Spodumene composite collecting agent, preparation method thereof and spodumene ore flotation method

Abstract

The invention provides a spodumene composite collecting agent, a preparation method of the spodumene composite collecting agent and a spodumene ore flotation method. The spodumene composite collecting agent is prepared from, by mass, 30%-50% of sulfonic acid compounds, 20%-35% of amine compounds, 20%-38% of fatty acid or fatty acid salt compounds, 4%-6.5% of ether compounds, 1%-6% of alcohol compounds and 3%-5% of kerosene. The spodumene composite collecting agent is formed by mixing a sulfonic acid compound, an amine compound, a fatty acid or fatty acid salt compound, an ether compound, an alcohol compound and kerosene according to a preset proportion, and the spodumene flotation agent is moderate in viscosity and easy to prepare. And alcohol and kerosene are added into the spodumene composite collecting agent, some insoluble substances are easy to dissolve, and therefore the recovery rate of metal lithium in spodumene flotation can be increased. The spodumene composite collecting agent is low in cost, good in selectivity, high in collecting capacity and free of corrosion effect on equipment.

Description

Technical Field

[0001] The present application relates to the technical field of mineral flotation, and in particular to a spodumene composite collector and a preparation method thereof, and a spodumene ore flotation method. Background Art

[0002] Lithium has great economic benefits due to its high electrochemical activity, high reversibility and high energy density. These characteristics lead to its use as an energy element in the manufacture of batteries for electrical appliances such as automobiles, portable devices or energy storage systems. However, it is also used in other industries such as glass manufacturing, ceramics, lubricants and metallurgy. Currently, its main use is in the manufacture of lithium batteries, of which nearly 80% of lithium is used for this, followed by ceramics, glass industry and other industries. Currently, lithium is mainly extracted from spodumene, lepidolite and lithium-containing salt lakes, but spodumene is the most cost-effective because its composition has the highest theoretical percentage of lithium.

[0003] At present, the collectors commonly used in the flotation process of spodumene can generally be divided into anionic collectors and cationic collectors. Common anionic collectors mainly include: sodium oleate, oxidized paraffin soap, cyclopentane acid soap, sodium alkyl sulfate and hydroxamic acid. Although anionic collectors have good selectivity, their collection ability is weak, the required dosage is large, and the economic cost is high. Cationic collectors are mainly various amine compounds, such as: dodecylamine, hexadecylamine, coconut amine and mixed amines. The main active group of cationic collectors is amino group (-NH2), which has good collection ability, but poor selectivity. Summary of the invention

[0004] The present application provides a spodumene composite collector that is conducive to integrating excellent selectivity, collection capacity and cost-effectiveness, a preparation method thereof, and a spodumene ore flotation method.

[0005] In the first aspect, an embodiment of the present application provides a spodumene composite collector, wherein the formula mass ratio of the spodumene composite collector is: sulfonic acid compounds: 30-50%, amine compounds: 20-35%, fatty acids or fatty acid salt compounds: 20-38%, ether compounds: 4-6.5%, alcohol compounds: 1-6%, and kerosene 3-5%.

[0006] According to the first aspect, in a possible implementation, the sulfonic acid compound includes at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid and sodium olefin sulfonate.

[0007] According to the first aspect, in a possible implementation, the amine compound includes at least one of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, dodecyltrimethylammonium chloride and N,N-dimethylformamide.

[0008] According to the first aspect, in a possible implementation, the fatty acid or fatty acid salt compound includes at least one of oleic acid, linoleic acid, oxidized paraffin soap, cyclopentane acid soap, tall oil, peroxy fatty acid soap and rosin acid.

[0009] According to the first aspect, in a possible implementation manner, the ether compound includes one or more combinations of monoethers and mixed ethers.

[0010] According to the first aspect, in a possible implementation, the alcohol includes at least one of methanol, ethanol, n-butanol and the like.

[0011] According to the first aspect, in a possible implementation, the kerosene is a mixture containing carbon numbers of 7-13.

[0012] In a second aspect, the present application also provides a method for preparing the spodumene composite collector according to the first aspect, comprising:

[0013] Sulfonic acid compounds, amine compounds, fatty acids or fatty acid salt compounds, ether compounds, alcohol compounds, and kerosene are mixed in a preset ratio to form a spodumene composite collector.

[0014] In a third aspect, an embodiment of the present application further provides a spodumene ore flotation method, which uses the spodumene spodumene composite collector described in any one of claims 1 to 7 to float the spodumene ore.

[0015] The spodumene composite collector provided by the present application and its preparation method, and the spodumene ore flotation method, the spodumene composite collector is formed by mixing sulfonic acid compounds, amine compounds, fatty acids or fatty acid salt compounds, ether compounds, alcohol compounds, and kerosene in a preset ratio, and the spodumene flotation agent has moderate viscosity and is easy to prepare. In addition, the spodumene composite collector is added with alcohol and kerosene, and some insoluble substances are easy to dissolve, thereby improving the recovery rate of metallic lithium in spodumene flotation. The spodumene composite collector provided by the present application has low cost, good selectivity, strong capture ability, and no corrosion to equipment. DETAILED DESCRIPTION

[0016] The words "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that may provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0017] When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of the present invention.

[0019] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0020] The present application provides a spodumene composite collector, wherein the formula mass ratio of the spodumene composite collector is: sulfonic acid compounds: 30-50%, amine compounds: 20-35%, fatty acids or fatty acid salt compounds: 20-38%, ether compounds: 4-6.5%, alcohol compounds: 1-6%, and kerosene 3-5%.

[0021] Sulfonic acid compounds have strong acidity and good water solubility. In the flotation of spodumene, sulfonic acid compounds can provide the necessary acidic environment, which is helpful for the flotation separation of spodumene. In addition, sulfonic acid compounds can also improve the hydrophobicity of the surface by adsorbing on the surface of spodumene, thereby improving the collection effect.

[0022] Amine compounds can react with the functional groups on the surface of spodumene to form chemical bonds or ionic bonds, thereby firmly adsorbing on the surface of spodumene. This adsorption can not only enhance the hydrophobicity of spodumene, but also improve its separation effect from other minerals. In addition, amine compounds may further affect the flotation behavior of spodumene by adjusting the pH value of the solution.

[0023] Fatty acid compounds and fatty acid salt compounds usually have good surface activity and emulsification properties, which can reduce the surface tension of water and make it easier for the collector to penetrate into the surface of spodumene. At the same time, fatty acid compounds and fatty acid salt compounds can also react with metal ions on the surface of spodumene to form insoluble metal fatty acid salt precipitation, thereby enhancing the collection effect of spodumene. In addition, fatty acid compounds and fatty acid salt compounds may also synergize with other ingredients to further improve the selectivity and collection efficiency of the collector.

[0024] Ether compounds can act as regulators in collectors. They can affect the adsorption and dispersion behavior of collectors on the spodumene surface by changing the physical properties of the solution, such as polarity, viscosity and surface tension. In addition, ether compounds may also react chemically with other components to generate compounds with stronger collection capabilities.

[0025] In summary, the formula of the spodumene composite collector fully exerts the synergistic effect of the various components by carefully proportioning the various components, thereby achieving efficient collection and separation of spodumene.

[0026] The spodumene flotation agent of this invention has moderate viscosity and is easy to prepare. With the addition of alcohol and kerosene, some insoluble substances are easy to dissolve. JLLY-101-A can improve the recovery rate of metallic lithium in spodumene flotation. Combined with the use of gangue inhibitors, the flotation yield can reach 90.4%, and the Li2O grade of the concentrate can reach above 7.5. The spodumene flotation agent provided by this invention has low cost, good selectivity, strong capture ability, and no corrosion to equipment.

[0027] In addition, kerosene can also act as a foaming agent in the collector, reducing the surface tension of water and forming stable bubbles, thereby helping the collector to be better dispersed in the slurry. In addition, kerosene can also synergize with other ingredients to further improve the selectivity and collection efficiency of the collector.

[0028] According to the first aspect, in a possible implementation, the sulfonic acid compound includes at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid and sodium olefin sulfonate.

[0029] Sodium dodecylbenzene sulfonate (SDBS) is a commonly used anionic surfactant. It is a white or light yellow powder or flaky solid. It is difficult to volatilize and is easily soluble in water. It dissolves in water to form a translucent solution. Sodium dodecylbenzene sulfonate is chemically stable to alkali, dilute acid, and hard water, and is slightly toxic. In the flotation of spodumene, sodium dodecylbenzene sulfonate can provide the necessary acidic environment, which is conducive to the flotation separation of spodumene. At the same time, it can also be adsorbed on the surface of spodumene to improve its surface hydrophobicity, thereby improving the collection effect.

[0030] Sodium dodecyl sulfate, also known as sodium lauryl sulfate, is an organic compound. Sodium dodecyl sulfate is commonly used in the chemical and textile industries as an emulsifier, flotation agent and impregnation agent. In spodumene collectors, sodium dodecyl sulfate can also enhance its hydrophobicity by adsorbing on the surface of spodumene, thereby improving the collection efficiency. In addition, it may also synergize with other ingredients to further improve the selectivity and collection efficiency of the collector.

[0031] Fatty acid methyl ester sulfonic acid is the product of the reaction between fatty acid methyl ester and sodium sulfonate. Its molecular structure contains the characteristic group of sulfonic acid compounds, sulfonic acid. In spodumene collectors, fatty acid methyl ester sulfonic acid can provide the necessary acidic environment, which is conducive to the flotation separation of spodumene. At the same time, it may also react chemically with other components to generate compounds with stronger collection ability.

[0032] Sodium olefin sulfonate is a compound with an olefin structure and a sodium sulfonate functional group. In the spodumene collector, sodium olefin sulfonate reacts with the functional groups on the surface of spodumene to form chemical bonds or ionic bonds, thereby firmly adsorbing on the surface of spodumene. This adsorption can not only enhance the hydrophobicity of spodumene, but also improve its separation effect from other minerals.

[0033] In summary, sulfonic acid compounds such as sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid and sodium olefin sulfonate play an important role in spodumene composite collectors. They each have unique properties and uses, and together constitute an important component of the collector, and through synergistic effects, they achieve efficient collection and separation of spodumene.

[0034] According to the first aspect, in a possible implementation, the amine compound includes at least one of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, dodecyltrimethylammonium chloride and N,N-dimethylformamide.

[0035] Dodecylamine is an aliphatic amine compound that is easily soluble in water and most organic solvents. In spodumene collectors, dodecylamine can react with the functional groups on the surface of spodumene to form chemical bonds or ionic bonds, thereby firmly adsorbing on the surface of spodumene. This adsorption can not only enhance the hydrophobicity of spodumene, but also improve its separation effect from other minerals.

[0036] Tetradecamine is a long-chain fatty amine. It has good chemical stability and biodegradability. In spodumene collectors, tetradecamine can also improve the hydrophobicity of the surface by adsorbing on the spodumene surface, thereby improving the collection effect. In addition, it may also synergize with other ingredients to further improve the selectivity and collection efficiency of the collector.

[0037] Hexadecylamine is an organic amine compound, which is widely used in the fields of surfactants, catalysts, rubber additives, etc. In spodumene collectors, hexadecylamine may react with the functional groups on the surface of spodumene through its long chain structure to form a stable chemical bond. This effect can not only enhance the collection effect of spodumene, but also improve the selectivity of the collector.

[0038] Cocoamine, also known as coconut alkylamine or coconut primary amine, is an amine compound extracted from coconut oil. Cocoamine has good biodegradability and mildness, and is relatively friendly to the environment and the human body. In spodumene collectors, coconut amine may react with the functional groups on the surface of spodumene through its unique chemical structure and properties to form chemical bonds or ionic bonds. At the same time, it may also synergize with other ingredients to further improve the performance of the collector.

[0039] As a cationic surfactant, dodecyl trimethyl ammonium chloride is soluble in alcohol and hot water and produces a lot of foam when shaken. In the spodumene collector, dodecyl trimethyl ammonium chloride may react with the anionic functional groups on the surface of spodumene through its cationic properties to form ionic bonds. This effect can not only enhance the collection effect of spodumene, but also improve the selectivity and stability of the collector.

[0040] N,N-dimethylformamide (DMF) is an organic solvent belonging to the amide class of compounds. Although it is not usually used as the main component of the collector, DMF may be used as an auxiliary solvent or regulator in some specific spodumene collector formulations. It can affect the adsorption and dispersion behavior of the collector on the spodumene surface by changing the physical properties of the solution, such as polarity, viscosity and surface tension.

[0041] In summary, amine compounds such as dodecylamine, tetradecylamine, hexadecylamine, coconut amine, dodecyltrimethylammonium chloride and N,N-dimethylformamide play an important role in spodumene composite collectors. They each have unique properties and uses, together forming an important component of the collector, and through synergistic effects, they achieve efficient collection and separation of spodumene.

[0042] According to the first aspect, in a possible implementation, the fatty acid or fatty acid salt compound includes at least one of oleic acid, linoleic acid, oxidized paraffin soap, cyclopentane acid soap, tall oil, peroxy fatty acid soap and rosin acid.

[0043] Oleic acid is an unsaturated fatty acid with the chemical formula C18H34O2. It is an excellent solvent for oils, fatty acids and oil-soluble substances. In spodumene collectors, oleic acid can react with metal ions on the surface of spodumene through its carboxyl group to form insoluble metal fatty acid salt precipitation, thereby enhancing the collection effect of spodumene. At the same time, oleic acid also has good lubricity and dispersibility, which helps to evenly disperse the collector in the slurry.

[0044] Linoleic acid is also an unsaturated fatty acid with a chemical formula of C18H32O2. It is an essential fatty acid in human and animal nutrition. In spodumene collectors, linoleic acid can also react with metal ions on the surface of spodumene to form metal fatty acid salt precipitation, thereby enhancing the collection effect. In addition, linoleic acid also has the effects of lowering blood cholesterol and preventing atherosclerosis. Although these effects are not directly reflected in the collector, they indicate that it has good biocompatibility and safety.

[0045] Oxidized paraffin soap is a soap compound made by the reaction of fatty acids generated by oxidation of petroleum wax with metal ions. It contains long-chain fatty acids and can form complexes with the metal surfaces of various minerals to improve the hydrophobicity of the mineral surface. In spodumene collectors, oxidized paraffin soap can convert the hydrophilic functional groups on the surface of spodumene into hydrophobic functional groups through its complexation, thereby improving the flotation performance of spodumene.

[0046] Naphthenic acid soap is a general term for metal salts of naphthenic acid, including sodium naphthenic acid, calcium naphthenic acid and other compounds. They have good solubility and dispersibility, and can react with the functional groups on the surface of spodumene to form chemical bonds or ionic bonds. In spodumene collectors, naphthenic acid soap can improve the collection efficiency and selectivity of spodumene through its unique chemical structure and properties.

[0047] Tal oil, also known as tall oil, tall oil, pulp sludge, liquid rosin, is a mixture of fatty acids and rosin acids, in which fatty acids are mainly unsaturated acids, such as oleic acid, linoleic acid, etc., and a small amount of saturated acids. In spodumene collectors, tal oil can react with metal ions on the surface of spodumene through its fatty acid components to form metal fatty acid salt precipitation, and its rosin acid components may also have a positive impact on the collection effect.

[0048] Peroxy fatty acid soaps are soap compounds made by the reaction of higher fatty acids, such as peroxides of peroxylauric acid and peroxypalmitic acid, with metal ions. They have strong oxidizing properties and good dispersibility, and can react chemically with the functional groups on the surface of spodumene to change the chemical properties of its surface. In spodumene collectors, peroxy fatty acid soaps can improve the collection efficiency and flotation rate of spodumene through their oxidation.

[0049] Abietic acid is a natural resin acid, mainly found in the rosin of pine trees and other plants. It has good solubility and dispersibility, and can react with a variety of metal ions. In spodumene collectors, abietic acid may react with metal ions on the surface of spodumene through its carboxyl group to form metal rosinate precipitation, thereby enhancing the collection effect of spodumene. At the same time, abietic acid may also synergize with other ingredients to further improve the performance of the collector.

[0050] According to the first aspect, in a possible implementation manner, the ether compound includes one or more combinations of monoethers and mixed ethers.

[0051] Monoether (symmetrical ether / simple ether), monoether refers to ether compounds in which R and R' are the same. This type of compound is symmetrical in structure, hence the name. Monoethers are usually colorless liquids at room temperature, have a fragrance, a low boiling point, and are relatively stable in nature. They are widely used in organic synthesis, solvents, anesthetics, and other fields. For example, ethyl ether, dipropyl ether, etc.

[0052] Ether is one of the most common monoethers, also known as diethyl ether. Ether is a colorless liquid at room temperature with a sweet and pleasant smell. It is completely miscible with ethanol and organic solvents and slightly soluble in water. Ether is an excellent solvent for alkaloids, oils, dyes, fats, rubber, resins, nitrocellulose, rosin, spices, etc., and is widely used as a solvent for the production of rayon, guncotton, and nitrocellulose. In addition, ether can also be used as an anesthetic, refrigerant, dry cleaning agent, etc.

[0053] Dipropyl ether is also called di-n-propyl ether. It is a colorless liquid that is very flammable and has the smell of ether. It is slightly soluble in water and can be miscible with a variety of organic solvents. The properties of dipropyl ether are very similar to those of ether, and their uses are also similar. However, due to its higher boiling point, it has a relatively low vapor pressure and a lower solubility in water, so it can be used as an ideal extraction agent.

[0054] Mixed ethers (asymmetric ethers / mixed ethers) and mixed ethers refer to ether compounds in which R and R' are different. This type of compound is asymmetric in structure, hence the name. The properties and uses of mixed ethers often vary depending on the different hydrocarbon groups they contain. They are widely used in organic synthesis, surfactants, lubricants and other fields. For example, some mixed ethers can be used as efficient surfactants to improve the wettability and dispersibility of liquids.

[0055] Ethyl hydroxyethyl cellulose is a mixed ether composed of two hydrocarbon groups, ethyl and hydroxyethyl. It has good water solubility, stability and film-forming properties, so it is widely used in construction, coatings, inks, textiles, printing and dyeing, papermaking, medicine, food and other fields.

[0056] Methyl hydroxyethyl cellulose is also a mixed ether, composed of two hydrocarbon groups, methyl and hydroxyethyl. It also has good water solubility, stability and viscosity adjustment, so it is used as a thickener and water retainer for latex paints, and is also used in building mortar, adhesives, paint printing, ink, dyeing, ceramics, papermaking, medicine, cosmetics, food preservation, textile printing and dyeing, tobacco, pesticides, oil fields, daily chemicals and other fields.

[0057] Dibutyl ether is also called butyl ether. It is a colorless liquid with a slight pineapple aroma. It is almost insoluble in water and can be miscible with alcohols and ethers. Dibutyl ether has good solubility for many natural synthetic resins, rubbers, oils, fats, organic acids, esters, alkaloids, etc., so it can be used as an excellent solvent. At the same time, it can also be used as an extractant and organic synthesis reaction medium.

[0058] In practical applications, monoethers and mixed ethers can be used alone or in combination. The combined use can make full use of the advantages of different ether compounds to achieve better performance and application effects. For example, when preparing a composite collector, monoethers and mixed ethers can be combined to improve the selectivity and collection efficiency of the collector.

[0059] According to the first aspect, in a possible implementation, the alcohol includes at least one of methanol, ethanol, n-butanol and the like.

[0060] Methanol is a colorless, transparent liquid with a pungent odor, volatile, and miscible with water in any proportion. It is an important basic chemical raw material and organic solvent, widely used in the fields of chemical industry, medicine, pesticides, dyes, coatings, synthetic fibers, etc. Uses: Methanol can be used as a solvent, fuel, synthetic raw material, etc. It is also a raw material for many chemicals, such as formaldehyde, acetic acid, etc.

[0061] Ethanol, commonly known as alcohol, is a colorless, transparent liquid with a special aroma. It is miscible with water in any proportion and easily soluble in organic solvents. Ethanol is a flammable liquid that releases a large amount of heat when burned. Ethanol is a commonly used organic solvent and disinfectant. It is also used as a fuel (such as biodiesel), chemical raw material (such as acetaldehyde, ethyl acetate, etc.) and pharmaceutical raw material. In addition, ethanol is also used to make beverages, spices, coatings, etc.

[0062] n-Butanol is a colorless, transparent liquid with a special smell. It is miscible with water and easily soluble in organic solvents. n-Butanol has low volatility, but is flammable and explosive. n-Butanol is mainly used as an organic solvent, synthetic raw material, and plasticizer. In the coating, paint, ink and other industries, n-Butanol as a solvent can improve the gloss and adhesion of the product. In addition, n-Butanol is also used to make surfactants, fragrances, dyes, etc.

[0063] In the described implementation, these alcohol compounds can be used alone or in any proportion. Their specific application depends on the required chemical properties, reaction conditions and target products. For example, when preparing certain specific chemical reagents or catalysts, it may be necessary to use specific alcohol compounds or their mixtures. In addition, these alcohol compounds can also be used as solvents, reaction media or extraction agents, etc., and play an important role in chemical synthesis, separation and purification processes.

[0064] According to the first aspect, in a possible implementation, the kerosene is a mixture containing carbon numbers of 7-13.

[0065] In the above embodiments, the different components of benzenesulfonic acid, amine, carboxylic acid, ether, alcohol and kerosene mentioned can be freely combined without limitation.

[0066] In a second aspect, the present application also provides a method for preparing the spodumene composite collector according to the first aspect, comprising:

[0067] Sulfonic acid compounds, amine compounds, fatty acids or fatty acid salt compounds, ether compounds, alcohol compounds, and kerosene are mixed in a preset ratio to form a spodumene composite collector.

[0068] The prepared spodumene composite collector (JLLY-101 flotation reagent) is placed in an ultrasonic stirrer for stirring and mixing. The stirred reagent is placed steadily, and after the foam disappears, it is bottled for later use.

[0069] In a third aspect, an embodiment of the present application further provides a spodumene ore flotation method, which uses the spodumene spodumene composite collector described in any one of claims 1 to 7 to float the spodumene ore.

[0070] The following is a spodumene flotation experiment using the invented flotation reagent JLLY-101, which is described in detail.

[0071] (a) Spodumene flotation in South America.

[0072] By testing the spodumene ore sample from South America, the Li2O grade of the raw ore is 1.36%, that is, the content of Li2O in the raw ore is 1.36%. A spodumene beneficiation method is provided, comprising the following steps:

[0073] Step S11: The spodumene ore is placed in a ball mill and ground to a 200-mesh size of 65%-75% to form a slurry, and the slurry is collected.

[0074] Step S12: The slurry collected in step S11 is passed through a magnetic separator to remove magnetic minerals to obtain a magnetically separated concentrate.

[0075] Step S13: Add a concentration agent to the magnetic concentrate obtained in step S12, dry and concentrate, transfer the concentrated pulp to a flotation machine, adjust the flotation agent speed to 1800r / min, and adjust the temperature to room temperature. Stir the pulp in the flotation machine for 5 minutes. At the same time, weigh 1200g / t of sodium carbonate and dissolve it in water. Add the sodium carbonate solution to the pulp in small amounts and multiple times, continue stirring, and add the dissolved sodium hydroxide solution after 10 minutes. In the process of adding the sodium hydroxide solution, the amount of sodium hydroxide solution added should be determined according to the actual pH. After 10 minutes of sodium hydroxide being added, add 500g / t of calcium chloride as an activator, continue stirring for 10 minutes to form a mixed solution.

[0076] Step S14: slowly add 700 g / t of JLLY-101-A flotation reagent into the mixed solution, stir for 10 min, and then open the flotation machine for roughing to obtain roughing concentrate and roughing tailings.

[0077] The rougher tailings are added with JLLY-101-A flotation reagent 40g / t for scavenging, and the scavenged tailings are obtained. The scavenged tailings are returned to the rougher for refloatation.

[0078] Step S14: 200 g / t of JLLY-101-A flotation reagent is added to the roughing concentrate and the scavenged ore obtained from the roughing again, and the first concentrating is performed to obtain the first concentrating middlings and the first concentrating concentrate. The first concentrating middlings are returned to the roughing, and the first concentrating concentrates are subjected to the second concentrating. Similarly, after adding the JLLY-101-A flotation reagent, the concentrate is stirred, and then the concentrate participates in the next flotation, and the middlings return to the previous flotation operation. Finally, spodumene concentrate A1 is obtained.

[0079] After drying in an oven, the obtained spodumene concentrate A1 was collected and mixed for testing. The test results showed that the Li2O grade of the spodumene concentrate A1 was 7.56% and the recovery rate reached 90.3%.

[0080] According to the same ratio, no alcohol was added when preparing the JLLY-101 flotation reagent, and the obtained JLLY-101-B was flotated according to the above flotation steps. Finally, spodumene concentrate B1 was obtained.

[0081] After drying in an oven, the obtained spodumene concentrate B1 was collected and mixed for testing. The test results showed that the Li2O grade of the spodumene concentrate B1 was 4.21% and the recovery rate reached 78.9%.

[0082] According to the same ratio, without adding kerosene, the obtained JLLY-101-C was flotated according to the above flotation steps. Finally, spodumene concentrate C1 was obtained.

[0083] After drying in an oven, the obtained spodumene concentrate C1 was collected and mixed for testing. The test results showed that the Li2O grade of the spodumene concentrate C1 was 5.50% and the recovery rate reached 72.4%.

[0084] The concentrate grade floated by the developed JLLY-101-A spodumene flotation agent is 6.20 percentage points higher than the original ore grade.

[0085] During the flotation process of JLLY-101-A spodumene flotation agent, the foam size and height are moderate, and the foam fluidity and stability are good.

[0086] JLLY-101-A collector has good selectivity, strong collecting ability, stable emulsification ability and good dispersibility in solution.

[0087] (II) Spodumene flotation in Africa

[0088] By testing the spodumene ore sample from Africa, the ore grade is 1.70%, and a spodumene beneficiation method is provided, which comprises the following steps:

[0089] Step S21: The spodumene ore is placed in a ball mill and ground to 65%-75% of the 200 mesh to form a slurry, and the slurry is collected.

[0090] Step S22: The slurry collected in step S21 is passed through a magnetic separator to remove magnetic minerals, and after the magnetic minerals are removed, a magnetically separated concentrate is obtained.

[0091] Step S23: Add a concentration agent to the magnetic concentrate obtained in step S22, dry and concentrate, transfer the concentrated pulp to a flotation machine, adjust the flotation agent speed to 2000r / min, and adjust the temperature to room temperature. Stir the pulp in the flotation machine for 5 minutes, during which 1200g / t of sodium carbonate is weighed and dissolved in water. Add the sodium carbonate solution to the pulp in small amounts and multiple times, continue stirring, wait for 10 minutes, and then add the dissolved sodium hydroxide solution. Add 600g / t of sodium hydroxide. After 10 minutes, add 600g / t of calcium chloride as an activator and continue stirring for 10 minutes.

[0092] Step S24: Slowly add 700g / t of JLLY-101-A flotation reagent, stir for 10 minutes, and then open the flotation machine for roughing to obtain roughing concentrate and roughing tailings. Add 40g / t of JLLY-101-A flotation reagent to the roughing tailings for scavenging to obtain scavenged ore and scavenged tailings. The scavenged ore is returned to the roughing for refloatation.

[0093] Step S25: Add 200 g / t of JLLY-101-A flotation reagent to the rougher concentrate and the scavenged ore, perform the first concentration, and obtain the first concentrated ore and the first concentrated concentrate. The first concentrated ore is returned to the rougher, and the first concentrated concentrate is subjected to the second concentration. Similarly, after adding JLLY-101-A flotation reagent, stir, and then the concentrate participates in the next flotation, and the ore returns to the previous flotation operation. Finally, spodumene concentrate A2 is obtained.

[0094] The obtained spodumene concentrate was dried in an oven, collected and mixed for testing. The test results showed that the Li2O grade of the spodumene concentrate A2 was 7.73% and the recovery rate reached 90.4%.

[0095] According to the same ratio, no alcohol was added when preparing the JLLY-101 flotation reagent, and the obtained JLLY-101-B was flotated according to the above flotation steps. Finally, spodumene concentrate B2 was obtained.

[0096] The obtained spodumene concentrate was dried in an oven, collected and mixed for testing. The test results showed that the Li2O grade of the spodumene concentrate B2 was 4.47%, and the recovery rate reached 80.7%.

[0097] According to the same ratio, without adding kerosene, the obtained JLLY-101-C was flotated according to the above flotation steps. Finally, spodumene concentrate C2 was obtained.

[0098] The obtained spodumene concentrate was dried in an oven, collected and mixed for testing. The test results showed that the Li2O grade of the spodumene concentrate C2 was 6.03%, and the recovery rate reached 86.4%.

[0099] The grade of the concentrate floated by JLLY-101 spodumene flotation agent is 6.03 percentage points higher than that of the original ore.

[0100] For the convenience of viewing, the South American and African ores floated by JLLY-101 spodumene flotation reagent are made into the following table:

[0101]

[0102] In summary, the JLLY-101 flotation reagent developed by the present invention can not only improve the grade of spodumene concentrate to a large extent and reduce the subsequent roasting production cost, but also has a stable flotation effect and can achieve a good recovery rate for spodumene ores in different regions.

[0103] The applicant declares that the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the method of the present invention, addition of auxiliary steps, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A spodumene composite collector, characterized in that: The formula mass ratio of the spodumene composite collector is: sulfonic acid compounds: 30-50%, amine compounds: 20-35%, fatty acids or fatty acid salt compounds: 20-38%, ether compounds: 4-6.5%, alcohol compounds: 1-6%, and kerosene 3-5%.

2. The spodumene composite collector according to claim 1, characterized in that The sulfonic acid compound includes at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty acid methyl ester sulfonic acid and sodium olefin sulfonate.

3. The spodumene composite collector according to claim 1, wherein The amine compound includes at least one of dodecylamine, tetradecylamine, hexadecylamine, coconut amine, dodecyltrimethylammonium chloride and N,N-dimethylformamide.

4. The spodumene composite collector according to claim 1, wherein The fatty acid or fatty acid salt compound includes at least one of oleic acid, linoleic acid, oxidized paraffin soap, cyclopentane acid soap, tall oil, peroxy fatty acid soap and rosin acid.

5. The spodumene composite collector according to claim 1, wherein The ether compounds include one or more combinations of monoethers and mixed ethers.

6. The spodumene composite collector according to claim 1, characterized in that The alcohols include at least one of methanol, ethanol, n-butanol and the like.

7. The spodumene composite collector according to claim 1, characterized in that The kerosene is a mixture containing 7-13 carbon atoms.

8. A method for preparing a spodumene composite collector, characterized in that: The preparation method of the spodumene composite collector comprises: Sulfonic acid compounds, amine compounds, fatty acids or fatty acid salt compounds, ether compounds, alcohol compounds, and kerosene are mixed in a preset ratio to form a spodumene composite collector.

9. A spodumene ore flotation method, characterized in that: The spodumene composite collector described in any one of claims 1 to 7 is used to float spodumene ore.

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