A neutral flotation spodumene collector and a preparation method and application thereof

Abstract

The present application belongs to the field of beneficiation reagent, and relates to a neutral flotation spodumene collecting agent and a preparation method and application thereof. The present application takes a chain aliphatic acid soap commonly used in the spodumene flotation industry as a main raw material, adds a proper amount of an acid combined inhibitor with good compatibility and an oil-soluble corrosion inhibitor, and after compounding with the aliphatic acid soap, the present application is used as a brand-new neutral composite flotation collecting agent, can realize good separation of spodumene under neutral conditions, has good collecting capacity of the aliphatic acid, and also has good selectivity of the inhibitor. Meanwhile, due to the flotation in the neutral environment, the tail water can realize natural settlement, solves the problem that the previous collecting agent cannot consider the flotation index and tailing water settlement, and has good popularization and application value.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ore-dressing reagent, in particular to a neutral flotation spodumene collecting agent and a preparation method and application thereof. BACKGROUND

[0002] Spodumene is an important lithium ore resource, which has been enriched by ore-dressing method for a long time to improve the lithium grade, and then enters the downstream smelting process to produce lithium carbonate and lithium battery.

[0003] In the spodumene ore dressing industry, the most commonly used method is flotation. Spodumene flotation has been carried out under alkaline conditions for a long time. This is mainly because sodium carbonate and sodium hydroxide are important modifiers in spodumene flotation, which play a key role in adjusting the pH value of the slurry, inhibiting gangue minerals and promoting the dissolution of mineral surface ions during the flotation process, which is crucial for obtaining good indicators of spodumene flotation.

[0004] However, the tailings slurry after flotation under alkaline conditions is difficult to settle naturally due to the negative charge of the mineral particles, and the addition of flocculants and settling agents is usually required to help the settlement of the tailings slurry, so that the recycled water after settlement can be used. However, the addition of flocculants and settling agents to the recycled water has an impact on the flotation, which deteriorates the flotation indicators. If sodium carbonate and sodium hydroxide are not added, and spodumene is floated under neutral conditions, although the tailings can be settled naturally, the lack of the inhibitory effect of sodium carbonate and the scrubbing and stirring effect of sodium hydroxide makes it difficult to obtain good indicators of traditional collectors under neutral conditions. Therefore, traditional spodumene flotation cannot meet the requirements of good flotation indicators and natural tailings settlement.

[0005] Based on the above background analysis, the present application provides a neutral flotation spodumene collecting agent, which is one of the methods to solve this problem by developing a new type of neutral flotation collector. By preparing a composite collector, high-efficiency flotation of spodumene can be achieved without adding alkaline modifiers such as sodium carbonate and sodium hydroxide, and the tailings slurry can be settled naturally, reducing the adverse effects of recycled water on spodumene flotation. SUMMARY

[0006] The present application provides a neutral flotation spodumene collecting agent, which can achieve high-efficiency flotation of spodumene without adding alkaline modifiers such as sodium carbonate and sodium hydroxide, and the tailings slurry can be settled naturally, reducing the adverse effects of recycled water on spodumene flotation.

[0007] The application aims at realizing the object by the following technical scheme: a neutral flotation spodumene collector, including the following components in percentage by weight: 40-84% of fatty acid soap, 6-40% of acid combined depressor and 10-20% of oil-soluble corrosion inhibitor;

[0008] The fatty acid soap is prepared by saponification reaction of animal and vegetable fats and oils or petroleum chemical source fatty acid;

[0009] The preparation method of the collector is that the fatty acid soap obtained by saponification reaction is mixed with the acid combined depressor and the oil-soluble corrosion inhibitor while hot and stirred uniformly;

[0010] The acid combined depressor is mixed with polyacrylic acid sodium according to the mass ratio of 1-2:1, and the oil-soluble corrosion inhibitor includes one or more of nonyl phenoxy acetic acid, hexadecenyl succinic acid and octadecenyl succinic acid.

[0011] Further, the animal and vegetable fats and oils include soybean oil, rapeseed oil, rice bran oil, rosin acid, cow and sheep oil and tall oil; the petroleum chemical source fatty acid includes naphthenic acid, synthetic fatty acid and oxidized paraffin wax.

[0012] Further, the saponification reaction refers to adding 5-20% of sodium hydroxide or potassium hydroxide of the mass of the fatty acid and 0.5-1.5 times of water of the mass of the fatty acid for saponification reaction, the saponification reaction temperature is 50-90 degrees Celsius, the saponification reaction time is 0.5-2 hours and the stirring speed is 20-60 revolutions per minute.

[0013] Further, the neutral flotation refers to the pH value range of the spodumene flotation slurry being 6.0-8.5.

[0014] The application further provides an application of the above-mentioned neutral flotation spodumene collector to spodumene flotation.

[0015] Further, the dosage of the neutral flotation spodumene collector ranges from 1.5 to 2.5 kg / t of raw ore.

[0016] Further, the tailing slurry obtained by the spodumene flotation is recycled after natural sedimentation.

[0017] The main innovation of the application is explained as follows:

[0018] I. In the current conventional flotation of spodumene, the theoretical research and practice of numerous scientific researchers and mineral processing engineering technicians have proved that sodium carbonate and sodium hydroxide are essential modifiers for spodumene flotation. The neutral flotation collector prepared by the present application can still obtain good flotation indicators under the condition of lacking the key adjustment of sodium carbonate and sodium hydroxide, and can realize good indicators of spodumene flotation and natural sedimentation of tailings.

[0019] II. The prepared collector has good collecting ability of fatty acid and good selectivity of inhibitor. The key component is sodium polyacrylate with weak acidity, which has good selective inhibition effect on gangue minerals in the composite collector. The oil-soluble corrosion inhibitor as an auxiliary agent makes the components in the final composite collector have good compatibility, and the functions of the components are maximized. In the preparation of other conventional flotation collectors, components with collecting performance and selective inhibition performance are often mixed, but the collecting performance and selective inhibition performance of the two components are often offset after mixing, and the performance of the final composite collector is reduced. The oil-soluble corrosion inhibitor used in the present application can be miscible with the collecting component and the selective inhibition component in the composite collector, which increases the dispersion of the two components in the ore slurry, and has differential corrosion effect, so that the sodium polyacrylate preferentially reacts with the mineral surface, and the selective inhibition is enhanced, so that the flotation under neutral conditions can obtain good indicators comparable to the addition of sodium carbonate and sodium hydroxide.

[0020] The beneficial effects of the present application are:

[0021] The neutral flotation spodumene collector preparation provided by the present application uses commonly used fatty acid soap as the main raw material, adds an appropriate amount of acid combination inhibitor with good compatibility and oil-soluble corrosion inhibitor, and is compounded with fatty acid soap to become a new neutral composite flotation collector. The selectively inhibited components and the collecting agent performance components have good compatibility and good solubility, and the differential corrosion effect makes the spodumene flotation under neutral conditions obtain good indicators comparable to the addition of sodium carbonate and sodium hydroxide.

[0022] The collector has good technical advantages and environmental protection advantages for spodumene flotation under neutral conditions, and can be widely used in the field of spodumene flotation at home and abroad. DETAILED DESCRIPTION

[0023] The technical solutions of the present application will be described in detail below, but the protection scope of the present application is not limited to the following description.

[0024] Example 1

[0025] A kind of preparation of neutral flotation spodumene collector, comprising the following steps:

[0026] Fatty acid saponification: soybean oil fatty acid 10 parts, rosin acid 5 parts, tall oil fatty acid 15 parts, naphthenic acid 5 parts, mixed and heated to 60 degrees Celsius, sodium hydroxide 4 parts was dissolved in 31 parts of water, the dissolved sodium hydroxide solution was added to the fatty acid, the temperature was kept at 60℃, and the stirring reaction was carried out for 1.5 hours, the stirring speed was 40 revolutions per minute.

[0027] Compound collector: 70 parts of saponified fatty acid after saponification reaction, 10 parts of sodium polyacrylate, 5 parts of calcium lignosulfonate, and 5 parts of guar gum were added, stirred and mixed uniformly, then 10 parts of oil-soluble corrosion inhibitor hexadecenyl succinic acid was added, and stirred uniformly to obtain a well-compounded neutral composite collector with good fluidity.

[0028] The compounded neutral composite collector was used for spodumene flotation. The neutral composite collector prepared in Example 1 was used in an amount of 2.0 kg / t of raw ore, and a traditional spodumene collector, oxidized paraffin wax soap, was used in the same amount for comparison.

[0029] The test raw ore was a pegmatite type spodumene ore in western Sichuan, China. The raw ore was crushed, ground (fineness of-0.074 mm content 65%), and floated (one-stage roughing) to compare the flotation results under the conditions of adjusting the pulp to pH 10.8 with sodium carbonate and sodium hydroxide, and not adding sodium carbonate and sodium hydroxide with the pulp pH 7.6. The results are shown in Table 1 below:

[0030] Table 1: Results of collector comparison test examples

[0031]

[0032]

[0033] As shown in Table 1, the neutral composite collector prepared in Example 1 achieved better flotation indicators comparable to the traditional oxidized paraffin wax soap collector at pH 10.8 without adding sodium carbonate and sodium hydroxide, and the pulp pH was 7.6. The traditional oxidized paraffin wax soap collector significantly deteriorated at pH 7.6. This indicates that the prepared neutral composite collector has good implementation effect.

[0034] At the same time, the tailings pulp after flotation of the neutral composite collector prepared in Example 1 at pH 7.6 achieved natural sedimentation without adding any flocculating agent, compared to the tailings pulp after flotation at pH 10.8 under alkaline conditions, which required the addition of a flocculating agent for sedimentation. The neutral flotation maximally reduced the influence of the return water from tailings water treatment on flotation.

[0035] Example 2

[0036] A method for preparing a neutral spodumene flotation collector, comprising the following steps:

[0037] Fatty acid saponification: take 8 parts of rice bran oil fatty acid, 6 parts of beef fatty acid, 10 parts of tall oil fatty acid, 3 parts of naphthenic acid, 8 parts of oxidized paraffin, mix them evenly and heat to 75 degrees Celsius, take 4 parts of sodium hydroxide dissolved in 31 parts of water, add the dissolved sodium hydroxide solution to the fatty acid, keep the temperature at 75℃ and stir for 2 hours at a stirring speed of 30 revolutions per minute.

[0038] Compound collector: take 70 parts of saponified fatty acid soap, add 8 parts of sodium polyacrylate, 6 parts of humic acid, 3 parts of guar gum, mix them evenly after stirring, then add 13 parts of oil-soluble corrosion inhibitor hexadecenyl succinic acid, and stir evenly to obtain the compound neutral collector with good fluidity.

[0039] The prepared neutral composite collector is used for spodumene flotation. The neutral composite collector prepared in Example 2 is used in an amount of 2.3 kg / t of raw ore, and the same amount of traditional spodumene collector oxidized paraffin soap is used for comparison.

[0040] The test raw ore is a certain spodumene ore in southern Xinjiang, which is crushed, ground (fineness of-0.074 mm content of 62%) and floated (one-stage roughing) to compare the flotation under the conditions of adjusting the pulp to pH 11.0 by sodium carbonate and sodium hydroxide and not adding sodium carbonate and sodium hydroxide with pulp pH 7.3. The comparison test results are shown in Table 2 as follows:

[0041] Table 2 Comparison test results of collectors

[0042]

[0043]

[0044] As shown in Table 2, the neutral composite collector prepared in Example 2 achieves better flotation indexes comparable to the traditional oxidized paraffin soap collector at pH 11.0 without adding sodium carbonate and sodium hydroxide with pulp pH 7.3. The traditional oxidized paraffin soap collector significantly deteriorates at pH 7.3. It shows that the prepared neutral composite collector has good implementation effect.

[0045] Similarly, the tailings slurry after flotation of the neutral composite collector prepared in Example 2 at pH 7.3 realizes natural sedimentation without adding any flocculating agent, which is compared with the tailings slurry after flotation at pH 11.0 under alkaline conditions, and the neutral flotation reduces the influence of the return water of tailings water treatment on flotation to the greatest extent.

[0046] Example 3

[0047] Preparation of a neutral flotation spodumene collector, comprising the following steps:

[0048] Fatty acid saponification: take 8 parts of rapeseed oil fatty acid, 6 parts of soybean oil fatty acid, 8 parts of synthetic fatty acid, and 8 parts of naphthenic acid, mix them evenly and heat to 50 degrees Celsius, take 4 parts of sodium hydroxide dissolved in 26 parts of water, add the dissolved sodium hydroxide solution to the fatty acid, keep the temperature at 50 degrees Celsius and stir for 1 hour at a stirring speed of 50 revolutions per minute.

[0049] Compound collector: take 60 parts of saponified fatty acid soap, add 15 parts of sodium polyacrylate, 6 parts of humic acid, and 4 parts of calcium lignosulfonate, mix them evenly, then add 15 parts of oil-soluble corrosion inhibitor hexadecenyl succinic acid, mix evenly to obtain the compound neutral collector.

[0050] The compound neutral collector is used for spodumene ore flotation. Take the neutral compound collector prepared in Example 3, the dosage is 1.8 kg / t of raw ore, and the same amount of traditional oxidized paraffin wax soap is used for comparison.

[0051] The test raw ore is a certain spodumene ore in the Pilbara region of Western Australia, Australia. The raw ore is crushed and ground (fineness of-0.074 mm content of 56%) and then subjected to a flotation process (one-stage roughing). The comparison test results under the conditions of adjusting the pulp to pH 11.3 with sodium carbonate and sodium hydroxide and not adding sodium carbonate and sodium hydroxide with pulp pH 7.9 are shown in Table 3.

[0052] Table 3 Comparison test results of collectors

[0053]

[0054]

[0055] As shown in Table 3, the neutral compound collector prepared in Example 3 achieves better flotation indexes comparable to the traditional oxidized paraffin wax collector at pH 11.3 without adding sodium carbonate and sodium hydroxide and with pulp pH 7.9. The traditional oxidized paraffin wax collector significantly deteriorates at pH 7.9. This shows that the prepared neutral compound collector has good implementation effect.

[0056] Similarly, the tailings pulp after flotation of the neutral compound collector prepared in Example 3 at pH 7.9 is naturally settled without adding any flocculating agent, which is better than the tailings pulp after flotation at pH 11.3 under alkaline conditions, and the neutral flotation reduces the influence of the return water of tailings water treatment on flotation to the greatest extent.

[0057] The foregoing is considered as illustrative only of the principles of the application. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the application to the exact construction and operation described. Accordingly, all such variations are intended to be included within the scope of the present application as defined in the claims below and their equivalents.

Claims

1. A neutral flotation collector for spodumene, characterized in that, It comprises the following components by weight percentage: 40-84% fatty acid soap, 6-40% acidic combination inhibitor and 10-20% oil-soluble corrosion inhibitor; The fatty acid soap is prepared by saponification of fatty acids derived from animal or vegetable oils or petrochemical sources. The method for preparing the collector is as follows: a fatty acid soap is obtained by saponification reaction, and then mixed evenly with an acidic combination inhibitor and an oil-soluble corrosion inhibitor while hot. The acidic combination inhibitor is prepared by mixing one or more of calcium lignosulfonate, humic acid and guar gum with sodium polyacrylate in a mass ratio of 1 to 2:1; the oil-soluble corrosion inhibitor includes one or more of nonylphenoxyacetic acid, hexadecenylsuccinic acid and octadecenylsuccinic acid.

2. The neutral flotation collector for spodumene according to claim 1, characterized in that, The animal and vegetable oils include soybean oil, rapeseed oil, rice bran oil, rosin acid, beef and mutton tallow, and tallow; the fatty acids prepared from petrochemical sources include naphthenic acids, synthetic fatty acids, and oxidized paraffin.

3. The neutral flotation collector for spodumene according to claim 1, characterized in that, The saponification reaction refers to adding 5-20% sodium hydroxide or potassium hydroxide by mass of fatty acids and 0.5-1.5 times the mass of water by mass of fatty acids to carry out the saponification reaction. The saponification reaction temperature is 50-90 degrees Celsius, the saponification time is 0.5-2 hours, and the stirring speed is 20-60 rpm.

4. The neutral flotation collector for spodumene according to claim 1, characterized in that, Neutral flotation refers to flotation pulp with a pH range of 6.0 to 8.

5.

5. The application of the neutral flotation collector for spodumene as described in any one of claims 1-4 in the flotation of spodumene.

6. The application according to claim 5, characterized in that, The dosage range of the neutral flotation spodumene collector is 1.5–2.5 kg / ton of raw ore.

7. The application according to claim 5, characterized in that, The tailings slurry obtained from spodumene flotation is recycled after natural settling.

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