Dressing agents, flotation separation reagent groups comprising the dressing agents, and methods for separating lithium from aluminum smelting residue containing lithium

Abstract

The application discloses a pulp conditioning agent, a flotation separation reagent group containing the pulp conditioning agent and a method for separating lithium from lithium-containing aluminum smelting slag, and belongs to the technical field of comprehensive utilization of mineral resources. The flotation separation reagent group comprises a pulp conditioning agent, a gangue mineral inhibitor, a lithium complexing agent and a collector, wherein the pulp conditioning agent comprises an adjusting agent and a scrubbing mineral dressing agent, the adjusting agent comprises at least one of NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, MgCl2 and CaCl2, and the scrubbing mineral dressing agent comprises at least one of water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap and sodium tripolyphosphate. The flotation separation reagent group can expand the floatability difference among four kinds of fluorine-containing minerals, reduce the influence of high-temperature melting on the internal crystal structure properties of lithium-containing aluminum smelting slag, and effectively realize the separation and enrichment of molten lithium fluoride.

Description

Technical Field

[0001] This invention relates to the field of comprehensive utilization of mineral resources, and more specifically, to a slurry conditioner, a flotation separation reagent kit containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag. Background Technology

[0002] The lithium-bearing aluminum slag produced after smelting aluminum from bauxite using the "direct reduction-electric furnace smelting" process contains 50%-60% F, 20%-25% Na2O, 10%-15% Al2O3, 2%-5% CaO, 1.5%-3% Li2O, and 1%-3% K2O. It exhibits high levels of fluorine, sodium, and aluminum, but lower levels of calcium, lithium, and potassium. Compared to lithium concentrate obtained from the ore, the lithium in the lithium-bearing aluminum slag is mainly concentrated in the molten lithium fluoride phase. Other associated phases include cryolite (Na3AlF6), potassium cryolite (KAlF4), and fluorite (CaF2). All associated minerals in the molten state are fluorine-containing minerals with complex crystal structures, blurred boundaries between phases, and similar mineral properties, making separation and beneficiation difficult.

[0003] The main uses of lithium fluoride in lithium-containing aluminum smelting slag include: as a raw material for lithium batteries, lithium glass, and as a deoxidizer. In bauxite smelting, excessively high lithium fluoride content in the added electrolyte can lead to slow heating during the melting process and high energy consumption for maintaining high temperatures. By beneficiating and separating lithium from lithium-containing aluminum smelting slag, high-lithium concentrate products can be obtained. Simultaneously, low-lithium aluminum slag products can be recycled as electrolytes in the bauxite smelting process, improving acidolysis conditions during melting, reducing production costs, and providing important guidance for expanding the application range of lithium-containing aluminum smelting slag.

[0004] The mineral crystals in lithium-containing aluminum slag produced by high-temperature smelting are extremely small (around 0.1μm-20μm), resulting in poor mineral processing, separation, and enrichment. Recent research has yielded some scientific results in modifying the structural properties of lithium-containing aluminum slag (on the one hand, using slow cooling to increase the two-dimensional length of the mineral crystals in the aluminum slag to achieve industrial enrichment and separation properties; on the other hand, optimizing the interphase connection mode between lithium-containing substances and other minerals in the lithium-containing aluminum slag). However, due to the similar properties among fluorine-containing minerals, the high difficulty in separation and enrichment, the low recovery rate of lithium concentrate, and the complexity of the process, industrial application has not yet been realized.

[0005] In view of the above problems, it is necessary to provide a slurry conditioner, a flotation separation reagent kit containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag. Summary of the Invention

[0006] The purpose of this invention is to overcome the defects of the prior art by providing a slurry conditioner, a flotation separation reagent group containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag.

[0007] The technical problem solved by this invention is achieved by the following technical solution.

[0008] This invention provides a slurry conditioner for separating lithium from lithium-containing aluminum smelting slag. The conditioner comprises a modifier and a scrubbing agent. The modifier includes at least one selected from NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, MgCl2, and CaCl2. The scrubbing agent includes at least one selected from water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap, and sodium tripolyphosphate. The dosage of the modifier is 4000-9000 g / t of lithium-containing aluminum smelting slag, and the dosage of the scrubbing agent is 300-700 g / t of lithium-containing aluminum smelting slag.

[0009] This invention provides an application of the above-mentioned slurry conditioner in the slurry conditioning for lithium separation from lithium-containing aluminum smelting slag.

[0010] This invention provides a flotation separation reagent kit for separating lithium from lithium-containing aluminum smelting slag. This flotation separation reagent kit is mainly used for roughing of lithium-containing aluminum smelting slag. It includes a slurry conditioner, gangue mineral inhibitor, lithium complexing agent, and collector. The slurry conditioner includes a modifier and a scrubbing agent. The modifier includes at least one of NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, MgCl2, and CaCl2. The scrubbing agent includes at least one of water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap, and sodium tripolyphosphate.

[0011] This invention provides an application of the above-mentioned flotation separation reagent group in the flotation separation of lithium in lithium-containing aluminum smelting slag.

[0012] The present invention provides a method for separating lithium from lithium-containing aluminum smelting slag using the above-mentioned flotation separation reagent group, comprising: adding a slurry conditioner to the slurry obtained by grinding lithium-containing aluminum smelting slag and starting stirring; during the stirring process, adding gangue mineral inhibitor, lithium complexing agent and collector in sequence; and obtaining lithium concentrate by flotation separation.

[0013] The present invention has the following beneficial effects:

[0014] This invention provides a slurry conditioner, a flotation separation reagent kit containing the slurry conditioner, and a method for separating lithium from lithium-bearing aluminum smelting slag. When the slurry conditioner is applied, it is added to the slurry to adjust it into a suitable ionic solution. Then, a scrubbing reagent is added to clean the mineral surface, removing the influence of high-temperature calcination on the mineral phases and improving the surface property differences between the lithium mineral phase and the gangue mineral phase, thus creating conditions for flotation separation. Furthermore, when the flotation separation reagent kit containing the slurry conditioner is used for roughing separation, ionic slurry scrubbing, suppression of gangue minerals, complexation of lithium fluoride, and finally collection of lithium fluoride yield a high-quality lithium concentrate. The solution provided by this invention solves key technical problems in the beneficiation of lithium-bearing aluminum smelting slag and is one of the effective ways to improve the utilization rate of lithium resources in lithium-bearing bauxite. Attached Figure Description

[0015] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0016] Figure 1 This is a schematic diagram of the process for separating lithium from lithium-containing aluminum smelting slag using the flotation separation reagent kit provided in the embodiments of the present invention. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0018] This invention proposes a slurry conditioner, a flotation separation reagent group containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag. This method aims to recover and utilize lithium in lithium-containing aluminum smelting slag formed by direct reduction and electric furnace smelting of bauxite, expand the application scope of aluminum smelting slag, and solve the problem of low lithium resource utilization in lithium-containing bauxite in my country.

[0019] The following is a detailed description of a slurry conditioner, a flotation separation reagent kit containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag, provided by embodiments of the present invention.

[0020] In a first aspect, embodiments of the present invention provide a slurry conditioner for separating lithium from lithium-containing aluminum smelting slag. The slurry conditioner includes a modifier and a scrubbing agent. The modifier includes at least one of NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, MgCl2, and CaCl2. The scrubbing agent includes at least one of water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap, and sodium tripolyphosphate. The dosage of the modifier is 4000-9000 g / t of lithium-containing aluminum smelting slag, and the dosage of the scrubbing agent is 300-700 g / t of lithium-containing aluminum smelting slag.

[0021] Current methods for separating lithium from lithium-containing aluminum smelting slag typically involve acid or alkali reactions, requiring multiple separations and multi-step reactions. This results in low yields, high production costs, and weak market competitiveness. The difficulty in separating lithium from lithium-containing aluminum smelting slag stems from the fact that it is a man-made ore, primarily composed of four fluorine-containing minerals formed under high-temperature, long-term conditions. This alters the surface crystal structure and significantly changes the interphase distribution of the minerals. Lithium fluoride exhibits very little difference in floatability compared to the other three fluorine-containing minerals, making it difficult to inhibit separation by gangue minerals. This leads to difficulties in enriching and separating lithium fluoride, rendering conventional beneficiation reagent combinations and processes ineffective.

[0022] This invention provides a slurry conditioner for lithium separation in lithium-containing aluminum smelting slag. The slurry conditioner includes a modifier and a scrubbing agent. When the slurry conditioner is applied, the modifier is added to the slurry to adjust it into a suitable ionic solution. Then, the scrubbing agent is added to clean the mineral surface, removing the influence of high-temperature calcination on the mineral phases and improving the surface property differences between the lithium mineral phase and the gangue mineral phase, thus creating conditions for flotation separation. It can be seen that using a slurry conditioner to adjust the slurry can expand the floatability differences among the four fluorine-containing minerals, reduce the influence of high-temperature melting on the internal crystal structure properties of lithium-containing aluminum smelting slag, effectively achieve the separation and enrichment of molten lithium fluoride, and solve the key technical problems in the beneficiation of lithium-containing aluminum smelting slag.

[0023] Secondly, embodiments of the present invention provide an application of the above-mentioned slurry conditioner in the slurry conditioning for lithium separation from lithium-containing aluminum smelting slag.

[0024] Thirdly, embodiments of the present invention provide a flotation separation reagent group for separating lithium from lithium-containing aluminum smelting slag. This flotation separation reagent group is mainly used for roughing of lithium-containing aluminum smelting slag and includes a slurry conditioner, gangue mineral inhibitor, lithium complexing agent and collector. The slurry conditioner includes a modifier and a scrubbing beneficiation agent.

[0025] This invention provides a flotation separation reagent kit for separating lithium from lithium-containing aluminum smelting slag. This kit is primarily used for roughing of lithium-containing aluminum smelting slag and includes a slurry conditioner, gangue mineral inhibitor, lithium complexing agent, and collector. The kit effectively separates lithium from the slurry because: the conditioner adjusts the slurry to a suitable ionic solution; the scrubbing agent cleans the mineral surface, removing the effects of high-temperature calcination on the mineral phases and improving the surface property differences between the lithium and gangue mineral phases, creating conditions for flotation separation; the gangue mineral inhibitor suppresses non-lithium-containing gangue minerals; the lithium complexing agent complexes lithium minerals to form aggregates; and the collector captures lithium, ultimately obtaining lithium concentrate through flotation separation.

[0026] In an optional embodiment, the modifier includes at least one of the following: NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, MgCl2, and CaCl2. The scrubbing agent includes at least one of the following: water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap, and sodium tripolyphosphate. The dosage of the modifier is 4000-9000 g / t of lithium-containing aluminum smelting slag. The dosage of the scrubbing agent is 300-700 g / t of lithium-containing aluminum smelting slag.

[0027] In an optional embodiment, the gangue mineral inhibitor includes at least one of sodium hexametaphosphate, starch, water glass, sodium fluorosilicate, and carboxymethyl cellulose;

[0028] Preferably, the dosage of gangue mineral inhibitor is 100-1000 g / t of lithium-containing aluminum smelting slag.

[0029] In an optional embodiment, the lithium complexing agent includes at least one of carboxymethyl cellulose, sodium petroleum sulfonate, refined paste, modified starch, sodium hexametaphosphate, and ferric chloride.

[0030] Preferably, the amount of lithium complexing agent used is 200-800 g / t of lithium-containing aluminum smelting slag.

[0031] In an optional implementation, the collector includes a primary collector and an auxiliary collector;

[0032] Preferably, the main collector includes at least one of dodecylamine, sodium petroleum sulfonate, oxidized paraffin soap, hydroxamic acid, sodium oleate, and sodium benzylarsinate;

[0033] Preferably, the auxiliary collector includes at least one of turpentine, kerosene, diesel oil, and modified No. 2 oil;

[0034] Preferably, the dosage of the main collector is 200-1000 g / t of lithium-containing aluminum smelting slag, and the dosage of the auxiliary collector is 20-100 g / t of lithium-containing aluminum smelting slag. More preferably, the dosage of the main collector is 100-500 g / t of lithium-containing aluminum smelting slag, and the dosage of the auxiliary collector is 20-50 g / t of lithium-containing aluminum smelting slag.

[0035] Fourthly, embodiments of the present invention provide an application of the above-mentioned flotation separation reagent group in the flotation separation of lithium from lithium-containing aluminum smelting slag.

[0036] Fifthly, embodiments of the present invention provide a method for separating lithium from lithium-containing aluminum smelting slag using the above-mentioned flotation separation reagent group, comprising: adding a slurry conditioner to the slurry obtained by grinding lithium-containing aluminum smelting slag and starting stirring; during the stirring process, adding gangue mineral inhibitor, lithium complexing agent and collector in sequence; and obtaining lithium concentrate by flotation separation.

[0037] In an optional implementation, the specific steps of flotation separation are as follows: lithium-containing aluminum smelting slag is subjected to flotation at a pulp concentration of 15-30%. The flotation adopts one roughing and one to four cleaning stages. In the roughing stage, the lithium-containing aluminum smelting slag is added to the flotation cell, a pulp conditioner is added to adjust the pulp, and stirring is started to control the pulp mass concentration at 15-30% and the pulp temperature at 5-30°C. During the stirring process, gangue mineral inhibitors, lithium complexing agents, and collectors are added in sequence. Then, the lithium concentrate obtained after roughing is cleaned, and high-grade lithium concentrate is obtained after flotation.

[0038] In an optional embodiment, the step of adding a slurry conditioner to the slurry obtained by grinding lithium-containing aluminum slag is as follows: add a conditioner to the slurry obtained by grinding lithium-containing aluminum slag to adjust it into a suitable ionic solution, then add a scrubbing and beneficiation agent to clean the mineral surface, and maintain the pH value of the slurry at 7.

[0039] Preferably, the slurry is prepared by the following steps: the lithium-containing aluminum smelting slag formed by direct reduction-electric furnace melting of bauxite and water quenching is crushed, screened, and ground to obtain the slurry.

[0040] Preferably, the screening process involves a closed-circuit crushing and screening method using a crusher and a vibrating screen to crush lithium-containing aluminum smelting slag to -2mm.

[0041] Preferably, the grinding process involves wet grinding of the crushed lithium-containing aluminum smelting slag using a rod mill to obtain a slurry with 40% particle size of 0.045mm to 60% particle size of -0.074mm.

[0042] As can be seen from the above, the embodiments of the present invention provide a slurry conditioner, a flotation separation reagent group containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag. The flotation scheme provided by the embodiments of the present invention can effectively achieve the flotation enrichment of lithium in the lithium-containing aluminum smelting slag produced after bauxite undergoes "direct reduction-electric furnace smelting", obtaining high-quality lithium concentrate, thereby expanding the comprehensive utilization pathways and scope of aluminum smelting slag, achieving a significant increase in the added value of aluminum smelting slag, and effectively improving the utilization rate of lithium resources in bauxite.

[0043] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0044] This invention provides a method for beneficiating lithium-containing aluminum smelting slag, comprising the following steps:

[0045] The lithium-containing aluminum slag, formed by direct reduction and electric furnace smelting of bauxite, is crushed to -2mm using a closed-circuit crusher and vibrating screen.

[0046] The crushed lithium-containing aluminum smelting slag was wet-milled using a rod mill to obtain a slurry with 40% particle size of 0.045 mm to 60% particle size of -0.074 mm.

[0047] Flotation of the ore pulp:

[0048] Ion conditioning and scrubbing: Add the conditioning agent to the above slurry, and at the same time add scrubbing and beneficiation agent to clean the mineral surface, reduce the influence of melting on the mineral lattice phases, improve the surface property differences between lithium fluoride mineral phase and other fluorine-containing gangue mineral phases, create conditions for lithium fluoride flotation separation and enrichment, and maintain the pH of the slurry at 7.

[0049] Suppression: Gangue mineral inhibitors are added to the slurry after slurry preparation and scrubbing. The purpose of adding gangue mineral inhibitors is to suppress gangue minerals such as cryolite (Na3AlF6), potassium cryolite (KAlF4), and fluorite (CaF2) glass.

[0050] Complexation: Lithium complexing agents are added to the pulp containing gangue mineral inhibitors to form complex chemical chains with lithium fluoride.

[0051] Collection: Continue to add the main collector to the slurry containing lithium complexing agent to collect lithium fluoride complexes, and the auxiliary collector to assist in the collection of finer lithium fluoride particles. Continue to add collectors for 1-4 rounds of fine selection to enhance the collection of lithium fluoride complexes in low-concentration slurry and increase the adhesion of lithium fluoride complexes to foam.

[0052] The reagent dosage for roughing the slurry obtained from wet grinding of lithium-containing aluminum smelting slag is as follows:

[0053] The modifier includes at least one of the following: NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, MgCl2, and CaCl2. The scrubbing agent includes at least one of the following: water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap, and sodium tripolyphosphate. The dosage of the modifier is 4000-9000 g / t of aluminum smelting slag. The dosage of the scrubbing agent is 300-700 g / t of aluminum smelting slag.

[0054] Gangue mineral inhibitors include at least one of sodium hexametaphosphate, starch, water glass, sodium fluorosilicate, and carboxymethyl cellulose; the dosage of gangue mineral inhibitors is 100-1000 g / t aluminum smelting slag.

[0055] The lithium complexing agent includes at least one of carboxymethyl cellulose, sodium petroleum sulfonate, refined paste, modified starch, sodium hexametaphosphate, and ferric chloride; the amount of lithium complexing agent used is 200-800 g / t aluminum smelting slag.

[0056] Collectors include primary collectors and secondary collectors; primary collectors include at least one of dodecylamine, sodium petroleum sulfonate, oxidized paraffin soap, hydroxamic acid, sodium oleate, and sodium benzylarsinate; secondary collectors include at least one of turpentine, kerosene, diesel oil, and modified No. 2 oil; the dosage of primary collectors is 200-1000 g / t aluminum smelting slag, and the dosage of secondary collectors is 20-100 g / t aluminum smelting slag.

[0057] The multi-element chemical analysis of the lithium-aluminum slag used in the following examples is shown in Table 1 below:

[0058] Table 1. Multi-element chemical analysis of lithium-containing aluminum smelting slag

[0059] Element Li F Na2O Al2O3 K2O CaO SiO2 Fe2O3 MgO P2O3 content 1.81 56.9 23.2 12.7 1.10 1.83 0.044 0.016 0.195 0.020

[0060] The present invention provides a slurry conditioner, a flotation separation reagent kit containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag, comprising the following steps:

[0061] (1) Weigh 300g of representative aluminum smelting slag (-2mm), grind the raw slag to a suitable fineness using a rod mill, add the modifier, scrubbing agent, inhibitor, complexing agent, main collector and auxiliary collector to the slurry in sequence, stir for 2 minutes, and obtain the roughing product slurry by flotation.

[0062] (2) Add complexing agent, main collector and auxiliary collector to the rough product slurry in sequence, stir for 2 minutes to obtain the first fine product slurry.

[0063] (3) Add complexing agent, main collector and auxiliary collector to the first fine product slurry in sequence, stir for 2 minutes to obtain the second fine product slurry.

[0064] (4) The main collector and auxiliary collector are added to the second-selected product slurry in sequence, and stirred for 1 minute to obtain lithium product.

[0065] Example 1

[0066] The mineral processing reagent combination is as follows:

[0067] The reagent combination and content for the coarse selection stage are as follows:

[0068] Grinding fineness - 0.074mm accounts for 50%.

[0069] The modifier is NaCl, used at a dosage of 6000g / t containing aluminum smelting slag.

[0070] The scrubbing agent consists of sodium tripolyphosphate, carboxymethyl cellulose, and water glass, and is used at a dosage of 600g / t of lithium-containing aluminum smelting slag.

[0071] The inhibitor is sodium hexametaphosphate, used at a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0072] The complexing agent is modified starch, and the dosage is 200g / t of lithium-containing aluminum smelting slag.

[0073] The main collector is a combination of sodium petroleum sulfonate and oxidized paraffin soap in a 1:1 weight ratio, with a total dosage of 400g / t of lithium-containing aluminum smelting slag.

[0074] The auxiliary collector is modified No. 2 oil, used at a dosage of 40g / t of lithium-containing aluminum smelting slag.

[0075] The following is a selected combination and dosage of medicine:

[0076] h) The complexing agent is modified starch, used at a rate of 100 g / t of lithium-containing aluminum smelting slag.

[0077] i) The main collector is a mixture of sodium petroleum sulfonate and oxidized paraffin soap, in a weight ratio of 1:1, with a total dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0078] j) The auxiliary collector is modified No. 2 oil, with a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0079] The selected two-stage drug combination and its content are as follows:

[0080] k) The main collector is a mixture of sodium petroleum sulfonate and oxidized paraffin soap, in a weight ratio of 1:1, with a total dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0081] l) The auxiliary collector is modified No. 2 oil, with a dosage of 20g / t of lithium-containing aluminum smelting slag.

[0082] Finally, lithium concentrate A was obtained.

[0083] Example 2 and Example 3

[0084] The modifiers were changed to a combination of CaCl2 and NaNO3 in a weight ratio of 1:1 and KCl, and the complexing agent was changed to conventional starch. Other reagents and their amounts remained unchanged, resulting in lithium concentrate B and lithium concentrate C.

[0085] Example 4

[0086] The mineral processing reagent combination is as follows:

[0087] The components and contents of the reagents in the coarse selection stage are as follows:

[0088] a) Grinding fineness - 0.074 mm accounts for 50%.

[0089] b) The modifier is a combination of Na(NO3)2 and Ca(NO3)2 in a 1:1 ratio, with a total dosage of 6000 g / t including aluminum smelting slag.

[0090] c) The scrubbing agent is sodium tripolyphosphate, carboxymethyl cellulose, and water glass, with a dosage of 400g / t of lithium-containing aluminum smelting slag.

[0091] d) The inhibitor is sodium hexametaphosphate, used at a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0092] e) The complexing agent is modified starch, and the dosage is 200g / t of lithium-containing aluminum smelting slag.

[0093] f) The main collector is hydroxamic acid, used at a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0094] g) The auxiliary collector is turpentine oil, used at a dosage of 40 g / t of lithium-containing aluminum smelting slag.

[0095] The following is a selected combination and dosage of medicine:

[0096] h) The complexing agent is modified starch, used at a rate of 100 g / t of lithium-containing aluminum smelting slag.

[0097] i) The main collector is hydroxamic acid, and the dosage is 100g / t of lithium-containing aluminum smelting slag.

[0098] j) The auxiliary collector is turpentine oil, used at a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0099] The selected two-stage drug combination and its content are as follows:

[0100] k) The main collector is hydroxamic acid, used at a rate of 50 g / t of lithium-containing aluminum smelting slag.

[0101] l) The auxiliary collector is turpentine oil, with a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0102] Finally, lithium concentrate D was obtained.

[0103] Example 5

[0104] The mineral processing reagent combination is as follows:

[0105] The components and contents of the reagents in the coarse selection stage are as follows:

[0106] a) Grinding fineness - 0.074 mm accounts for 50%.

[0107] b) The modifier is MgCl2, used at a dosage of 6000 g / t containing aluminum smelting slag.

[0108] c) The scrubbing agent is sodium tripolyphosphate, carboxymethyl cellulose, and water glass, with a dosage of 400g / t of lithium-containing aluminum smelting slag.

[0109] d) The inhibitor is sodium hexametaphosphate, used at a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0110] e) The complexing agent is modified starch, and the dosage is 200g / t of lithium-containing aluminum smelting slag.

[0111] f) The main collector is hydroxamic acid, used at a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0112] j) Turpentine oil as an auxiliary collector, at a dosage of 40 g / t of lithium-containing aluminum smelting slag.

[0113] The following is a selected combination and dosage of medicine:

[0114] h) The complexing agent is modified starch, used at a rate of 100 g / t of lithium-containing aluminum smelting slag.

[0115] i) The main collector is hydroxamic acid, and the dosage is 100g / t of lithium-containing aluminum smelting slag.

[0116] j) The auxiliary collector is turpentine oil, used at a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0117] The selected two-stage drug combination and its content are as follows:

[0118] k) The main collector is hydroxamic acid, used at a rate of 50 g / t of lithium-containing aluminum smelting slag.

[0119] l) The auxiliary collector is turpentine oil, with a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0120] Finally, lithium concentrate E was obtained.

[0121] Comparative Example 1

[0122] Keeping all other components of Example 1 unchanged, without adding complexing agent e

[0123] The reagent combination and content for the coarse selection stage are as follows:

[0124] Grinding fineness - 0.074mm accounts for 50%.

[0125] b) The modifier is NaCl, with a dosage of 6000 g / t containing aluminum smelting slag.

[0126] c) The scrubbing agent consists of sodium tripolyphosphate, carboxymethyl cellulose, and water glass, with a dosage of 600 g / t of lithium-containing aluminum smelting slag.

[0127] d) The inhibitor is sodium hexametaphosphate, used at a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0128] e) The main collector is a combination of sodium petroleum sulfonate and oxidized paraffin soap, in a weight ratio of 1:1, with a total dosage of 400 g / t of lithium-containing aluminum smelting slag.

[0129] f) The auxiliary collector is modified No. 2 oil, with a dosage of 40 g / t of lithium-containing aluminum smelting slag.

[0130] The following is a selected combination and dosage of medicine:

[0131] g) The complexing agent is modified starch, and the dosage is 100g / t of lithium-containing aluminum smelting slag.

[0132] h) The main collector is a combination of sodium petroleum sulfonate and oxidized paraffin soap, in a weight ratio of 1:1, with a total dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0133] i) The auxiliary collector is modified No. 2 oil, and the dosage is 20g / t of lithium-containing aluminum smelting slag.

[0134] The selected two-stage drug combination and its content are as follows:

[0135] j) The main collector is a combination of sodium petroleum sulfonate and oxidized paraffin soap, in a weight ratio of 1:1, with a total dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0136] k) The auxiliary collector is modified No. 2 oil, with a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0137] Finally, lithium concentrate F was obtained.

[0138] Comparative Example 2

[0139] Keeping the other components of Example 4 unchanged, the main collector is changed to tributyl phosphate.

[0140] The reagent combination and content for the coarse selection stage are as follows:

[0141] a) Grinding fineness - 0.074 mm accounts for 50%.

[0142] b) The modifier is a combination of Na(NO3)2 and Ca(NO3)2 in a 1:1 ratio, with a total dosage of 6000 g / t including aluminum smelting slag.

[0143] c) The scrubbing agent is sodium tripolyphosphate, carboxymethyl cellulose, and water glass, with a dosage of 400g / t of lithium-containing aluminum smelting slag.

[0144] d) The inhibitor is sodium hexametaphosphate, used at a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0145] e) The complexing agent is a fine paste, and the dosage is 200g / t of lithium-containing aluminum smelting slag.

[0146] f) The main collector is tributyl phosphate, with a dosage of 200 g / t of lithium-containing aluminum smelting slag.

[0147] g) The auxiliary collector is turpentine oil, used at a dosage of 40 g / t of lithium-containing aluminum smelting slag.

[0148] The following is a selected combination and dosage of medicine:

[0149] h) The complexing agent is a fine paste, and the dosage is 100g / t of lithium-containing aluminum smelting slag.

[0150] i) The main collector is tributyl phosphate, with a dosage of 100 g / t of lithium-containing aluminum smelting slag.

[0151] j) The auxiliary collector is turpentine oil, used at a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0152] The selected two-stage drug combination and its content are as follows:

[0153] k) The main collector is tributyl phosphate, with a dosage of 50 g / t of lithium-containing aluminum smelting slag.

[0154] l) The auxiliary collector is turpentine oil, with a dosage of 20 g / t of lithium-containing aluminum smelting slag.

[0155] Finally, lithium concentrate G was obtained.

[0156] Table 2 below shows the Li2O content (%) and Li2O recovery rate (%) in the lithium concentrates obtained in Examples 1-5 and Comparative Examples 1-2.

[0157] Table 2

[0158]

[0159]

[0160] Table 3 below shows the content of each component in lithium concentrate A obtained in Example 1.

[0161] Table 3

[0162] Element F <![CDATA[Na2O]]> <![CDATA[Al2O3]]> <![CDATA[K2O]]> CaO content 56.9 20.2 12.7 1.10 1.83 Element <![CDATA[SiO2]]> <![CDATA[Fe2O3]]> MgO <![CDATA[P2O3]]> <![CDATA[Li2O]]> content 0.044 0.016 0.195 0.020 6.45

[0163] Based on the data listed in Table 2, it can be seen that the method provided by the embodiments of the present invention can separate lithium concentrate from lithium-containing aluminum smelting slag, and the Li2O content (%) and Li2O recovery rate (%) in the lithium concentrate obtained in Examples 1-5 are higher than those in the lithium concentrate obtained in Comparative Examples 1-2.

[0164] The following is a detailed evaluation of the lithium concentrate grade obtained from the examples and comparative examples:

[0165] Comparing Example 1 and Example 2, with other components remaining the same, the modifier was changed from NaCl to a combination of CaCO3 and NaNO3, and the complexing agent was changed from modified starch to ordinary starch. The lithium concentrate grade was improved, showing that the combined modifier and ordinary starch can have a better inhibitory effect on other associated cryolite (Na3AlF6), potassium cryolite (KAlF4), and fluorite (CaF2), while also having a certain inhibitory effect on lithium concentrate.

[0166] Comparing Example 1 and Example 3, with other components remaining the same, the modifier was changed from NaCl to KCl, and the complexing agent was changed from modified starch to ordinary starch. The lithium concentrate grade decreased, indicating that the modifier KCl had a weaker inhibitory effect on associated cryolite (Na3AlF6), potassium cryolite (KAlF4), and fluorite (CaF2) than NaCl.

[0167] Comparing Examples 2 and 3, with other components remaining the same, the modifier was changed from the CaCO3+NaNO3 combination to KCl, resulting in a decrease in lithium concentrate grade. This indicates that the modifier KCl has a weaker inhibitory effect on associated cryolite (Na3AlF6), potassium cryolite (KAlF4), and fluorite (CaF2) than the CaCO3+NaNO3 combination.

[0168] Comparing Examples 1-3, the inhibitory effects on associated cryolite (Na3AlF6), potassium cryolite (KAlF4), and fluorite (CaF2) minerals were observed. The modifier played a certain role, and the inhibition intensity was compared as follows: NaCl > CaCO3 + NaNO3 combination > KCl, and complexing agent modified starch > ordinary starch.

[0169] Table 3 shows the quality test results of the lithium concentrate obtained in Example 1. The combined content of Li2O and F is 63.35%, and the combined content of Na2O and Al2O3 is 32.9%. K2O and CaO are only 1.10% and 1.83%, respectively. This indicates that the reagent combination used in Example 1 can have a good inhibitory effect on the associated minerals potassium cryolite (KAlF4) and fluorite (CaF2), but the inhibitory effect on cryolite (Na3AlF6) is weak.

[0170] Comparing Example 1 and Example 4, the modifier was changed from NaCl to MgCl2, and the main collector was changed from a combination of sodium petroleum sulfonate and oxidized paraffin soap to hydroxamic acid. The lithium concentrate grade and recovery rate decreased simultaneously, indicating that the combination of sodium petroleum sulfonate and oxidized paraffin soap collector has a good selective collecting effect on lithium concentrate.

[0171] Comparing Examples 4 and 5, with other components remaining the same, the modifier was changed from the combination of Na(NO3)2 and Ca(NO3)2 to MgCl2. The lithium concentrate grade and recovery rate both decreased, indicating that the combined modifier is superior to MgCl2.

[0172] Comparing Example 1 and Comparative Example 1, with other components being the same and no complexing agent e added, the grade and recovery rate of lithium concentrate F were extremely low, indicating that the complexing agent has a significant impact on the lithium concentrate product.

[0173] Comparing Example 4 and Comparative Example 2, with other components being the same but the main collector being changed to tributyl phosphate, the lithium concentrate grade G and recovery rate were extremely low, indicating that the collector has a significant impact on the lithium concentrate product.

[0174] As can be seen, the embodiments of the present invention provide a slurry conditioner, a flotation separation reagent group containing the slurry conditioner, and a method for separating lithium from lithium-containing aluminum smelting slag. The lithium-containing aluminum smelting slag used for flotation is molten slag produced by aluminum smelting of bauxite through the "direct reduction-electric furnace smelting" process and is water-quenched. It has a wide range of sources. The specific steps of flotation separation are as follows: the lithium-containing aluminum smelting slag is ground and then placed into a flotation cell. Ionic reagents and scrubbing reagents are added stepwise to condition the slurry. Stirring changes the mineral suspension force and reduces the influence of high-temperature melting on the mineral phase. Then, a high molecular weight complex is added to form a lithium complex aggregate. Inhibitors, collectors, and auxiliary collectors are added to the neutral slurry. Through flotation separation, the efficient enrichment of lithium in the lithium-containing aluminum smelting slag is achieved. If the reagent system used in the flotation separation process is incomplete or the dosage is inconsistent, the recovery rate of lithium concentrate will be greatly reduced. This is because each step in the separation and flotation process is complementary, and the selected reagents need to be added sequentially to achieve the purpose of effectively separating lithium from lithium-containing aluminum smelting slag. The method for separating lithium from lithium-containing aluminum smelting slag provided in the embodiments of the present invention, for aluminum smelting slag containing 1.5%-3% Li2O, adopts a new mineral processing technology to effectively enrich lithium fluoride minerals in lithium-containing aluminum smelting slag, and obtain high-quality lithium concentrate. The new technology is one of the effective ways to improve the utilization rate of lithium resources in lithium-containing bauxite. Using the present invention, lithium can be effectively recovered from bauxite smelting slag, expanding the utilization pathways and application scope of lithium-containing aluminum smelting slag, and improving the comprehensive utilization level of lithium resources in bauxite.

[0175] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The application of a slurry conditioner in lithium separation slurry conditioning of lithium-containing aluminum smelting slag, characterized in that, The slurry conditioning agent includes a modifier and a scrubbing and beneficiation agent. The modifier includes at least one of NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, and MgCl2. The scrubbing and beneficiation agent includes at least one of water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap, and sodium tripolyphosphate. The dosage of the modifier is 4000-9000 g / t of lithium-containing aluminum smelting slag, and the dosage of the scrubbing and beneficiation agent is 300-700 g / t of lithium-containing aluminum smelting slag.

2. The application according to claim 1, characterized in that, A flotation separation reagent group for separating lithium from lithium-containing aluminum smelting slag is used for roughing of lithium-containing aluminum smelting slag, and includes the aforementioned slurry conditioner, gangue mineral inhibitor, lithium complexing agent and collector.

3. The application according to claim 2, characterized in that, The gangue mineral inhibitor includes at least one of sodium hexametaphosphate, starch, water glass, sodium fluorosilicate, and carboxymethyl cellulose; The dosage of the gangue mineral inhibitor is 100-1000 g / t of lithium-containing aluminum smelting slag.

4. The application according to claim 2, characterized in that, The lithium complexing agent includes at least one of carboxymethyl cellulose, sodium petroleum sulfonate, refined paste, modified starch, sodium hexametaphosphate, and ferric chloride. The amount of lithium complexing agent used is 200-800 g / t of lithium-containing aluminum smelting slag.

5. The application according to claim 2, characterized in that, The collector includes a main collector and an auxiliary collector; The main collector includes at least one of dodecylamine, sodium petroleum sulfonate, oxidized paraffin soap, hydroxamic acid, sodium oleate, and sodium benzylarsinate; The auxiliary collector includes at least one of turpentine, kerosene, diesel, and modified No. 2 oil; The dosage of the main collector is 200-1000 g / t of lithium-containing aluminum smelting slag, and the dosage of the auxiliary collector is 20-100 g / t of lithium-containing aluminum smelting slag.

6. A method for separating lithium from lithium-containing aluminum smelting slag using a flotation separation reagent group, characterized in that, include: A slurry conditioner is added to the slurry obtained by grinding the lithium-containing aluminum smelting slag and stirring is started. During the stirring process, gangue mineral inhibitor, lithium complexing agent and collector are added in sequence, and lithium concentrate is obtained by flotation separation. The slurry conditioning agent includes a modifier and a scrubbing and beneficiation agent. The modifier includes at least one of NaNO3, Mg(NO3)2, Ca(NO3)2, NaCl, KCl, and MgCl2. The scrubbing and beneficiation agent includes at least one of water glass, phosphoric acid, oxalic acid, sodium petroleum sulfonate, oxidized paraffin soap, and sodium tripolyphosphate. The dosage of the modifier is 4000-9000 g / t of lithium-containing aluminum smelting slag, and the dosage of the scrubbing and beneficiation agent is 300-700 g / t of lithium-containing aluminum smelting slag.

7. The method according to claim 6, characterized in that, The specific steps of flotation separation are as follows: Lithium-containing aluminum smelting slag is subjected to flotation at a pulp concentration of 15%-30%. The flotation adopts one roughing and one to four cleaning stages. In the roughing stage, the lithium-containing aluminum smelting slag is added to the flotation cell, a pulp conditioner is added to adjust the pulp, and stirring is started to control the pulp mass concentration at 15%-30% and the pulp temperature at 5℃-25℃. During the stirring process, gangue mineral inhibitors, lithium complexing agents, and collectors are added in sequence. Then, the lithium concentrate obtained after roughing is cleaned, and high-grade lithium concentrate is obtained after flotation.

8. The method according to claim 7, characterized in that, The step of adding a slurry conditioner to the slurry obtained by grinding the lithium-containing aluminum slag is as follows: the conditioner is added to the slurry obtained by grinding the lithium-containing aluminum slag to adjust it into a suitable ionic solution, and then the scrubbing and beneficiation agent is added to clean the mineral surface and maintain the pH value of the slurry at 7.

9. The method according to claim 8, characterized in that, The slurry is prepared by the following steps: the lithium-containing aluminum smelting slag formed by direct reduction-electric furnace melting of bauxite and water quenching is crushed, screened and ground.

10. The method according to claim 8, characterized in that, The screening process uses a closed-circuit crushing and screening system consisting of a crusher and a vibrating screen to crush lithium-containing aluminum smelting slag to -2mm.

11. The method according to claim 8, characterized in that, The grinding process involves using a rod mill to wet grind the crushed lithium-containing aluminum smelting slag to obtain a slurry with 40% particle size of 0.045mm to 60% particle size of -0.074mm.

12. The method according to claim 6, characterized in that, The gangue mineral inhibitor includes at least one of sodium hexametaphosphate, starch, water glass, sodium fluorosilicate, and carboxymethyl cellulose; the dosage of the gangue mineral inhibitor is 100-1000 g / t of lithium-containing aluminum smelting slag. The lithium complexing agent includes at least one of carboxymethyl cellulose, sodium petroleum sulfonate, refined paste, modified starch, sodium hexametaphosphate, and ferric chloride; the dosage of the lithium complexing agent is 200-800 g / t of lithium-containing aluminum smelting slag. The collector includes a main collector and an auxiliary collector; The main collector includes at least one of dodecylamine, sodium petroleum sulfonate, oxidized paraffin soap, hydroxamic acid, sodium oleate, and sodium benzylarsinate; The auxiliary collector includes at least one of turpentine, kerosene, diesel, and modified No. 2 oil; The dosage of the main collector is 200-1000 g / t of lithium-containing aluminum smelting slag, and the dosage of the auxiliary collector is 20-100 g / t of lithium-containing aluminum smelting slag.

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