CN114054212B - Composite inhibitor and application thereof - Google Patents

Abstract

The invention discloses a method for preparing and using a low-grade scheelite coarse selection combination regulator, which mainly includes inorganic phosphate and organic phosphate; the structure of the inorganic phosphate is shown in formula 1:

Wherein, X is 2-5; The structure of described organophosphate is as shown in formula 2:

Wherein, n is 2‑8. Under the appropriate dosage and usage, this patent can realize efficient separation of calcium-containing minerals under the premise of ensuring the recovery rate of the target minerals. The combination adjuster has strong adaptability and less dosage, and realizes precise separation of different calcium-containing minerals through the control of component distribution ratio.

Description

A kind of composite inhibitor and its application

technical field

The invention relates to the application of a compound inhibitor in scheelite flotation, and belongs to the technical field of calcium-containing gangue mineral inhibitors.

Background technique

Due to the similar physical and chemical properties on the surface of calcium-containing minerals, the separation of calcium-containing minerals has always been a difficult problem in the beneficiation industry. Flotation is the main technical method for recovering calcium-containing minerals. As the main collector for calcium-containing mineral flotation, fatty acid has good collection capacity, but its selectivity is extremely poor, and the target calcium-containing minerals and calcium-containing veins cannot be realized. Separation of stone minerals. Therefore, inhibitors are often added during the flotation separation of calcium-containing minerals to enhance the separation effect. Taking scheelite as an example, affected by the mineralization process, it is usually associated with calcium-containing minerals such as fluorite, calcite, apatite and wollastonite. Water glass is usually added to the flotation process to suppress fluorite, calcite, apatite and wollastonite which are of low economic value. Water glass is not strong in inhibiting ability, and excessive dosage will affect the recovery of scheelite. After the silicic acid is enriched in the mineral processing water, it will cause the tailings to be difficult to settle, the water reuse effect of the tailings pond will be poor, and the flotation index will drop sharply, resulting in a large loss of resources and a sharp drop in the economic benefits of the enterprise.

For a long time, in order to solve the difficult problem of flotation separation of calcium-containing minerals, relevant technical personnel have taken many measures, such as using hydroxamic acid, copper iron and other more selective chelating collectors to replace fatty acids. Although the selectivity is greatly improved, its collection capacity is low, the dosage is large, and the unit price is high, which leads to a sharp increase in the cost of beneficiation, and the target minerals cannot be fully recovered, and the production process of these chemicals is more polluting. There are also some technicians who choose small molecule carboxylic acid, lignosulfonate, etc. as inhibitors of calcium-containing gangue minerals. Although they have achieved certain results in the laboratory single mineral flotation process, they cannot adapt to actual ore flotation. In the complicated slurry environment, the production indicators are still not ideal. Chinese patents CN110773324A, CN111215247A, CN108906335A, CN108654844B, etc. all relate to the application of a single inorganic phosphate or a single organic phosphate in mineral flotation. Although the single inorganic phosphate or organic phosphate announced by it has achieved a certain effect in the flotation of related ores, when the raw ore grade and calcium-containing gangue mineral content fluctuate, it can only be adjusted by adjusting the amount of inhibitor. Improve the sorting efficiency, but even if the amount of inhibitor is greatly increased, the effect of the flotation efficiency is quite limited. Especially for the low-grade scheelite whose raw ore properties fluctuate greatly, the adjustability and operability are still lacking. Moreover, if the amount of the inhibitor is added too much, not only the cost will be greatly increased, but also quite a lot of negative effects. At the same time, the inventions provided by some patents have only been implemented in the pure mineral test, and the laboratory micro-flotation test is quite different from the actual ore. The practical effect is far from the ideal state of the laboratory.

Contents of the invention

The object of the present invention is to provide a compound inhibitor, which can produce a positive synergistic effect by adjusting the ratio and structure of the combined agent according to the content of calcium-containing gangue minerals in the raw ore. Without affecting the roughing recovery rate of scheelite, the roughing efficiency of low-grade scheelite can be maximized to provide better quality rough concentrate for subsequent heating and selection of scheelite, and reduce the heating and refining of scheelite. Selection load and cost.

To achieve the above object, the technical scheme of the present invention is as follows:

A composite inhibitor comprises 5-95 parts of inorganic phosphate and 5-95 parts of organic phosphate in parts by weight.

Described inorganic phosphate structure is as shown in formula 1:

Among them, X is 2-5;

The structure of the organic phosphate is shown in formula 2:

Wherein, n is 2-8.

Further preferably, the 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, the n is 2 or 6.

Further preferably, the organic phosphate is sodium hexamethylenediamine tetramethylene phosphate, potassium hexamethylenediamine tetramethylene phosphate, sodium ethylenediamine tetramethylene phosphate, potassium ethylenediamine tetramethylene phosphate one or both.

Preferably, the composite inhibitor includes 25-75 parts of sodium tripolyphosphate and 25-75 parts of sodium ethylenediamine tetramethylene phosphate in parts by weight.

Preferably, the composite inhibitor includes 25-75 parts of sodium hexametaphosphate and 25-75 parts of sodium hexamethylenediamine tetramethylene phosphate in parts by weight.

The present invention claims to protect the application of the above composite depressant in the field of mineral flotation, and it is found through research that it exhibits excellent flotation performance in the field of mineral flotation.

The inventor further researched and found that the organic phosphoric acid compound with the structure described in the present invention has better selectivity to calcium-containing gangue minerals and has a good flotation effect, for example, compared with the water glass commonly used in the art and other inhibitors, the composite inhibitor of the present invention can show excellent selectivity and recovery rate at a small dosage.

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

Preferably, in the above application, the flotation agent of the flotation inhibitor is added to the raw ore, and the concentrate is obtained by flotation.

Further preferably, the flotation agent also includes a collector, the inhibitor is added to the raw ore, and then a small amount of collector is added to obtain the coarse ore after flotation.

The collector can be a commonly used agent in the industry with collector performance, without special collectors, such as sodium oleate, sodium carbonate and the like.

Preferably, the flotation slurry environment adapted to by the flotation inhibitor is pH 2-12.

Further preferably, the flotation slurry environment suitable for the flotation inhibitor is pH 10±0.2.

At this preferred pH, the flotation effect is better, especially in the scheelite flotation process, controlled at this preferred pH, can unexpectedly further significantly improve the selectivity, improve the taste and quality of the flotation concentrate Recovery rate.

Preferably, the temperature of the flotation pulp that the flotation inhibitor is suitable for is 0-100°C.

The method of flotation can adopt the existing conventional method.

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

a) After the raw ore is ground, add the flotation cell;

b) Add sodium carbonate, inhibitor and sodium oleate in turn to the slurry, stir and adjust the slurry for 2-5 minutes for rough separation.

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

a) After grinding the raw ore to a fineness of -0.074mm accounting for 55%-78%, add the flotation cell;

b) After adding sodium carbonate to the slurry, stir and adjust the slurry for 2-5 minutes

b) Then add the inhibitor, stir and adjust the slurry for 2 to 5 minutes;

c) Then add sodium oleate, stir for 3-4 minutes and then perform flotation. The flotation time is 3-6 minutes.

The present invention is further explained below:

Under the appropriate proportion and dosage, the combined agent has good compatibility among the components, and can realize the precise separation of calcium-containing gangue minerals such as scheelite, calcite, fluorite, apatite and wollastonite. And the recovery rate of the target mineral can be guaranteed. The main principles are:

1. The adsorption behavior of flotation reagents on the surface of calcium-containing minerals mainly occurs between the solid-affinity groups of the reagents and calcium ions. When the combination regulator occupies the calcium ion sites on the mineral surface, the adsorption sites for the fatty acid collector will be reduced, and the hydrophilicity of the mineral surface will be enhanced and inhibited. Inorganic phosphate can also complex free calcium ions and then precipitate on the surface of calcium-containing gangue minerals, making the gangue minerals form a hydrophilic surface.

2. The difference in calcium ion density on the surface of different calcium-containing minerals and the energy of calcium-related chemical bonds in the mineral lattice lead to different adsorption behaviors of the same flotation agent on the surface of different calcium-containing minerals. The number of phosphate groups in the structure of inorganic phosphate and organic phosphate, the length of the hydrophobic chain, etc. also affect the matching degree of the calcium ion binding with the mineral surface. When a single inorganic phosphate and organic phosphate are mixed in a certain ratio, if the inhibitory ability is too strong or too weak, exceeding the adjustable threshold, positive synergistic effect cannot be obtained, and the ideal index cannot be achieved. Therefore, it is possible to adapt its application in flotation separation of different calcium-containing mineral combinations by controlling the number of phosphate radicals in the inorganic phosphate and the length of the hydrocarbon chain in the organic phosphate in the regulator, making the regulator better and more Selectively adsorbed on the surface of calcium gangue minerals.

3. Under the appropriate proportion and dosage, inorganic phosphate and organic phosphate show good compatibility, and at the same time play a role in directly adsorbing on the surface of calcium-containing gangue minerals or complexing part of the calcium ions in the pulp and precipitate on calcium-containing gangue minerals. The effect on the surface of gangue minerals, but has little effect on the surface of scheelite, prevents the adsorption of subsequent collectors, thereby enhancing the inhibition of calcium-containing gangue minerals.

The present invention has the following advantages:

1. The combination regulator is made of organic phosphate and inorganic phosphate as raw materials. The raw materials are easy to obtain, the preparation process is simple, the cost is low, the environment is friendly, and it is easy to degrade. It has great practical promotion value and market potential.

2. The present invention can realize precise separation of low-grade scheelite and calcium-containing gangue minerals without affecting the recovery rate of the target minerals, realize efficient recycling of scheelite resources, have strong adaptability to different ore slurries, and have a wide range of applications.

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

Description of drawings

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

Fig. 1 is the flotation flow chart of embodiment 1 among the present invention;

Fig. 2 is the flotation flow chart of embodiment 2 in the present invention;

Fig. 3 is the flotation flow chart of embodiment 3 in the present invention.

Detailed ways

In order to facilitate a clear understanding of the technical solution of the present invention, the content of the present invention will be further described below in conjunction with some embodiments, which is obviously not required to limit the protection scope of the claims of the present invention.

Example 1

The composite inhibitor contains 50% of inorganic phosphate and 50% of organic phosphate, calculated by weight percentage. The inorganic phosphate is sodium tripolyphosphate, and the organic phosphate is sodium ethylenediamine tetramethylene phosphate. Add each component into the mixing tank according to the above weight ratio; then, add clear water into the mixing tank, the ratio of the regulator to the clear water is 1:99 in parts by weight.

The application effect of compound inhibitors in the roughing process of a low-grade scheelite with WO3 content of 0.09% was investigated. The mine is a typical scheelite-calcite-fluorite ore, that is, the gangue minerals are mainly calcite and fluorite, as well as feldspar, chlorite, amphibole, mica, and quartz. The flotation process is shown in Figure 1. According to the flow chart in Figure 1, after the raw ore is ground to a fineness of -0.074mm, accounting for 55%-78%, it is added to the flotation cell. The flotation agent and depressant are added in the roughing stage, followed by two sweeps after roughing. According to the flow chart in Figure 1, the dosages of sodium carbonate and sodium oleate were investigated first without adding chemicals, and the specific results are shown in Table 1.

Table 1 Sodium Carbonate Consumption and Sodium Oleate Consumption Test Results

It can be seen from the flotation agent dosage test that with the increase of sodium carbonate dosage, the grade of scheelite crude concentrate is on the rise, and the recovery of scheelite rises first and then declines. Considering comprehensively, the appropriate dosage of sodium carbonate is 1800g/t. With the increase of the dosage of sodium oleate, the grade of scheelite crude concentrate gradually decreases, and the recovery first increases and then tends to balance. Considering comprehensively, the suitable dosage of sodium oleate is 150g/t.

On the premise that the dosage of sodium carbonate is fixed at 1800g/t and that of sodium oleate is 150g/t, the effects of different inhibitors are investigated. The types and results of specific inhibitors are shown in Table 2.

Table 2 Effect of different inhibitors

From the results in Table 2, it can be seen that when adding a single inorganic phosphate or organic phosphate, although the grade of scheelite coarse concentrate can be improved, when sodium tripolyphosphate is used alone, the recovery rate of scheelite roughing drops greatly. The grade of rough concentrate is higher. When sodium ethylenediamine tetramethyl phosphate is used alone, the recovery rate of scheelite roughing does not change significantly, but the grade of rough concentrate is not as high as that of sodium tripolyphosphate. The composite inhibitor in Example 1 increases the crude scheelite concentrate grade from 1.75% to 2.25%, and the recovery rate of scheelite roughing also increases from 84.12% to 87.67%. At the same time, inorganic phosphate and organic phosphonate can only exert the best synergistic effect under the appropriate ratio. In the comparative test, when the proportioning ratio of sodium tripolyphosphate and sodium ethylenediaminetetramethylene phosphate was 25:75, although the combined inhibitor could also improve the crude concentrate grade and recovery rate at the same time, it was not as good as that of Example 1. compound inhibitors. When the ratio is 75:25, although the grade of the concentrate has a greater increase, the recovery rate has a certain loss. It shows that only under the proper ratio can the inhibitor components show the best compatibility.

The complex inhibitors of Example 1 were studied in different dosages, and the dosages of other medicaments remained unchanged. The results are shown in Table 3.

Table 3 dosage test results

The dosage test results prove that the grade and recovery rate of scheelite crude concentrate are improved at the same time when 50g/t of compound inhibitor of Example 1 is added compared with no inhibitor, showing a good positive synergistic effect.

Example 2

The composite inhibitor of Example 2 contains 5% of inorganic phosphate and 95% of organic phosphate by weight percentage. The inorganic phosphate is sodium hexametaphosphate, and the organic phosphate is sodium hexamethylenediamine tetramethylene phosphate. Add each component into the mixing tank according to the above weight ratio; then, add clean water into the mixing tank, and the ratio of the regulator to the clear water is 15:85 by weight.

The application effect of the composite inhibitor in Example 2 in the roughing process of ultra-low-grade scheelite with a WO3 content of 0.015% was investigated. Compared with the calcium-containing gangue in the raw ore of embodiment 1, the type and content of calcium-containing gangue minerals in embodiment 2 have changed, and each group in the combination regulator can be adjusted according to the calcium-containing gangue mineral content and type. Component content, so that the combination regulator can produce the best compatibility, produce a positive synergistic effect, and realize the precise separation of scheelite and calcium-containing gangue. According to the flow chart in Figure 2, after the raw ore is ground to a fineness of -0.074mm, accounting for 55%-78%, it is added to the flotation cell. The flotation agent and depressant are added in the roughing stage, followed by two sweeps after roughing. Also according to the flow process of Fig. 2, under the situation of not adding any medicament, the consumption of sodium carbonate and sodium oleate is investigated respectively, as a result, it can be seen that the suitable sodium carbonate consumption is 1200g/t, the compound inhibitor of embodiment 2 The dosage is 30g/t, and the optimum sodium oleate is 180g/t.

Under the premise of fixing the dosage of reagents, the flotation tests were carried out on different flotation agents, and the results are shown in Table 4.

Table 4 The results of different flotation agents

From the results of the second comparison test, it can be seen that when sodium hexametaphosphate or sodium hexamethylenediamine tetramethylene phosphate is added alone, although the grade of scheelite crude concentrate increases to a certain extent, the recovery rate decreases greatly. When using Example 2, inorganic sodium phosphate and organic sodium phosphate produced good compatibility, under the situation that scheelite recovery rate improved slightly, the grade of rough concentrate was increased from 0.307% to 0.581%, and the yield of rough concentrate was increased from 3.45% to 0.581%. % dropped to 1.84%, a drop of more than 40%, which means that the amount of rough concentrate entering the subsequent heating and beneficiation has also been reduced by more than 40%, and the corresponding variable cost of beneficiation has also dropped by 40%. Economic feasibility of ultra-low-grade scheelite recovery.

Example 3

The composite inhibitor of Example 3 contains 95% of inorganic phosphate and 5% of organic phosphate, calculated by weight percentage. The inorganic phosphate is sodium tripolyphosphate, and the organic phosphate is sodium ethylenediaminetetramethylphosphate. Add each component into the mixing tank according to the above weight ratio; then, add clean water into the mixing tank, and the ratio of the regulator to the clear water is 15:85 by weight.

The application effect of the compound inhibitor of Example 3 in the roughing process of a low-grade high wollastonite scheelite was examined. The content of WO3 in the raw ore was 0.15%, and the content of wollastonite was about 30%. According to the content and type of calcium-containing gangue minerals, the content of each component in the combination regulator is adjusted, so that the combination regulator can produce the best compatibility, produce positive synergy, and realize the precise separation of scheelite and calcium-containing gangue . According to the flow chart in Figure 3, after the raw ore is ground to a fineness of -0.074mm, accounting for 55%-78%, it is added to the flotation cell. The flotation agent and depressant are added in the roughing stage, followed by two sweeps after roughing. Also according to the flow process of Fig. 3, under the situation of not adding any medicament, the consumption of sodium carbonate and sodium oleate is investigated respectively, as a result, the preferred sodium carbonate consumption is 2100g/t, and sodium oleate consumption is 120g/t t.

The complex inhibitors of Example 3 were studied in different dosages, and the dosages of other medicaments were unchanged, and the results are shown in Table 5.

Table 5 dosage test results

The test results of the dosage of the inhibitor in Example 3 prove that at the appropriate dosage of 35g/t, when the composite inhibitor of Example 3 is added, not only the grade of scheelite rough concentrate can be improved, but also the recovery rate of scheelite can be improved , showing a good positive synergistic effect. However, when the amount is too large, compared with the appropriate amount, the recovery rate of scheelite is reduced.

Under the premise of fixing the dosage of reagents, the flotation tests were carried out on different flotation agents, and the results are shown in Table 4.

Table 6 Results of different flotation agents

It can be known from the results that when there is a single inorganic phosphorus phosphate component, the grade of scheelite crude concentrate is 2.316%, and the recovery rate is 76.53%. Although the grade of coarse concentrate has increased, the recovery rate has lost a lot. When sodium tripolyphosphate and sodium aminotrimethylphosphate are used together, since the inhibitory ability of the two components is relatively strong, exceeding the regulation threshold of the optimal condition, although the grade of coarse concentrate can reach 2.528%, the recovery rate will be lost Increase, can not take into account the rough concentrate grade and recovery rate. When sodium tripolyphosphate is used in conjunction with polyamino polyether methylene phosphate, because the inhibition ability of polyamino polyether methylene phosphate is weak, although the recovery rate can reach 82.62%, the crude concentrate grade is only 1.971%. Similarly, when sodium ethylenediaminetetramethylene phosphate is combined with other inorganic phosphates, the regulatory threshold for optimal conditions will also be exceeded. For example, when combined with sodium pyrophosphate, due to the weak inhibitory ability of sodium pyrophosphate, although the recovery rate is not greatly lost, the increase in concentrate grade is relatively low. When combined with sodium hexametaphosphate, due to the strong inhibitory ability of sodium hexametaphosphate, the recovery rate of scheelite will be greatly lost. When using the combination regulator provided by this patent, the components show good compatibility, the grade of scheelite crude concentrate is 2.535%, and the recovery rate is 85.51%.

Similarly, the compound inhibitors prepared in Example 1 and Example 2 were similarly paired with different inorganic phosphates and organic phosphates, and it was found that for the specific minerals in Example 1 and Example 2, only the The compound inhibitors specified in Example 1 and Example 2 had the best effect.

In summary, it can be seen that not all inorganic phosphates and organic phosphonates will have a positive synergistic effect. Different inorganic phosphates and organic phosphates interact differently with calcium-containing mineral surfaces of different minerals. The inhibitory ability of inorganic phosphate and organic phosphate is too strong or too weak will exceed the adjustable threshold, that is, the optimal effect cannot be achieved no matter in which ratio or used alone. According to the pairing of specific inorganic phosphate and organic phosphate selected according to different minerals in the present invention, the effect on calcium-containing minerals can be well matched. For ores with different proportions of calcium-containing minerals, by adjusting the proportion of the components, the combination regulator can exert a positive synergistic effect, resulting in a synergistic effect of 1+1>2.

The above descriptions are only preferred implementations of the present invention, and the scope of protection of the present invention is not limited to the above examples. For those skilled in the art, improvements and transformations obtained without departing from the technical concept of the present invention should also be regarded as the protection scope of the present invention.

Claims (5)

1. A composite depressant applied to the flotation field of calcium-containing gangue minerals, characterized in that, by weight, it comprises 5-95 parts of inorganic phosphate and 5-95 parts of organic phosphate; Described inorganic phosphate structure is as shown in formula 1:

Among them, X is 2-6; The structure of the organic phosphate is shown in formula 2:

Wherein, n is 2-8; The composite inhibitor includes 25-75 parts by weight of sodium tripolyphosphate and 25-75 parts of sodium ethylenediamine tetramethylene phosphate, or includes 25-75 parts of sodium hexametaphosphate and 25-75 parts of hexamethylene diphosphate Sodium Amine Tetramethylene Phosphate. 2. The application of the composite depressant as claimed in claim 1 in the flotation field of calcium-containing gangue minerals. 3. The application according to claim 2, wherein the calcium-containing gangue mineral is at least one of calcite, fluorite, apatite and wollastonite. 4. The application according to claim 3, characterized in that a flotation agent containing the composite inhibitor is added to the raw ore, and the concentrate is obtained by flotation. 5. application according to claim 3, is characterized in that, described flotation agent also comprises collector, adds described inhibitor in raw ore, then adds a small amount of collector after flotation and can obtain Coarse ore.

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