Spodumene flotation complex collector and application thereof

Abstract

The application discloses a complex collector for spodumene flotation and application thereof, and belongs to the technical field of mineral processing and flotation reagent. The complex collector is composed of acyl amino acid salt, fatty alcohol polyoxyethylene ether phosphate and alkyl amide propyl betaine, and the three components account for 40-50%, 30-50% and 10-20% respectively according to the total mass of effective active substances. The complex collector can be used as a collector and a foaming agent, the three components have synergistic effect, the grade and recovery rate of spodumene flotation are considered, the acyl amino acid salt is beneficial to enhancing selective adsorption on the aluminum active sites on the surface of spodumene, the fatty alcohol polyoxyethylene ether phosphate is beneficial to improving the collecting capacity, and the alkyl amide propyl betaine is a amphoteric inner salt, which is beneficial to adjusting the interaction between anion components and improving the foam properties of the system. The application of the complex collector in spodumene flotation can obtain high-grade spodumene concentrate through grinding, slurry preparation and activation and then one-time roughing.

Description

Technical Field

[0001] This invention relates to the field of mineral processing and flotation reagents, and in particular to a compound collector for spodumene flotation and its application in the flotation of spodumene ore, especially suitable for the flotation separation of pegmatite-type spodumene ore that is closely associated with silicate gangue minerals such as quartz, feldspar, and mica. Background Technology

[0002] Lithium is a key resource for power batteries in new energy vehicles, large-scale energy storage, and aluminum-lithium alloys in aerospace. Spodumene (LiAl(Si2O6)) is the most important hard rock mineral raw material for lithium extraction. Spodumene is mainly found in granite pegmatites, closely associated with silicate gangue minerals such as quartz, albite, and potassium feldspar. The surface physicochemical properties of these minerals are similar, making flotation separation extremely difficult.

[0003] Collectors are the core reagents that determine the separation effect of spodumene flotation. In existing technologies, industrially widely used single fatty acid anionic collectors such as oleic acid and sodium oleate have poor selectivity for silicate gangue, resulting in an inherent drawback where it is difficult to balance concentrate grade and recovery: at low dosages, the grade is acceptable but the recovery is insufficient; at high dosages, the recovery increases, but a large amount of gangue floats to the surface, causing a sharp drop in grade. While amine cationic collectors and anionic-cationic combined collectors have strong collecting capabilities, the pure cationic components exhibit strong electrostatic adsorption on negatively charged quartz, feldspar, and slime, resulting in poor selectivity. This typically requires the addition of large amounts of depressants such as water glass or sodium hexametaphosphate, leading to difficulties in settling the flotation product. Furthermore, when the slime content is high, the cationic components can also float the slime, causing it to accumulate and circulate in the process, making it difficult to guarantee concentrate grade. While single amino acid collectors offer good selectivity, their collecting capacity is weak and recovery rates are insufficient. Furthermore, some varieties (such as sodium cocoyl glycinate) exhibit poor foaming performance when used alone, sometimes failing to form an effective foam layer and rendering flotation impossible. Single phosphate ester collectors possess strong collecting capacity, but they also exhibit non-selective adsorption of gangue minerals, resulting in low concentrate grades. Single betaine-type amphoteric surfactants show mediocre collection performance for spodumene, and produce overly stable foam with significant entrainment of fine mud. In addition, sodium oleate, oleic acid, and phosphate ester collectors have limited foaming capacity themselves. In industrial practice, it is usually necessary to add additional foaming agents such as pine oil (No. 2 oil) and methyl isobutyl methanol (MIBC), leading to complex reagent formulations, increased costs, and improper control of foaming agent dosage, which can easily result in sticky foam, foam runoff, or difficulty in defoaming.

[0004] To address the aforementioned drawbacks of single collectors, combined / compounded collector solutions have been proposed in the art, among which the prior art closest to this invention is as follows:

[0005] Chinese invention patent CN115814956A discloses a beneficiation method for recovering spodumene from lithium ore by flotation. The method employs a composite collector PL2-01 composed of anionic collector styrene phosphonic acid, cationic collector 3-triethoxysilylpropyltrimethylammonium chloride, and cottonseed oil soap. It utilizes the strong complexing ability of the O atoms in the phosphonic acid groups to adsorb spodumene, and relies on the electrostatic association between the anionic and cationic collectors to form multilayer adsorption on the mineral surface to enhance collection. This collector follows a typical "anionic + pure cationic" association route. The cationic component is a permanently positively charged quaternary ammonium salt, which always carries a positive charge in the alkaline slurry. It may electrostatically adsorb onto negatively charged quartz, feldspar surfaces, and fine-grained slime, requiring control of the formulation and slurry preparation to ensure selectivity. Furthermore, its collecting power mainly depends on the phosphonic acid groups, but it exhibits non-selective adsorption on gangue minerals, resulting in a low concentrate grade.

[0006] Chinese invention patent CN115213019A discloses a coarse-grained spodumene enhanced flotation collector and its application. The collector comprises, by weight, 20-30 parts sodium carbonate, 60-75 parts fatty acid, 10-20 parts betaine series surfactants, 5-10 parts neutral oil, and 3-6 parts terpineol (No. 2 oil) or methyl isobutyl methanol (MIBC). The betaine series surfactants are selected from at least one of carboxylic acid betaine, sulfobetaine, sulfate betaine, and phosphate betaine. The embodiments and preferred schemes use C12-C14 alkyl dimethyl betaine, and alkylamidopropyl betaine is not specifically exemplified. Its application requires obtaining spodumene concentrate through one roughing, one cleaning, and one scavenging under conditions of coarse grinding (-0.074 mm accounts for 45%-70%), magnetic separation pretreatment, and calcium ion activation. The main collectors in this scheme are long-chain fatty acids such as oleic acid, accounting for more than 60% of the total reagents. However, it still has the inherent defects of fatty acid reagents, such as insufficient selectivity for silicate gangue, poor low-temperature dispersibility, and high consumption. The betaine used is carboxylic acid type, sulfonyl, sulfate ester and phosphate ester betaine. In the examples, all are alkyl dimethyl betaine, and betaine is only used as an auxiliary agent to enhance the flotation of coarse particles and adjust the foam structure. In addition, this scheme requires the addition of 3 to 6 parts of terpineol or MIBC foaming agent and 5 to 10 parts of neutral oil (kerosene, liquid paraffin and other mineral oils) to the reagents. There are as many as five types of reagent components, and non-biodegradable mineral oil components are introduced. This scheme is for coarse grinding particles and relies on magnetic separation pretreatment and calcium ion activation, requiring a multi-stage operation of coarsening, polishing and scavenging.

[0007] In summary, existing spodumene compound collector technologies either rely on the electrostatic association of pure cationic components, leading to risks of gangue adsorption and slime flotation, or use fatty acids as the main collector and require the addition of neutral oil and external frothers such as terpineol and MIBC, resulting in numerous components and limitations in selectivity and environmental friendliness. Furthermore, none of these technologies have overcome the technical obstacle of insufficient foaming by amino acid-based green reagents, nor have they achieved the integration of collection and foaming functions. To date, no technical solution has been disclosed for the compounding of acyl amino acid salts, fatty alcohol polyoxyethylene ether phosphates, and alkylamidopropyl betaine in a specific effective active ingredient mass ratio for spodumene flotation. Therefore, developing a compound collector with strong selectivity, good collection ability, suitable foaming performance, the ability to simultaneously balance spodumene concentrate grade and recovery rate, and environmental friendliness is an urgent technical problem to be solved in this field. Summary of the Invention

[0008] The technical problem to be solved by this invention is to overcome the shortcomings of the prior art and provide a compound collector for spodumene flotation and its application. Through the synergistic effect of different ion types and different solid-loving functional group components, it solves the technical problems of difficulty in achieving both grade and recovery rate of single collectors, insufficient foaming of amino acid reagents, and poor selectivity of cationic reagents.

[0009] The technical solution adopted by this invention to solve its technical problem is:

[0010] A spodumene flotation compound collector, based on the total mass of effective active matter, is composed of the following components: acyl amino acid salt (component A) 40%~50%, fatty alcohol polyoxyethylene ether phosphate (component B) 30%~50%, and alkylamidopropyl betaine (component C) 10%~20%.

[0011] The spodumene flotation complex collector of the present invention utilizes the amide carbonyl group and carboxylate group in the acyl amino acid salt molecule to expose the highly active Al on the cleavage surface of spodumene. 3+ The chelation at the site enables selective adsorption, ensuring the grade of the concentrate, and is the "grade component" of the system;

[0012] Secondly, the O atoms in the phosphate groups of fatty alcohol polyoxyethylene ether phosphate have high fixative activity and strong complexing ability, resulting in high adsorption strength on the spodumene surface. Furthermore, the polyoxyethylene ether chain gives it good water solubility and dispersibility, which is beneficial to improving the collection capacity and ensuring the recovery rate. It is the "recovery rate component" of the system.

[0013] Third, betaine-based amphoteric surfactants are amphoteric intrasalt type surfactants. The quaternary ammonium positive charge centers within the molecule do not disappear with pH changes. When introduced in an appropriate proportion, they can insert themselves between the anionic molecules of acyl amino acid salts and fatty alcohol polyoxyethylene ether phosphates through electrostatic interactions, reducing the electrostatic repulsion between the polar anionic groups and increasing the adsorption density of the collector on the mineral surface. Simultaneously, their hydrocarbon chains undergo hydrophobic association with the hydrocarbon chains of acyl amino acid salts and fatty alcohol polyoxyethylene ether phosphates, which is beneficial for forming a denser mixed hydrophobic adsorption layer. Furthermore, alkylamidopropyl betaine produces fine and abundant foam. The rich content of the compound collector can compensate for the insufficient foaming of amino acid components, enabling the flotation of sodium cocoyl glycinate systems with poor foaming performance. Simultaneously, the amamidopropyl betaine structure of alkylamidopropyl betaine produces fine and rich foam, while the polyoxyethylene ether chain of fatty alcohol polyoxyethylene ether phosphate has auxiliary foaming and foam-regulating effects. These two components, together with acyl amino acid salts, form a three-phase foam layer with moderate toughness, good fluidity, and easy defoaming. This allows the compound collector to function as both a collector and a foaming agent, eliminating the need for additional foaming agents such as pine oil or MIBC during the entire flotation process under the specified conditions. The three components of the compound collector of this invention achieve synergistic effects on the surface of spodumene through complementary adsorption of "carboxyl chelation + strong phosphate complexation + zwitterionic densification," while adsorption on the surfaces of quartz, feldspar, and mica is weaker, thus achieving highly efficient and selective separation of spodumene and gangue minerals.

[0014] The proportion of alkylamidopropyl betaine is controlled at a low level of 10% to 20%. This can not only give full play to its synergistic function of regulating the interaction of anionic components and improving foam properties, but also avoid the problems of excessive foam stability and aggravated fine mud entrainment caused by an excessively high proportion of betaine.

[0015] The compound collector of this invention is based on an acyl amino acid salt and a phosphate ester dual oxygen-containing functional group component as the main collecting system. It does not contain fatty acids, thus avoiding the inherent defects of fatty acid-based agents such as insufficient selectivity for silicate gangue, poor low-temperature dispersibility, and high consumption. Moreover, all three components are mild surfactants that are maturely used in the daily chemical and food industries, with wide availability, green environmental protection, and easy industrialization. The acyl amino acid salt and the phosphate ester dual oxygen-containing functional group component complement each other for adsorption. The betaine-type amphoteric internal salt has a self-balanced positive and negative charge within the molecule in alkaline slurry, and is electrically neutral overall. It can also regulate the interaction between the anionic components of the acyl amino acid salt and the fatty alcohol polyoxyethylene ether phosphate ester. This compound collector is activated with magnesium ions at conventional grinding fineness, and good indicators can be obtained in a single roughing process.

[0016] In one exemplary embodiment, the acyl amino acid salt is an acyl glycinate salt and / or an acyl sarcosine salt; the acyl glycinate salt is potassium cocoyl glycinate or sodium cocoyl glycinate, and the acyl sarcosine salt is sodium lauroyl sarcosine.

[0017] Fatty alcohol polyoxyethylene ether phosphate is one or more of fatty alcohol polyoxyethylene ether phosphate monoester, phosphate diester and their salts, wherein the fatty alcohol group is C. 12 ~C 18 The alkyl polyoxyethylene ether has an average degree of polymerization of 3 or 9, preferably AEO-3P with an average degree of polymerization of 3;

[0018] Alkylamidopropyl betaine is cocamidopropyl betaine and / or lauramidopropyl betaine.

[0019] Preferably, based on the total mass of the effective active ingredient, it is composed of the following components, with the mass ratio of acyl amino acid salt, fatty alcohol polyoxyethylene ether phosphate, and alkylamidopropyl betaine being 5:4:1, 4:5:1, or 5:3:2.

[0020] Another technical solution adopted by the present invention to solve its technical problem is as follows:

[0021] Application of a compound collector for spodumene flotation in spodumene flotation.

[0022] The spodumene flotation process includes the following steps:

[0023] The raw spodumene ore is crushed, ground, and deslimed, then activated with an activator and prepared into an alkaline slurry.

[0024] Add the compound collector, stir, and then perform aeration flotation and foam scraping. The foam product is spodumene concentrate, and the product in the tank is tailings.

[0025] The total amount of the compound collector is 400~800 g / t; after adding the compound collector, stir for 2~3 min, then aerate and float and skim the bubbles for 3~5 min.

[0026] The method for adding the compound collector is as follows:

[0027] Acyl amino acid salts, fatty alcohol polyoxyethylene ether phosphates, and alkylamidopropyl betaine are pre-mixed evenly in proportion and then added to the slurry all at once.

[0028] Alternatively, the slurry can be added in the following order: acyl amino acid salt, fatty alcohol polyoxyethylene ether phosphate, and alkylamidopropyl betaine. When adding the components sequentially, the slurry conditioning time between adjacent components is 1 to 3 minutes.

[0029] The activator is magnesium chloride, the spodumene ore is a pegmatite-type spodumene ore, the ore has a Li2O grade of not less than 0.8%, and the gangue minerals include one or more of quartz, albite, potassium feldspar, and mica.

[0030] When the raw ore has a Li2O grade of 0.8% to 1.6%, the spodumene concentrate obtained after one roughing process has a Li2O grade of not less than 4.0% and a Li2O recovery rate of not less than 78%. When the raw ore has a Li2O grade of not less than 1.3% and the total amount of the compound collector is 600 to 800 g / t, the spodumene concentrate obtained after one roughing process has a Li2O grade of not less than 4.5% and a Li2O recovery rate of not less than 80%.

[0031] No foaming agent is added after the addition of the compound collector.

[0032] The beneficial effects of this invention's spodumene flotation compound collector and its application are as follows:

[0033] (1) Balancing grade and recovery rate. The three components of this compound collector have complementary functions, overcoming the shortcomings of insufficient recovery rate (around 62%) of single acyl amino acid salts, low grade of single phosphate esters, and mediocre index of single betaine. A single roughing process can obtain spodumene concentrate with a Li2O grade of 4.0%~5.1% and a recovery rate of 78%~90%. Compared with the same batch of raw ore and the same total amount of reagents, the comprehensive index is superior to traditional sodium oleate collector, oleic acid collector, single agent of component A and component B, and three binary combinations of A+B, A+C, and B+C. The single agent test of component C on another batch of similar ore also shows that its index is limited when used alone. The synergistic effect of the ternary system is significant.

[0034] (2) Replacing pure cationic components with amphoteric internal salts reduces the risk of selectivity. Component C is a betaine-type zwitterion rather than an amine cation. It is in an electrically neutral internal salt state in alkaline slurry and has weak electrostatic adsorption on negatively charged quartz, feldspar and ore slime. It does not require the addition of large amounts of water glass and other inhibitors, thus avoiding the problems of ore slime floating and product settling difficulties caused by anion-cation combined collectors.

[0035] (3) It solves the technical obstacle of "no foam, no use" for amino acid reagents. Sodium cocoyl glycinate cannot form an effective foam layer when used alone, and cannot be used for flotation at all; after the introduction of component C, the foaming performance of the system is restored to normal, so that the inexpensive sodium salt amino acid surfactant can be used for spodumene flotation, which broadens the source of reagents and reduces the cost of reagents.

[0036] (4) Strong adaptability to ore. The compound collector of this invention can achieve good separation index for pegmatite spodumene ore in Africa as well as pegmatite spodumene ore with different mineral compositions and different Li2O grades (0.8%~1.6%) in Sichuan, Jiangxi and other places in China, and has wide adaptability.

[0037] (5) It has both collecting and foaming functions, simplifying the reagent system. The compound collector of this invention has excellent foaming performance and moderate foam toughness. It can be used as both a collector and a foaming agent. Under the implementation conditions, no additional foaming agents such as pine oil and MIBC are needed in the entire flotation process, reducing the types of reagents and the number of dosing points, reducing reagent costs, simplifying production operations and foam control, and further improving industrial adaptability.

[0038] (6) Green and environmentally friendly, easy to industrialize. The hydrophobic chains of the three components can be derived from vegetable oils such as coconut oil, which are mild surfactants that are maturely used in the daily chemical and food industries. The raw materials are widely available and industrially accessible. The compound collector has good water solubility and dispersibility, and ordinary tap water can be used for flotation. The method follows the conventional process of "grinding - pulp preparation - activation - flotation", which does not require additional equipment investment and is easy to promote industrially.

[0039] (7) The application of the compound collector of the present invention in the flotation of spodumene: when the grade of Li2O in the raw ore is 0.8%~1.6%, the grade of Li2O in the spodumene concentrate obtained by one roughing is not less than 4.0%, and the Li2O recovery rate is not less than 78%; when the grade of Li2O in the raw ore is not less than 1.3% and the total amount of the compound collector is 600~800 g / t, the grade of Li2O in the spodumene concentrate obtained by one roughing is not less than 4.5%, and the Li2O recovery rate is not less than 80%. Attached Figure Description

[0040] Figure 1 —This is a process flow diagram of the application of a compound collector for spodumene flotation in spodumene flotation in Example 1; Detailed Implementation

[0041] The present invention will be further described below with reference to the accompanying drawings and embodiments, but the scope of protection of the present invention is not limited thereto.

[0042] 1) Spodumene raw material used in spodumene flotation:

[0043] The raw ore used in Examples 1-5, 9, 10 and Comparative Examples 1, 2, 4-8 was a pegmatite-type spodumene deposit in Africa. The raw ore had a Li2O grade of 1.58%, and the main gangue minerals were quartz, albite, and potassium feldspar.

[0044] The raw ore used in Comparative Example 3 was a pegmatite spodumene ore of the same type, with a Li₂O grade of 1.2%;

[0045] The raw ore used in Example 6 was a granite pegmatite-type spodumene deposit in Aba Prefecture, Sichuan Province, with a Li2O grade of 1.35%.

[0046] The raw ore used in Example 7 was a granite pegmatite type spodumene deposit in Yichun, Jiangxi Province, with a Li2O grade of 1.51%, high content of quartz and feldspar, and a small amount of muscovite.

[0047] The raw ore used in Example 8 was a low-grade granite pegmatite type spodumene ore in Xinjiang, with a Li2O grade of 0.88%.

[0048] 2) Spodumene flotation process:

[0049] Except for the type, composition, and dosage of the collector, the process conditions in Examples 1-10 and Comparative Examples 1-8 are the same, specifically:

[0050] The raw ore was crushed to -2 mm. 400 g of ore sample was weighed each time, and water and sodium carbonate (1250 g / t) were added for grinding for 7 min (75% of the sample was -200 mesh). The flotation test was carried out on an LFM01 flotation machine with a flotation cell volume of 1 L. Ordinary tap water was used for flotation. The slurry was deslimed and adjusted to a mass concentration of 30%. Magnesium chloride (100 g / t) was added for activation, and sodium hydroxide (200 g / t) was added to adjust the pH to 10.5 to obtain an alkaline slurry.

[0051] Subsequently, a collector was added for a roughing process. The modifier, activator and collector were added in sequence, and the slurry was stirred and adjusted between adjacent agents for 3 minutes. After adding the compound collector, the mixture was stirred for 3 minutes, followed by aeration flotation and continuous skimming of bubbles for 4 minutes. The foam product and the product in the tank were filtered, dried, weighed and tested for Li2O grade, and the recovery rate was calculated.

[0052] The Li2O recovery rate is calculated using the formula ε = γ × β / α, where ε is the Li2O recovery rate (%), γ is the concentrate yield (%), β is the concentrate Li2O grade (%), and α is the raw ore Li2O grade (%). All values ​​are expressed as percentages.

[0053] It should be noted that no frothers such as pine oil or MIBC were added during the flotation process of Examples 1-10 and Comparative Examples 1-8 described below.

[0054] In Examples 1-10: Component A is potassium cocoyl glycinate (abbreviation: GCK-30), sodium cocoyl glycinate (abbreviation: GCS-30), or sodium lauroyl sarcosinate (abbreviation: LS-30); Component B is fatty alcohol polyoxyethylene ether phosphate AEO-3P or AEO-9P; Component C is cocamidopropyl betaine (abbreviation: CAPB) or lauroamide propyl betaine (abbreviation: LAB-35). The proportions and amounts of each component are based on the mass of the effective active ingredient, and commercial reagents are calculated based on their nominal effective content. All components are pre-mixed evenly according to the set mass ratio and then added all at once.

[0055] Example 1

[0056] This embodiment of a spodumene flotation compound collector, based on the total mass of effective active matter, consists of the following components: potassium cocoyl glycinate (abbreviation: GCK-30, component A) 50%, fatty alcohol polyoxyethylene ether phosphate AEO-3P (abbreviation: AEO-3P, component B) 40%, and cocamidopropyl betaine (abbreviation: CAPB, component C) 10%.

[0057] See Figure 1 This embodiment describes the application of a compound collector for spodumene flotation in spodumene flotation. The flotation process includes the following steps:

[0058] The spodumene ore was crushed to -2 mm. 400 g of ore sample was weighed each time, and water and sodium carbonate (1250 g / t) were added for grinding for 7 min (75% of the sample was -200 mesh). The flotation test was carried out on an LFM01 flotation machine with a flotation cell volume of 1 L. Ordinary tap water was used for flotation. The slurry was deslimed and adjusted to a mass concentration of 30%. Sodium hydroxide (200 g / t) was added to adjust the pH to 10.5, and then magnesium chloride (100 g / t) was added for activation.

[0059] Subsequently, components A, B, and C of the compound collector were premixed evenly, and then the collector was added to the slurry all at once for roughing. The modifier, activator, and collector were added in sequence, and the slurry was stirred for 3 minutes between adjacent reagents. After adding the compound collector at a rate of 400 g / t, the mixture was stirred for 3 minutes, followed by aeration flotation and continuous skimming for 4 minutes. The froth product was the spodumene concentrate, and the product in the tank was the tailings. The froth product and the product in the tank were filtered, dried, weighed, and tested for Li2O grade, and the recovery rate was calculated.

[0060] A roughing process was performed using the flotation flow described above, resulting in a spodumene concentrate with a Li₂O grade of 5.12% and a Li₂O recovery rate of 78.3%. At the same total dosage of 400 g / t as Comparative Examples 1, 4, 5a, and 6-8, the spodumene concentrate obtained in this embodiment had a grade 1.54 percentage points higher than that obtained with sodium oleate (3.58%), a recovery rate 16.3 percentage points higher than that obtained with GCK-30 single agent (62.01%), and a recovery rate 34.6 percentage points higher than that obtained with AEO-3P single agent (43.67%). Furthermore, both the grade and recovery rate were significantly superior to the three binary combinations A+B, A+C, and B+C (Comparative Examples 6-8), confirming that components A, B, and C are indispensable and that the ternary system exhibits genuine synergistic effects. During the flotation process, the foam is fine and abundant, with moderate toughness, smooth foam scraping, and easy defoaming after scraping. No foaming agent was added throughout the process, which proves that the compound collector of the present invention can simultaneously perform the functions of collection and foaming.

[0061] Example 2

[0062] This embodiment of a spodumene flotation compound collector, based on the total mass of effective active matter, consists of the following components: potassium cocoyl glycinate (abbreviation: GCK-30, component A) 40%, fatty alcohol polyoxyethylene ether phosphate AEO-3P (abbreviation: AEO-3P, component B) 50%, and cocamidopropyl betaine (abbreviation: CAPB, component C) 10%.

[0063] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in flotation process:

[0064] The total dosage of the compound collector is 600 g / t.

[0065] A roughing process using the above flotation procedure yielded a spodumene concentrate with a Li₂O grade of 4.86% and a Li₂O recovery rate of 86.5%. By appropriately increasing the proportion and total amount of phosphate ester components, the recovery rate was further improved to over 86%, while the grade remained above 4.8%, achieving a good balance between grade and recovery rate.

[0066] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in flotation process 2:

[0067] The total dosage of the compound collector is 600 g / t.

[0068] The method for adding the compound collector is as follows: add it step by step in the order of component A, then component B, and finally component C, and conduct parallel tests (the adjustment time between adjacent components is 2 min).

[0069] A roughing process was performed using the above flotation procedure, and the resulting spodumene concentrate had a Li2O grade of 4.83% and a recovery rate of 86.1%. Comparing the two application methods, the components of the compound collector added sequentially and the indicators of the premixed compound collector added at once were comparable, indicating that both dosing methods are feasible.

[0070] Example 3

[0071] This embodiment of a spodumene flotation compound collector, based on the total mass of effective active matter, consists of the following components: potassium cocoyl glycinate (abbreviation: GCK-30, component A) 50%, fatty alcohol polyoxyethylene ether phosphate AEO-3P (abbreviation: AEO-3P, component B) 30%, and cocamidopropyl betaine (abbreviation: CAPB, component C) 20%.

[0072] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0073] The total dosage of the compound collector is 800 g / t.

[0074] Following the above process flow for a single roughing stage, the resulting spodumene concentrate had a Li2O grade of 4.63% and a Li2O recovery rate of 90.1%. This example demonstrates that, with a higher total dosage and a higher CAPB ratio, the froth layer is stable, the flotation process is smooth, the recovery rate can reach over 90%, and the grade remains above 4.6%. Furthermore, no obvious fine mud entrainment was observed, confirming that component C, cocamidopropyl betaine, does not impair the system's selectivity within the (0.5~2) ratio range.

[0075] Example 4

[0076] The spodumene flotation compound collector of this embodiment is composed of the following components based on the total mass of effective active matter: sodium cocoyl glycinate (abbreviation: GCS-30, component A) 50%, fatty alcohol polyoxyethylene ether phosphate AEO-3P (abbreviation: AEO-3P, component B) 40%, and cocamidopropyl betaine (abbreviation: CAPB, component C) 10%.

[0077] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0078] The total dosage of the compound collector is 600 g / t.

[0079] Sodium cocoyl glycinate alone cannot form an effective foam layer and cannot be used for flotation (see Comparative Example 5b). However, in this example, after the introduction of component C, the system has rich and delicate foam, and flotation is carried out smoothly. The obtained spodumene concentrate has a Li2O grade of 4.75% and a Li2O recovery rate of 83.8%, which is comparable to the indicators of the potassium salt system (Example 2). This proves that component C can eliminate the foaming defects of sodium salt amino acid components, enabling the inexpensive sodium salt reagent, which was originally completely unusable for flotation, to obtain excellent separation indicators.

[0080] Example 5

[0081] The spodumene flotation compound collector of this embodiment is composed of the following components by total mass of effective active matter: 50% potassium cocoyl glycinate (abbreviation: GCK-30, component A), 40% fatty alcohol polyoxyethylene ether phosphate AEO-9P (abbreviation: AEO-9P, component B) and 10% cocamidopropyl betaine (abbreviation: CAPB, component C).

[0082] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0083] The total dosage of the compound collector is 600 g / t.

[0084] Following the above process flow for a single roughing stage, the resulting spodumene concentrate had a Li₂O grade of 4.58% and a Li₂O recovery rate of 88.7%. AEO-9P can also form an effective ternary compound system with components A and C, indicating that the average degree of polymerization of polyoxyethylene ether in the phosphate ester component can achieve synergistic effects within the range of 3 to 9. However, the concentrate grade in this embodiment is lower than that in Example 2 using AEO-3P. Considering both concentrate grade and recovery rate, AEO-3P is a more preferred phosphate ester component.

[0085] Example 6

[0086] This embodiment of a spodumene flotation compound collector, based on the total mass of effective active matter, consists of the following components: potassium cocoyl glycinate (abbreviation: GCK-30, component A) 50%, fatty alcohol polyoxyethylene ether phosphate AEO-3P (abbreviation: AEO-3P, component B) 40%, and cocamidopropyl betaine (abbreviation: CAPB, component C) 10%.

[0087] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0088] The spodumene ore used was from a granite pegmatite-type spodumene deposit in Aba Prefecture, Sichuan Province (Li₂O grade 1.35%).

[0089] The total dosage of the compound collector is 600 g / t.

[0090] Following the above process flow for a single roughing stage, the resulting spodumene concentrate had a Li₂O grade of 4.52% and a Li₂O recovery rate of 84.6%. This embodiment demonstrates that the compound collector of the present invention also exhibits excellent separation performance for low-grade spodumene ores in China.

[0091] Example 7

[0092] This embodiment provides a spodumene flotation compound collector, which is the same as in Example 6, wherein the compound collector consists of GCK-30, AEO-3P and CAPB in a mass ratio of 5:4:1.

[0093] Compared with Example 6, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0094] The spodumene ore was sourced from a granite pegmatite-type spodumene deposit in Yichun, Jiangxi Province (Li2O grade 1.51%, high quartz and feldspar content, distributed as follows: quartz 35%, potassium feldspar 13%, plagioclase 20%, sodium feldspar 8%).

[0095] Following the above process flow, the first roughing stage yielded a spodumene concentrate with a Li2O grade of 4.81% and a Li2O recovery rate of 82.4%. This embodiment demonstrates that for difficult-to-process spodumene ores with high quartz and feldspar content, the compound collector of this invention can still maintain good selectivity and exhibits strong ore adaptability.

[0096] Example 8

[0097] This embodiment provides a spodumene flotation compound collector, which is the same as in Example 6, wherein the compound collector consists of GCK-30, AEO-3P and CAPB in a mass ratio of 5:4:1.

[0098] Compared with Example 6, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0099] The spodumene ore was sourced from a low-grade granite pegmatite-type spodumene deposit in Xinjiang (Li2O grade 0.88%).

[0100] Following the above process flow, a single roughing stage yielded a spodumene concentrate with a Li₂O grade of 4.05% and a Li₂O recovery rate of 79.6%. This embodiment demonstrates that for low-grade spodumene ores with Li₂O grades as low as 0.9%, the compound collector of this invention, after a single roughing stage, can still enrich the concentrate grade by more than 4 times while maintaining a high recovery rate. This fully proves that the present invention has good adaptability to spodumene ores with Li₂O grades ranging from 0.8% to 1.6%.

[0101] Example 9

[0102] This embodiment of a spodumene flotation compound collector, based on the total mass of effective active ingredients, consists of the following components: 50% acyl sarcosine salt—sodium lauroyl sarcosine (abbreviation: LS-30, component A), 40% fatty alcohol polyoxyethylene ether phosphate AEO-3P (abbreviation: AEO-3P, component B), and 10% cocamidopropyl betaine (abbreviation: CAPB, component C).

[0103] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0104] The total dosage of the compound collector is 600 g / t.

[0105] Following the above flotation process, the first roughing stage yielded a spodumene concentrate with a Li₂O grade of 4.51% and a Li₂O recovery rate of 85.3%. This example demonstrates that when component A is an acylsarcosine salt or other acyl amino acid salt, it can still achieve synergistic effects with components B and C, resulting in good separation performance.

[0106] Example 10

[0107] This embodiment of a spodumene flotation compound collector, based on the total mass of effective active matter, consists of the following components: 50% potassium cocoyl glycinate (abbreviation: GCK-30, component A), 40% fatty alcohol polyoxyethylene ether phosphate AEO-3P (abbreviation: AEO-3P, component B), and 10% lauramidopropyl betaine (abbreviation: LAB-35, component C).

[0108] Compared with Example 1, the application of a spodumene flotation compound collector in the flotation of spodumene in this example has the following differences in the flotation process:

[0109] The total dosage of the compound collector is 600 g / t.

[0110] Following the above flotation process, the first roughing stage yielded a spodumene concentrate with a Li₂O grade of 4.68% and a Li₂O recovery rate of 83.5%. This example demonstrates that when component C is lauramide propyl betaine or other betaine-type amphoteric surfactants, it can also exert a synergistic effect of densifying adsorption and improving foaming.

[0111] Comparative Example 1

[0112] This comparative example uses a single agent of the traditional collector sodium oleate at a dosage of 400 g / t, and the other conditions are the same as in Example 1.

[0113] When the collector in this embodiment was used for spodumene flotation, the resulting concentrate had a Li₂O grade of 3.58% and a recovery rate of 78.26%. Compared with Example 1, the grade was 1.54 percentage points lower with a similar recovery rate, indicating that traditional fatty acid reagents are not selective enough for quartz and feldspar.

[0114] Comparative Example 2

[0115] This comparative example uses a single traditional collector, oleic acid, at a dosage of 400 g / t, with the other conditions being the same as in Example 1.

[0116] When the collector in this embodiment is used for spodumene flotation, the resulting concentrate has a Li₂O grade of 5.00% and a recovery rate of only 41.97%. Compared with Example 1, the grade is similar, but the recovery rate is 36.3 percentage points lower, resulting in severe lithium resource loss and an inability to balance grade and recovery rate.

[0117] Comparative Example 3

[0118] This comparative example uses component C, cocamidopropyl betaine (CAPB), as a single reagent at a dosage of 400 g / t. The raw ore has a Li2O grade of 1.2%, and the other conditions are the same as those in the example.

[0119] When the collector in this embodiment is used in the flotation of spodumene, the grade of Li2O in the concentrate obtained from the first roughing stage is 3.8%, and the recovery rate is 60%. When CAPB is used alone, both the grade and recovery rate are at a low level, and the foam is too stable with obvious entrainment of fine mud, proving that its collection and selection performance is limited when used alone. It can only exert synergistic value when compounded with components A and B in the proportion of this invention.

[0120] Comparative Example 4

[0121] This comparative example uses component A, potassium cocoyl glycinate (GCK-30), as a single agent at a dosage of 400 g / t, with the other conditions being the same as in Example 1.

[0122] When the collector in this embodiment is used for spodumene flotation, the resulting concentrate has a Li2O grade of 4.27% and a recovery rate of only 62.01%, indicating insufficient collecting capacity. Both the grade and recovery rate are significantly lower than those in Example 1 with the same dosage.

[0123] Comparative Example 5

[0124] This comparative example examines the following:

[0125] (a) Component B, fatty alcohol polyoxyethylene ether phosphate (AEO-3P), as a single reagent, at a dosage of 400 g / t, yielded a concentrate with a Li2O grade of 4.89% and a recovery rate of only 43.67%. When the dosage was increased to 1000 g / t, the recovery rate increased to 98.64%, but the grade decreased to 4.77% and the gangue inclusions were significantly aggravated.

[0126] (b) Component A, sodium cocoyl glycinate (GCS-30), is a single reagent used at a dosage of 400 g / t. It cannot form an effective foam layer during the flotation process, and therefore cannot produce foam products, making flotation impossible.

[0127] The results of the single collectors in Comparative Examples 1-5 for spodumene flotation show that, regardless of whether traditional fatty acid collectors such as oleic acid are used or the single-component collectors of this invention are used, single collectors have inherent defects in terms of grade, recovery rate or foaming performance.

[0128] Comparative Example 6

[0129] This comparative example uses a binary compound of component A (GCK-30) and component B (AEO-3P), that is, GCK-30 and AEO-3P are compounded at a mass ratio of 5:4 (excluding component C), with a total dosage of 400 g / t, and the other conditions are the same as in Example 1.

[0130] When the collector in this embodiment is used for spodumene flotation, the resulting concentrate has a Li₂O grade of 4.72% and a recovery rate of 69.5%. Compared with Example 1 (ternary system), the grade is 0.40 percentage points lower and the recovery rate is 8.8 percentage points lower, indicating that component C makes an indispensable contribution to the system by reducing the electrostatic repulsion between anionic components, increasing adsorption density, and improving foam performance. The technical effect of ternary compound formulation cannot be achieved by simple binary combination.

[0131] Comparative Example 7

[0132] This comparative example uses a binary compound of component A and component C, that is, GCK-30 and CAPB are compounded at a mass ratio of 5:1 (excluding component B), with a total dosage of 400 g / t, and the other conditions are the same as in Example 1.

[0133] When the collector in this embodiment was used for spodumene flotation, the resulting concentrate had a Li₂O grade of 4.45% and a recovery rate of 66.8%. The lack of the phosphate ester component significantly reduced the system's collecting power, resulting in a recovery rate 11.5 percentage points lower than that of Example 1.

[0134] Comparative Example 8

[0135] This comparative example uses a binary compound of component B and component C, that is, AEO-3P and CAPB are compounded at a mass ratio of 4:1 (excluding component A), with a total dosage of 400 g / t, and the other conditions are the same as in Example 1.

[0136] When the collector in this embodiment was used for spodumene flotation, the resulting concentrate had a Li₂O grade of 4.12% and a recovery rate of 58.4%. Without the acyl amino acid salt chelating component, the system's selectivity and collecting power decreased simultaneously, with the grade being 1.00 percentage point lower and the recovery rate 19.9 percentage points lower than in Example 1.

[0137] Comparative Examples 6-8 show that the grades and recoveries of the three binary combinations of components A+B, A+C, and B+C are all lower than those of the ternary system (Example 1), confirming that none of the three components can be omitted.

[0138]

[0139] Note: The concentrate yield and tailings Li2O grade in Table 1 are calculated based on the raw ore Li2O grade, concentrate Li2O grade and Li2O recovery rate according to the material balance of the two products.

[0140] Table 1 shows that each single agent has significant shortcomings: sodium oleate has a low grade, oleic acid and AEO-3P have low recovery rates, GCK-30 has weak collecting power, GCS-30 is unusable due to lack of foaming, and CAPB has both low grade and low recovery rate with significant foam entrainment. Although the three binary systems A+B, A+C, and B+C (comparative examples 6-8) show some improvement over their corresponding single agents, their grade and recovery rate are still significantly lower than those of the ternary systems. This invention combines three different ion types and different solid-loving functional groups in a specific ratio. Through the synergistic effect of carboxyl chelation, strong phosphate complexation and zwitterionic densification adsorption, a single roughing process can obtain spodumene concentrate with a Li2O grade of 4.5%~5.1% and a recovery rate of 78%~90%. Taking Example 1 as an example, under the same batch of raw ore and the same total dosage of 400 g / t, its grade (5.12%) and recovery rate (78.3%) are not only comprehensively superior to sodium oleate, oleic acid, GCK-30 and AEO-3P single agents (Comparative Examples 1, 2, 4, 5a), but also comprehensively superior to the three binary combinations of A+B, A+C, and B+C (Comparative Examples 6~8). In another batch of the same type of ore, the CAPB single agent test (Comparative Example 3) used for spodumene flotation showed that its grade and recovery rate were both low, indicating that component C, cocamidopropyl betaine, has limited performance when used alone. The above results confirm that there is a real synergistic effect among the three components, rather than a simple mixture and additive effect.

[0141] It should be noted that Comparative Examples 6-8 are component-deficient control experiments with a fixed total effective active amount (400 g / t). After deleting one component, the actual amounts of the remaining components increased accordingly, but their indicators were still comprehensively lower than those of the ternary system, further confirming the authenticity of the ternary synergy. Examples 6-8 further demonstrate that this compound system has good adaptability to spodumene ores of different properties and grades (Li₂O 0.8%~1.6%) in Sichuan, Jiangxi, Xinjiang, and other regions of China. Examples 9 and 10 confirm that the synergistic effect still exists when component A is replaced with other acyl amino acid salts and component C is replaced with other betaine-type amphoteric surfactants, supporting the component selection range defined in the claims. Furthermore, all the above examples were completed under conditions without the addition of any frother and obtained good indicators, confirming that the compound collector of this invention has both collector and frother functions.

[0142] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A compound collector for spodumene flotation, characterized in that, Based on the total mass of effective active ingredients, the spodumene flotation compound collector is composed of the following components: 40%~50% acyl amino acid salt, 30%~50% fatty alcohol polyoxyethylene ether phosphate, and 10%~20% alkylamidopropyl betaine.

2. The spodumene flotation compound collector as described in claim 1, characterized in that, The acyl amino acid salt is an acyl glycine salt and / or an acyl sarcosine salt.

3. The spodumene flotation compound collector as described in claim 2, characterized in that, The acylglycinate is potassium cocoylglycinate or sodium cocoylglycinate, and the acylsarcosine salt is sodium lauroylsarcosine.

4. The spodumene flotation compound collector as described in claim 1, characterized in that, Fatty alcohol polyoxyethylene ether phosphate is one or more of fatty alcohol polyoxyethylene ether phosphate monoester, phosphate diester and their salts, wherein the fatty alcohol group is C. 12 ~C 18 The average degree of polymerization of alkyl polyoxyethylene ethers is 3 or 9.

5. The spodumene flotation compound collector as described in claim 1, characterized in that, Alkylamidopropyl betaine is cocamidopropyl betaine and / or lauramidopropyl betaine.

6. The spodumene flotation compound collector as described in any one of claims 1-5, characterized in that, Based on the total mass of effective active ingredients, the mass ratio of acyl amino acid salt, fatty alcohol polyoxyethylene ether phosphate, and alkylamidopropyl betaine in the spodumene flotation compound collector is 5:4:1, 4:5:1, or 5:3:

2.

7. The application of the spodumene flotation compound collector as described in any one of claims 1-6 in spodumene flotation.

8. The application of the spodumene flotation compound collector as described in claim 7 in spodumene flotation, characterized in that, The spodumene flotation process includes the following steps: The raw spodumene ore is crushed, ground, and deslimed, then activated with an activator and prepared into an alkaline slurry. Add the compound collector, stir, and then perform aeration flotation and foam scraping. The foam product is spodumene concentrate, and the product in the tank is tailings. The spodumene ore is a pegmatite-type spodumene ore with a Li2O grade of not less than 0.8% and gangue minerals including one or more of quartz, albite, potassium feldspar, and mica.

9. The application of the spodumene flotation compound collector as described in claim 8 in spodumene flotation, characterized in that, The activator is magnesium chloride, and the total amount of the compound collector is 400~800 g / t. After adding the compound collector, stir for 2~3 min, then aerate and float and skim for 3~5 min. No frother is added after adding the compound collector.

10. The application of the spodumene flotation compound collector as described in claim 8 in spodumene flotation, characterized in that, The method for adding the compound collector is as follows: Acyl amino acid salts, fatty alcohol polyoxyethylene ether phosphates, and alkylamidopropyl betaine are pre-mixed evenly in proportion and then added to the slurry all at once. Alternatively, the slurry can be added in the following order: acyl amino acid salt, fatty alcohol polyoxyethylene ether phosphate, and alkylamidopropyl betaine. When adding the components sequentially, the slurry conditioning time between adjacent components is 1 to 3 minutes.

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