trade Co ltd; Central South University
Priority date: 2021-10-21
Filing date: 2021-10-21
Publication date: 2022-02-18
Anticipated expiration: 2041-10-21
Also published as: CN114054212B

Abstract

The invention discloses a preparation and use method of a low-grade scheelite rough selection combined regulator, which mainly comprises inorganic phosphate and organic phosphate; the structure of the inorganic phosphate is shown as a formula 1:

wherein X is 2-5; the structure of the organic phosphate is shown as a formula 2:

Description

Composite inhibitor and application thereof

Technical Field

The invention relates to an application of a composite inhibitor in scheelite flotation, belonging to the technical field of calcium-containing gangue mineral inhibitors.

Background

Due to the similar physical and chemical properties of the surfaces of the calcium-containing minerals, the separation of the calcium-containing minerals is always a difficult problem in the mineral separation field. Flotation is a main technical means for recovering calcium-containing minerals, and fatty acid serving as a main collector for flotation of the calcium-containing minerals has good collecting capacity but extremely poor selectivity, so that the separation of the target calcium-containing minerals and the target calcium-containing gangue minerals cannot be realized. Therefore, depressants are often added during the separation of calcium-containing minerals by flotation to enhance the separation. In the case of scheelite, it is usually associated with calcium-containing minerals such as fluorite, calcite, apatite and wollastonite, which are affected by the mineralization process. Water glass is usually added during flotation to suppress the economically less valuable fluorites, calcites, apatites and wollastonite. The water glass has weak inhibition ability, and the recycling of scheelite is influenced by excessive using amount. After silicic acid is circularly enriched in mineral processing water, tailings are difficult to settle, the recycling effect of tailing reservoir water is poor, flotation indexes are rapidly reduced, a large amount of resources are lost, and the economic benefit of an enterprise is greatly reduced.

For a long time, in order to solve the problem of flotation separation of calcium-containing minerals, related technicians take many measures, for example, a chelate collecting agent with better selectivity, such as hydroximic acid, cupferron and the like, is adopted to replace fatty acid. Although the selectivity is greatly improved, the collecting capacity is low, the using amount is large, the unit price is high, the ore dressing cost is increased sharply, the target minerals cannot be recovered fully, and the pollution of the production process of the reagents is large. Still some technicians select micromolecular carboxylic acid, lignosulfonate etc. as the inhibitor of calcium-containing gangue mineral, although certain effect has been obtained in laboratory monomineral flotation process, can't adapt to the complicated ore pulp environment of actual ore flotation, and the production index is still not ideal. Chinese patents CN110773324A, CN111215247A, CN108906335A, CN108654844B and the like all relate to the application of single inorganic phosphate or single organic phosphate in mineral flotation. Although the single inorganic phosphate or organic phosphate disclosed therein has a certain effect in the flotation of the relevant ores, when the raw ore grade and the content of the calcium-containing gangue minerals fluctuate, the separation efficiency can be improved only by adjusting the amount of the inhibitor, but even if the amount of the inhibitor is greatly increased, the influence of the flotation efficiency is quite limited. Especially, in the case of low-grade scheelite with large fluctuations in the properties of the raw ore, the adjustability and operability are still lacking. Moreover, the addition of an excessive amount of inhibitor not only increases the cost greatly, but also has considerable negative effects. Meanwhile, the inventions provided by some patents are only implemented in pure mineral tests, and laboratory micro-flotation tests are greatly different from actual ores. The practical effect is far from the ideal state of a laboratory.

Disclosure of Invention

The invention aims to provide a composite inhibitor which can generate positive synergistic effect by adjusting the proportion and the structure of a combined medicament according to the content of calcium-containing gangue minerals in raw ores. Under the condition of not influencing the scheelite roughing recovery rate, the roughing efficiency of the low-grade scheelite is improved to the maximum extent, the rough concentrate with better quality is provided for the subsequent scheelite heating and concentration, and the load and the cost of the scheelite heating and concentration section are reduced.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a composite inhibitor comprises, by weight, 5-95 parts of inorganic phosphate and 5-95 parts of organic phosphate.

The structure of the inorganic phosphate is shown as a formula 1:

wherein X is 2-5;

the structure of the organic phosphate is shown as a formula 2:

wherein n is 2 to 8.

Further preferably, X is 2 or 3.

Further preferably, the inorganic phosphate is one or more of sodium tripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate, sodium hexametaphosphate and potassium hexametaphosphate.

Further preferably, n is 2 or 6.

Further preferably, the organic phosphate is one or two of hexamethylene diamine tetramethylene sodium phosphate, hexamethylene diamine tetramethylene potassium phosphate, ethylene diamine tetramethylene sodium phosphate and ethylene diamine tetramethylene potassium phosphate.

Preferably, the composite inhibitor comprises 25-75 parts by weight of sodium tripolyphosphate and 25-75 parts by weight of ethylene diamine tetramethylene sodium phosphate.

Preferably, the composite inhibitor comprises 25-75 parts by weight of sodium hexametaphosphate and 25-75 parts by weight of sodium hexamethylenediamine tetramethylenephosphate.

The invention claims the application of the composite inhibitor in the field of mineral flotation, and researches show that the composite inhibitor has excellent flotation performance in the field of mineral flotation.

The inventor further researches and discovers that the organic phosphoric acid compound with the structure has better selectivity on calcium-containing gangue minerals and good flotation effect, for example, compared with inhibitors such as water glass and the like commonly used in the field, the composite inhibitor can show excellent selectivity and recovery rate under a smaller using amount.

Preferably, the calcium-containing gangue mineral is at least one of calcite, fluorite, apatite and wollastonite.

Preferably, in the application, the flotation reagent of the flotation inhibitor is added into raw ore, and concentrate is obtained through flotation.

Preferably, the flotation reagent further comprises a collecting agent, the inhibitor is added into the raw ore, and then a small amount of the collecting agent is added to the raw ore to perform flotation so as to obtain the coarse ore.

The collecting agent can be a medicament with collecting performance commonly used in the industry, and special collecting agents such as sodium oleate, sodium carbonate and the like are not needed.

Preferably, the flotation inhibitor is suitable for the flotation pulp environment with the pH of 2-12.

Further preferably, the flotation depressor is applicable to flotation pulp with the pH of 10 +/-0.2.

At the preferred pH, the flotation effect is better, particularly in the scheelite flotation process, and the selectivity, the taste and the recovery rate of flotation concentrate can be further obviously improved when the preferred pH is controlled.

Preferably, the temperature of the flotation inhibitor adapted to the flotation pulp environment is 0-100 ℃.

The flotation method can adopt the conventional method.

In the invention, the flotation separation of scheelite and gangue minerals by using the composite inhibitor comprises the following main steps:

a) grinding raw ore, and adding the ground raw ore into a flotation tank;

b) sequentially adding sodium carbonate, an inhibitor and sodium oleate into the ore pulp, stirring and mixing for 2-5 min for roughing.

Preferably, the flotation separation of the scheelite and the gangue minerals by using the composite inhibitor comprises the following main steps:

a) grinding raw ore to the fineness of 55-78% of-0.074 mm, and adding the ground raw ore into a flotation tank;

b) adding sodium carbonate into the ore pulp, stirring and mixing for 2-5 min

b) Adding an inhibitor, and stirring and mixing for 2-5 min;

c) and adding sodium oleate, stirring and mixing the slurry for 3-4 min, and then carrying out flotation for 3-6 min.

The invention is further explained below:

the components of the composite medicament have good compatibility under the appropriate proportion and dosage, can realize the accurate separation of scheelite, calcite, fluorite, apatite, wollastonite and other calcium-containing gangue minerals, and can ensure the recovery rate of target minerals. The main principle is as follows:

1. the adsorption behavior of the flotation reagent on the surface of calcium-containing minerals occurs mainly between the hydrophilic base of the reagent and the calcium ions. When the combined modifier occupies calcium ion sites on the surface of the mineral, the adsorption sites left for the fatty acid collecting agent are reduced, and the hydrophilicity of the surface of the mineral is enhanced and inhibited. The inorganic phosphate may also complex free calcium ions and then precipitate on the surface of the calcium-containing gangue minerals, causing the gangue minerals to form a hydrophilic surface.

2. The differences of the calcium ion density on the surfaces of different calcium-containing minerals and the chemical bond energy related to calcium in the crystal lattices of the minerals cause different adsorption behaviors of the same flotation agent on the surfaces of different calcium-containing minerals. The quantity of phosphate radicals and the length of hydrophobic chains in the structures of inorganic phosphate and organic phosphate also influence the matching degree of the inorganic phosphate and organic phosphate combined with calcium ions on the surface of the mineral. When the inorganic phosphate and the organic phosphate are mixed singly or in a certain ratio, if the inhibition ability is too strong or too weak and exceeds an adjustable threshold, positive synergism cannot be obtained, and the ideal index cannot be achieved. Therefore, the application of the inorganic phosphate and the hydrocarbon chain length of the organic phosphate in the regulator in the flotation separation of different calcium-containing mineral combinations can be adapted by controlling the number of phosphate in the inorganic phosphate and the length of the hydrocarbon chain in the organic phosphate, so that the regulator is more selectively adsorbed on the surface of the calcium-containing gangue mineral.

3. Under the appropriate proportion and dosage, the inorganic phosphate and the organic phosphate show good compatibility, and simultaneously play the role of directly adsorbing or complexing partial calcium ions in ore pulp on the surface of the calcium-containing gangue mineral and precipitating on the surface of the calcium-containing gangue mineral, but have little influence on the surface of scheelite, prevent the adsorption of a subsequent collecting agent, thereby enhancing the inhibition on the calcium-containing gangue mineral.

The invention has the following advantages:

1. the combined regulator is prepared by mixing organic phosphate and inorganic phosphate serving as raw materials, is easy to obtain the raw materials, simple in preparation process, low in cost, environment-friendly and easy to degrade, and has great practical popularization value and market potential.

2. The method can realize the accurate separation of the low-grade scheelite and the calcium-containing gangue minerals without influencing the recovery rate of the target minerals, realizes the efficient recycling of scheelite resources, and has strong adaptability to different ore pulps and wide application range.

3. The method can greatly reduce the content of the calcium-containing gangue in the scheelite rough concentrate, and reduce the energy consumption and the medicament cost of the subsequent scheelite rough concentrate heating flotation section.

Drawings

In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings used in the embodiments are briefly described below.

FIG. 1 is a flotation scheme of example 1 of the present invention;

FIG. 2 is a flotation scheme of example 2 of the present invention;

figure 3 is a flotation scheme of example 3 of the present invention.

Detailed Description

In order to facilitate clear understanding of the technical solutions of the present invention, the following examples are further used to illustrate the present invention, and it is obvious that the present invention is not limited by the scope of the claims of the present invention.

Example 1

The composite inhibitor contains 50% of inorganic phosphate and 50% of organic phosphate by weight percentage. The inorganic phosphate is sodium tripolyphosphate and the organic phosphate is ethylene diamine tetramethylene sodium phosphate. Adding the components into a stirring barrel according to the weight ratio; then, clear water is added into the stirring barrel, and the ratio of the regulator to the clear water is 1:99 in parts by weight.

The application effect of the composite inhibitor in the roughing process of certain low-grade scheelite with the WO3 content of 0.09% is examined. The ore is typically of the scheelite-calcite-fluorite type, i.e. the gangue minerals are mainly calcite and fluorite, as well as feldspar, chlorite, amphibole, mica, quartz, etc. The flotation process is shown in figure 1. According to the flow of the figure 1, raw ore is ground to the fineness of 55-78% of-0.074 mm and then is added into a flotation tank. Flotation agent and depressor are added in the rough concentration stage, and after rough concentration, scavenging is carried out twice. According to the flow of fig. 1, the dosage of sodium carbonate and sodium oleate was examined on the premise of no addition of the medicament, and the specific results are shown in table 1.

TABLE 1 sodium carbonate and sodium oleate test results

As can be known from the flotation reagent dosage test, the grade of the scheelite rough concentrate is in an increasing trend along with the increase of the dosage of the sodium carbonate, the scheelite recovery rate is increased firstly and then decreased, and the appropriate dosage of the sodium carbonate is 1800g/t by comprehensive consideration. Along with the increase of the using amount of the sodium oleate, the grade of the scheelite rough concentrate is gradually reduced, the recovery rate is increased firstly and then tends to be balanced, and the appropriate using amount of the sodium oleate is 150g/t in comprehensive consideration.

The action of the different inhibitors was investigated on the premise that the amount of fixed sodium carbonate was 1800g/t and the amount of sodium oleate was 150 g/t. The types of specific inhibitors and the results are shown in table 2.

TABLE 2 Effect of different inhibitors

From the results in table 2, it can be seen that, although the grade of the scheelite rough concentrate can be improved by adding a single inorganic phosphate or organic phosphate, the scheelite rough concentration recovery rate is greatly reduced and the rough concentrate grade is high when sodium tripolyphosphate is used alone, and the scheelite rough concentration recovery rate is not significantly changed when sodium ethylene diamine tetra-methyl phosphate is used alone, but the rough concentrate grade is not as high as that when sodium tripolyphosphate is used alone. The composite inhibitor of the embodiment 1 improves the grade of the scheelite rough concentrate from 1.75 percent to 2.25 percent, and the recovery rate of the scheelite rough concentrate is also improved from 84.12 percent to 87.67 percent. Meanwhile, the inorganic phosphate and the organic phosphonate can only play the optimal synergistic effect under the proper proportion. In a comparative test, when the ratio of the sodium tripolyphosphate to the ethylene diamine tetramethylene sodium phosphate is 25:75, the combined inhibitor can improve the grade and the recovery rate of the rough concentrate at the same time, but is not as good as the composite inhibitor of the example 1. When the ratio is 75:25, the concentrate grade is promoted more greatly, but the recovery rate is lost to a certain extent. It is shown that the inhibitor components show the best compatibility only under the proper proportion.

The results of examining the amount of the composite inhibitor of example 1 used, and keeping the amounts of other agents added, are shown in table 3.

Table 3 results of the dose test

The result of the dosage test proves that when 50g/t of the composite inhibitor in the embodiment 1 is added, compared with the condition that no inhibitor is added, the grade and the recovery rate of the scheelite rough concentrate are simultaneously improved, and a good positive synergistic effect is shown.

Example 2

The composite inhibitor of example 2 contains 5% inorganic phosphate and 95% organic phosphate by weight. The inorganic phosphate is sodium hexametaphosphate, and the organic phosphate is hexamethylene diamine tetramethylene sodium phosphate. Adding the components into a stirring barrel according to the weight ratio; and then, adding clear water into the stirring barrel, wherein the ratio of the regulator to the clear water is 15:85 in parts by weight.

The application effect of the composite inhibitor in example 2 in the course of roughing certain ultralow-grade scheelite with the WO3 content of 0.015% is examined. Compared with the raw ore containing the calcium-containing gangue in the example 1, the kind and content of the calcium-containing gangue minerals in the example 2 are changed, and the content of each component in the combined regulator can be adjusted according to the content and type of the calcium-containing gangue minerals, so that the combined regulator generates optimal compatibility, positive synergistic effect is generated, and the precise separation of scheelite and the calcium-containing gangue is realized. According to the flow of figure 2, raw ore is ground to a fineness of 55-78% of-0.074 mm and then added into a flotation tank. Flotation agent and depressor are added in the rough concentration stage, and after rough concentration, scavenging is carried out twice. Similarly, according to the flow chart of FIG. 2, the amounts of sodium carbonate and sodium oleate were examined separately without adding any chemical agent, and it was found that the appropriate amount of sodium carbonate was 1200g/t, the composite inhibitor of example 2 was 30g/t, and the optimum amount of sodium oleate was 180 g/t.

Flotation tests were performed on different flotation agents with the use of fixed amounts of the agents, and the results are shown in table 4.

Table 4 results for different flotation agents

From the second comparative test, it can be seen that when sodium hexametaphosphate or hexamethylenediamine tetramethylenesodium phosphate is added alone, the grade of the scheelite rough concentrate is increased to a certain extent, but the recovery rate is reduced to a large extent. When the second embodiment is used, the inorganic sodium phosphate and the organic sodium phosphate have good compatibility, and under the condition that the recovery rate of the scheelite is improved in a small range, the grade of the rough concentrate is improved to 0.581% from 0.307%, the yield of the rough concentrate is reduced to 1.84% from 3.45%, and the reduction range is over 40%, which means that the quantity of the rough concentrate entering the subsequent heating concentration is also reduced by over 40%, and the corresponding concentration variation cost is also reduced by 40%, so that the economic feasibility of the recovery of the ultralow-grade scheelite is realized.

Example 3

The composite inhibitor of example 3 contains 95% inorganic phosphate and 5% organic phosphate by weight. The inorganic phosphate is sodium tripolyphosphate and the organic phosphate is sodium ethylene diamine tetra methyl phosphate. Adding the components into a stirring barrel according to the weight ratio; and then, adding clear water into the stirring barrel, wherein the ratio of the regulator to the clear water is 15:85 in parts by weight.

The application effect of the composite inhibitor in the embodiment 3 in the roughing process of certain low-grade high-wollastonite scheelite is examined, and the content of WO3 in the raw ore is 0.15%, and the content of wollastonite is about 30%. According to the content and the type of the calcium-containing gangue minerals, the content of each component in the combined regulator is adjusted, so that the combined regulator generates the optimal compatibility and positive synergistic effect, and the precise separation of the scheelite and the calcium-containing gangue is realized. According to the flow of figure 3, raw ore is ground to a fineness of 55-78% of-0.074 mm and then added into a flotation tank. Flotation agent and depressor are added in the rough concentration stage, and after rough concentration, scavenging is carried out twice. Similarly, according to the flow chart of FIG. 3, the amounts of sodium carbonate and sodium oleate are examined respectively without adding any other agent, and the preferable amount of sodium carbonate is 2100g/t and the preferable amount of sodium oleate is 120 g/t.

The results of examining the amount of the composite inhibitor of example 3 used, and keeping the amounts of other agents added, are shown in table 5.

Table 5 results of the amount test

The result of the dosage test of the inhibitor in example 3 proves that when the composite inhibitor in example 3 is added under the appropriate dosage of 35g/t, the grade of the scheelite rough concentrate can be improved, the recovery rate of the scheelite can be improved, and a good positive synergistic effect is shown. However, when the amount is too large, the scheelite recovery rate is lowered as compared with the appropriate amount.

TABLE 6 results for different flotation agents

From the results, it is found that when the inorganic phosphate component is used alone, the grade of the scheelite rough concentrate is 2.316%, the recovery rate is 76.53%, and although the grade of the rough concentrate is improved, the recovery rate loss is large. When sodium tripolyphosphate and amino sodium trimethylphosphate are used in a matched mode, the inhibiting capacity of the two components is high and exceeds the regulation threshold of the optimal condition, the coarse concentrate grade can reach 2.528%, but the recovery rate loss is increased, and the coarse concentrate grade and the recovery rate cannot be considered at the same time. When the sodium tripolyphosphate is matched with the polyamino polyether methylene phosphate for use, the polyamino polyether methylene phosphate has weak inhibition capacity, although the recovery rate can reach 82.62%, the grade of the rough concentrate is only 1.971%. Similarly, when the sodium ethylene diamine tetramethylenephosphate is combined with other inorganic phosphate, the regulation threshold of the optimal condition is also exceeded. For example, when the sodium pyrophosphate is combined with the sodium pyrophosphate, the sodium pyrophosphate has weak inhibition capacity, the loss of the recovery rate is not large, but the concentrate grade is improved to a low extent. When the sodium hexametaphosphate is combined, the sodium hexametaphosphate has too strong inhibition capacity, so that the scheelite recovery rate loss is large. When the combined regulator provided by the patent is used, the components show good compatibility, the grade of the scheelite rough concentrate is 2.535%, and the recovery rate is 85.51%.

Similarly, the composite inhibitors prepared in example 1 and example 2 were paired with different inorganic phosphates and organic phosphates, and as a result, it was found that only the composite inhibitors specified in example 1 and example 2 were most effective against the specific minerals of example 1 and example 2.

In summary, it can be seen that not all inorganic phosphates and organic phosphonates produce a positive synergy. Different inorganic and organic phosphates have different strengths of action with calcium-containing mineral surfaces of different minerals. The inorganic phosphate and organic phosphate have too strong or too weak an inhibiting ability to exceed a controllable threshold, i.e., no optimal effect can be achieved in either of those proportions or when used alone. The invention can match the function of calcium-containing mineral according to the specific inorganic phosphate and organic phosphate pairing selected by different minerals. Aiming at ores with different calcium-containing mineral proportions, the positive synergistic effect can be exerted by combining the regulating agents by regulating the component proportion, and the synergistic effect of 1+1>2 is generated.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims

1. The composite inhibitor is characterized by comprising 5-95 parts by weight of inorganic phosphate and 5-95 parts by weight of organic phosphate;

the structure of the inorganic phosphate is shown as a formula 1:

wherein X is 2-5;

the structure of the organic phosphate is shown as a formula 2:

wherein n is 2 to 8.

2. The compound inhibitor of claim 1, wherein X is 2 or 3.

3. The compound inhibitor as defined in claim 2, wherein the inorganic phosphate is one or more of sodium tripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate, sodium hexametaphosphate and potassium hexametaphosphate.

4. The compound inhibitor of claim 1, wherein n is 2 or 6.

5. The compound inhibitor of claim 1, wherein the organic phosphate is one or two of hexamethylenediamine tetramethylenesodium phosphate, hexamethylenediamine tetramethylenepotassium phosphate, ethylenediaminetetramethylenesodium phosphate, and ethylenediaminetetramethylenepotassium phosphate.

6. The compound inhibitor according to any one of claims 1 to 5, wherein the compound inhibitor comprises 25 to 75 parts by weight of sodium tripolyphosphate and 25 to 75 parts by weight of sodium ethylenediamine tetramethylene phosphate.

7. The compound inhibitor according to any one of claims 1 to 5, wherein the compound inhibitor comprises 25 to 75 parts by weight of sodium hexametaphosphate and 25 to 75 parts by weight of sodium hexamethylenediamine tetramethylenephosphate.

8. Use of a composite depressant according to any of the claims 1 to 7 in the field of flotation of calcium-containing gangue minerals.

9. The use according to claim 8, wherein the calcium-containing gangue minerals are at least one of calcite, fluorite, apatite and wollastonite; preferably, in the application, the flotation reagent of the flotation inhibitor is added into raw ore, and concentrate is obtained through flotation.

10. The use of claim 9, wherein the flotation reagent further comprises a collector, and the crude ore is obtained by adding the inhibitor to the crude ore and then adding a small amount of the collector for flotation.