A highly efficient spodumene collector and its preparation method

Abstract

This invention discloses a high-efficiency spodumene collector and its preparation method, relating to the field of mineral flotation collector technology. The collector of this invention is composed of the following raw materials in the indicated mass percentages: 25%-50% unsaturated fatty acid collector, 15%-30% sulfonated fatty acid collector, 3%-25% hydrocarbon oil auxiliary collector, 3%-15% hydroxamic acid collector, 1%-10% phosphonate auxiliary collector, 1%-5% arsenoic acid auxiliary collector, 1%-5% sulfonate auxiliary collector, and 1%-5% nonionic surfactant. This collector effectively solves the problem of difficult beneficiation of high-mud, low-grade spodumene ore, while maintaining excellent activity at low temperatures, thus solving the problem of the rapid drop in activity of conventional flotation collectors at low temperatures. Furthermore, the production process is simple and low-cost when compounding the reagents, making it suitable for industrial flotation of spodumene ore. It is used after saponification, just like traditional collectors, without altering the industrial flotation process.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation reagents and reagent application technology, and in particular to a highly efficient spodumene collector and its preparation method. Background Technology

[0002] Since its commercial production began in the early 20th century, lithium has been widely used in industries such as batteries, ceramics, glass, lubricants, refrigerants, nuclear industry, and optoelectronics, serving as a strategic resource for defense technology and civilian industrial development. Currently, pegmatite-type lithium deposits and brine-type lithium deposits are the main sources of lithium resources. While brine resources are abundant, their development and utilization are relatively difficult. Therefore, extracting lithium from minerals such as spodumene found in pegmatite-type lithium deposits remains an important way to obtain lithium raw materials.

[0003] With the rapid development of new energy vehicles, higher requirements and more sophisticated production processes are being placed on lithium mining and refining. Lithium, now considered the "white oil" of the 21st century, is a key metal for strategic emerging industries such as new energy and new materials. With the booming development of the global new energy vehicle, energy storage system, and electronic equipment industries, the demand for lithium resources is experiencing explosive growth.

[0004] However, due to the large-scale development of spodumene mines in recent years, high-grade, easily beneficiated spodumene deposits are becoming increasingly scarce. Currently, most exploitable spodumene deposits are low-grade, high in clay content, and have complex occurrence conditions and environments. Therefore, research on beneficiation technologies for low-grade, clay-containing, and difficult-to-benefit spodumene is particularly important for the development of the national economy.

[0005] Spodumene, as a major mineral raw material for the lithium industry, is crucial for ensuring the supply of lithium resources through efficient enrichment. Currently, flotation is the most economical and effective technique for separating spodumene. Its core lies in utilizing the selective adsorption of collectors on the mineral surface, causing the hydrophobic spodumene to float.

[0006] Traditional spodumene collectors, such as oleic acid and its soaps, and oxidized paraffin soaps, exhibit poor selectivity for low-grade spodumene with high mud content, resulting in low flotation concentrate grades and significantly reduced target ore yields. To address this issue, traditional processes employ pre-desliming, reducing concentrate yield, and adding flotation steps to achieve the required concentrate grade for the target ore. For spodumene ores with high mud content, a desliming process is necessary before flotation. Desliming utilizes the difference in specific gravity between mud and target components in the pulp to partially remove fine mud; however, desliming typically results in a 5-15% loss of the target component. Furthermore, reduced concentrate yield significantly decreases profitability, and adding flotation steps increases flotation production costs.

[0007] Meanwhile, traditional collectors exhibit strong temperature dependence; in low-temperature pulp, their collecting capacity and selectivity decline sharply, constituting a core technical bottleneck in low-temperature flotation. To solve the challenges of low-temperature flotation, industrial production is often forced to adopt a "heated flotation" approach. Specifically, this involves heating the pulp to above 25°C before flotation to restore collector activity. While this method can partially restore efficacy, it brings a series of problems, including a dramatic increase in energy consumption, high costs, and increased carbon emissions, severely eroding economic benefits.

[0008] Patent CN119462426 A discloses a low-temperature resistant spodumene flotation collector, its preparation method, and its application. This collector uses hydroxamic acids synthesized in the patent as the main component, compounded with auxiliary collectors such as sulfonic acids, amines, aliphatic acids, and alcohols, exhibiting good low-temperature activity. However, the patent requires the hydroxamic acids to be produced using sodium alkoxide as a raw material, imposing extremely strict production conditions and significantly increasing safety costs. Using commercially available hydroxamic acids as the main raw material results in extremely high prices. Furthermore, this technical solution, in addition to the conventional use of sodium carbonate and sodium hydroxide, cannot eliminate its dependence on calcium chloride activator. This requirement not only increases the complexity of the process but also introduces calcium ions that may non-selectively activate some gangue minerals, thus introducing uncertainty and risk to the selectivity control of the entire flotation process. Moreover, residual calcium ions may have a potential negative impact on subsequent hydrometallurgical processes.

[0009] Patent CN121360652A discloses a low-temperature resistant spodumene flotation collector, its preparation method, and its application. This collector is a compound of traditional collectors, anionic fatty acid collectors, sulfonates, hydroxamic acid, and nonionic surfactants. While it exhibits good low-temperature resistance to some extent, it shows little improvement in selectivity for high-mud ore. Furthermore, the disclosed preparation process requires high-speed stirring and heating, significantly increasing the energy consumption cost of reagent production.

[0010] There is an urgent need in this field to develop a new type of high-efficiency spodumene flotation collector that can effectively enrich and purify spodumene ore under high-mud and low-grade conditions, and maintain strong collection capacity and excellent selectivity for spodumene at low temperatures without the need for pulp heating. This would completely solve the technical bottleneck of low-grade, high-mud, low-temperature flotation, eliminate dependence on desliming and high-energy-consuming heating processes, and provide key technical support for the efficient and green development of lithium resources. Summary of the Invention

[0011] The purpose of this invention is to provide a highly efficient spodumene flotation collector and its preparation method to solve the problems existing in the prior art.

[0012] To achieve the above objectives, the present invention provides a highly efficient spodumene collector, which is composed of the following raw materials in the indicated mass percentages: 25%-50% unsaturated fatty acid collector, 15%-30% sulfonated fatty acid collector, 3%-25% hydrocarbon oil auxiliary collector, 3%-15% hydroxamic acid collector, 1%-10% phosphate ester auxiliary collector, 1%-5% arsenoic acid auxiliary collector, 1%-5% sulfonate auxiliary collector, and 1%-5% nonionic surfactant.

[0013] The unsaturated fatty acid collectors described in this invention include, but are not limited to, one or more of oleic acid, linoleic acid, linolenic acid, rice bran oleic acid, and ricinoleic acid.

[0014] The sulfonated fatty acid collectors described in this invention include, but are not limited to, one or more mixtures of sulfonated oleic acid, sulfonated castor oil acid, and sulfonated taloleic acid.

[0015] The hydrocarbon-based auxiliary collectors of this invention include one or more of the following liquid hydrocarbons: alkanes, alkenes, aromatics, and cycloalkanes.

[0016] The hydroxamic acid auxiliary collector described in this invention is an alkyl hydroxamic acid, with the general formula R-CONHOH, where R is C5-C. 17 Alkyl groups.

[0017] The phosphate ester auxiliary collectors of the present invention include hydrocarbon phosphate monoesters with the general formula RO-PO(OH)2 and dihydrocarbon phosphate esters with the general formula (RO)2PO(OH), where R is alkyl, alkenyl and aromatic, and can be used alone or in combination.

[0018] The arsenoic acid-based auxiliary collectors described in this invention are benzylarsenoic acid and benzoarsenoic acid, used alone or in combination.

[0019] The sulfonate-based auxiliary collector described in this invention is one or a mixture of sodium petroleum sulfonate, calcium petroleum sulfonate, and sodium alkylnaphthalene sulfonate.

[0020] The nonionic surfactant described in this invention is a nonylphenol polyoxyethylene ether (NP) series.

[0021] The present invention also provides a method for preparing the above-mentioned high-efficiency spodumene flotation collector, comprising the following steps: adding arsonic acid, sulfonate, and nonionic surfactant NP to unsaturated fatty acids, processing them into a stable oily liquid in a rod mill, and then adding the aforementioned liquid, sulfonated fatty acids, phosphate esters, and alkyl hydroxyxamic acid to hydrocarbon oil, stirring and mixing to obtain the high-efficiency spodumene collector.

[0022] In this invention, unsaturated fatty acid collectors serve as the main active ingredients, providing basic collection capabilities for spodumene. The added sulfonated fatty acids reduce foam viscosity and prevent sticking and runoff in high-mud ore. The combination of sulfonates, hydrocarbon oils, and nonionic surfactants significantly improves the dispersibility and stability of the entire system in low-temperature slurry. In particular, the combined effect of sulfonates and hydrocarbon oils breaks down mud clumps and prevents clay adsorption on the lithium surface. Hydroxyxamic acid collectors simultaneously improve the selectivity, low-temperature resistance, and mud resistance of the collectors. They exhibit weak adsorption on common associated veins of spodumene, such as quartz and feldspar, and are resistant to calcium and magnesium ions. The addition of phosphate esters reduces the flotation of feldspar, mica, and quartz, lowers the viscosity of foam under alkaline conditions, provides good selectivity for spodumene, and is beneficial for improving concentrate grade, while also exhibiting good low-temperature dispersibility. The addition of arsenopyrates strengthens the hydrophobicity of spodumene through chelation chemisorption, while also exhibiting strong resistance to hard water and mud.

[0023] Specifically, in alkaline slurry, unsaturated fatty acids partially dissociate, and their polar carboxylate ions (-COO) - Li and incompletely coordinated Li at the fracture surface of the spodumene lattice (LiAlSi2O6) + Al 3+ Stable chemical bonds are formed, with the unsaturated long hydrocarbon chains (R-) facing outwards, creating a dense, hydrophobic monolayer that makes the mineral surface hydrophobic. The -SO3 group of sulfonated fatty acids... - With -COOH - The bianionic groups generate electrostatic repulsion in the slurry, breaking up fine mud agglomerates and preventing mud from covering the spodumene surface. Simultaneously, they improve foam viscosity and slurry flowability, reducing the entrainment and loss of target minerals, thus significantly increasing the recovery rate of low-grade ore. Sulfonic acid groups (-SO3) - Sulfonate groups exhibit stronger polarity and hydration than carboxylic acid groups, and their salts are generally more soluble than their corresponding fatty acid salts. They also block clay adsorption on lithium surfaces. Sulfonate molecules have better solubility and dispersibility, and can preferentially adsorb onto certain active regions or defects on the spodumene surface. Hydroxyxamic acid (-CONHOH) - It is a typical chelating collector, which not only improves the overall selectivity of the reagent for spodumene, but also has a very strong selective complexing ability for metal ions such as aluminum and lithium. Hydroxime ions react with Al on the surface of spodumene. 3+ The formation of chelates exhibits strong reaction driving forces even at low temperatures, with firm adsorption and minimal desorption. Furthermore, hydroxamic acid exhibits strong affinity for Al... 3+ The high selectivity of the composite agent membrane and its stronger overall adsorption capacity reduce the dependence on Ca. 2+Activation is not required during flotation; calcium chloride, an activator, is not needed. The hydrophilic groups in nonionic surfactants bind to water via hydrogen bonds, enhancing emulsification and more effectively emulsifying the aforementioned hydrophobic reagents into small, uniformly distributed micelles or emulsion droplets. This essentially constitutes a "pre-dispersion" of the reagents, ensuring good dispersibility and stability of the compounded reagents at low temperatures. The excellent dispersibility of nonionic surfactants reduces the mechanical covering of spodumene by fine mud agglomeration. Hydrocarbon oils spread through physical adsorption (van der Waals forces) between the adsorbed polar collector hydrocarbon chains, forming a dense, hydrophobic double layer, making foam adhesion more robust. Simultaneously, the NP of hydrocarbon oils and medium-sized foams better optimizes the viscosity and brittleness of the foam, resulting in excellent foaming properties in the flotation cell while preventing excessive viscosity and subsequent runoff in the next stage. Phosphate esters (-OPO(OH)) 2- It exhibits high selectivity for spodumene, is resistant to hard water, and is particularly suitable for fine-grained, difficult-to-select spodumene. Arsonic acids (-AsO(OH)) 2- Can form Al 3+ Stable five-membered ring chelates with high bond energy and strong adsorption exhibit excellent selectivity. The selected arsonic acid organic groups form a hydrophobic film with an antenna angle of up to 110°, while showing almost no adsorption to feldspar and quartz. Furthermore, the reagent combination may show better selectivity for spodumene than for gangue minerals (such as feldspar, mica, and quartz), reducing the rigid requirement for pre-desliming to remove interfering fine mud.

[0024] In summary, the addition of sulfonated fatty acids provides excellent mud resistance and high selectivity; the combination of NP and hydrocarbon oils provides foam stability and good dispersibility; arsonic acids provide good selectivity and mud resistance to spodumene; and hydroxyxamic acids provide low-temperature activity. The optimized combination ratio results in the collector of this invention exhibiting excellent selectivity and recovery rate, as well as superior low-temperature activity, under conditions of high mud, low grade, and low temperature.

[0025] The aforementioned components, when optimized in proportion and using conventional equipment and processes, form a homogeneous and stable oily liquid. This makes the collector highly advantageous for difficult-to-process spodumene ores, such as those with high mud content and low grade. It is also suitable for conventional veins, requiring a significantly lower dosage than traditional collectors. With optimized combination, its overall cost is roughly similar to that of traditional collectors, while the dosage is drastically reduced in conventional vein flotation, thus lowering production costs. The reduced reagent dosage also lowers subsequent wastewater treatment costs. Furthermore, the highly efficient collector of this invention maintains high flotation activity even at low temperatures, effectively overcoming the problem of a sharp decline in collecting capacity caused by temperature drops in traditional collectors. Additionally, the synergistic effect of the components eliminates the need for traditional auxiliary processes such as pre-desliming and calcium chloride activation, simplifying the process and improving flotation efficiency.

[0026] The preparation process of the collector of the present invention is simple, requiring only conventional equipment and processes for mixing, without the need for complex equipment or high energy consumption conditions, and the raw materials are readily available and the overall cost is low. Attached Figure Description

[0027] Figure 1 The process flow diagram for the flotation of reagents in this invention is a roughing and cleaning process. Implementation Cases

[0028] Case 1 This embodiment provides a high-efficiency spodumene collector, with the raw materials formulated in the following proportions: 45% industrial oleic acid, 25% sulfonated oleic acid, 13% 15# white oil, 12% alkyl hydroxamic acid, 1% styrene phosphate, 1% benzyl arsenoic acid, 1% sodium petroleum sulfonate, and 2% NP10. The preparation method is as follows: benzyl arsenoic acid, sodium petroleum sulfonate, and industrial oleic acid are added to a rod mill, along with NP10, and processed into a homogeneous oily liquid. The oily liquid, alkyl hydroxamic acid, styrene phosphate, and sulfonated oleic acid are then added to 15# white oil and stirred to obtain the high-efficiency spodumene collector of this embodiment. Simultaneously, a comparative experiment was conducted on this collector and oleic acid in ordinary ores, using... Figure 1 The flotation process was carried out at room temperature using ordinary spodumene ore, and a comparative flotation experiment was conducted on the high-efficiency spodumene collector and oleic acid using a roughing and cleaning method.

[0029] Case 2 A comparative experiment was conducted using the high-efficiency spodumene collector and oleic acid from Case Study 1, employing methods such as... Figure 1 The flotation process was used to conduct flotation experiments on high-mud, low-grade spodumene ore at room temperature.

[0030] Case 3 A comparative experiment was conducted using the high-efficiency spodumene collector and oleic acid from Case Study 1, employing methods such as... Figure 1 The flotation process was carried out at 5°C for the flotation of ordinary spodumene ore.

[0031] Case 4 This embodiment provides a highly efficient spodumene collector, with the following components in the following proportions: 45% ricinoleic acid, 30% sulfonated ricinoleic acid, 12% aromatic oil S1000, 5% alkyl hydroxamic acid, 3% isooctyl diphosphate, 1% benzoarsine, 2% sodium alkylnaphthalene sulfonate, and 2% NP10. The preparation method is as follows: Benzoarsine, sodium alkylnaphthalene sulfonate, NP10, and ricinoleic acid are added to a rod mill and processed into a homogeneous oily liquid. The above oily liquid, sulfonated ricinoleic acid, isooctyl diphosphate, and alkyl hydroxamic acid are added to aromatic oil S1000 and stirred to obtain the highly efficient spodumene collector of Example 4. [The text abruptly ends here, likely due to an incomplete translation or source material.] Figure 1In the flotation process, a flotation experiment of high mud and low grade spodumene was carried out at 5℃. A roughing and cleaning comparison experiment was conducted using the collector compounded by patent CN121360652 A and the collector in this case.

[0033] Table 1. Analysis of raw common spodumene ore (partial composition) point <![CDATA[Li2O]]> <![CDATA[SiO2]]> <![CDATA[Al2O3]]> <![CDATA[Na2O]]> <![CDATA[K2O]]> <![CDATA[Fe2O3]]> content% 1.51 70.02 15.84 4.73 3.73 2.69 Table 2. Analysis of high-mud, low-grade spodumene ore (partial composition) Element <![CDATA[Li2O]]> <![CDATA[SiO2]]> <![CDATA[Al2O3]]> <![CDATA[Na2O]]> <![CDATA[K2O]]> <![CDATA[Fe2O3]]> CaO content% 0.75 68.12 18.15 5.1 4.2 1.53 1.45 Table 3 Comparison Data of Implementation Cases

[0034] In the flotation experiment of ordinary grade spodumene ore, the present invention showed that when the amount of collector was reduced by half compared with oleic acid, the Li2O recovery rate increased by more than 3%. For high-mud, low-grade spodumene ore, regardless of whether it is at room temperature or low temperature, compared with oleic acid, including patent CN121360652A, the Li2O recovery rate increased by at least 5%.

[0035] In summary, this invention provides a high-efficiency, low-temperature spodumene collector. Through the scientific formulation of specific main and auxiliary components, it successfully achieves excellent flotation characteristics for high-mud, low-grade spodumene, eliminating the need for additional auxiliary processes such as pre-desliming or calcium chloride activation. Furthermore, the significant synergistic effect of the components is also evident in its low-temperature adaptability. This flotation collector can efficiently recover spodumene at temperatures above 5°C, while maintaining high Li₂O recovery and concentrate grade. This collector simplifies the process flow, reduces reagent costs and operational complexity, and demonstrates significant technical benefits, exhibiting outstanding substantive characteristics and advancements.

Claims

1. A highly efficient spodumene collector, characterized in that, It is composed of the following raw materials by mass percentage: 25%-50% unsaturated fatty acid collectors, 15%-30% sulfonated fatty acid collectors, 3%-25% hydrocarbon oil auxiliary collectors, 3%-15% hydroxamic acid collectors, 1%-10% phosphate ester auxiliary collectors, 1%-5% arsenoic acid auxiliary collectors, 1%-5% sulfonate auxiliary collectors, and 1%-5% nonionic surfactants.

2. The high-efficiency spodumene collector according to claim 1, characterized in that, The unsaturated fatty acid collectors include, but are not limited to, one or more mixtures of oleic acid, linoleic acid, linolenic acid, rice bran oleic acid, and ricinoleic acid.

3. The high-efficiency spodumene collector according to claim 1, characterized in that, The sulfonated fatty acid collectors include, but are not limited to, one or more mixtures of sulfonated oleic acid, sulfonated castor oil acid, and sulfonated taloleic acid.

4. The high-efficiency spodumene collector according to claim 1, characterized in that, The hydrocarbon-based auxiliary collector includes one or more of the following liquid hydrocarbons: alkanes, alkenes, aromatics, and cycloalkanes.

5. The high-efficiency spodumene collector according to claim 1, characterized in that, The hydroxamic acid auxiliary collector is an alkyl hydroxamic acid, and the general structural formula of the alkyl hydroxamic acid is R-CONHOH, where R is C5-C6. 17 Alkyl groups.

6. The high-efficiency spodumene collector according to claim 1, characterized in that, The phosphonate-based auxiliary collectors are alkyl phosphate monoesters with the general formula RO-PO(OH)2 and dialkyl phosphate esters with the general formula (RO)2PO(OH), where R is alkyl, alkenyl, or aromatic, and can be used alone or in combination.

7. The high-efficiency spodumene collector according to claim 1, characterized in that, The arsenoic acid-based auxiliary collector is benzylarsenoic acid or benzoarsenoic acid, used alone or in combination.

8. The high-efficiency spodumene collector according to claim 1, characterized in that, The sulfonate-based auxiliary collector is one or more of sodium petroleum sulfonate, calcium petroleum sulfonate, and sodium alkylnaphthalene sulfonate.

9. The high-efficiency spodumene collector according to claim 1, characterized in that, The nonionic surfactant is a nonylphenol polyoxyethylene ether (NP) series surfactant.

10. The method for preparing the high-efficiency spodumene collector according to any one of claims 1-9, characterized in that, Includes the following steps: A1. Arsonic acids, sulfonates, NPs, and unsaturated fatty acids are added to a rod mill and processed into a stable oily liquid. A2. The above oily liquid, sulfonated fatty acids, phosphate ester auxiliary collectors, and alkyl hydroxyxamic acid collectors are added to hydrocarbon oil and stirred evenly to obtain the high-efficiency spodumene collector.

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