Strong weathered spodumene ore all-mud flotation collecting agent and preparation method and application thereof

Abstract

The invention belongs to the technical field of beneficiation engineering, and relates to a strong weathered spodumene ore all-mud flotation collecting agent and a preparation method and application thereof. The collecting agent comprises vegetable oil fatty acid, sodium percarbonate, lithium chloride, a nonionic surfactant and the like. The preparation method comprises the following steps: adding the sodium percarbonate and the lithium chloride into the vegetable oil fatty acid, and adding the nonionic surfactant into a product obtained after low-temperature reaction for compounding. According to the all-mud flotation collecting agent for the strongly weathered spodumene ore, through reaction targeted combination of characteristic functional groups, the collecting agent with good selective collecting capacity for the strongly weathered ore is synthesized, the influence of weathered ore mud on spodumene flotation can be remarkably reduced, and all-mud flotation of the strongly weathered spodumene is effectively achieved.

Description

Technical Field

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

[0002] Lithium is an important strategic resource and enjoys the reputation of "industrial MSG". Its products are currently widely used in many fields such as lithium batteries, aerospace, medical care, ceramics, etc. It is also a key resource for the development of strategic emerging industries.

[0003] Extracting lithium from spodumene ore is an important way to obtain lithium at home and abroad. At present, the main method for enriching and extracting lithium from spodumene ore is flotation. The performance of the collector in the flotation process is directly related to the quality of flotation grade and recovery rate. It is of great significance to improve the output and quality of lithium concentrate through efficient collectors, ensure the safety of raw material supply in the downstream lithium battery industry, and ensure the rapid and healthy development of the new energy industry.

[0004] During the mining process of spodumene, the strong weathering caused by the weathered surface ore and the development of groundwater fissures brings a large amount of weathered ore mud into the flotation operation, which is a major problem faced by spodumene flotation. Traditional spodumene flotation generally uses fatty acid collectors as the main agent. Since this type of collector is not resistant to mudification, it is usually necessary to add desludging operations before flotation operations. This brings benefits to the subsequent floating lithium, but it is bound to lead to some loss of lithium in the ore mud. If flotation without desludging is adopted, the strongly weathered ore will easily lead to production problems such as reduced selectivity of fatty acid collectors during flotation, significantly increased dosage of reagents, high viscosity of flotation foam, deterioration of flotation indicators, and difficulty in dehydrating concentrate tailings, resulting in reduced quality, recovery rate and production economic benefits of lithium concentrate, which is not conducive to the efficient development and utilization of lithium resources.

[0005] Therefore, based on the above-mentioned difficulties, the present invention provides a full-mud flotation collector for strongly weathered spodumene ore, and a preparation method and application thereof. By introducing peroxide carboxylic acid groups and α-hydroxyl groups, and the synergistic effect of the remaining carbonate ions in the reaction, and compounding an appropriate amount of non-ionic surfactant, the mud resistance of the prepared collector is significantly improved, and the full-mud flotation of strongly weathered spodumene ore without desludging can be performed. While simplifying the separation process, the efficient development and utilization recovery rate of this type of lithium resources is significantly improved, and the collector has great value for promotion and application. Summary of the invention

[0006] The present invention aims at the problem that the conventional non-de-sliming flotation index is poor in the flotation of strongly weathered spodumene ore, and the loss of lithium in the ore mud is increased during the de-sliming flotation. A full-slime flotation collector for strongly weathered spodumene ore is provided. By optimizing, adjusting and compounding the functional groups of the collector, the full-slime (non-de-sliming) flotation of such strongly weathered spodumene ore can be achieved.

[0007] The object of the present invention is achieved through the following technical scheme: a strongly weathered spodumene ore full mud flotation collector, the preparation method of the strongly weathered spodumene ore full mud flotation collector comprises the following steps: adding lithium chloride to vegetable oil fatty acid at a temperature of 0 to 10°C, adding sodium percarbonate after mixing evenly, and then adding water to react for 5 to 8 hours;

[0008] Wherein, the mass ratio of the vegetable oil fatty acid, lithium chloride, sodium percarbonate and water is 1000:10-50:150-350:1000-3000.

[0009] Furthermore, the vegetable oil fatty acid includes one or more of soybean oil fatty acid, palm oil fatty acid, castor oil fatty acid, and cottonseed oil fatty acid, and the iodine value of the vegetable oil fatty acid is ≥130g / 100g. The iodine value is determined according to the method of national standard GB / T5532-2008.

[0010] Furthermore, the highly weathered spodumene ore whole mud flotation collector is used in combination with a non-ionic surfactant, and the mass dosage of the non-ionic surfactant is 1 to 20 g / 1000 g of the mass dosage of the vegetable oil fatty acid.

[0011] Furthermore, the types of nonionic surfactants include one or more of polyoxyethylene type, polyol type, alkanolamide type, polyether type, and amine oxide type nonionic surfactants.

[0012] Furthermore, continuous stirring is required during the preparation of the highly weathered spodumene ore whole mud flotation collector.

[0013] Furthermore, the lithium chloride is industrial pure lithium chloride hexahydrate or a lithium chloride product of a higher purity.

[0014] Furthermore, the sodium percarbonate is a common sodium percarbonate product with CAS registration number 15630-89-4.

[0015] Furthermore, the water is ordinary municipal tap water.

[0016] The present invention also provides an application of the above-mentioned strongly weathered spodumene ore full mud flotation collector in the strongly weathered spodumene ore full mud flotation beneficiation.

[0017] Furthermore, the dosage range of the highly weathered spodumene ore full mud flotation collector for highly weathered spodumene ore full mud flotation beneficiation is: 1.5kg / t original ore to 3.0kg / t original ore.

[0018] Furthermore, when the highly weathered spodumene ore is subjected to full mud flotation beneficiation, the raw spodumene ore pulp is directly subjected to flotation and lithium separation without desludging, which is the meaning of full mud flotation in the present invention.

[0019] The main innovative features of the present invention are explained as follows:

[0020] First, a strong oxidant, sodium percarbonate, is used as one of the raw materials for synthesizing the collector, and peroxycarboxylic acid groups are synthesized by deep oxidation under low temperature conditions. The percarboxylic acid groups generated by the reaction can form a more stable five-membered ring with the metal active sites on the mineral surface, thereby enhancing the capture ability of the collector.

[0021]

[0022] In the formula, R is a straight chain or branched hydrocarbon group with a carbon chain length of 8 to 22 carbon atoms. M is a metal active particle on the surface of the mineral.

[0023] Second, since the peroxycarboxylic acid group is unstable, the present invention adopts the addition of lithium chloride as a stabilizer, and reacts at a low temperature of 0 to 10° C., thereby inhibiting the decomposition of the peroxide group and increasing the stability of the product, solving the problem of poor stability of traditional peroxycarboxylic acids, thereby obtaining a relatively stable peroxycarboxylic acid product, and providing an effective way for the preparation of the collector.

[0024] 3. The present invention effectively utilizes the sodium carbonate produced by the oxidation reaction of sodium percarbonate, and the carbonate ions and the collector act synergistically to improve the selectivity and anti-sludge performance of the collector.

[0025] The beneficial effects of the present invention are as follows: the present invention adopts a novel synthesis method to prepare a stable collector containing peroxycarboxylic acid, carbonate ions and non-ionic surfactants, which enhances the collector's collection capacity and selectivity while significantly improving the collector's resistance to mudification. The collector can be used to realize direct full mud flotation of strongly weathered spodumene ore without desludging, provides a new way for efficient recycling of such lithium resources, and can be widely used in the flotation industry of strongly weathered spodumene ore. DETAILED DESCRIPTION

[0026] 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.

[0027] Example 1

[0028] A preparation method of a fully-sludge flotation collector for strongly weathered spodumene ore comprises the following steps:

[0029] 100 parts of soybean oil fatty acid with an iodine value of 145g / 100g are cooled to 3°C, 4 parts of lithium chloride are added while stirring, and after stirring and mixing evenly, 25 parts of sodium percarbonate powder are added under the stirring condition, and then 171 parts of clean water are added and stirred for 6 hours, and the temperature is kept at 0-10°C throughout the process. After the reaction is completed, 1 part of pentaerythritol nonionic surfactant is added to prepare the collector.

[0030] The collector prepared in Example 1 was used in the flotation of a strongly weathered spodumene ore. A surface weathered spodumene ore in Ganzi, Sichuan was used to compare the implementation of the traditional oxidized paraffin soap collector in the ore. The results are as follows:

[0031] The surface weathering type spodumene ore was crushed-grinded (fineness of -0.074mm content 92%)-direct full mud flotation (first stage roughing) process flow, and the comparative flotation was slurried with sodium carbonate and sodium hydroxide to a pH of 10.7, and the collector prepared in Example 1 or the traditional oxidized paraffin soap collector was added respectively, and the addition amount was the same, both 2kg / t (relative to the original ore), and the comparative test results are shown in Table 1 below:

[0032] Table 1 Results of comparative test of two collectors

[0033]

[0034] Example 2

[0035] A preparation method of a fully-sludge flotation collector for strongly weathered spodumene ore comprises the following steps:

[0036] 100 parts of linseed oil fatty acid with an iodine value of 155g / 100g are cooled to 6°C, 5 parts of lithium chloride are added while stirring, and after stirring and mixing evenly, 35 parts of sodium percarbonate powder are added under the stirring condition, and then 250 parts of clean water are added and stirred for reaction for 7 hours, and the temperature is kept at 0-10°C throughout the process. After the reaction is completed, 1.5 parts of lauroyl diethanolamine nonionic surfactant are added to prepare the collector.

[0037] The collector prepared in Example 2 is used in the flotation of a strongly weathered spodumene ore. A middling ore in a heavy medium lithium separation process in Australia is taken. Due to long-term weathering and the accumulation of sludge in the middling ore during the heavy medium lithium separation process, the ore has a serious mud content. This example also compares the flotation results of the traditional oxidized paraffin soap collector in the ore.

[0038] The ore was subjected to the process of grinding (fineness of -0.074mm and content of 98%) - direct whole mud flotation (first stage roughing), and the comparative flotation was slurried with sodium carbonate and sodium hydroxide to a pH of 11.1, and the collector prepared in Example 2 or the traditional oxidized paraffin soap collector was added respectively, with the same addition amount, which was 2.3kg / t (relative to the original ore). The comparative test results are shown in Table 2 below:

[0039] Table 1 Results of comparative test of two collectors

[0040]

[0041] The collector prepared by the preparation method of the present invention obtained significantly better flotation concentrate Li2O grade and recovery rate in both examples. In contrast, the flotation index of the traditional oxidized paraffin soap collector was significantly poor. Therefore, the collector has good applicability for the full mud flotation of strongly weathered spodumene ore and has good implementation effect.

[0042] 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 strongly weathered spodumene ore full mud flotation collector, characterized in that: The preparation method of the whole mud flotation collector of strongly weathered spodumene ore comprises the following steps: adding lithium chloride to vegetable oil fatty acid at a temperature of 0 to 10° C., adding sodium percarbonate after mixing evenly, and then adding water to react for 5 to 8 hours; Wherein, the mass ratio of the vegetable oil fatty acid, lithium chloride, sodium percarbonate and water is 1000:10-50:150-350:1000-3000.

2. A strongly weathered spodumene ore full mud flotation collector according to claim 1, characterized in that: The vegetable oil fatty acid includes one or more of soybean oil fatty acid, palm oil fatty acid, castor oil fatty acid, and cottonseed oil fatty acid, and the iodine value of the vegetable oil fatty acid is ≥130g / 100g.

3. A strongly weathered spodumene ore full mud flotation collector according to claim 1 or 2, characterized in that: The highly weathered spodumene ore whole mud flotation collector is used in combination with a nonionic surfactant, and the mass dosage of the nonionic surfactant is 1 to 20 g / 1000 g of the mass dosage of the vegetable oil fatty acid.

4. A strongly weathered spodumene ore full mud flotation collector according to claim 3, characterized in that: The types of the nonionic surfactant include one or more of polyoxyethylene type, polyol type, alkanolamide type, polyether type, and amine oxide type nonionic surfactants.

5. Application of the whole mud flotation collector of strongly weathered spodumene ore according to any one of claims 1 to 4 in whole mud flotation beneficiation of strongly weathered spodumene ore.

6. The use according to claim 5, characterized in that: The dosage range of the strongly weathered spodumene ore full mud flotation collector for the strongly weathered spodumene ore full mud flotation beneficiation is: 1.5kg / t original ore to 3.0kg / t original ore.

7. The use according to claim 5, characterized in that: When the highly weathered spodumene ore is subjected to full mud flotation beneficiation, the raw spodumene ore pulp is directly subjected to flotation and lithium beneficiation without desludging.

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