A compound reagent for fine spodumene flotation separation in low temperature environment and its application method

Abstract

The present application relates to a kind of for low temperature environment fine particle spodumene flotation separation complex reagent and its application method, solve the low temperature adaptability of conventional spodumene flotation collector, fine particle mineral recovery rate is low, flotation needs heating and leads to higher cost etc.;The collector GL-101 complex mass percentage is: mixed fatty acid component 70~95%, mixed amine and its derivative component 5~15%, alcohol compound component 3~10%, emulsifier component 3~10%;Before flotation, the raw ore is crushed, and grinding is ground to-75 μm fraction ratio 60~70%, after weak magnetic iron removal, control desliming amount 5%~8%, using "one rough one fine two sweep" closed-circuit flotation process, under low temperature slurry condition, realize spodumene efficient separation;The complex reagent of the present application has good dispersibility, strong low temperature resistance, without heating to ore pulp, can guarantee the grade of spodumene concentrate and significantly improve recovery rate, can effectively reduce the cost of fine particle spodumene beneficiation under low temperature environment, improve beneficiation efficiency.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, and in particular to a compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions and its application method. Background Technology

[0002] Lithium, as a key strategic resource in the new energy field, continues to see its application scale expand in areas such as power batteries, energy storage, and aerospace. Spodumene is currently the main mineral raw material for industrial lithium extraction, accounting for more than 80% of global lithium resource supply. With the decreasing availability of easily beneficiated, coarse-grained, high-grade spodumene resources, fine-grained, low-grade spodumene ores have become the focus of industry development.

[0003] Currently, there are three major technical bottlenecks in the flotation of fine-grained spodumene: Fine-grained minerals are difficult to recover: fine-grained minerals have a large specific surface area and high surface energy, and are prone to heterogeneous aggregation with gangue mud. Conventional collectors have insufficient collection capacity, resulting in serious loss of fine-grained spodumene. Poor adaptability to low temperatures: In northern winters, high-altitude areas, and low-temperature mine water conditions, the pulp temperature is generally below 15℃. Conventional fatty acid collectors have reduced solubility and poor dispersibility, resulting in a significant decrease in collection capacity and selectivity, which cannot meet the flotation requirements. High cost of heated flotation: In order to ensure flotation performance, the pulp temperature is often raised to above 20°C by steam heating during production, which leads to high energy consumption and a significant increase in mineral processing costs. At the same time, it also poses safety hazards and environmental pressures.

[0004] Existing single collectors cannot simultaneously achieve low-temperature resistance, strong collecting ability, and excellent selectivity, thus failing to fundamentally solve the technical challenges of low-temperature flotation of fine-grained spodumene. Therefore, developing a compound collector and supporting flotation process that is low-temperature resistant, has strong collecting ability, excellent selectivity, and requires no heating of the slurry has significant engineering application value for achieving efficient and economical recovery of fine-grained spodumene.

[0005] Therefore, this invention provides a compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions and its application method. Summary of the Invention

[0006] This invention addresses the technical problems existing in the prior art by providing a compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions and its application method. It addresses the problems of poor low-temperature adaptability, low recovery rate of fine-grained minerals, and high cost of heated flotation of existing spodumene flotation reagents. It achieves efficient separation of fine-grained spodumene without heating the slurry, while simultaneously improving concentrate grade and recovery rate and reducing the cost of low-temperature mineral processing.

[0007] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: On the one hand, a compound reagent for flotation separation of fine-grained spodumene under low-temperature environment is provided, wherein the collector GL-101 comprises: mixed fatty acids, mixed amines and their derivatives, alcohol compounds, and emulsifier components; The mass percentage of each component in the collector GL-101 is as follows: 70-95% mixed fatty acid component, 5-15% mixed amine and its derivative component, 3-10% alcohol compound component, and 3-10% emulsifier component.

[0008] Furthermore, the mixed fatty acids are composed of dodecanoic acid (lauric acid), palmitic acid (palmitic acid), and stearic acid (stearic acid) in a mass ratio of 0.5~1.5:0.5~1.5:7.5~8.5.

[0009] Furthermore, the mixed amines and their derivatives are prepared by mixing dodecylamine (laurylamine) and cocoylamine in a mass ratio of 0.5~1.5:0.5~1.5.

[0010] Furthermore, the alcohol compound is prepared by mixing ethylene glycol and No. 2 oil (pine oil) in a mass ratio of 1.5~2.5:0.5~1.5.

[0011] Furthermore, the emulsifier is octylphenol polyoxyethylene ether (OP-10).

[0012] On the other hand, a method for preparing a compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions is provided, comprising the following steps: Mixed fatty acids were added to a reaction vessel in proportion and stirred for 30-50 minutes in a constant temperature water bath at 30-40℃ and stirring at 500-700 r / min until the system was homogeneous. Mixed amines and their derivatives were added and stirred for 0.8-1.1 hours while maintaining the same temperature and stirring speed. Then alcohol compounds and emulsifiers were added and stirred at a uniform speed for 20-40 minutes to obtain the compound collector GL-101.

[0013] On the other hand, a method for applying a compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions is provided. The method for low-temperature flotation of fine-grained spodumene using this compound reagent includes the following steps: S1 Crushing: The raw spodumene ore is pre-crushed by a jaw crusher and then finely crushed by a double roll crusher to a particle size of <2mm. The +2mm particle size is returned to the double roll crusher for further crushing. S2 grinding: The crushed ore is mixed and reduced in size, and then ground to a -75μm content of 60-70% under the condition of 40-60% slurry concentration; S3 Magnetic Separation for Iron Removal: A high-gradient magnetic separator is used to perform weak magnetic separation on the grinding slurry with a magnetic field strength of 0.5 to 0.8T to remove magnetic iron impurities and obtain a non-magnetic product. S4 Desliming: Desliming is performed on non-magnetic products, with the amount of desliming controlled at 5% to 8% of the original ore mass. Fine mud interference is removed to obtain deslimed slurry. S5 Thickening and Slurry Preparation: The deslimed slurry is concentrated to a slurry concentration of 25-30% in preparation for flotation operations; S6 roughing: 1000-1800 g / t of sodium carbonate aqueous solution with a mass concentration of 3-5% is stirred for 4-6 min, 200-500 g / t of sodium hydroxide aqueous solution with a mass concentration of 3-5% is stirred for 4-6 min, 10-200 g / t of calcium chloride aqueous solution with a mass concentration of 2.5-5% is stirred for 2-4 min, 800-1400 g / t of compound collector GL-101 is stirred for 2-4 min, and aeration and foaming are carried out to obtain rough concentrate and roughing tailings; S7 Fine Concentration: After one fine concentration of the rough concentrate, add 300~600g / t of sodium carbonate aqueous solution with a mass concentration of 3~5% and stir for 2~4min. Aerate and scrape the bubbles to obtain spodumene concentrate and middlings 1. S8 Scavenging: The tailings are subjected to a first scavenging and a second scavenging in sequence. In both scavenging processes, 10~30g / t of calcium chloride is added and stirred for 2~4min. Then, 200~400g / t of compound collector GL-101 is added and stirred for 2~4min. The process is followed by aeration and foaming to obtain middlings 2, middlings 3 and the final tailings. S9 Closed-loop cycle: Middle ore 1 and Middle ore 2 return to roughing operation, and Middle ore 3 returns to scavenging operation, forming a closed-loop flotation process of one roughing, one cleaning and two scavenging operations.

[0014] Furthermore, in step S3, the recovery rate of non-magnetic product Li2O in the magnetic separation operation is ≥98.5%, and the removal rate of magnetic iron impurities is ≥90%.

[0015] Furthermore, it is suitable for low-temperature environments with slurry temperatures of 8–15°C, enabling efficient spodumene separation without the need for slurry heating.

[0016] Furthermore, the spodumene concentrate has a Li2O grade of ≥6.1% and a Li2O recovery rate of ≥76% from the raw ore.

[0017] The beneficial effects of this invention are: Outstanding low-temperature performance: The compound system significantly improves the solubility and dispersibility of reagents at low temperatures through the synergistic effect of fatty acids, amines, alcohols and emulsifiers. It still maintains strong collection ability under low temperature pulp conditions of 8~15℃, without the need for pulp heating, greatly reducing energy consumption and beneficiation costs, and solving the flotation problems in northern winters and high-altitude areas.

[0018] Strong adaptability to fine particles: Collector GL-101 has both strong collecting ability and good selectivity. It has a strong ability to cover fine spodumene particles, which can effectively reduce the loss of -75μm fine mineral particles and significantly improve the recovery rate of fine spodumene particles, solving the industry pain point of difficult recovery of fine embedded spodumene particles.

[0019] Reasonable control of desliming amount: The desliming amount is controlled between 5% and 8%, which can eliminate the negative impact of fine mud and avoid the loss of fine spodumene with mud, while taking into account the concentrate grade and metal recovery rate, and achieving the optimal balance of indicators.

[0020] The process is simple and stable: it adopts a closed-loop process of "one roughing, one refining, and two scavenging", the reagent system is simple, the middlings return logic is reasonable, the indicators are stable and controllable, and it is suitable for industrial field promotion and application.

[0021] Excellent overall performance: It can simultaneously ensure the grade and recovery rate of spodumene concentrate under low temperature conditions, achieve efficient enrichment of fine-grained spodumene, and achieve high beneficiation efficiency. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the process of fine-grained spodumene magnetic separation pre-impurity removal-desliming-lithium metal enrichment beneficiation method using the compound reagents described in this invention under low-temperature conditions. Detailed Implementation

[0023] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0024] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the stated features. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified.

[0025] In the description of this application, the term "for example" is used to mean "used as an example, illustration, or description." Any embodiment described as "for example" in this application is not necessarily to be construed as being more preferred or advantageous than other embodiments. The following description is provided to enable any person skilled in the art to make and use the invention. Details are set forth in the following description for purposes of explanation. It should be understood that those skilled in the art will recognize that the invention can be made without using these specific details. In other instances, well-known structures and processes will not be described in detail to avoid obscuring the description of the invention with unnecessary detail. Therefore, the invention is not intended to be limited to the embodiments shown, but is consistent with the broadest scope of the principles and features disclosed in this application.

[0026] Example 1

[0027] Ore properties: A fine-grained spodumene ore with a Li2O grade of 1.26% and main gangue minerals of quartz, feldspar, and mica. The pulp temperature is 10℃.

[0028] Grinding particle size: -75μm accounts for 60~70%, slurry grinding concentration is 40~60%.

[0029] Magnetic separation iron removal indicators: High gradient magnetic separator is used, magnetic field strength is 0.5~0.7T, magnetic separation output is 92~94%, non-magnetic product Li2O grade is 1.2~1.3%, Li2O recovery rate is 97~99%, and magnetic iron impurity removal rate is 90~92%.

[0030] Desliming indicators: Desliming yield 6.5~8%, Li2O grade of desliming product 0.40~0.42%, metal loss rate of desliming 2.3~2.6%.

[0031] Flotation process: one roughing, one cleaning, and two scavenging closed-circuit flotation.

[0032] Pharmaceutical system: Rough selection: Sodium carbonate 1300~1500g / t (mass concentration 5%), Sodium hydroxide 200~400g / t (mass concentration 5%), Calcium chloride 110~130g / t (mass concentration 3%), GL-10 1900~1100g / t; Selected: Sodium carbonate 400~600g / t (5% mass concentration); One-time scavenging: calcium chloride 10~30g / t, GL-101 200~400g / t.

[0033] Secondary scavenging: calcium chloride 10~30g / t, GL-101 200~400g / t.

[0034] Flotation parameters: Lithium spodumene concentrate Li₂O grade: 6.1~6.3%; Recovery rate of raw ore: 77.5%~78%; At a low temperature of 10℃, using the GL-101 collector, a spodumene concentrate grade of over 6.1% can be obtained, with a recovery rate exceeding 77.5%. This demonstrates that GL-101 can effectively collect spodumene at low temperatures and exhibits good selectivity, effectively separating gangue and thus obtaining a high concentrate grade. The high recovery rate also proves the agent's ability to collect fine-grained spodumene. The fact that no heating of the slurry is required is particularly important, directly reducing operating costs and energy consumption.

[0035] Example 2

[0036] Properties of raw ore: Li2O grade of raw ore is 1.1~1.2%, and pulp temperature is 7~9℃.

[0037] Grinding particle size: -75μm accounts for 60~70%, slurry grinding concentration is 40~60%.

[0038] Magnetic separation iron removal indicators: High gradient magnetic separator is used, magnetic field strength is 0.6~0.8T, magnetic separation output is 92~94%, non-magnetic product Li2O grade is 1.2~1.3%, Li2O recovery rate is 98.5~99.5%, and magnetic iron impurity removal rate is 92~94%.

[0039] Desliming indicators: Desliming yield 7-8%, Li2O grade of desliming product 0.35-0.4%, metal loss rate of desliming 2-3%.

[0040] Chemical formulation: GL-101 dosage 1100~1300g / t, scavenging and cleaning conditions are the same as in Example 1.

[0041] Flotation parameters: Lithium spodumene concentrate Li₂O grade: 6.0~7.0%; Recovery rate of raw ore: 76-77%; Even at temperatures as low as 7-9℃, GL-101 collector maintains a concentrate grade of over 6.0% and a recovery rate of over 76%. This fully demonstrates GL-101's excellent low-temperature resistance. At such low temperatures, the solubility and dispersibility of conventional reagents decrease significantly, and their collecting ability weakens considerably. However, the GL-101 compound system (synergistic effect of fatty acids, amines, alcohols, and emulsifiers) effectively overcomes the adverse effects of low temperatures, maintaining stable collecting ability and selectivity.

[0042] Example 3

[0043] Properties of raw ore: Li2O grade of raw ore is 1.2~1.4%, and pulp temperature is 14~16℃.

[0044] Grinding particle size: -75μm accounts for 60~70%, slurry grinding concentration is 40~60%.

[0045] Magnetic separation iron removal indicators: High gradient magnetic separator is used, magnetic field strength is 0.4~0.6T, magnetic separation output is 91~92%, non-magnetic product Li2O grade is 1.4~1.5%, Li2O recovery rate is 99.00~99.55%, and magnetic iron impurity removal rate is 90~91%.

[0046] Desliming indicators: Desliming yield 8-9%, Li2O grade of desliming product 0.35-0.40%, metal loss rate of desliming 2-3%.

[0047] Chemical formulation: GL-101 dosage 800~1000g / t, scavenging and cleaning conditions are the same as in Example 1.

[0048] Flotation parameters: Lithium spodumene concentrate Li₂O grade: 6.2~6.5%; Recovery rate of raw ore: 78-80%.

[0049] At temperatures between 14 and 16°C, the performance of the GL-101 collector was further improved, with concentrate grades reaching over 6.2% and recovery rates reaching 78% to 80%. This indicates that GL-101's collecting and selectivity capabilities are further enhanced at higher temperatures, achieving optimal overall performance. Simultaneously, the dosage of GL-101 decreased (800-1000 g / t), demonstrating higher efficiency and more flexible cost control at suitable temperatures. Desliming yield increased slightly (8-9%), and good control of fine slime was also achieved at higher temperatures.

[0050] Comparative example: Conditions: Same raw ore (Li2O grade 1.2~1.4%), same grinding particle size (-75μm percentage 60~70%), same pulp temperature 9~11℃, conventional oxidized paraffin soap + naphthenic acid collector, and the rest of the process (magnetic separation, desliming, roughing, cleaning and scavenging) is the same as in Example 1.

[0051] Comparison metrics: Li2O grade in concentrate: 5.40%~5.70%; Recovery rate of raw ore: 62.00%~66.00%; The results are shown in Table 1: Table 1 Comparison of the low-temperature flotation effects of the present invention and conventional collectors. The concentrate grade in the comparative example was only 5.40%~5.70%, far lower than the 6.1% or more achieved by GL-101 at 10°C in Example 1. This clearly demonstrates that conventional reagents have insufficient collecting ability and poor selectivity at low temperatures, easily introducing more gangue, leading to a significant decrease in concentrate grade; The recovery rate of the comparative example was only 62.00%~66.00%, which is more than 10% lower than the recovery rates of over 77.5% in Example 1 and over 76% in Example 2. This indicates that conventional reagents are severely inadequate in collecting fine-grained spodumene at low temperatures, resulting in a large amount of fine-grained spodumene being lost with the tailings. The description of the proportions explicitly states that "heating is required," which means that in actual production, additional energy costs must be incurred to raise the temperature of the slurry in order to achieve even relatively low targets.

[0052] In summary, the GL-101 compound reagent and its application method, through innovative reagent formulation and optimized flotation process, successfully solved the key technical bottlenecks of difficult flotation recovery and high cost of fine-grained spodumene under low-temperature conditions, providing a practical solution for the efficient, economical and environmentally friendly mining of spodumene.

[0053] The device embodiments described above are merely illustrative. The units described as separate components may or may not be physically separate; that is, they may be located in one place or distributed across multiple network units. Some or all of the modules can be selected to achieve the purpose of this embodiment according to actual needs.

[0054] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention.

[0055] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions, characterized in that, The collector GL-101 comprises: mixed fatty acids, mixed amines and their derivatives, alcohol compounds, and emulsifier components; The mass percentage of each component in the collector GL-101 is as follows: 70-95% mixed fatty acid components, 5-15% mixed amines and their derivatives components, 3-10% alcohol compounds components, and 3-10% emulsifier components.

2. The compound reagent for flotation separation of fine-grained spodumene under low-temperature conditions according to claim 1, characterized in that, The mixed fatty acids are composed of dodecanoic acid (lauric acid), palmitic acid (palmitic acid), and stearic acid (stearic acid) in a mass ratio of 0.5~1.5:0.5~1.5:7.5~8.

5.

3. The compound reagent for flotation separation of fine-grained spodumene under low-temperature conditions according to claim 1, characterized in that, The mixed amines and their derivatives are prepared by mixing dodecylamine (laurylamine) and cocoylamine in a mass ratio of 0.5~1.5:0.5~1.

5.

4. The compound reagent for flotation separation of fine-grained spodumene under low-temperature conditions according to claim 1, characterized in that, The alcohol compounds are prepared by mixing ethylene glycol and No. 2 oil (pine oil) in a mass ratio of 1.5~2.5:0.5~1.

5.

5. The compound reagent for flotation separation of fine-grained spodumene under low-temperature conditions according to claim 1, characterized in that, The emulsifier is octylphenol polyoxyethylene ether (OP-10).

6. A method for preparing a compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions, characterized in that, Includes the following steps: Mixed fatty acids were added to a reaction vessel in proportion and stirred for 30-50 minutes in a constant temperature water bath at 30-40℃ and stirring at 500-700 r / min until the system was homogeneous. Mixed amines and their derivatives were added and stirred for 0.8-1.1 hours while maintaining the same temperature and stirring speed. Then alcohol compounds and emulsifiers were added and stirred at a uniform speed for 20-40 minutes to obtain the compound collector GL-101.

7. A method for applying a compound reagent for the flotation separation of fine-grained spodumene under low-temperature conditions, characterized in that, A method for low-temperature flotation of fine-grained spodumene using a compound reagent as described in claims 1-5 for flotation separation of fine-grained spodumene under low-temperature conditions includes the following steps: S1 Crushing: The raw spodumene ore is pre-crushed by a jaw crusher and then finely crushed by a double roll crusher to a particle size of <2mm. The +2mm particle size is returned to the double roll crusher for further crushing. S2 grinding: The crushed ore is mixed and reduced in size, and then ground to a -75μm content of 60-70% under the condition of 40-60% slurry concentration; S3 Magnetic Separation for Iron Removal: A high-gradient magnetic separator is used to perform weak magnetic separation on the grinding slurry with a magnetic field strength of 0.5 to 0.8T to remove magnetic iron impurities and obtain a non-magnetic product. S4 Desliming: Desliming is performed on non-magnetic products, with the amount of desliming controlled at 5% to 8% of the original ore mass. Fine mud interference is removed to obtain deslimed slurry. S5 Thickening and Slurry Preparation: The deslimed slurry is concentrated to a slurry concentration of 25-30% in preparation for flotation operations; S6 roughing: 1000-1800 g / t of sodium carbonate aqueous solution with a mass concentration of 3-5% is stirred for 4-6 min, 200-500 g / t of sodium hydroxide aqueous solution with a mass concentration of 3-5% is stirred for 4-6 min, 10-200 g / t of calcium chloride aqueous solution with a mass concentration of 2.5-5% is stirred for 2-4 min, 800-1400 g / t of compound collector GL-101 is stirred for 2-4 min, and aeration and foaming are carried out to obtain rough concentrate and roughing tailings; S7 Fine Concentration: After one fine concentration of the rough concentrate, add 300~600g / t of sodium carbonate aqueous solution with a mass concentration of 3~5% and stir for 2~4min. Aerate and scrape the bubbles to obtain spodumene concentrate and middlings 1. S8 Scavenging: The tailings are subjected to a first scavenging and a second scavenging in sequence. In both scavenging processes, 10~30g / t of calcium chloride is added and stirred for 2~4min. Then, 200~400g / t of compound collector GL-101 is added and stirred for 2~4min. The process is followed by aeration and foaming to obtain middlings 2, middlings 3 and the final tailings. S9 Closed-loop cycle: Middle ore 1 and Middle ore 2 return to roughing operation, and Middle ore 3 returns to primary scavenging operation, forming a closed-loop flotation process of one roughing, one cleaning, and two scavenging operations.

8. The application method of the compound reagent for flotation separation of fine-grained spodumene under low-temperature environment according to claim 7, characterized in that, In step S3, the recovery rate of non-magnetic product Li2O in the magnetic separation operation is ≥98.5%, and the removal rate of magnetic iron impurities is ≥90%.

9. The application method of the compound reagent for flotation separation of fine-grained spodumene under low-temperature environment according to claim 7, characterized in that, It is suitable for low-temperature environments with slurry temperatures of 8–15°C, and can achieve efficient spodumene separation without heating the slurry.

10. The method for applying the compound reagent for flotation separation of fine-grained spodumene under low-temperature conditions according to claim 7, characterized in that, The spodumene concentrate has a Li2O grade of ≥6.1% and a Li2O recovery rate of ≥76% from the raw ore.

Images