High-selectivity Gemini esterquats compound system and spodumene flotation enrichment method

Abstract

The invention relates to the technical field of lithium resource extraction, and relates to the key words of lithium resource efficient extraction, energy conservation and emission reduction. The invention discloses a high-selectivity Gemini esterquats compound system and a spodumene flotation enrichment method. The compound system comprises, by weight, 50%-70% of Gemini esterquats, 10%-20% of auxiliary collecting agents, 5%-15% of inhibitors and 3%-8% of foaming agents. The flotation enrichment method comprises the steps that the dissociation degree of spodumene is increased to 90% in a two-section ore grinding and hydraulic desliming mode, then the agent adding amount is dynamically regulated and controlled based on a kinetic model, finally, the inflation rate, the impeller rotating speed and the bubble scraping frequency are optimized, and then the flotation process is completed. The method has the beneficial effects that the grade and the recovery rate of Li2O are improved, the total dosage of chemicals is reduced, and the entrainment rate of symbiotic minerals is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium resource extraction, in particular to a highly selective Gemini ester-based quaternary ammonium salt complex system and a spodumene flotation enrichment method. Background Art

[0002] At present, spodumene flotation mainly adopts single collector (such as oleic acid, dodecylamine) or simple compound (fatty acid + diesel) flotation method. For example: sodium oleate system: depends on the reaction of oleate and Li at pH = 8-9. + complexation, but easily with Al in feldspar 3 + Combination, poor selectivity; Amine compounding: The combination of dodecylamine and pine oil can improve foam stability, but the inhibition of quartz is insufficient and a large amount of water glass (>2kg / t) is required; New agents: such as hydroxamic acids, although they have high selectivity, are expensive (>2000 US dollars / ton), and industrialization is limited.

[0003] In order to solve the above technical problems, those skilled in the art have disclosed a highly selective Gemini ester quaternary ammonium salt complex system and a spodumene flotation enrichment method: a patent for a spodumene ore flotation collector and a preparation method thereof and a spodumene ore flotation method (hereinafter referred to as the first comparative document), the publication number of which is: CN110369146B. The first comparative document is mainly to solve the problems of poor solubility and low selectivity of the collector in low-temperature slurry, and to improve the flotation efficiency and concentrate grade of low-grade spodumene ore (paragraph

[0004] of the specification), and the collector formula is: dodecyl A mixture of 10-30 parts dimethyl tertiary amine, 150-450 parts vegetable oleic acid, and 25-75 parts sodium hydroxide is used (paragraph

[0007] of the specification); the vegetable oleic acid is preferably soybean oleic acid with an iodine value of 120-140 (paragraph

[0011] of the specification); the flotation method employed in Reference Document No. 1 is to control the grinding fineness to -0.074 mm, accounting for 70-80% (paragraph

[0016] of the specification); the reagent dosage is 400-1000 g / t of collector and 10-20 g / t of calcium chloride as an activator (paragraph

[0017] of the specification). The technical effect achieved by Reference Document No. 1 is flotation in a slurry at 5-25°C, with a concentrate Li2O grade of 4.17-5.76% and a recovery rate of 62-86% (Table 1-2; paragraphs

[0050] -

[0067] of the specification).

[0004] In addition, those skilled in the art also disclosed a highly selective Gemini ester quaternary ammonium salt complex system and a spodumene flotation enrichment method: a spodumene composite collector and its preparation method, a patent for a spodumene ore flotation method (hereinafter referred to as the second comparative document), the publication number of which is: CN119303732A. The second comparative document is mainly intended to solve the problem of balancing the advantages and disadvantages of anionic / cationic collectors and improving flotation recovery and concentrate grade (paragraph

[0004] of the specification); the collector formula is: sulfonic acid (30-50%), amine (20- The invention discloses a six-component mixture comprising: sulphonic acid (35%), fatty acids (20-38%), ethers (4-6.5%), alcohols (1-6%), and kerosene (3-5%) (Claim 1; paragraph

[0020] of the specification); wherein the sulfonic acid comprises sodium dodecylbenzene sulfonate, etc. (paragraph

[0028] of the specification); the flotation method employed in the second comparative document is combined with magnetic separation for iron removal (paragraph

[0073] of the specification), with the dosage of the collector being 700g / t and the activator calcium chloride being 500-600g / t (paragraphs

[0076] and

[0092] of the specification). The technical effect achieved by the second comparative document is to increase the Li2O grade of the concentrate to 7.56% (South American ore) and 7.73% (African ore), and to increase the recovery rate to 90.3-90.4% (Table 3; paragraphs

[0079] and

[0094] of the specification).

[0005] However, the above two comparative documents still have limitations in their specific implementation, as follows:

[0006] First, the two comparative documents are not selective enough;

[0007] Comparative Document No. 1 relies on a calcium chloride activator (10-20 g / t) to enhance adsorption (paragraph

[0017] of the specification), but does not solve the feldspar / quartz co-floatation problem (the Li2O grade of the concentrate is only 5.76%, Table 2); and the inhibition rate of paragenetic minerals is not quantified, resulting in a limited improvement in the concentrate grade (only 4.17-5.76%).

[0008] The composite components of Comparative Document No. 2 are complex (6 types), but no special components (such as phosphates) are designed to selectively inhibit paragenetic minerals (paragraph

[0020] of the specification). Its high grade depends on pre-enrichment of the raw ore (magnetic separation to remove iron), and it has poor adaptability to mud-containing ores (no mention of control of fine mud entrainment).

[0009] Secondly, the dosage of the zero-reference document is large;

[0010] The total dosage of reagents in Reference Document No. 1 is a collector (400-1000 g / t) + an activator (10-20 g / t) + a regulator (sodium carbonate / sodium hydroxide ≥ 1600 g / t) (paragraphs

[0017] and

[0010] of the specification). This results in high total reagent costs and a heavy wastewater treatment burden.

[0011] The collector dosage in the No. 2 comparative document is 700 g / t (paragraph

[0076] of the specification), and additional activator calcium chloride (500-600 g / t) and adjuster (sodium carbonate / sodium hydroxide ≥ 1800 g / t) are required (paragraphs

[0076] and

[0092] of the specification). The multi-component compounding leads to high overall costs and poor industrial economic efficiency.

[0012] Thirdly, the two comparison documents lack dynamic adjustment and optimization in dosage;

[0013] Both comparative documents use fixed reagent addition amount and operation parameters (e.g., the flotation time of comparative document No. 1 is fixed at 5 minutes, Figure 1 ; The stirring time in the No. 2 comparative document is fixed at 10 minutes, paragraph

[0076] of the specification); the above-mentioned reagent addition and operation process cannot dynamically adjust the parameters according to the properties of the ore (such as embedded particle size, surface charge), resulting in unstable recovery rate when the ore grade fluctuates (the recovery rate in the No. 1 comparative document is 62-86%), and poor adaptability to special minerals such as high-oxide iron ore.

[0014] Finally, the two comparative documents are relatively weak in the selective synergistic mechanism of the agents;

[0015] Reference No. 1 relies on a simple saponification reaction of vegetable oleic acid and tertiary amine (paragraph

[0012] of the specification), and fails to establish a mechanism by which the "competition-shielding" effect inhibits paragenetic minerals;

[0016] Comparative Document No. 2 adopts a physical mixture of six components (paragraph

[0067] of the specification) without considering directional adsorption or inhibitor-collector synergistic mechanism.

[0017] In summary, those skilled in the art need a highly selective compound system and a spodumene flotation enrichment method that can improve the flotation quality of spodumene, inhibit the flotation of paragenetic minerals (such as feldspar and quartz), and reduce the total dosage of reagents. Summary of the Invention

[0018] The purpose of the present invention is to solve the above problems and design a highly selective Gemini ester quaternary ammonium salt complex system and a spodumene flotation enrichment method.

[0019] The technical solution of the present invention for achieving the above-mentioned purpose is a highly selective Gemini ester quaternary ammonium salt compound system, which is composed of 50-70% Gemini ester quaternary ammonium salt, 10-20% auxiliary collector (ester), 5-15% inhibitor (phosphate) and 3-8% foaming agent (polyether) by weight;

[0020] in,

[0021] Gemini ester quaternary ammonium salt is: didodecyl dimethyl diester quaternary ammonium salt (chemical formula: C 28 H 58 N2O4 + 2Cl - ), which serves as the main collector, and its main function is to enhance the directional adsorption of spodumene through the amphiphilic group and inhibit the hydrophobization of the paragenetic minerals;

[0022] Auxiliary collector (esters) is: isopropyl oleate (chemical formula: C 21 H 40 O2), whose main function is to adjust the surface tension of Gemini ester quaternary ammonium salt, promote the spreading of Gemini molecules on the mineral interface, and enhance the adsorption kinetics;

[0023] The inhibitor (phosphate) is sodium hexametaphosphate (SHMP) (chemical formula: (NaPO3)6), which mainly functions to selectively complex the metal ions (such as Al 3+ 、Fe 3+ ), inhibiting its combination with the collector;

[0024] Foaming agent (polyether) is: polyoxyethylene (20) sorbitan monooleate (chemical formula: C 64 H 124 O 26 ), its main function is to form a stable foam layer, reduce bubble mergers, and improve the carrying efficiency of spodumene particles.

[0025] The compounding ratio of the Gemini ester quaternary ammonium salt, the auxiliary collector (ester), the inhibitor (phosphate) and the foaming agent (polyether) is 6:1.5:0.5:0.3.

[0026] The Gemini ester quaternary ammonium salt is first produced by esterifying a long-chain fatty acid with triethanolamine to form an ester intermediate, and then reacting the ester intermediate with a quaternizing agent (such as methyl chloride) to form a diquaternary ammonium salt structure; it should be noted that: the esterification temperature is 80-100°C, the quaternization reaction pH is 8-10, and the reaction time is 4-6h.

[0027] The auxiliary collector (ester) is synthesized by transesterification of fatty acids with short-chain alcohols (such as isopropyl alcohol), and the catalyst for the reaction is concentrated sulfuric acid.

[0028] The inhibitor (phosphate) is a composite phosphate colloid generated by co-precipitation of sodium phosphate and a metal salt (such as AlCl3).

[0029] The foaming agent (polyether) is prepared by compounding and modifying polyoxyethylene ether (such as Tween-80), and the added amount is optimized by HLB value.

[0030] A spodumene flotation enrichment method, which uses the highly selective Gemini ester quaternary ammonium salt compound system described in any one of claims 1 to 6 to realize the spodumene flotation process.

[0031] The method comprises the following steps:

[0032] Step 1, ore pretreatment, mainly addresses the problem of fine-grained ore and complex paragenetic minerals. A two-stage grinding process is adopted. The first stage of grinding coarsely grinds the mineral particles to 0.3mm. The second stage of grinding finely grinds the mineral particles to 0.074mm, ensuring that the 0.074mm mineral particles account for 80% of the total mineral particles. Then, hydraulic classification is used for desliming to obtain the ore pulp to be flotated. The purpose of step 1 is to increase the dissociation degree of spodumene monomer to more than 90%;

[0033] Step 2: Intelligent addition of reagents, which is mainly to solve the problems of slow adsorption kinetics and selectivity of traditional collectors. The intelligent control model is used to dynamically correlate the surface properties of minerals, the mechanism of action of reagents and operating parameters (concentration, time, temperature), and the required dosage of reagents for slurries of different properties is calculated based on the correlation. Then, according to the calculation results, a highly selective Gemini ester-based quaternary ammonium salt complex system reagent is added to the slurry to be floated, thereby achieving the technical effect of increasing the adsorption rate of spodumene by 40% and reducing the adsorption of paragenetic minerals by 30%;

[0034] Step 3, flotation separation, is mainly to solve the technical problem of low concentrate grade caused by foam entrainment during flotation. The ore pulp to be floated is aerated and stirred with a highly selective Gemini ester quaternary ammonium salt compound system reagent. The aeration rate is 0.2m 3 / min, the impeller speed is 1200rpm, and the scraping frequency is 5 times / min; the grade of lithium oxide (Li2O) in the flotation separation concentrate is increased from 4.5% to 6.2%, ensuring that the recovery rate of the lithium oxide (Li2O) in the concentrate is greater than 85%.

[0035] The intelligent control model in step 2 is:

[0036] R=k·C Gemini ·e -Ea / (rT) ·t 0.5

[0037] Where R is the spodumene recovery rate and is also the target optimization value for adjusting the amount of reagent added. Its main function is to determine the concentration of Gemini ester quaternary ammonium salt based on the dynamic correlation between the mineral surface properties, the reagent action mechanism and the operating parameters (concentration, time, temperature), and then determine the amount of reagent added required for slurries with different properties; k is the kinetic constant, which is related to the mineral surface properties (such as porosity and charge density); CGemini is the concentration of Gemini ester quaternary ammonium salt, that is, the amount of the main capture agent in the composite system; E a is the adsorption activation energy, which is mainly used to characterize the energy barrier for the combination of collector and mineral; T is the slurry temperature; r is the gas constant 8.314 J / (mol·K); t is the action time;

[0038] The intelligent control model can quickly determine the Gemini concentration (C) required to achieve the target recovery rate (such as R>85%) under specific ore properties (such as embedded particle size and surface charge) through calculation. Gemini ) and slurry mixing time (t), avoiding the high cost and low efficiency of traditional trial and error method

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] 1. The present invention adopts a composite system and flotation method to effectively improve the lithium grade, and can increase the Li2O grade from 4.5% to 6.2% (Gemini strong selective adsorption + inhibitor shielding Al 3+ );

[0041] 2. The compounding system adopted by the present invention can effectively reduce the reagent cost and enhance the Gemini adsorption efficiency by using auxiliary collectors, thereby reducing the total amount of flotation reagents by 30%;

[0042] 3. The present invention can effectively improve the flotation rate and increase the recovery rate by 20% by using the slurry adjustment parameters guided by the mathematical model, while effectively reducing the cost of reagents;

[0043] 4. The present invention utilizes a diquaternary ammonium salt head group and an ester tail chain to enhance the directional adsorption of the Al-O bond of spodumene. At the same time, through a complex synergistic mechanism, an inhibitor (phosphate) is utilized to preferentially complex the metal ions of the paragenetic minerals, forming a "competition-shielding" effect with Gemini, thereby improving the reselection efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is a flow chart of a spodumene flotation enrichment method according to the present invention;

[0045] Figure 2 This is an effect analysis table of Examples 1-3 of the present invention;

[0046] Figure 3 is a curve diagram of the dynamic association implemented by the intelligent control model of the present invention;

[0047] Figure 4 It is a curve diagram of the recovery rate of the present invention;

[0048] Figure 5 It is a comparative analysis table of the present invention and two comparative documents. DETAILED DESCRIPTION

[0049] The present invention will be described in detail below with reference to the accompanying drawings. Figure 1 and Figure 5 As shown;

[0050] A highly selective Gemini ester-based quaternary ammonium salt compound system, comprising the following weight percentages: 50-70% Gemini ester-based quaternary ammonium salt, 10-20% auxiliary collector (ester), 5-15% inhibitor (phosphate) and 3-8% foaming agent (polyether);

[0051] in,

[0052] Gemini ester quaternary ammonium salt is: didodecyl dimethyl diester quaternary ammonium salt (chemical formula: C 28 H 58 N2O4 + 2Cl - ), is a diquaternary ammonium salt structure containing two ester groups (-COO-) connected, which is used as the main collector. Its main function is to enhance the directional adsorption of spodumene through the amphiphilic group and inhibit the hydrophobization of the paragenetic minerals;

[0053] Auxiliary collector (esters) is: isopropyl oleate (chemical formula: C 21 H 40 O2), structural formula: CH3(CH2)7CH=CH(CH2)7COOCH(CH3)2, its main function is to adjust the surface tension of Gemini ester quaternary ammonium salt, promote the spreading of Gemini molecules on the mineral interface, and enhance adsorption kinetics;

[0054] The inhibitor (phosphate) is sodium hexametaphosphate (SHMP) (chemical formula: (NaPO3)6), which has a cyclic hexamer structure consisting of 6 PO3 - The units are connected by oxygen bridges, whose main function is to selectively complex the metal ions (such as Al 3+ 、Fe 3+ ), inhibiting its combination with the collector;

[0055] Foaming agent (polyether) is: polyoxyethylene (20) sorbitan monooleate (chemical formula: C 64 H 124 O 26 ), whose structural formula is a sorbitol backbone connected to an oleic acid chain (C 18 H 34 O2) and 20 ethylene oxide (EO) units, whose main function is to form a stable foam layer, reduce bubble mergers, and improve the carrying efficiency of spodumene particles.

[0056] The compounding ratio of Gemini ester quaternary ammonium salt, auxiliary collector (ester), inhibitor (phosphate) and foaming agent (polyether) is 6:1.5:0.5:0.3.

[0057] Gemini ester quaternary ammonium salts are first produced by the esterification reaction of long-chain fatty acids with triethanolamine to form an ester intermediate, which is then reacted with a quaternizing agent (such as methyl chloride) to form a diquaternary ammonium salt structure. It should be noted that the esterification temperature is 80-100°C, the quaternization reaction pH is 8-10, and the reaction time is 4-6h.

[0058] Among them, the esterification reaction is to convert the raw material dodecyl fatty acid (C 12 H 24 O2) and triethanolamine (C6H 15 NO3), reacting at a temperature of 80-100°C under concentrated sulfuric acid catalysis for 3 hours to generate an ester intermediate;

[0059] The quaternization reaction is to react the intermediate with methyl chloride (CH3Cl) at pH = 8-10 and a temperature of 50°C for 6 hours to generate a diquaternary ammonium salt, and then use ethanol recrystallization to remove unreacted products.

[0060] In the traditional mineral flotation process, the role of Gemini ester quaternary ammonium salts is to adsorb on the silicate surface through the double quaternary ammonium group, which is used for the flotation of quartz / feldspar with low selectivity; the calcium ion complexing ability of the carboxylic acid ester group can also be relied upon to separate fluorite and calcite; and the role of Gemini ester quaternary ammonium salts in the technical solution of the present invention is to utilize the ester group to form a hydrogen bond with the Al-O bond on the spodumene surface, and the double quaternary ammonium group to neutralize the negative charge on the spodumene surface, thereby enhancing selectivity, while utilizing the steric hindrance effect to hinder the adsorption of large molecules on the feldspar / quartz surface and inhibit the growth of paragenetic minerals.

[0061] Auxiliary collectors (esters) are synthesized by transesterification of fatty acids with short-chain alcohols (such as isopropyl alcohol), and the catalyst for the reaction is concentrated sulfuric acid; the raw materials: oleic acid (C 18 H 34 O2) and isopropyl alcohol (C3H8O) were reacted under concentrated sulfuric acid catalysis at 60°C for 4 hours, and after stratification, the product was purified by vacuum distillation;

[0062] Isopropyl oleate is commonly used in the flotation process of apatite and coal. In the apatite flotation process, it is used as an auxiliary collector in combination with fatty acids to reduce the viscosity of the slurry. In the coal flotation process, its role is to enhance hydrophobicity and increase the yield of clean coal. In the technical solution of the present application, the main function of isopropyl oleate is to reduce the surface tension of spodumene from 72mN / m to 45mN / m, promote the spreading of Gemini molecules on the mineral interface, and promote the co-adsorption of ester groups and Gemini hydrophobic chains to form a dense hydrophobic film.

[0063] The inhibitor (phosphate) is a composite phosphate colloid formed by co-precipitation of sodium phosphate and a metal salt (such as AlCl3); sodium dihydrogen phosphate (NaH2PO4) is melt-polymerized at 600°C for 1 hour, quenched to form a glassy solid, and then the glassy solid is crushed and dissolved to form a composite phosphate colloid.

[0064] In the traditional process, the main function of the composite phosphate colloid is to suppress hematite and activated quartz in the reverse flotation process of iron ore, or to suppress chalcopyrite and improve the grade of molybdenum concentrate. In the technical solution of this application, the main function of the composite phosphate colloid is to use PO3 - With Al in feldspar 3+ Formation of [Al(PO3)6] 3- It stabilizes the complex, shields the active sites, and reduces the interference of -10μm fine mud on flotation through electrostatic repulsion.

[0065] The foaming agent (polyether) is prepared by compounding and modifying polyoxyethylene ether (such as Tween-80) and optimizing the added amount through the HLB value. The specific preparation process is to use sorbitan monooleate and ethylene oxide as raw materials, add an alkaline catalyst (KOH), and react under the conditions of pressure 0.3MPa and temperature 120℃, and stop the reaction when the EO addition number reaches 20.

[0066] A spodumene flotation enrichment method, which uses the high-selectivity Gemini ester quaternary ammonium salt compound system of any one of claims 1 to 6 to realize the spodumene flotation process.

[0067] The method comprises the following steps:

[0068] Step 1, ore pretreatment, mainly addresses the problem of fine-grained ore and complex paragenetic minerals. A two-stage grinding process is adopted. The first stage of grinding coarsely grinds the mineral particles to 0.3mm. The second stage of grinding finely grinds the mineral particles to 0.074mm, ensuring that the 0.074mm mineral particles account for 80% of the total mineral particles. Then, hydraulic classification is used for desliming to obtain the ore pulp to be flotated. The purpose of step 1 is to increase the dissociation degree of spodumene monomer to more than 90%;

[0069] Step 2: Intelligent addition of reagents, which is mainly to solve the problems of slow adsorption kinetics and selectivity of traditional collectors. The intelligent control model is used to dynamically associate the mineral surface properties, reagent action mechanism and operating parameters (concentration, time, temperature), and calculate the required reagent dosage and expected recovery rate of slurries with different properties based on the correlation, such as Figure 3 and Figure 4 As shown, according to the calculation results, a highly selective Gemini ester quaternary ammonium salt compound system reagent is added to the ore pulp to be floated, thereby achieving the technical effect of increasing the spodumene adsorption rate by 40% and reducing the adsorption of paragenetic minerals by 30%;

[0070] Step 3, flotation separation, is mainly to solve the technical problem of low concentrate grade caused by foam entrainment during flotation. The ore pulp to be floated is aerated and stirred with a highly selective Gemini ester quaternary ammonium salt compound system reagent. The aeration rate is 0.2m 3 / min, the impeller speed is 1200rpm, and the scraping frequency is 5 times / min; the grade of lithium oxide (Li2O) in the flotation separation concentrate is increased from 4.5% to 6.2%, ensuring that the recovery rate of the lithium oxide (Li2O) in the concentrate is greater than 85%.

[0071] The intelligent control model in step 2 is:

[0072] R=k·C Gemini ·e -Ea / (rT) ·t 0.5

[0073] Where R is the spodumene recovery rate and is also the target optimization value for adjusting the amount of reagent added. Its main function is to determine the concentration of Gemini ester quaternary ammonium salt based on the dynamic correlation between the mineral surface properties, the reagent action mechanism and the operating parameters (concentration, time, temperature), and then determine the amount of reagent added required for slurries with different properties; k is the kinetic constant, which is related to the mineral surface properties (such as porosity and charge density); C Gemini is the concentration of Gemini ester quaternary ammonium salt, that is, the amount of the main capture agent in the composite system; E a is the adsorption activation energy, which is mainly used to characterize the energy barrier for the combination of collector and mineral; T is the slurry temperature; r is the gas constant 8.314 J / (mol·K); t is the action time;

[0074] The intelligent control model can quickly determine the Gemini concentration (C) required to achieve the target recovery rate (such as R>85%) under specific ore properties (such as embedded particle size and surface charge). Gemini ) and slurry mixing time (t), avoiding the high cost and low efficiency of the traditional trial and error method.

[0075] It should be noted that the intelligent control model can dynamically control the relationship between reagent concentration and time. Through model calculation, the Gemini concentration (C) required to achieve the target recovery rate (such as R>85%) under specific ore properties (such as embedded particle size and surface charge) can be quickly determined. Gemini ) and slurry mixing time (t), avoiding the high cost and low efficiency of the traditional trial and error method; at the same time, quantifying the temperature effect, the exponential term e in the model -Ea / (RT) Directly related to temperature (T) and adsorption rate, the slurry heating / cooling strategy can be optimized (e.g. 25-30℃ is the optimal range). For example: if the ore surface roughness is high (large k value), the C Gemini Or shorten tt to achieve the same recovery rate and save more than 30% of the reagent cost.

[0076] In addition, the intelligent control model implies the competitive adsorption effect between Gemini and inhibitor (phosphate), and the inhibitor preferentially adsorbs Al on the surface of paragenetic minerals (such as feldspar and quartz). 3+ 、Fe 3+ Complexation, occupying its active sites, the highly selective adsorption of Gemini occurs only on the surface of spodumene (depending on the directional binding of Al-O-Si bonds). At this time, the k value in the model corresponds only to spodumene, while the k of the paragenetic minerals approaches 0. The ratio of inhibitor to Gemini can be optimized by model inversion (for example, when the phosphate ratio is >10%, the adsorption of paragenetic minerals decreases by 35%). If the inhibitor is excessive (such as phosphate >15%), the Ea in the model will increase due to excessive passivation of the mineral surface, and the ratio needs to be adjusted to balance the inhibition effect and lithium recovery rate.

[0077] When the ore grade fluctuates (such as Li2O drops from 1.2% to 0.8%), by adjusting C Gemini and t (e.g., extending the slurry preparation time by 20%) to maintain a stable recovery rate; model parameters (k, E a ) can be calibrated in a small laboratory test and directly used for the calculation of process parameters of production-line-level flotation cells, shortening the commissioning cycle by more than 50%.

[0078] Existing technologies rely on empirical reagent ratios (such as fixed concentrations or fixed time), while this model dynamically associates mineral surface properties, reagent action mechanisms, and operating parameters (concentration, time, temperature) through the coupling of adsorption kinetics and thermodynamics, achieving precise control of "one mine, one policy". For example: for spodumene ore with high iron oxide content (E a The temperature needs to be raised to 30°C to reduce the adsorption energy barrier. At this time, the model can directly derive the optimal solution, avoiding the blindness of manual debugging.

[0079] This intelligent control model not only serves as a "digital twin" of the flotation process but also provides a quantitative bridge for leveraging the synergistic effects of a complex system (Gemini + inhibitor). Its core value lies in transforming the traditional "black box" adsorption process in flotation into a transparent, calculable, and optimizable parameter system, thereby systematically addressing the industry's pain points of low selectivity and inefficient efficiency.

[0080] Example 1

[0081] Application of the present invention in the flotation of high-grade spodumene ore;

[0082]

[0083] Example 2

[0084] Application of the present invention in flotation of low-grade muddy spodumene ore;

[0085]

[0086]

[0087] Example 3

[0088] Application of the present invention in the flotation of high iron oxide type spodumene ore;

[0089]

[0090] The data analysis table of Examples 1-3 is as follows: Figure 2 shown.

[0091] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include," "comprise," or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or device that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or device. In the absence of further limitations, the phrase "includes an element defined by..." does not exclude the presence of other identical elements in the process, method, article, or device that includes the element.

[0092] The above technical solutions only reflect the preferred technical solutions of the technical solutions of the present invention. Any changes that may be made to certain parts thereof by those skilled in the art all reflect the principles of the present invention and fall within the scope of protection of the present invention.

Claims

1. A highly selective Gemini ester quaternary ammonium salt complex system, characterized in that: The weight percentage composition of the composite system is: 50-70% of Gemini ester quaternary ammonium salt, 10-20% of auxiliary collector, 5-15% of inhibitor and 3-8% of foaming agent.

2. The highly selective Gemini ester quaternary ammonium salt compounding system according to claim 1, wherein The compounding ratio of the Gemini ester quaternary ammonium salt, the auxiliary collector, the inhibitor and the foaming agent is 6:1.5:0.5:0.

3.

3. The highly selective Gemini ester quaternary ammonium salt composite system according to claim 2, wherein The Gemini ester quaternary ammonium salt is firstly prepared by esterifying a long-chain fatty acid with triethanolamine to generate an ester intermediate, and then reacting the ester intermediate with a quaternizing agent to generate a diquaternary ammonium salt structure.

4. The highly selective Gemini ester quaternary ammonium salt compounding system according to claim 2, wherein The auxiliary collector is synthesized by transesterification of fatty acids and short-chain alcohols, and the catalyst of the reaction is concentrated sulfuric acid.

5. The highly selective Gemini ester quaternary ammonium salt compounding system according to claim 2, wherein The inhibitor is a composite phosphate colloid generated by co-precipitation of sodium phosphate and metal salt.

6. The highly selective Gemini ester quaternary ammonium salt compounding system according to claim 2, wherein The foaming agent is formed by compounding and modifying polyoxyethylene ether.

7. A spodumene flotation enrichment method, characterized in that: The method adopts the high-selectivity Gemini ester quaternary ammonium salt complex system described in any one of claims 1 to 6 to realize the spodumene flotation process.

8. The method according to claim 7, characterized in that The method comprises the following steps: Step 1: Ore pretreatment, using a two-stage grinding process to finely grind the mineral to a particle size of 0.074 mm, and then use hydraulic classification to desludging to obtain the ore pulp to be flotated; Step 2: Intelligent reagent addition. The intelligent control model is used to calculate the amount of reagent required for different properties of slurries. Then, based on the calculated results, a highly selective Gemini ester-based quaternary ammonium salt compound system reagent is added to the slurry to be floated. Step three: flotation separation, aerating and stirring the slurry with added reagents, and flotation separation of lithium oxide concentrate.

9. A highly selective Gemini ester quaternary ammonium salt complex system and spodumene flotation enrichment method according to claim 8, characterized in that: The intelligent control model in step 2 is: Where R is the spodumene recovery rate, k is the kinetic constant, C Gemini is the concentration of Gemini ester quaternary ammonium salt, E a is the adsorption activation energy, T is the slurry temperature, r is the gas constant, and t is the action time.

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