Coarse-grained spodumene reinforced flotation collector and application thereof

Abstract

The present application relates to the technical field of mineral flotation, in particular to a kind of coarse-grained spodumene reinforced flotation collector and application.The collector includes specific content of sodium carbonate, fatty acid, betaine series surfactant, neutral oil and terpineol or methyl isobutyl carbinol.The present application also provides the application of the collector, which focuses on the reinforced flotation of pegmatite coarse-grained spodumene ore.The key is that the grinding fineness of spodumene ore only needs to be 45%-70% of-0.074mm, after removing magnetic gangue minerals from the ore slurry by magnetic separation, the above-mentioned collector is used for one roughing, one cleaning and one scavenging to obtain spodumene concentrate product.When the Li2O grade of raw ore is 0.8%-1.8%, the spodumene concentrate grade can reach 5.8%-6.5% and the recovery rate is 80%-90% by using the above-mentioned process with the collector of the present application.The present application not only greatly reduces the grinding load and cost of spodumene ore, but also simplifies the process flow and improves the separation efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral flotation, and in particular to a coarse-grained spodumene enhanced flotation collector and its application. Background Art

[0002] Lithium is hailed as the "new energy metal of the 21st century." Lithium and its compounds are widely used in batteries, lubricants, solid fuels, catalysts, the nuclear industry, and other fields, earning it the title "the key element driving the world forward." With the development and advancement of science and technology, market demand for lithium resources continues to grow rapidly.

[0003] Spodumene is one of the major lithium resources currently available for development. Spodumene is a pegmatite-type deposit with a generally coarse crystal size. The grade of exploitable pegmatite-type spodumene ore ranges from 1% to 2.5%. Gangue minerals are primarily quartz and feldspar, with smaller amounts of aluminosilicate minerals such as mica, amphibole, and chlorite. Common methods for spodumene beneficiation include hand sorting, flotation, gravity separation, and gravity-flotation combined separation. Flotation is the most common and effective method for processing spodumene. The classic reagents used in spodumene flotation are "three alkalis and two soaps": sodium carbonate, sodium hydroxide, and sodium sulfide as conditioning agents, and oxidized paraffin soap and naphthenic acid soap as collectors.

[0004] With current reagent systems, coarse grinding fineness makes it difficult for larger spodumene particles to float, resulting in low recovery rates. Consequently, most spodumene concentrators typically select more than 75% of the -74μm particle size, with some even increasing the grinding fineness to over 80% of the -74μm particle size. Fine grinding reduces the flotation rate of spodumene. Furthermore, due to the similarities in surface properties between aluminosilicate minerals such as feldspar, quartz, mica, chlorite, and amphibole and their similarities to spodumene, these gangue minerals easily enter the spodumene concentrate with the foam, making it difficult to improve the grade of the spodumene concentrate. In recent years, research has been conducted on the flotation recovery of spodumene using combined anionic and cationic reagents. However, the inclusion of fatty amine collectors in these reagents results in large and sticky flotation volumes, making them difficult to implement in practical production. Therefore, developing an efficient collector and flotation process to enhance the flotation of coarse-grained spodumene is an important way to achieve a balance between the grade and recovery rate of spodumene concentrate, which is of great significance to maximizing resource value, building a resource-saving society, and ensuring strategic resource reserves. Summary of the Invention

[0005] To address the problems of poor flotation efficiency and resulting energy waste in coarse-grained spodumene ores, the present invention provides a coarse-grained spodumene enhanced flotation collector and flotation process. This collector can not only serve as a highly efficient collector for conventional-sized spodumene, but can also significantly improve the flotation of coarse-grained spodumene. This collector can be applied to the flotation recovery of pegmatite-type spodumene ores under coarse grinding conditions, yielding spodumene concentrates with high grade and recovery rates.

[0006] To achieve the above object, the present invention provides a coarse-grained spodumene enhanced flotation collector and a flotation process, comprising:

[0007] A coarse-grained spodumene enhanced flotation collector comprises the following components, calculated by mass: 20-30 parts of sodium carbonate, 60-75 parts of fatty acid, 10-20 parts of betaine series surfactant, 5-10 parts of neutral oil, and 3-6 parts of terpineol (2# oil) or methyl isobutyl carbinol (MIBC).

[0008] As a preferred coarse-grained spodumene enhanced flotation collector, the fatty acid is a long-chain fatty acid or a mixture thereof having a carbon chain length greater than 12. Of course, industrial products based on oleic acid or oleic acid can also be used in the present invention.

[0009] As a preferred coarse-grained spodumene enhanced flotation collector, the betaine series surfactant is selected from at least one of carboxylic acid betaine, sulfobetaine, sulfate betaine, phosphate betaine, or industrial products with the above substances as the main components. As a further preferred embodiment; the betaine surfactant is C 12 –C 14 Alkyl dimethyl betaine.

[0010] As a preferred coarse-grained spodumene enhanced flotation collector, the neutral oil is a C4-C 16 The neutral oil is preferably kerosene or liquid paraffin.

[0011] The present invention provides a coarse-grained spodumene enhanced flotation collector; the preparation method thereof comprises the following steps:

[0012] 1) dissolving sodium carbonate prepared according to a set component ratio into an appropriate amount of water to prepare sodium carbonate solution A;

[0013] 2) Fatty acids, betaine series surfactants, neutral oil, terpineol (2# oil) or methyl isobutyl carbinol (MIBC) are added to solution A in a set proportion and mixed evenly, and heated and stirred until the reaction is complete to form a uniform solution, which is the coarse-grained spodumene enhanced flotation collector.

[0014] The present invention discloses an application of a coarse-grained spodumene enhanced flotation collector, wherein the collector is used in the coarse-grained spodumene flotation process; the flotation process comprises the following steps:

[0015] 1) Crushing the spodumene ore to -2mm;

[0016] 2) Grinding the crushed spodumene ore to obtain a spodumene slurry, wherein the grinding fineness is -0.074 mm and the spodumene content is 45%-70%;

[0017] 3) diluting the obtained spodumene slurry and removing magnetic gangue minerals in advance by magnetic separation;

[0018] 4) adding sodium carbonate solution to the slurry from which the magnetic gangue minerals have been removed to adjust the pH of the slurry;

[0019] 5) adding alkaline earth metal ions to the pH-adjusted slurry as an activator for spodumene;

[0020] 6) adding the activated slurry to the spodumene flotation collector, stirring and then aerating, and flotation to obtain spodumene concentrate and tailings products.

[0021] In the above application process, the heating and stirring conditions in step 2) are a temperature of 70-90°C and a time of 10-30 min.

[0022] In the above application process, all reagents can also be prepared without mixing and heating, and can be added in sequence before flotation.

[0023] In the above application process, 2-4 kg / t of sodium carbonate is added during the grinding process in step 2).

[0024] In the above application process, the magnetic field strength of the magnetic separation in step 3) is 0.6-1.2T.

[0025] In the above application process, the slurry concentration in step 4) is 30%-50% (mass percentage concentration) and the pH is 9.7-11.5. Preferably, the slurry concentration is 35%-45% and the pH is 10.3-11.2.

[0026] In the above application process, the alkaline earth metal ion activator in step 5) is represented by calcium ion, and its usage is 100-200 g / t. Preferably, the activator is calcium chloride, and its usage is 200-400 g / t.

[0027] In the above application process, the flotation in step 6) includes one roughing, one cleaning, and one scavenging; the amount of collector used for enhanced flotation of coarse spodumene particles during the roughing process is 700-1300 g / t; no collector is added during the cleaning process; and the amount of collector used for enhanced flotation of coarse spodumene particles during the scavenging process is 200-600 g / t. Preferably, the amount of collector used for enhanced flotation of coarse spodumene particles during the roughing process is 900-1200 g / t; no collector is added during the cleaning process, and the slurry pH is adjusted to the same level as the roughing process; and the amount of collector used for enhanced flotation of coarse spodumene particles during the scavenging process is 300-500 g / t.

[0028] The present invention provides a coarse-grained spodumene enhanced flotation collector and a flotation process. The key to this collector is that, in addition to containing specific amounts of fatty acids and sodium carbonate, it also innovatively incorporates a betaine surfactant, neutral oil, and a frother, 2# oil or MIBC. Betaine, neutral oil, and frother serve as auxiliary agents that can enhance the flotation of coarse-grained ore, adjust the foam structure, and significantly improve the flotation recovery rate of coarse-grained spodumene. During use, the betaine, neutral oil, and frother can be added sequentially or pre-mixed into a mixed solution. The preparation method comprises the following steps: dissolving sodium carbonate in an appropriate amount of water to prepare a sodium carbonate solution; adding fatty acids, betaine surfactants, neutral oil, and 2# oil or MIBC to the solution, mixing uniformly, and heating and stirring until the reaction is complete to form a uniform solution, thereby obtaining the coarse-grained spodumene enhanced flotation collector. Based on the development of the coarse-grained spodumene enhanced flotation collector, the present invention also provides a flotation process compatible with this collector. This process requires only grinding the spodumene ore to -0.074mm, which accounts for 45%–70% of the ore. After magnetic separation to remove magnetic gangue minerals, the ore pulp is adjusted to a pH of 9.7–11.5. The collector described above is then used to perform a roughing, a cleaning, and a scavenging process to produce a spodumene concentrate. The collector described herein enhances the flotation of coarse-grained spodumene and provides excellent selectivity. Using this process, when the raw ore has an incoming Li₂O grade of 0.8%–1.8%, the spodumene concentrate grade can reach 5.8%–6.5%, with a recovery rate of 80%–90%. This agent and process not only significantly reduce the grinding load and cost of spodumene ore, but also simplify the process flow and improve separation efficiency. This is of great significance for maximizing resource value, building a resource-conserving society, and safeguarding strategic resource reserves. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a process flow chart of the flotation process of the present invention. DETAILED DESCRIPTION

[0030] In order to better understand the present invention, the following embodiments are further described in conjunction with the present invention, but the present invention is not limited to the following embodiments. Without departing from the main purpose of the present invention, other replacements, modifications, changes and deletions can be made to the design, operating conditions and parameters of the following exemplary embodiments. All such modifications should be included within the scope of the present invention. The endpoints and any value of the scope disclosed in this article are not limited to this accurate scope or value, and these scopes or values ​​should be interpreted as comprising values ​​approaching these scopes or values. For numerical range, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and the independent point value, and between the independent point value, can be combined with each other and obtain one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed in this article.

[0031] The present invention will be described below with reference to specific embodiments.

[0032] Example 1

[0033] Add 15g of sodium carbonate to an appropriate amount of water and stir thoroughly until it is completely dissolved. Add 35g of oleic acid, 12g of tetradecyl dimethyl betaine, 8g of liquid paraffin and 4g of 2# oil to the obtained sodium carbonate solution, heat and stir at 90°C for 20 minutes to allow it to react completely. The resulting homogeneous solution is the coarse-grained spodumene enhanced flotation collector, which can be diluted to a specific concentration before use.

[0034] Example 2

[0035] Add 8g of sodium carbonate to an appropriate amount of water and stir thoroughly until it is completely dissolved. Add 20g of linoleic acid, 10g of octadecyl dimethyl betaine, 3g of liquid paraffin and 2g of MIBC to the obtained sodium carbonate solution, heat and stir at 80°C for 30 minutes to allow it to react completely. The resulting homogeneous solution is the coarse-grained spodumene enhanced flotation collector, which can be diluted to a specific concentration before use.

[0036] Example 3

[0037] Add 25g of sodium carbonate to an appropriate amount of water and stir thoroughly until it is completely dissolved. Add 60g of oleic acid, 20g of dodecyl dimethyl betaine, 10g of liquid paraffin and 8g of 2# oil to the obtained sodium carbonate solution, heat and stir at 90°C for 30 minutes to allow it to react completely. The resulting homogeneous solution is the coarse-grained spodumene enhanced flotation collector, which can be diluted to a specific concentration before use.

[0038] Application Example 1

[0039] The spodumene ore is taken from the Sichuan methyl card ore mine, and Li in the raw ore O content is 1.45%.It is 55% that the spodumene raw ore is ground to-0.074mm content, after magnetic separation removes magnetic gangue mineral, adds sodium carbonate and adjusts slurry pH to 10.3, after stirring 3min, adds calcium chloride solution (take mass fraction as 2.5% solution to add, the calcium chloride consumption is 250g / t), after stirring 3min, then adds the collecting agent that embodiment 1 makes, the collecting agent consumption is 1100g / t spodumene raw ore, carries out aeration flotation after stirring 5min, obtains roughing concentrate and tailings.In roughing tailings, add calcium chloride 100g / t, add the collecting agent 400g / t that embodiment 1 makes after stirring 3min, carry out scavenging after stirring 5min, obtain scavenging ore concentrate and tailings, and scavenging ore concentrate returns to roughing. Sodium carbonate is added to the roughing concentrate to adjust the pH to 10.3, and then stirred for 3 minutes for concentration to obtain concentrated middlings and concentrates. The concentrated middlings are returned to the roughing, and the concentrated concentrate is spodumene concentrate, and the scavenging tailings are spodumene tailings. Figure 1 The flotation indexes are shown in Table 1. For the methylka spodumene with a raw ore Li2O content of 1.45%, the reagent and process of the present invention can be used to obtain a spodumene concentrate with a Li2O grade of 6.19% and a recovery rate of 89.07%.

[0040] Table 1 Flotation index of new collector for methylka spodumene mine

[0041]

[0042] Application Comparative Example Series 1

[0043] The raw materials and process are the same as those in Experimental Example 1, except that the new coarse-grained spodumene enhanced flotation collector is replaced by other combined reagents. The experimental results are shown in Table 2.

[0044] Table 2 Flotation indexes of methylka spodumene ore

[0045]

[0046] Experimental Example 2

[0047] The experiment spodumene raw ore is taken from Sichuan Lijiagou, and Li in the raw ore O content is 1.49%.It is 61% that the spodumene raw ore is ground to-0.074mm content, after magnetic separation removes magnetic gangue mineral, adds sodium carbonate and adjusts ore pulp pH to 10.5, after stirring 3min, adds calcium chloride solution (take mass fraction as 2.5% solution to add, calcium chloride consumption is 300g / t), after stirring 3min, then add the collecting agent that embodiment 2 makes, the collecting agent consumption is 1200g / t spodumene raw ore, carries out aeration flotation after stirring 5min, obtains roughing concentrate and tailings.In roughing tailings, add calcium chloride 120g / t, add the collecting agent 450g / t that embodiment 3 makes after stirring 3min, carry out scavenging after stirring 5min, obtain scavenging ore concentrate and tailings, scavenging ore concentrate returns to roughing. Sodium carbonate is added to the roughing concentrate to adjust the pH to 10.5, and then stirred for 3 minutes before concentrating to obtain concentrating middlings and concentrates. The concentrating middlings are returned to the roughing, the concentrating concentrate is spodumene concentrate, and the scavenging tailings are spodumene tailings. Figure 1 The flotation indexes are shown in Table 2. For the Lijiagou spodumene with a raw ore Li2O content of 1.49%, the reagent and process of the present invention can be used to obtain a spodumene concentrate with a Li2O grade of 6.14% and a recovery rate of 88.23%.

[0048] Table 3 Flotation index of new collector for Lijiagou spodumene mine

[0049]

[0050] Application Comparative Example Series 2

[0051] The raw materials and process are the same as those in Experimental Example 2, except that the new coarse-grained spodumene enhanced flotation collector is replaced by other combined reagents. The experimental results are shown in Table 4.

[0052] Table 4 Flotation indexes of Lijiagou spodumene mine

[0053]

[0054]

[0055] Application Comparative Example 3

[0056] Only the grinding fineness was changed to -0.074 mm, and the contents were 82.17% and 88.32% respectively. Other conditions such as raw materials and experimental process were the same as those in Experimental Example 2. The experimental results are shown in Table 5. When the grinding fineness exceeded the optimal range, the grade of spodumene decreased significantly, and the recovery rate remained basically unchanged.

[0057] Table 5 Flotation indexes of Lijiagou spodumene mine with different grinding fineness

[0058]

Claims

1. A coarse-grained spodumene enhanced flotation collector, characterized in that: It includes the following components, calculated in parts by mass: 20–30 parts sodium carbonate, 60–75 parts fatty acids, 10-20 parts of betaine series surfactant, 5–10 parts neutral oil, 3-6 parts of terpineol or methyl isobutyl carbinol; the betaine series surfactant is selected from at least one of carboxylic acid betaine, sulfobetaine, sulfate betaine, and phosphate betaine.

2. The coarse-grained spodumene enhanced flotation collector according to claim 1, wherein: The fatty acid is a long-chain fatty acid with a carbon chain length greater than 12 or a mixture thereof.

3. The coarse-grained spodumene enhanced flotation collector according to claim 1, wherein: The neutral oil is a C4-C 16 Alkanes, aromatic hydrocarbons or their mixtures, or industrial products with the above substances as the main components.

4. The coarse-grained spodumene enhanced flotation collector according to claim 1, wherein: The preparation method comprises the following steps: 1) dissolving sodium carbonate prepared according to a set component ratio into an appropriate amount of water to prepare sodium carbonate solution A; 2) Fatty acids, betaine series surfactants, neutral oil, terpineol or methyl isobutyl carbinol are added to solution A in a set proportion and mixed evenly, and heated and stirred until the reaction is complete to form a uniform solution, which is the coarse-grained spodumene enhanced flotation collector.

5. The coarse-grained spodumene enhanced flotation collector according to claim 4, characterized in that: The heating and stirring temperature in step 2) is 70–90°C, and the time is 10–30 min.

6. An application of a coarse-grained spodumene enhanced flotation collector as claimed in any one of claims 1 to 5, wherein The invention is characterized in that the collector is used in the flotation process of coarse-grained spodumene; the flotation process comprises the following steps: 1) Crushing the spodumene ore to −2 mm; 2) Grinding the crushed spodumene ore to obtain spodumene slurry with a grinding fineness of − 0.074 mm and a spodumene content of 45%–70%; 3) diluting the obtained spodumene slurry and removing magnetic gangue minerals in advance by magnetic separation; 4) adding sodium carbonate solution to the slurry from which the magnetic gangue minerals have been removed to adjust the pH of the slurry; 5) adding alkaline earth metal ions to the pH-adjusted slurry as an activator for spodumene; 6) Adding coarse-grained spodumene enhanced flotation collector to the activated pulp, stirring and aerating, and flotation to obtain spodumene concentrate and tailings products.

7. The use of a coarse-grained spodumene enhanced flotation collector as claimed in claim 6, characterized in that: In step 2), 2–4 kg / t of sodium carbonate is added during the grinding process; The magnetic field strength of the magnetic separation in step 3) is 0.6–1.2 T; In step 4), the pH of the slurry is 9.7–11.

5.

8. The use of a coarse-grained spodumene enhanced flotation collector as claimed in claim 6, characterized in that: The alkaline earth metal ion activator in step 5) is represented by calcium ion, and its usage is 100-200 g / t.

9. The use of a coarse-grained spodumene enhanced flotation collector as claimed in claim 6, characterized in that At: The flotation in step 6) includes one roughing, one cleaning and one scavenging; The collector dosage for enhanced flotation of coarse spodumene particles in the roughing process is 700–1300 g / t; No collector is added during the selection process; The amount of collector used for enhanced flotation of coarse spodumene particles during the scavenging process is 200–600 g / t.

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