Neutral flotation spodumene collecting agent and preparation method and application thereof

Abstract

The invention belongs to the field of beneficiation reagents, and relates to a neutral flotation spodumene collecting agent and a preparation method and application thereof. The chain fatty acid soap commonly used in the spodumene flotation industry is used as a main raw material, a proper amount of the acidic combined inhibitor and the oil-soluble corrosion inhibitor which are good in compatibility are added, the mixture is compounded with the fatty acid soap to serve as a brand-new neutral composite flotation collecting agent, spodumene can be well sorted under the neutral condition, and the flotation efficiency of spodumene is improved. The flotation collecting agent has good collecting capacity of fatty acid, also exerts good selectivity of the inhibitor, meanwhile, due to flotation in a neutral environment, tail water can achieve natural sedimentation, the problem that flotation indexes and tailing water sedimentation cannot be both considered by an existing collecting agent is solved, and the flotation collecting agent has good application and popularization value.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing agents, in particular to a neutral flotation spodumene collector and a preparation method and application thereof. Background Art

[0002] As an important lithium extraction mineral resource, spodumene has long been enriched from the original ore through mineral processing methods to increase the lithium grade, and then enters the downstream smelting link to produce lithium carbonate, lithium batteries, etc.

[0003] In the spodumene ore dressing industry, flotation is the most commonly used method. Spodumene flotation has always been carried out under alkaline conditions. This is mainly because: it has been proved in practice that sodium carbonate and sodium hydroxide are important regulators in spodumene flotation. They play a role in adjusting the pH value of the ore pulp, inhibiting gangue minerals and promoting ion dissolution on the surface of minerals during the flotation process. This plays a key role in obtaining better indicators for spodumene flotation.

[0004] However, after flotation under alkaline conditions, the tailings slurry is difficult to settle naturally due to the large repulsive force because the mineral particles are all negatively charged. The usual practice is to add flocculants, sedimentation agents, etc. to help sedimentation so that the return water after sedimentation can be recycled. However, the return water with flocculants and sedimentation agents often has an impact on flotation, which deteriorates the flotation index. If sodium carbonate and sodium hydroxide are not added, spodumene is floated under neutral conditions. Although the tail water can settle naturally, the traditional collector flotation effect under neutral conditions is poor due to the lack of the inhibitory effect of sodium carbonate and the scrubbing and stirring of sodium hydroxide. It is difficult to obtain better indicators. Therefore, it is difficult for traditional spodumene flotation to take into account both good flotation indicators and the problem of natural sedimentation of tail water.

[0005] Based on the above background analysis, the present invention proposes a neutral flotation collector for spodumene. The research and development of a new neutral flotation collector is one of the methods to solve this problem. By preparing a composite collector, efficient flotation of spodumene can be achieved without adding alkaline adjusters such as sodium carbonate and sodium hydroxide, while the tailings slurry settles naturally, reducing the adverse effect of backwater on spodumene flotation. Summary of the invention

[0006] Aiming at the problem that traditional spodumene flotation is difficult to achieve both good flotation index and natural sedimentation of tail water, the present invention provides a neutral flotation spodumene collector, which can realize efficient flotation of spodumene without adding alkaline adjusting agents such as sodium carbonate and sodium hydroxide, and at the same time, the tailing slurry naturally settles, thereby reducing the adverse effect of backwater on spodumene flotation.

[0007] The object of the present invention is achieved by the following technical scheme: a neutral flotation spodumene collector, comprising the following components by weight percentage: 40-84% fatty acid soap, 6-40% acid combination inhibitor and 10%-20% oil-soluble corrosion inhibitor;

[0008] Wherein, the fatty acid soap is prepared by saponification reaction of fatty acids prepared from animal and plant fats or petrochemical sources;

[0009] The preparation method of the collector comprises: obtaining fatty acid soap by saponification reaction, stirring and mixing the fatty acid soap with the acid combination inhibitor and the oil-soluble corrosion inhibitor while the soap is hot;

[0010] The acidic combination inhibitor is prepared by mixing one or more of calcium lignin sulfonate, 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, hexadecene succinic acid and octadecene succinic acid.

[0011] Furthermore, the animal and plant oils include soybean oil, rapeseed oil, rice bran oil, rosin acid, beef and sheep oil, and tall oil; the fatty acids prepared from petrochemical sources include cyclohexane acid, synthetic fatty acids, and oxidized paraffin.

[0012] Furthermore, the saponification reaction refers to adding 5 to 20% of the mass of fatty acids in sodium hydroxide or potassium hydroxide, and adding 0.5 to 1.5 times the mass of fatty acids in water for saponification reaction, the saponification reaction temperature is 50 to 90 degrees Celsius, the saponification time is 0.5 to 2 hours, and the stirring speed is 20 to 60 rpm.

[0013] Furthermore, the neutral flotation refers to the spodumene flotation slurry having a pH value ranging from 6.0 to 8.5.

[0014] The present invention also provides an application of the neutral flotation spodumene collector for spodumene flotation.

[0015] Furthermore, the dosage of the neutral flotation spodumene collector ranges from 1.5 to 2.5 kg per ton of raw ore.

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

[0017] The main innovative features of the present invention are explained as follows:

[0018] 1. In the current conventional flotation operation of spodumene, the theoretical research and practice of many scientific researchers and mineral processing engineering and technical personnel have proved that sodium carbonate and sodium hydroxide are necessary adjusting agents for spodumene flotation. The neutral flotation collector innovatively prepared by the present invention can achieve better flotation indexes in the absence of the key adjusting effect of sodium carbonate and sodium hydroxide, and achieves the balance between better spodumene flotation indexes and natural sedimentation of tailings slurry.

[0019] Second, the collector prepared by the present invention has good fatty acid capture ability and good selectivity of inhibitor. Its key component is weakly acidic sodium polyacrylate, which has good selective inhibition effect on gangue minerals in the composite collector. At the same time, the compounded oil-soluble corrosion inhibitor is used as an auxiliary agent, so that each component in the final composite collector has good compatibility and the role of each component is maximized. Other conventional flotation collectors are often mixed with components with capture performance and selective inhibition performance, but often the capture and selective inhibition of the two components offset each other after mixing, and the performance of the final composite collector is reduced. The oil-soluble corrosion inhibitor used in the present invention is in the composite collector. First, it plays a role in mutual dissolution with the capture component and the selective inhibition component, increasing the dispersion of the two components in the slurry, and second, it plays a differential corrosion inhibition role, so that sodium polyacrylate preferentially acts on the mineral surface, enhancing the selective inhibition, so that the flotation under neutral conditions obtains a good index equivalent to that when sodium carbonate and sodium hydroxide are added.

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

[0021] The invention provides a preparation method for a neutral flotation spodumene collector, which uses commonly used fatty acid soap as the main raw material, adds an appropriate amount of an acid combination inhibitor with good compatibility and an oil-soluble corrosion inhibitor, and is compounded with the fatty acid soap to form a new neutral composite flotation collector. The selective inhibition component cleverly screened has good compatibility and solubility with the collector performance component, and the differential corrosion inhibition enables the spodumene flotation under neutral conditions to obtain better indicators comparable to those when sodium carbonate and sodium hydroxide are added.

[0022] The use of this collector to float spodumene ore under neutral conditions has good technical and environmental advantages and can be widely used in the field of spodumene ore flotation at home and abroad. DETAILED DESCRIPTION

[0023] The technical solution of the present invention is further described in detail below, but the protection scope of the present invention is not limited to the following.

[0024] Example 1

[0025] A preparation method for a neutral flotation spodumene collector comprises the following steps:

[0026] Fatty acid saponification: weigh 10 parts of soybean oil fatty acid, 5 parts of rosin acid, 15 parts of tall oil fatty acid, and 5 parts of cyclohexane acid, mix well and heat to 60 degrees Celsius, weigh 4 parts of sodium hydroxide and dissolve it in 31 parts of water, add the dissolved sodium hydroxide solution to the fatty acid, maintain the temperature at 60 degrees Celsius and stir the reaction for 1.5 hours at a stirring speed of 40 rpm.

[0027] Compound collector: Take 70 parts of fatty acid soap after saponification reaction, add 10 parts of sodium polyacrylate, 5 parts of calcium lignin sulfonate, and 5 parts of guar gum, stir and mix evenly, then add 10 parts of oil-soluble corrosion inhibitor hexadecene succinic acid, stir evenly to obtain a compounded neutral composite collector with good fluidity.

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

[0029] The test ore was a pegmatite spodumene mine in western Sichuan. The ore was crushed-grinded (fineness was -0.074 mm and content was 65%)-flotation (one-stage roughing) and compared with the flotation under two conditions: sodium carbonate and sodium hydroxide were added to the slurry to pH 10.8 and the pH of the slurry was 7.6 without adding sodium carbonate and sodium hydroxide. The comparative test results are shown in Table 1 below:

[0030] Table 1 Collector comparison test results

[0031]

[0032]

[0033] As shown in Table 1, the neutral composite collector prepared in Example 1 of the present invention achieves good flotation indexes comparable to those of the conventional oxidized paraffin soap collector at pH 10.8 without adding sodium carbonate and sodium hydroxide and at a pulp pH of 7.6. However, the flotation index of the conventional oxidized paraffin soap collector is significantly deteriorated at a pH of 7.6. This indicates that the prepared neutral composite collector has a good implementation effect.

[0034] At the same time, the tailings slurry after flotation with the neutral composite collector prepared in Example 1 under pH 7.6 achieved natural sedimentation without adding any flocculants. Compared with the tailings slurry after flotation under alkaline conditions of pH 10.8 with the addition of flocculants, the neutral flotation minimized the impact of the return water from the tailings water treatment on the flotation.

[0035] Example 2

[0036] A preparation method for a neutral flotation spodumene collector comprises the following steps:

[0037] Fatty acid saponification: weigh 8 parts of rice bran oil fatty acid, 6 parts of tallow fatty acid, 10 parts of tall oil fatty acid, 3 parts of cyclohexane acid, and 8 parts of oxidized paraffin, mix well and heat to 75 degrees Celsius, weigh 4 parts of sodium hydroxide and dissolve it in 31 parts of water, add the dissolved sodium hydroxide solution to the fatty acid, maintain the temperature at 75°C and stir the reaction for 2 hours at a stirring speed of 30 rpm.

[0038] Compound collector: Take 70 parts of saponified fatty acid soap, add 8 parts of sodium polyacrylate, 6 parts of humic acid, and 3 parts of guar gum, stir and mix evenly, then add 13 parts of oil-soluble corrosion inhibitor hexadecene succinic acid, stir evenly to obtain a compounded neutral composite collector with good fluidity.

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

[0040] The test ore was a spodumene mine in southern Xinjiang. The ore was crushed-grinded (fineness was -0.074 mm and content was 62%)-flotation (a rough selection). The flotation was compared under two conditions: sodium carbonate and sodium hydroxide were added to the slurry to pH 11.0 and the pH of the slurry was 7.3 without adding sodium carbonate and sodium hydroxide. The comparative test results are shown in Table 2 below:

[0041] Table 2 Collector comparison test results

[0042]

[0043]

[0044] As shown in Table 2, the neutral composite collector prepared in Example 2 of the present invention achieves good flotation indexes comparable to those of the conventional oxidized paraffin soap collector at pH 11.0 without adding sodium carbonate and sodium hydroxide and at a pulp pH of 7.3. However, the flotation index of the conventional oxidized paraffin soap collector is significantly deteriorated at a pH of 7.3. This indicates that the prepared neutral composite collector has a good implementation effect.

[0045] Similarly, the tailings slurry after flotation with the neutral composite collector prepared in Example 2 at a pH of 7.3 achieved natural sedimentation without adding any flocculants. Compared with the tailings slurry after flotation under alkaline conditions of pH 11.0 with the addition of flocculants, the neutral flotation minimized the impact of the return water from the tailings water treatment on the flotation.

[0046] Example 3

[0047] A preparation method for a neutral flotation spodumene collector comprises the following steps:

[0048] Fatty acid saponification: weigh 8 parts of rapeseed oil fatty acid, 6 parts of soybean oil fatty acid, 8 parts of synthetic fatty acid, and 8 parts of cyclohexane acid, mix well and heat to 50 degrees Celsius, weigh 4 parts of sodium hydroxide and dissolve it in 26 parts of water, add the dissolved sodium hydroxide solution to the fatty acid, maintain the temperature at 50 degrees Celsius and stir the reaction for 1 hour at a stirring speed of 50 rpm.

[0049] Compound collector: Take 60 parts of saponified fatty acid soap, add 15 parts of sodium polyacrylate, 6 parts of humic acid, 4 parts of calcium lignin sulfonate, stir and mix evenly, then add 15 parts of oil-soluble corrosion inhibitor hexadecene succinic acid, stir evenly to obtain the compounded neutral composite collector.

[0050] The prepared neutral composite collector was used for the flotation of spodumene ore. The neutral composite collector prepared in Example 3 was used at a dosage of 1.8 kg / ton of raw ore, and the same dosage of traditional oxidized paraffin soap was used for the flotation of spodumene ore for comparison.

[0051] The test ore was a spodumene mine in the Pilbara region of Western Australia, Australia. The ore was crushed-grinded (fineness of -0.074 mm, content of 56%)-flotation (a roughing process). The flotation was compared under two conditions: sodium carbonate and sodium hydroxide were added to the slurry to pH 11.3 and the pH of the slurry was 7.9 without adding sodium carbonate and sodium hydroxide. The comparative test results are shown in Table 3 below:

[0052] Table 3 Collector comparison test results

[0053]

[0054]

[0055] As shown in Table 3, the neutral composite collector prepared in Example 3 of the present invention achieves good flotation indexes comparable to those of the conventional oxidized paraffin soap collector at pH 11.3 without adding sodium carbonate and sodium hydroxide and at a pulp pH of 7.9. However, the flotation index of the conventional oxidized paraffin soap collector is significantly deteriorated at a pH of 7.9, indicating that the prepared neutral composite collector has a good implementation effect.

[0056] Similarly, the tailings slurry after flotation with the neutral composite collector prepared in Example 3 at a pH of 7.9 achieved natural sedimentation without adding any flocculants. Compared with the tailings slurry after flotation under alkaline conditions of pH 11.3 with the addition of flocculants, the neutral flotation minimized the impact of the return water from the tailings water treatment on the flotation.

[0057] The above is only a preferred embodiment of the present invention. It should be understood that the present invention is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the concept described herein through the above teachings or the technology or knowledge of the relevant field. The changes and modifications made by those skilled in the art shall not deviate from the spirit and scope of the present invention, and shall be within the scope of protection of the claims attached to the present invention.

Claims

1. A neutral flotation spodumene collector, characterized in that: The composition comprises the following components by weight percentage: 40-84% fatty acid soap, 6-40% acid combination inhibitor and 10-20% oil-soluble corrosion inhibitor; Wherein, the fatty acid soap is prepared by saponification reaction of fatty acids prepared from animal and plant fats or petrochemical sources; The preparation method of the collector comprises: obtaining fatty acid soap by saponification reaction, stirring and mixing the fatty acid soap with the acid combination inhibitor and the oil-soluble corrosion inhibitor while the soap is hot; The acidic combination inhibitor is prepared by mixing one or more of calcium lignin sulfonate, 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, hexadecene succinic acid and octadecene succinic acid.

2. A neutral flotation spodumene collector according to claim 1, characterized in that, The animal and plant oils include soybean oil, rapeseed oil, rice bran oil, rosin acid, beef and sheep oil, and tall oil; the fatty acids prepared from petrochemical sources include cyclohexane acid, synthetic fatty acids, and oxidized paraffin.

3. A neutral flotation spodumene collector according to claim 1, characterized in that, The saponification reaction refers to adding 5-20% of the mass of fatty acids in sodium hydroxide or potassium hydroxide, and adding 0.5-1.5 times the mass of fatty acids in water for 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. A neutral flotation spodumene collector according to claim 1, characterized in that: The neutral flotation refers to the spodumene flotation slurry pH value range of 6.0 to 8.

5.

5. Use of the neutral flotation spodumene collector according to any one of claims 1 to 4 for spodumene flotation.

6. The use according to claim 5, characterized in that: The dosage of the neutral flotation spodumene collector ranges from 1.5 to 2.5 kg per ton of raw ore.

7. The use according to claim 5, characterized in that: The tailings slurry obtained by the spodumene flotation is recycled after natural sedimentation.

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