Composite fluorite collecting agent and application thereof

Abstract

The invention provides a composite fluorite collecting agent and application thereof, and belongs to the technical field of ore flotation. The composite fluorite collecting agent consists of the following raw materials in percentage by mass: 30-60% of oleic acid, 5-15% of lower alcohol, 0.05-0.2% of an esterification catalyst, 2-10% of an alkali compound, 2-8% of an emulsifier, 0.5-2% of a water repellent agent, 2-5% of a synergist, 1-5% of a cosolvent, 0.01-0.2% of a defoaming agent and the balance of water. Wherein the oleic acid comprises two or more of low-iodine-value oleic acid, high-iodine-value oleic acid, ricinoleic acid and tall oil fatty acid. By improving the formula and process of the collecting agent, the concentrate purity is greatly improved, the average grade of concentrate powder is 93% or above, the average concentrate recovery rate is 80% or above, and the average concentrate and middling recovery rate reaches 90%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ore flotation, in particular to a composite fluorite collecting agent and application thereof. BACKGROUND

[0002] Fluorite (calcium fluoride, CaF2) is an important strategic non-metallic mineral, which is widely used in metallurgy, chemical industry, building materials, new energy and other fields, especially in the fluorine chemical industry chain. With the increasing demand for high-grade fluorite concentrate (CaF2 content ≥ 97%) in industrial development, the development of efficient flotation technology has become one of the research hotspots in the field of mineral processing. In the chemical industry, high-grade fluorite concentrate is the raw material for the preparation of hydrofluoric acid, aluminum fluoride and other key fluorine chemical products. In addition, the demand for high-purity fluorite in optical lenses, laser crystals and lithium battery electrolyte materials is also increasing. However, fluorite in nature often occurs with gangue minerals such as quartz (SiO2), calcite (CaCO3), and barite (BaSO4), and as the high-quality fluorite resources are gradually depleted, the ore is becoming poor, fine and impure, making it more difficult to upgrade and reduce impurities.

[0003] At present, flotation is still the most important mineral processing method for fluorite recovery, and flotation collector is the most critical part of the flotation process, whose performance directly affects the grade and recovery rate of fluorite concentrate. The selection and optimization of the collector directly determine the hydrophobicity, selectivity and separation efficiency of the mineral surface, and are the key factors affecting the grade and recovery rate of the concentrate. The commonly used collectors for fluorite flotation include oleic acid, sulfonate, hydroxamic acid and new composite reagents. Due to the similarity of the physical and chemical properties of fluorite and gangue minerals (such as quartz and calcite), the use of traditional fatty acid collectors has the problems of difficult flotation separation, poor selectivity, large reagent consumption, and the need for a large amount of depressants and multiple cleaning steps to improve the grade of fluorite concentrate, which results in a complex process and difficult control. At the same time, due to the poor low-temperature resistance and hard water resistance of traditional oleic acid collectors, the collecting ability is insufficient, the bubble performance is poor, and the consumption is large at low temperature in winter, which leads to a significant reduction in the recovery rate and concentrate grade.

[0004] In the prior art, in order to solve the problem of the deficiency of oleic acid as a fluorite collector, patent CN113441285A discloses a preparation method of a fluorite flotation collector, which adopts sulfonated oleic acid and emulsified oleic acid for compounding. Although the solubility, dispersibility and low-temperature resistance of the oleic acid and the recovery rate of the concentrate are improved to a certain extent, the preparation of the collector requires the use of strong corrosive acids such as concentrated sulfuric acid, fuming sulfuric acid and chlorosulfonic acid, which has certain danger and complexity, and it is difficult to control the sulfonation degree in industry. In addition, the collector has large and sticky foam in the flotation process, which is easy to overflow and run out of the tank, a large amount of water is needed to wash the foam, water resources are wasted, and the selectivity of the concentrate is not high, which needs to be continuously cleaned for 7 times to reach the concentrate grade index. Patent CN120243284A uses sulfuric acid and benzene as raw materials to prepare sulfated oleic acid and fatty acid benzene sulfonate, which has the problems of high toxicity and danger and is difficult to control in industrialization. Patents CN117483117A, CN115999775A, CN115532441A and CN119525027A all use a plurality of emulsifiers to compound oleic acid to prepare a collector, but they all have the problems of easy stratification of the emulsified oleic acid system product, excessive and stable foam in the flotation process, and difficulty in defoaming, which causes overflow and other problems. Although the recovery rate is high, the selectivity is not high, which causes the concentrate grade to be difficult to meet the standard and the number of cleaning times to be increased.

[0005] Therefore, it is very important to develop a fluorite collector which is cheap, low-toxic, environmentally friendly, biodegradable, has high collecting capacity and strong selectivity. SUMMARY

[0006] The purpose of the present application is to provide a composite fluorite collector and its application, in order to solve the problem of the low grade of the concentrate and the low recovery rate of the collector using oleic acid as the collector in the prior art.

[0007] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions: The present application provides a composite fluorite collector, which is composed of the following raw materials in mass fraction: 30-60% of oleic acid, 5-15% of low-carbon alcohol, 0.05-0.2% of esterification catalyst, 2-10% of alkali compound, 2-8% of emulsifier, 0.5-2% of hydrophobic agent, 2-5% of synergist, 1-5% of cosolvent, 0.01-0.2% of defoaming agent, and the balance of water. The preparation process of the composite fluorite collector comprises the following steps: The oleic acid, low-carbon alcohol and esterification catalyst are mixed to perform esterification reaction to obtain a fatty acid ester; The alkali compound and water are mixed, the obtained alkali aqueous solution and the fatty acid ester are mixed to perform saponification reaction to obtain a saponification product; The saponification product, emulsifier, hydrophobic agent, synergist and cosolvent are mixed to perform stirring to obtain a mixture; Mixing the mixture and defoaming agent to obtain the composite fluorite collector.

[0008] Preferably, the oleic acid includes two or more of low-iodine-value oleic acid, high-iodine-value oleic acid, ricinoleic acid and tall oil fatty acid; The iodine value of the low-iodine-value oleic acid ranges from 80 to 110, and the iodine value of the high-iodine-value oleic acid ranges from 110 to 140; The low-iodine-value oleic acid, the high-iodine-value oleic acid independently includes one or two of soybean oil acid, rice bran oil acid, rapeseed oil acid and cottonseed oil acid; The mass of the low-iodine-value oleic acid is 10-35% of the mass of the composite fluorite collector, the mass of the high-iodine-value oleic acid is 20-40% of the mass of the composite fluorite collector, the mass of the ricinoleic acid is 5-15% of the mass of the composite fluorite collector, and the mass of the tall oil fatty acid is 5-15% of the mass of the composite fluorite collector.

[0009] Preferably, the low-carbon alcohol includes one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol and glycerol; The esterification catalyst includes one or more of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, sulfuric acid and ferric trichloride.

[0010] Preferably, the alkali compound includes one or both of inorganic alkali and organic alcohol amine; The inorganic alkali includes one or more of sodium hydroxide and sodium carbonate; The organic alcohol amine includes one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and triisopropanolamine.

[0011] Preferably, the emulsifier includes one or more of non-ionic emulsifier, low-foaming fatty alcohol polyoxyethylene ether, fatty alcohol block polyether and amide emulsifier; The non-ionic emulsifier includes one or more of Tween-80 and Span 80; The low-foaming fatty alcohol polyoxyethylene ether includes one or more of AEO-3, AEO-5 and AEO-7; The fatty alcohol block polyether includes one or more of RT42 and RT64; The amide emulsifier includes one or more of X42 and IE101.

[0012] Preferably, the hydrophobic agent includes one or two of alpha-olefin wax, olefin oil, line-cutting oil, vaseline and kerosene; The synergist includes dodecyl dimethyl betaine, cocamide propyl betaine, oleic acid amidopropyl hydroxysultaine or sodium lauroyl amino acid; The cosolvent includes one of ethanol, ethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether; The defoamer includes silicone ether defoamer or No. 2 oil.

[0013] Preferably, the esterification reaction is carried out at a temperature of 65-80°C for 2-3 hours.

[0014] Preferably, the concentration of the alkaline aqueous solution is 20-30%; The saponification reaction is carried out at a temperature of 60-80°C for 2-3 hours.

[0015] Preferably, the stirring speed is 80~300 rpm and the stirring time is 20~30 min.

[0016] This invention provides the application of the above-mentioned composite fluorite collector in the flotation of medium- and low-grade fluorite ore, and the method of application includes the following steps: The composite fluorite collector is mixed with water to obtain the collector working solution; The collector working solution is applied to the flotation separation of medium and low grade fluorite ore by adding it dropwise according to the dosage. The flotation separation temperature is 5~30℃; The closed-circuit process used for flotation separation includes sequentially performing one-stage roughing, one-stage scavenging, two-stage roughing, two-stage cleaning, and two-stage scavenging. The two-stage cleaning includes sequentially performing two-stage primary cleaning, two-stage secondary cleaning, two-stage tertiary cleaning, two-stage quaternary cleaning, two-stage quinary cleaning, and two-stage sixth cleaning.

[0017] The beneficial effects of this invention are: This invention utilizes partial oleic acid esterification to form a low-HLB ester collector, which masks oxygen-containing functional groups on the ore surface, making the fluorite surface more hydrophobic and blocking the adsorption of associated oxygen-containing ores. By leveraging its synergistic effect with oleic acid, it significantly improves the selectivity for fluorite, resulting in a marked improvement in concentrate grade compared to conventional fatty acid collectors. It also addresses the issues of stratification and excessively high viscosity associated with conventional oleic acid and oleic acid soap mixtures, enhancing product stability. Furthermore, by improving the formulation and optimizing the combination of highly efficient emulsifiers, oil-based hydrophobic modifiers, and highly selective synergists, the solubility and dispersibility of the collector under low-temperature conditions are significantly enhanced.

[0018] The composite fluorite collector obtained by this invention has a high collection rate and requires a small amount of collector, which can significantly reduce the number of cleaning cycles and improve the grade of fluorite concentrate while ensuring a high collection rate: for medium and low grade fluorite ore, six cleaning cycles can yield concentrate powder with a CaF2 content greater than 92%, meeting the index requirements of high-grade chemical powder. The average concentrate recovery rate is over 80%, and the average recovery rate of concentrate + middlings reaches 90%. At the same time, the foam size is stable and controllable during industrial flotation, solving the problems of product stratification, sedimentation, flotation cell foam overflow and material loss that occur in existing processes, and greatly reducing water consumption.

[0019] The fluorite collector of this invention has a wide range of raw material sources, a simple preparation process, is easy to operate, has low production cost, and is highly efficient and stable in performance. It has already been applied in production lines. At the same time, it is non-toxic, easily biodegradable, has high application value, and generates good economic benefits. Attached Figure Description

[0020] Figure 1 This is a flowchart of a closed-circuit flotation experiment for the application of the fluorite collector of the present invention in fluorite flotation. Detailed Implementation

[0021] This invention provides a composite fluorite collector, composed of the following raw materials in the indicated mass fractions: oleic acid 30-60%, lower alcohols 5-15%, esterification catalyst 0.05-0.2%, alkali compound 2-10%, emulsifier 2-8%, hydrophobic agent 0.5-2%, synergist 2-5%, cosolvent 1-5%, defoamer 0.01-0.2%, with the balance being water; The preparation process of the composite fluorite collector includes the following steps: Oleic acid, lower alcohols, and esterification catalysts are mixed and esterified to obtain fatty acid esters. An alkaline compound is mixed with water, and the resulting alkaline aqueous solution is mixed with the fatty acid ester to carry out a saponification reaction, thereby obtaining a saponified product. The saponified product, emulsifier, hydrophobic agent, synergist and cosolvent are mixed and stirred to obtain a mixture; The mixture is combined with an antifoaming agent to obtain a composite fluorite collector.

[0022] In this invention, unless otherwise specified, all raw materials required for preparation are commercially available products well known to those skilled in the art.

[0023] In the composite fluorite collector provided by this invention, the mass fraction of oleic acid is preferably 30-60%, more preferably 50%; the oleic acid preferably includes two or more of low-iodine-value oleic acid, high-iodine-value oleic acid, ricinoleic acid, and tall oil fatty acids, more preferably low-iodine-value oleic acid, high-iodine-value oleic acid, and tall oil fatty acids; this invention uses a mixture of oleic acid, ricinoleic acid, and tall oil fatty acids with different iodine values ​​to fully utilize the differences in the adsorption sites of different types of acids on fluorite, resulting in different hydrophobicity and adsorption capacity on the fluorite surface. By adjusting the optimal ratio, the critical micelle concentration is reduced by two to three orders of magnitude compared to a single-component acid. The lower the critical micelle concentration, the more favorable it is for the collector to produce bubbles of appropriate size and stability, thus significantly improving the selectivity of fluorite ore while increasing the collection rate.

[0024] In this invention, the iodine value of the low-iodine-value oleic acid is preferably in the range of 80-100, more preferably 82-90, and even more preferably 85; the iodine value of the high-iodine-value oleic acid is preferably in the range of 110-140, more preferably 125-138, and even more preferably 128-135.

[0025] In this invention, the low-iodine-value oleic acid and the high-iodine-value oleic acid preferably include one or two of soybean oleic acid, rice bran oleic acid, rapeseed oleic acid and cottonseed oleic acid, and more preferably soybean oleic acid.

[0026] In this invention, the mass of the low-iodine-value oleic acid is preferably 10-35% of the mass of the composite fluorite collector, more preferably 26-30%, and even more preferably 28%; the mass of the high-iodine-value oleic acid is preferably 20-40% of the mass of the composite fluorite collector, more preferably 22-36%, and even more preferably 24-28%; the mass of the castor oil oleic acid is preferably 5-15% of the mass of the composite fluorite collector, more preferably 6-10%; and the mass of the tall oil fatty acid is preferably 5-15% of the mass of the composite fluorite collector, more preferably 7-10%.

[0027] In the composite fluorite collector provided by the present invention, the mass fraction of the low-carbon alcohol is preferably 5-15%, more preferably 10%; the low-carbon alcohol preferably includes one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol and glycerol, more preferably one or two of methanol, ethanol and isopropanol.

[0028] In the composite fluorite collector provided by the present invention, the mass fraction of the esterification catalyst is preferably 0.05~0.2%, more preferably 0.1%; the esterification catalyst preferably includes one or more of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, sulfuric acid and ferric chloride, more preferably dodecylbenzenesulfonic acid or p-toluenesulfonic acid.

[0029] In the composite fluorite collector provided by the present invention, the mass fraction of the alkali compound is preferably 2-10%, more preferably 4.2-8.3%, and even more preferably 5.7-7.3%.

[0030] In this invention, the alkali compound preferably includes one or two of inorganic alkalis and organic alcohol amines. The inorganic alkali preferably includes one or more of sodium hydroxide and sodium carbonate, and more preferably sodium hydroxide. The organic alcohol amine preferably includes one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and triisopropanolamine, and more preferably triethanolamine or triisopropanolamine.

[0031] In the composite fluorite collector provided by the present invention, the mass fraction of the emulsifier is preferably 2-8%, more preferably 2.5-5.4%, and even more preferably 3.2-5.2%.

[0032] In this invention, the emulsifier preferably includes one or more of nonionic emulsifiers, low-foaming fatty alcohol polyoxyethylene ethers, fatty alcohol block polyethers, and amide emulsifiers, more preferably nonionic emulsifiers and amide emulsifiers; the nonionic emulsifier preferably includes one or more of Tween-80 and Span 80, more preferably Tween-80; the low-foaming fatty alcohol polyoxyethylene ether preferably includes one or more of AEO-3, AEO-5, and AEO-7, more preferably AEO-7; the fatty alcohol block polyether preferably includes one or more of RT42 and RT64, more preferably RT42; the amide emulsifier preferably includes one or more of X42 and IE101, more preferably X42.

[0033] In the composite fluorite collector provided by the present invention, the mass fraction of the hydrophobic agent is preferably 0.5-2%, more preferably 0.9-1.3%, and even more preferably 1-1.2%.

[0034] In this invention, the hydrophobic agent preferably includes one or two of α-olefin wax, olefin oil, line-reducing oil, petrolatum, and kerosene, and more preferably includes one or two of α-olefin wax, line-reducing oil, and petrolatum; the line-reducing oil preferably includes 32# line-reducing oil or 46# line-reducing oil.

[0035] In the composite fluorite collector provided by the present invention, the mass fraction of the synergist is preferably 2-5%, more preferably 2.5-4.5%, and even more preferably 3-3.9%.

[0036] In this invention, the synergist preferably includes dodecyl dimethyl betaine, cocamidopropyl betaine, oleamidopropyl hydroxysulfonyl betaine, or sodium lauroyl sarcosinate, and more preferably dodecyl dimethyl betaine or sodium lauroyl sarcosinate; the sodium lauroyl sarcosinate used in the examples is preferably sodium lauroyl sarcosinate 4202.

[0037] In the composite fluorite collector provided by the present invention, the mass fraction of the co-solvent is preferably 1-5%, more preferably 2.4-3%, and even more preferably 2.5%.

[0038] In this invention, the cosolvent preferably includes one of ethanol, ethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether, and more preferably ethylene glycol or ethylene glycol monomethyl ether.

[0039] In the composite fluorite collector provided by the present invention, the mass fraction of the defoamer is preferably 0.01~0.2%, more preferably 0.03~0.15%, and even more preferably 0.05~0.1%.

[0040] In this invention, the defoamer preferably includes a silicone ether defoamer or No. 2 oil, and more preferably a silicone ether defoamer; the silicone ether defoamer is preferably silicone ether defoamer 682 or silicone ether defoamer 685.

[0041] In this invention, oleic acid, lower alcohols and esterification catalyst are mixed to carry out an esterification reaction to obtain fatty acid esters.

[0042] In this invention, the temperature of the esterification reaction is preferably 65~80℃, more preferably 70~78℃, even more preferably 75℃, and the time is preferably 2~3h, even more preferably 2.5h.

[0043] In this invention, after the esterification reaction is completed, an alkaline aqueous solution is added to the reaction vessel to carry out a saponification reaction and obtain a saponified product.

[0044] In this invention, the mass concentration of the alkaline aqueous solution is preferably 20-30%, and more preferably 25%.

[0045] In this invention, the saponification reaction temperature is preferably 60~80℃, more preferably 70~78℃, and the time is preferably 2~3h, more preferably 2.5h.

[0046] In this invention, after the saponification reaction is completed, emulsifier, hydrophobic oil, synergist and cosolvent are added and stirred to obtain a mixture.

[0047] In this invention, the stirring speed is preferably 80~300 rpm, more preferably 120 rpm, and the stirring time is preferably 20~30 min, more preferably 25 min.

[0048] In this invention, after the saponification reaction is completed and the mixture is cooled to room temperature, an antifoaming agent is added to the mixture to obtain a composite fluorite collector.

[0049] This invention also provides the application of the above-mentioned composite fluorite collector in the flotation of medium- and low-grade fluorite ore, wherein the method of application preferably includes the following steps: The composite fluorite collector is mixed with water to obtain the collector working solution; The collector working solution is applied dropwise to the flotation separation of medium- and low-grade fluorite ore.

[0050] In this invention, the mass ratio of the composite fluorite collector to water is preferably 1:9.

[0051] In this invention, the flotation separation conditions are preferably room temperature flotation, the flotation separation temperature is preferably 5~30℃, more preferably 25℃, and the composite collector is preferably used in combination with a water glass inhibitor.

[0052] In this invention, the closed-circuit experiment using the composite collector for flotation separation preferably includes the following steps: The original fluorite ore is crushed and then ground for 20-25 minutes to obtain ore powder with a fineness of 325 mesh and a content of 65-80%. Water is added to prepare a slurry. The slurry is separated by flotation. The closed-circuit process used for flotation separation includes sequentially performing one roughing stage, one scavenging stage, two roughing stages, two cleaning stages, and two scavenging stages. The two cleaning stages include sequentially performing two primary cleaning stages, two secondary cleaning stages, two tertiary cleaning stages, two quaternary cleaning stages, two quinary cleaning stages, and two sixth cleaning stages. The preferred mass of the collector used in the first stage of roughing is 200-400 g / t, more preferably 200 g / t; the preferred mass of the water glass used is 500-2500 g / t, more preferably 1700 g / t; and the preferred pH is 10-10.5, more preferably 10. The mass of the collector used in the first stage of scavenging is preferably 30-45 g / t, and more preferably 30 g / t; The mass of the collector used in the second-stage roughing is preferably 20-30 g / t, and more preferably 20 g / t; The preferred mass of the collector used in the second stage of selection is 10-15 g / t, more preferably 10 g / t, and the preferred mass of the combined drug is 100-200 g / t, more preferably 150 g / t; Specifically, such as Figure 1As shown, the slurry undergoes a first-stage roughing and a first-stage scavenging process: Soda ash is added to the slurry and stirred for 3 minutes to adjust the initial pH to 10. Water glass inhibitor (1700 g / t) is then added and stirred for 3 minutes. A composite fluorite collector (200 g / t) is added and stirred for 3 minutes. A first-stage roughing process is then performed for 5 minutes, yielding a first-stage roughing concentrate and a first-stage roughing tailings. A collector (30 g / t) is added to the first-stage roughing tailings and stirred for 3 minutes. A first-stage scavenging process is then performed for 3 minutes, yielding the first tailings. Add soda ash to the first-stage roughing concentrate, stir for 3 minutes, adjust the pH to 10, add collector at a mass of 20 g / t, stir for 3 minutes, and then carry out second-stage roughing to obtain second-stage roughing concentrate and second tailings; the sum of the first tailings and the second tailings is the tailings obtained by flotation separation. The roughing concentrate is then subjected to a two-stage primary cleaning process (corresponding to...) Figure 1 (Intermediate and advanced level 1), Secondary and advanced level 2 selection (corresponding to) Figure 1 (Mid-level refined second), second stage three-stage refined (corresponding to) Figure 1 (Intermediate and advanced level 3), second stage, fourth stage (corresponding to) Figure 1 (Intermediate and advanced level 4), second stage five times of selection (corresponding to) Figure 1 (Mid-level five), second-stage six-times selected (corresponding to) Figure 1 The process involves two stages: a first stage of flotation (3 min), a second stage of flotation (2 min), and a third stage of flotation (2 min). Soda ash is added to the second stage concentrate, and the mixture is stirred for 3 min to adjust the pH to 7. A collector (10 g / t) is then added for 3 min to complete the third stage of flotation (2 min). A combined reagent (composed of water glass and sodium carbonate, with no specific mass ratio) of 50 g / t is added to the third stage concentrate, and the mixture is stirred for 3 min to complete the fourth stage of flotation (2 min). Another combined reagent of 50 g / t is added to the fourth stage concentrate, and the mixture is stirred for 3 min to complete the fifth stage of flotation (2 min). Finally, a sixth stage of flotation (2 min) is completed to obtain the final concentrate (the concentrate obtained from flotation separation). The mineral products obtained from the flotation separation are the tailings obtained after six cleaning processes in the two-stage cleaning process.

[0053] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0054] Example 1

[0055] In this embodiment, the composite fluorite collector is composed of the following raw materials by mass fraction: Oleic acid with low iodine value (iodine value 90) 25%, oleic acid with high iodine value (iodine value 135) 24%, castor oil 6%, p-toluenesulfonic acid 0.1%, ethanol 5%, sodium hydroxide 3.6%, monoisopropanolamine 2.5%, amide emulsifier X42 2.2%, Tween-80 2%, α-olefin wax 1.1%, sodium lauroyl sarcosinate 4202 3%, ethylene glycol monoethyl ether 3%, silicone ether defoamer 682 0.05%, balance is water; According to the above mass fractions, oleic acid with low iodine value, oleic acid with high iodine value and ricinoleic acid are mixed evenly, p-toluenesulfonic acid is dissolved in ethanol and added, and esterification reaction is carried out at 75°C for 2 hours to obtain ethyl oleate. Sodium hydroxide, monoisopropanolamine, and water were mixed, and the resulting aqueous solution was mixed with ethyl oleate. The mixture was then subjected to a saponification reaction at 75°C for 2.5 hours to obtain the saponified product. Add amide emulsifier X42, Tween-80, α-olefin wax, sodium lauroyl sarcosinate 4202 and ethylene glycol monoethyl ether to the above saponification product, and stir at 120 rpm for 30 min to obtain a mixture; After cooling to room temperature, silicone ether defoamer 682 was added to the above mixture to obtain a composite fluorite collector. After standing for 1 day, no precipitation was observed at the bottom of the collector.

[0056] Example 2

[0057] In this embodiment, the composite fluorite collector is composed of the following raw materials by mass fraction: Oleic acid with low iodine value (iodine value 82) 25%, oleic acid with high iodine value (iodine value 138) 25%, tall oil fatty acid 10%, dodecylbenzene sulfonic acid 0.2%, methanol 1.7%, ethanol 3.5%, sodium hydroxide 3.9%, triethanolamine 1.8%, fatty alcohol block polyether RT42 3.2%, 32# anti-corrosive oil 0.9%, dodecyl dimethyl betaine 2.5%, ethanol 1%, silicone ether defoamer 685 0.03%, balance is water; According to the above mass fractions, oleic acid with low iodine value, oleic acid with high iodine value and ricinoleic acid are mixed evenly, and dodecylbenzenesulfonic acid is dissolved in ethanol and methanol and added. The esterification reaction is carried out at 70°C for 2 hours to obtain fatty acid esters. Sodium hydroxide, triethanolamine and water were mixed, and the resulting aqueous solution was mixed with fatty acid esters. The mixture was then subjected to a saponification reaction at 70°C for 3 hours to obtain the saponified product. Add fatty alcohol block polyether RT42, 32# anti-corrosive oil, dodecyl dimethyl betaine, and ethanol to the above saponification product, and stir at 120 rpm for 30 min to obtain a mixture; After cooling to room temperature, silicone ether defoamer 685 was added to the above mixture to obtain a composite fluorite collector. After standing for 1 day, no precipitation was observed at the bottom of the collector.

[0058] Example 3

[0059] In this embodiment, the composite fluorite collector is composed of the following raw materials by mass fraction: Oleic acid with low iodine value (iodine value 90) 28%, oleic acid with high iodine value (iodine value 125) 30%, dodecylbenzenesulfonic acid 0.1%, anhydrous ferric chloride 0.1%, methanol 1%, ethanol 4.5%, sodium hydroxide 3%, triisopropanolamine 5.3%, fatty alcohol block polyether RT64 1.2%, emulsifier X42 2.2%, petrolatum 1%, cocamidopropyl betaine 2%, sodium lauroyl sarcosinate 420 22.5%, ethanol 1.5%, silicone ether defoamer 685 0.07%, balance water; According to the above mass fraction, oleic acid with low iodine value and oleic acid with high iodine value are mixed evenly, and dodecylbenzenesulfonic acid and anhydrous ferric chloride are dissolved in ethanol and added. The esterification reaction is carried out at 78°C for 2 hours to obtain fatty acid ester. Sodium hydroxide, triisopropanolamine and water were mixed, and the resulting aqueous solution was mixed with fatty acid esters. The mixture was then subjected to a saponification reaction at 78°C for 2.5 h to obtain the saponified product. Add fatty alcohol block polyether RT64, emulsifier X42, petrolatum cocamidopropyl betaine, ethanol, and sodium lauroyl sarcosinate 4202 to the above saponification product, and stir at 120 rpm for 30 min to obtain a mixture; After cooling to room temperature, silicone ether defoamer 685 was added to the above mixture to obtain a composite fluorite collector. After standing for 1 day, no precipitation was observed at the bottom of the collector.

[0060] Example 4

[0061] In this embodiment, the composite fluorite collector is composed of the following raw materials by mass fraction: Oleic acid with high iodine value (iodine value 125) 30%, castor oil 10%, tall oil fatty acid 10%, p-toluenesulfonic acid 0.2%, methanol 2.5%, isopropanol 3%, sodium hydroxide 4.2%, Tween-80 2.5%, dodecyl dimethyl betaine 2.8%, ethylene glycol 1.5%, sodium lauroyl sarcosinate 4202 1.1%, ethylene glycol monomethyl ether 2.5%, silicone ether defoamer 685 0.1%, balance water; According to the above mass fractions, oleic acid, ricinoleic acid and tall oil fatty acids with high iodine value are mixed evenly, and p-toluenesulfonic acid is dissolved in methanol and isopropanol and then added. The esterification reaction is carried out at 75°C for 3 hours to obtain fatty acid esters. Sodium hydroxide was mixed with water, and the resulting aqueous solution was mixed with fatty acid esters. The mixture was then subjected to a saponification reaction at 75°C for 3 hours to obtain the saponified product. Add Tween-80, No. 2 oil, dodecyl dimethyl betaine, ethylene glycol, and sodium lauroyl sarcosinate 4202 to the above saponification product, and stir at 120 rpm for 30 min to obtain a mixture; After cooling to room temperature, silicone ether defoamer 685 was added to the above mixture to obtain a composite fluorite collector. After standing for 1 day, no precipitation was observed at the bottom of the collector.

[0062] Example 5

[0063] In this embodiment, the composite fluorite collector is composed of the following raw materials by mass fraction: Oleic acid with low iodine value (iodine value 85) 27%, tall oil fatty acid (iodine value 128) 28%, dodecylbenzenesulfonic acid 0.2%, methanol 6.5%, sodium hydroxide 2.5%, triethanolamine 5.6%, Span 80 2.4%, Tween-80 2.8%, α-olefin wax 0.6%, 46# reduced-strength oil 0.6%, cocamidopropyl betaine 1.8%, sodium lauroyl sarcosinate 4202 1.2%, ethanol 2.5%, silicone ether defoamer 685 0.08%, balance water; According to the above mass fraction, oleic acid with low iodine value and tall oil fatty acid are mixed evenly, dodecylbenzenesulfonic acid is dissolved in methanol and added, and esterification reaction is carried out at 65°C for 2.5 h to obtain fatty acid ester. Sodium hydroxide, triethanolamine and water were mixed, and the resulting aqueous solution was mixed with fatty acid esters. The mixture was then subjected to a saponification reaction at 70°C for 3 hours to obtain the saponified product. Span 80, Tween-80, α-olefin wax, 46# anti-corrosive oil, cocamidopropyl betaine, sodium lauroyl sarcosinate 4202 and ethanol were added to the above saponification product and stirred at 120 rpm for 30 min to obtain a mixture. After cooling to room temperature, silicone ether defoamer 685 was added to the above mixture to obtain a composite fluorite collector. After standing for 1 day, no precipitation was observed at the bottom of the collector.

[0064] Example 6

[0065] In this embodiment, the composite fluorite collector is composed of the following raw materials by mass fraction: Oleic acid with high iodine value (iodine value 125) 20%, oleic acid with high iodine value (iodine value 140) 20%, tall oil fatty acid (iodine value 128) 18%, sulfuric acid 0.08%, ethanol 6.5%, sodium hydroxide 3.5%, diethanolamine 3.8%, AEO-7 1.5%, Tween-80 1.6%, Span 80 2.3%, α-olefin wax 0.6%, 46# anti-corrosive oil 0.5%, dodecyl dimethyl betaine 2.2%, sodium lauroyl sarcosinate 4202 1.2%, ethanol 2.0%, silicone ether defoamer 685 0.15%, balance water; According to the above mass fraction, oleic acid with high iodine value and tall oil fatty acid are mixed evenly, sulfuric acid is dissolved in ethanol and added, and esterification reaction is carried out at 75°C for 2.5 h to obtain fatty acid ester. Sodium hydroxide, diethanolamine and water were mixed, and the resulting aqueous solution was mixed with fatty acid ester. The mixture was then subjected to a saponification reaction at 75°C for 3 hours to obtain the saponified product. Add AEO-7, Tween-80, Span 80, α-olefin wax, 46# anti-corrosive oil, dodecyl dimethyl betaine, sodium lauroyl sarcosinate 4202 and ethanol to the above saponification product, and stir at 120 rpm for 30 min to obtain a mixture; After cooling to room temperature, silicone ether defoamer 685 was added to the above mixture to obtain a composite fluorite collector. After standing for 1 day, no precipitation was observed at the bottom of the collector.

[0066] Example 7

[0067] In this embodiment, the composite fluorite collector is composed of the following raw materials by mass fraction: Oleic acid with low iodine value (iodine value 85) 28%, oleic acid with high iodine value (iodine value 140) 22%, tall oil fatty acid (iodine value 128) 7%, dodecylbenzene sulfonic acid 0.15%, methanol 1.8%, ethanol 4.4%, sodium hydroxide 2.8%, monoethanolamine 3.5%, fatty alcohol block polyether RT42 1.2%, Tween-80 1.3%, Span 80 2.5%, 46# reduced-strength oil 1.3%, dodecyl dimethyl betaine 2.5%, ethylene glycol 2.4%, silicone ether defoamer 685 0.15%, balance is water; According to the above mass fractions, oleic acid with low iodine value, oleic acid with high iodine value and tall oil fatty acid are mixed evenly, and dodecylbenzenesulfonic acid is dissolved in methanol and ethanol and added. The esterification reaction is carried out at 70°C for 3 hours to obtain fatty acid ester. Sodium hydroxide, monoethanolamine and water were mixed, and the resulting aqueous solution was mixed with fatty acid esters. The mixture was then subjected to a saponification reaction at 70°C for 2 hours to obtain the saponified product. Add fatty alcohol block polyether RT42, Tween-80, Span 80, 46# anti-corrosive oil, dodecyl dimethyl betaine, and ethylene glycol to the above saponification product, and stir at 120 rpm for 30 min to obtain a mixture; After cooling to room temperature, silicone ether defoamer 685 was added to the above mixture to obtain a composite fluorite collector. After standing for 1 day, no precipitation was observed at the bottom of the collector.

[0068] Comparative Example 1

[0069] The collector in this comparative example consists of the following raw materials by mass fraction: Oleic acid with a high iodine value (iodine value 125) 65%, sodium hydroxide 4.38%, ethanol 4.5%, kerosene 1.2%; The preparation method of the collector includes the following steps: According to the above mass fraction, oleic acid with high iodine value is heated to 75°C and stirred continuously. Sodium hydroxide aqueous solution is added dropwise over 1.5 hours, and the reaction is maintained at the temperature for 2-3 hours. After cooling, kerosene and ethanol are added for dilution, and the mixture is stirred and mixed evenly to obtain the desired product. The obtained collector is observed after being left for 1 day. A precipitate appears at the bottom of the collector.

[0070] Comparative Example 2

[0071] The collector in this comparative example consists of the following raw materials by mass fraction: Oleic acid (iodine value 125) 30%, oleic acid (iodine value 140) 35%, sodium hydroxide 4.38%, ethanol 4.5%, kerosene 1.2%; The preparation method of the collector includes the following steps: According to the above mass fraction, oleic acid was mixed evenly, heated to 75℃ with continuous stirring, and sodium hydroxide aqueous solution was added dropwise over 1.5 hours. The reaction was maintained at this temperature for 2-3 hours. After cooling, kerosene and ethanol were added for dilution, and the mixture was stirred and mixed evenly to obtain the final product. After standing for 1 day, the collector showed stratification.

[0072] Comparative Example 3

[0073] The collector in this comparative example consists of the following raw materials by mass fraction: Oleic acid (iodine value 125) 30%, oleic acid (iodine value 140) 35%, sodium hydroxide 4.38%, Tween-80 2.8%, AEP-7 1.1%, Span 80 1.5%, silicone defoamer 685 0.05%, ethanol 4.5%; The preparation method of the collector includes the following steps: According to the above mass fraction, oleic acid is mixed evenly, heated to 75°C and stirred continuously, sodium hydroxide aqueous solution is added dropwise over 1.5 hours, and the reaction is maintained at the temperature for 2-3 hours; then cooled, Tween-80, AEP-7, Span 80 and ethanol are added for dilution, and then silicone ether defoamer 685 is added and stirred evenly to obtain the final product.

[0074] Performance testing

[0075] The flotation performance of the collectors obtained in Examples 1-7 and Comparative Examples 1-3 was evaluated by closed-circuit flotation experiments at 25℃. A total of five sets of experiments were conducted for each collector, and the data from the last two sets of experiments were averaged to obtain the effect evaluation of each collector. The results are shown in Table 1. The closed-circuit flotation experiment process includes the following steps: Weigh 10g of collector stock solution, slowly add tap water step by step, stir and disperse thoroughly, add a total of 90g of water to fully dissolve it, prepare a collector working solution with a mass fraction of 10%, and the qualified product is a uniform and stable emulsion, which can be used for flotation experiments. Weigh out 500g of fluorite ore with a fineness of 325 mesh, add water to prepare a slurry, adjust the pH of the slurry to 10.5, add the above-prepared collector working solution at a rate of 200 g / t, add water glass depressant at a rate of 1500 g / t, stir thoroughly for 5 min, and conduct a closed-circuit flotation experiment: the flotation process is as follows. Figure 1 As shown, the closed-circuit first stage involves one roughing and one scavenging process. The first roughing process uses 200 g / t of collector and 1700 g / t of water glass inhibitor, with a pH of 10, to obtain a rough concentrate. The rough concentrate is then regrinded. The second stage involves one roughing, six cleaning, and one scavenging process. The middlings obtained from the cleaning process are recycled back to the previous cleaning operation. The second roughing process uses 20 g / t of collector and a pH of 10. The third cleaning process uses 10 g / t of collector and a pH of 7. The fourth, fifth, and sixth cleaning processes each add 50 g / t of a combined reagent (composed of water glass and sodium carbonate, with no specific mass ratio of water glass to sodium carbonate). No collector is added. After two roughing processes, six cleaning processes, and two scavenging processes, concentrate, middlings, and tailings are obtained. The middlings product is the tailings obtained after six cleaning processes. The roughing tailings are then scavenged twice to obtain the tailings product.

[0076] Table 1 Results of closed-circuit flotation experiments using collectors in Examples 1-7 and Comparative Examples 1-3

[0077] Comparing Examples 1-7 and referring to Table 1, it can be seen that the present invention, through improvements to the collector formulation and process, avoids product stratification, sedimentation, flotation cell foam overflow, and material loss, significantly improving the purity of the concentrate. The average grade of the concentrate powder is above 93%, meeting the requirement of greater than 92% for chemical powder. The average concentrate recovery rate is above 80%, and the average recovery rate of concentrate + intermediates reaches 90%. In contrast, the concentrate grade of ordinary oleic acid-based collectors does not reach 92%, and the concentrate and intermediates recovery rates are far lower than those of the product of the present invention. This fully demonstrates that the collector of the present invention has strong collecting ability and good selectivity, overcoming the problems of low concentrate grade and recovery rate, meeting the requirements for producing high-quality fluorite powder, and greatly reducing mineral processing costs and improving the economic benefits of enterprises.

[0078] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A composite fluorite collector, characterized in that, The preparation raw materials are composed of the following components by mass fraction: oleic acid 30-60%, lower alcohols 5-15%, esterification catalyst 0.05-2%, alkali compounds 2-10%, emulsifier 2-8%, hydrophobic agent 0.5-2%, synergist 2-5%, cosolvent 1-5%, defoamer 0.01-0.2%, and the balance being water; The preparation process of the composite fluorite collector includes the following steps: Oleic acid, lower alcohols, and esterification catalysts are mixed and esterified to obtain fatty acid esters. An alkaline compound is mixed with water, and the resulting alkaline aqueous solution is mixed with the fatty acid ester to carry out a saponification reaction, thereby obtaining a saponified product. The saponified product, emulsifier, hydrophobic agent, synergist and cosolvent are mixed and stirred to obtain a mixture; The mixture is combined with an antifoaming agent to obtain a composite fluorite collector.

2. The composite fluorite collector according to claim 1, characterized in that, The oleic acid includes two or more of the following: low-iodine-value oleic acid, high-iodine-value oleic acid, ricinoleic acid, and tall oil fatty acids. The iodine value of the low-iodine-value oleic acid ranges from 80 to 110, and the iodine value of the high-iodine-value oleic acid ranges from 110 to 140. The low-iodine-value oleic acid and the high-iodine-value oleic acid independently include one or two of soybean oleic acid, rice bran oleic acid, rapeseed oleic acid and cottonseed oleic acid; The mass of the low-iodine-value oleic acid is 10-35% of the mass of the compound fluorite collector, the mass of the high-iodine-value oleic acid is 20-40% of the mass of the compound fluorite collector, the mass of the castor oil oleic acid is 5-15% of the mass of the compound fluorite collector, and the mass of the tall oil fatty acid is 5-15% of the mass of the compound fluorite collector.

3. The composite fluorite collector according to claim 1, characterized in that, The lower alcohols include one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, and glycerol; The esterification catalyst includes one or more of dodecylbenzenesulfonic acid, p-toluenesulfonic acid, sulfuric acid, and ferric chloride.

4. The composite fluorite collector according to claim 1, characterized in that, The base compounds include one or both of inorganic bases and organic alcohol amines; The inorganic base includes one or more of sodium hydroxide and sodium carbonate; The organic alcohol amines include one or more of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and triisopropanolamine.

5. The composite fluorite collector according to claim 1, characterized in that, The emulsifier includes one or more of the following: nonionic emulsifier, low-foaming fatty alcohol polyoxyethylene ether, fatty alcohol block polyether, and amide emulsifier; The nonionic emulsifier includes one or more of Tween-80 and Span 80; The low-foaming fatty alcohol polyoxyethylene ether includes one or more of AEO-3, AEO-5 and AEO-7; The fatty alcohol block polyether includes one or more of RT42 and RT64; The amide emulsifier includes one or more of X42 and IE101.

6. The composite fluorite collector according to claim 1, characterized in that, The hydrophobic agent includes one or two of α-olefin wax, olefin oil, anti-corrosion oil, petrolatum, and kerosene; The synergist includes dodecyl dimethyl betaine, cocamidopropyl betaine, oleamidopropyl hydroxysulfonyl betaine, or sodium lauroyl sarcosinate. The cosolvent includes one of ethanol, ethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether; The defoamer includes silicone ether defoamer or No. 2 oil.

7. The composite fluorite collector according to claim 1, characterized in that, The esterification reaction is carried out at a temperature of 65-80℃ for 2-3 hours.

8. The composite fluorite collector according to claim 1, characterized in that, The mass fraction of the alkaline aqueous solution is 20-30%; The saponification reaction is carried out at a temperature of 60-80°C for 2-3 hours.

9. The composite fluorite collector according to claim 1, characterized in that, The stirring speed is 80~300 rpm, and the stirring time is 20~30 min.

10. The application of the composite fluorite collector according to any one of claims 1 to 9 in the flotation of medium- and low-grade fluorite ore, characterized in that, The method of application includes the following steps: The composite fluorite collector is mixed with water to obtain the collector working solution; The collector working solution is applied to the flotation separation of medium and low grade fluorite ore by adding it dropwise according to the dosage. The flotation separation temperature is 5~30℃; The closed-circuit process used for flotation separation includes sequentially performing one-stage roughing, one-stage scavenging, two-stage roughing, two-stage cleaning, and two-stage scavenging. The two-stage cleaning includes sequentially performing two-stage primary cleaning, two-stage secondary cleaning, two-stage tertiary cleaning, two-stage quaternary cleaning, two-stage quinary cleaning, and two-stage sixth cleaning.

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