Phosphate ore low-temperature flotation collector, and preparation method and application thereof
By preparing a low-temperature flotation collector for phosphate rock containing vegetable oil, chlorinating agent, and alkaline compound, the problems of complex preparation, poor solubility, and high energy consumption of existing phosphate rock flotation agents are solved, achieving efficient and low-cost phosphate rock flotation.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUHAN HAILITE TECH CO LTD
- Filing Date
- 2024-12-30
- Publication Date
- 2026-05-22
Abstract
Description
Technical Field
[0001] This invention belongs to the field of phosphate rock flotation technology, and particularly relates to a low-temperature flotation collector for phosphate rock, its preparation method and application. Background Technology
[0002] Phosphate resources are abundant, but high-grade, easily beneficiated phosphate ore is mainly concentrated in Hubei, Hunan, Yunnan, and Guizhou provinces. Northern and northeastern regions primarily have medium- to low-grade phosphate ore, and the lower ambient temperatures increase the difficulty of mining and beneficiation. Direct flotation is one of the most effective methods for directly flotating high-grade phosphate concentrate from the ore pulp. Currently, research on phosphate flotation agents mainly focuses on: fatty acid anionic collectors, amine cationic collectors, amphoteric collectors, and nonionic collectors of hydrocarbon oils and esters. Among these, fatty acid collectors remain widely used due to their wide availability of raw materials, low cost, and strong adaptability. However, most existing fatty acid direct flotation collectors suffer from complex preparation processes, poor solubility, inconvenient on-site dissolution and dilution, and low mineral recovery rates. Furthermore, to ensure effective activation of the phosphate ore by the flotation agent, the ore pulp usually needs to be heated, increasing energy consumption and flotation costs.
[0003] Existing patent literature has disclosed numerous technical solutions for phosphate rock flotation collectors. For example, Chinese patent CN107029894A discloses a low-temperature resistant flotation collector for medium- and low-grade phosphate rock prepared from malic acid and its preparation method. This method includes the following steps: First, malic acid undergoes an esterification reaction with methanol under the action of a solid acid catalyst; then, the product reacts with ethanolamine to generate malic acid alkanolamide; subsequently, a sulfonic acid group is introduced through aminosulfonic acid, and a quaternary ammonium salt structure is further introduced under alkaline conditions to form an amphoteric malic acid derivative; finally, this derivative is mixed with sodium alkyl sulfonate and other components to obtain the final positive flotation collector. This collector can effectively float phosphate rock in a temperature range of 5–35℃, with a P2O5 recovery rate of 93–96%. Although this patent significantly improves the flotation recovery rate of medium- and low-grade phosphate rock under low-temperature conditions, its preparation process is relatively complex, involving multiple raw materials, and some reactions require higher temperatures, increasing the difficulty of product quality control and the safety risks in the production process, which is not conducive to large-scale production and widespread adoption. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the present invention aims to provide a low-temperature flotation collector for phosphate rock, its preparation method, and its application. The low-temperature collector prepared by this invention exhibits good water solubility and is easy to use. When applied to the flotation of low-grade phosphate rock, it displays uniform froth size and low viscosity, and a high flotation recovery rate. Furthermore, the collector has low overall operating costs, and its production process is simple, safe, and efficient.
[0005] The objective of this invention is achieved through the following technical solution:
[0006] A low-temperature flotation collector for phosphate rock is prepared from components comprising the following mass percentages: 5-25% vegetable oil, 1-5% chlorinating agent, 1-5% alkaline compound, 1-10% frother, and the balance being water.
[0007] Preferably, it is prepared from components comprising the following mass percentages: 15-20% vegetable oil, 2.2-2.5% chlorinating agent, 3.4-3.8% alkaline compound, 7-8.5% foaming agent, and the balance being water.
[0008] Preferably, the vegetable oil is at least one of soybean oil, corn oil, sunflower seed oil, flaxseed oil, and their corresponding acidified oils.
[0009] Preferably, the chlorinating agent is at least one of phosphorus trichloride, chloroacetic acid, thionyl chloride and trichloroisocyanuric acid.
[0010] Preferably, the alkaline compound is at least one of sodium hydroxide, potassium hydroxide, and ammonia water.
[0011] Preferably, the foaming agent is at least one of dodecylbenzenesulfonic acid, sodium dodecyl sulfate, pine oil, methyl isobutyl methanol, and polyol.
[0012] Preferably, the polyol is at least one selected from ethylene glycol, polyethylene glycol, and butanediol.
[0013] The preparation method of the above-mentioned low-temperature flotation collector for phosphate rock includes the following steps:
[0014] First, mix the vegetable oil and water according to the specified proportions evenly, then add the chlorinating agent and carry out the chlorination reaction at 70~120℃. After the chlorination reaction is completed, add the alkaline compound at 70~100℃ and carry out the saponification reaction at a constant temperature. After the saponification reaction is completed, add the foaming agent and stir evenly. After keeping warm and stirring, the low-temperature flotation collector for phosphate rock is obtained.
[0015] Preferably, the vegetable oil and water are mixed evenly by stirring.
[0016] In some embodiments, stirring is performed at a speed of 120 r / min to ensure that the vegetable oil and water are thoroughly mixed.
[0017] Preferably, the chlorination reaction takes 0.5 to 3 hours, and the saponification reaction takes 0.5 to 3 hours.
[0018] Preferably, the chlorination reaction temperature is 75~80℃ and the chlorination reaction time is 2~2.5h; the saponification reaction temperature is 90~95℃ and the saponification reaction time is 2.5h.
[0019] Preferably, the specific operation of heat preservation and stirring is as follows: heat preservation and stirring at 90℃ for 1~1.5h.
[0020] The application of the above-mentioned low-temperature flotation collector for phosphate rock as a positive flotation collector for low-grade phosphate rock includes the following steps: the phosphate rock after grinding is prepared into a slurry with a concentration of 25~35wt%, and the above-mentioned low-temperature flotation collector for phosphate rock is added to the slurry at a dosage of 0.3~1.0kg / t under the condition of temperature below 20℃. After stirring evenly, flotation is carried out. The flotation froth obtained is then separated into solid and liquid to obtain refined phosphate rock.
[0021] Preferably, the phosphorus content of low-grade phosphate rock is 2-5%.
[0022] Preferably, the phosphate rock low-temperature flotation collector is added to the slurry at a temperature of 15~17℃ at a dosage of 0.3~1.0 kg / t.
[0023] Preferably, the portion of phosphate rock ground to a particle size of -0.074 mm accounts for 25-35% of the total mass of phosphate rock, and then a slurry with a concentration of 25-35 wt% is prepared.
[0024] The reaction mechanism involved in this invention is as follows: The molecular structure of vegetable oil is altered by adding a chlorinating agent to enhance its water solubility and dispersion / adsorption properties on the surface of mineral powder. Subsequently, the modified vegetable oil is treated with an alkaline compound to convert it into fatty acid salts. These fatty acid salts, as the main collector components, can adhere more effectively to the surface of phosphate rock. Furthermore, a frother is added to ensure normal foaming and adjust the foam state during the flotation process. This series of steps significantly improves the flotation effect.
[0025] Compared with the prior art, the beneficial effects of the present invention include:
[0026] (1) The low-temperature flotation collector for phosphate rock prepared in this invention can significantly improve the flotation recovery rate of phosphate rock. The flotation foam is uniform in size and has low viscosity, which is convenient for on-site operation and control, and effectively avoids the phenomenon of foam overflowing or spilling during the flotation process.
[0027] (2) The collector prepared by this invention has good water solubility, is convenient for on-site use, reduces the amount of hot water required for dissolving the agent, and lowers the overall cost of use. In addition, the product is environmentally friendly and has little harm to the human body, meeting the requirements of green environmental protection.
[0028] (3) The collector prepared by the present invention is suitable for flotation of slurry at temperatures below 20°C, which greatly reduces the beneficiation cost caused by heating the slurry and improves economic efficiency. Detailed Implementation
[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.
[0030] Examples 1-3 used the same flotation equipment, and all flotation parameters and conditions, unless otherwise specified, remained consistent.
[0031] Example 1
[0032] A low-temperature flotation collector for phosphate rock is prepared from the following components in the indicated mass percentages: 13.5% corn oil, 6.5% soybean oil, 1.1% phosphorus trichloride, 1.1% thionyl chloride, 3.8% sodium hydroxide, 3.5% sodium dodecyl sulfate, 4.5% methyl isobutyl methanol, and the balance being water.
[0033] The specific steps for preparing the above-mentioned low-temperature flotation collector for phosphate rock are as follows:
[0034] First, the weighed water was added to the reaction vessel according to the proportions, and the stirrer was started and the speed was set to 120 r / min. Then, corn oil and soybean oil were added to the reaction vessel and stirred evenly. Phosphorus trichloride and thionyl chloride were then slowly added to the reaction vessel through a dropper. The chlorination reaction was carried out at a constant temperature of 75°C for 2.5 h. After the chlorination reaction was completed, the system temperature was raised to 90°C, and sodium hydroxide was added while stirring. The saponification reaction was carried out at a constant temperature of 90°C for 2.5 h. After the saponification reaction was completed, sodium dodecyl sulfate and methyl isobutyl methanol were added, stirred evenly, and then kept at 90°C for 1 h to obtain a uniform and stable liquid, which is the low-temperature flotation collector for phosphate rock.
[0035] The specific operating steps for using the above-mentioned low-temperature flotation collector for low-grade phosphate rock flotation are as follows:
[0036] (1) The portion of phosphate rock with a phosphorus content of 2.8% that is ground to a particle size of -0.074 mm accounts for 25-35% of the total mass of phosphate rock. Then, it is poured into a flotation cell and water is added to prepare a slurry with a concentration of 30 wt%.
[0037] (2) Cool the slurry from step (1) to 15°C and add the phosphate rock flotation collector at a dosage of 0.35 kg / t. After stirring evenly, perform roughing; then add the phosphate rock flotation collector at a dosage of 0.15 kg / t to scavenger the tailings after roughing, combine the flotation froth from roughing and scavenging, and separate the solid and liquid phases to obtain refined phosphate rock.
[0038] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 18.89%, and the phosphorus recovery rate is 75.92%.
[0039] Example 2
[0040] A low-temperature flotation collector for phosphate rock is prepared from the following components in the indicated mass percentages: 12% soybean oil, 4% sunflower seed oil, 0.9% chloroacetic acid, 0.9% thionyl chloride, 0.4% trichloroisocyanuric acid, 3.4% potassium hydroxide, 2.5% dodecylbenzenesulfonic acid, 2.5% methyl isobutyl methanol, 2% ethylene glycol, and the balance being water.
[0041] The specific steps for preparing the above-mentioned low-temperature flotation collector for phosphate rock are as follows:
[0042] First, the weighed water was added to the reaction vessel according to the grouping ratio, and the stirrer was started and the speed of the stirrer was set to 120 r / min. Then, sunflower seed oil and soybean oil were added to the reaction vessel and stirred evenly. Next, chloroacetic acid, thionyl chloride and trichloroisocyanuric acid were slowly added to the reaction vessel through a dropper. The chlorination reaction was carried out at a constant temperature of 75°C for 2 hours. After the chlorination reaction was completed, the system temperature was raised to 95°C, and sodium hydroxide was added while stirring. The saponification reaction was carried out at a constant temperature of 95°C for 2.5 hours. After the saponification reaction was completed, dodecylbenzenesulfonic acid, methyl isobutyl methanol and polyol were added. After stirring evenly, the mixture was kept at 90°C and stirred for 1 hour to obtain a uniform and stable liquid, which is the low-temperature flotation collector for phosphate rock.
[0043] The specific operating steps for using the above-mentioned low-temperature flotation collector for low-grade phosphate rock flotation are as follows:
[0044] (1) The portion of phosphate rock with a phosphorus content of 2.8% that is ground to a particle size of -0.074 mm accounts for 25-35% of the total mass of phosphate rock. Then, it is poured into a flotation cell and water is added to prepare a slurry with a concentration of 30 wt%.
[0045] (2) Cool the slurry from step (1) to 17°C and add the phosphate rock flotation collector at a dosage of 0.35 kg / t. After stirring evenly, perform roughing; then add the phosphate rock flotation collector at a dosage of 0.15 kg / t to scavenger the tailings after roughing, combine the flotation froth from roughing and scavenging, and separate the solid and liquid phases to obtain refined phosphate rock.
[0046] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 19.37%, and the phosphorus recovery rate is 82.64%.
[0047] Example 3
[0048] A low-temperature flotation collector for phosphate rock is prepared from the following components in the indicated mass percentages: 10% soybean oil, 2.5% corn oil, 2.5% linseed oil, 1.8% phosphorus trichloride, 1.7% chloroacetic acid, 3.5% sodium hydroxide, 3% dodecylbenzene sulfonic acid, 3% pine oil, 2.5% polyethylene glycol, with the balance being water.
[0049] The specific steps for preparing the above-mentioned low-temperature flotation collector for phosphate rock are as follows:
[0050] First, the weighed water was added to the reaction vessel according to the proportions, and the stirrer was started and the speed was set to 120 r / min. Then, flaxseed oil, corn oil and soybean oil were added to the reaction vessel and stirred evenly. Then, phosphorus trichloride and chloroacetic acid were slowly added to the reaction vessel through a dropper. The chlorination reaction was carried out at a constant temperature of 80℃ for 2.5 h. After the chlorination reaction was completed, the system temperature was raised to 95℃, and sodium hydroxide was added while stirring. The saponification reaction was carried out at a constant temperature of 95℃ for 2.5 h. After the saponification reaction was completed, dodecylbenzene sulfonic acid, pine oil and polyol were added. After stirring evenly, the mixture was kept at 90℃ and stirred for 1.5 h to obtain a uniform and stable liquid, which is the low-temperature flotation collector for phosphate rock.
[0051] The specific operating steps for using the above-mentioned low-temperature flotation collector for low-grade phosphate rock flotation are as follows:
[0052] (1) The portion of phosphate rock with a phosphorus content of 2.8% that is ground to a particle size of -0.074 mm accounts for 25-35% of the total mass of phosphate rock. Then, it is poured into a flotation cell and water is added to prepare a slurry with a concentration of 28 wt%.
[0053] (2) Cool the slurry from step (1) to 15°C and add the phosphate rock flotation collector at a dosage of 0.4 kg / t. Stir evenly and then perform roughing. Then add the phosphate rock flotation collector at a dosage of 0.2 kg / t and scaveng the tailings after roughing. Combine the flotation froth from roughing and scavenging, and then separate the solid and liquid phases to obtain refined phosphate rock.
[0054] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 17.43%, and the phosphorus recovery rate is 83.25%.
[0055] The specific embodiments described herein do not constitute a limitation on the scope of protection of this invention. Any other corresponding changes and modifications made in accordance with the technical concept of this invention should be included within the scope of protection of the claims of this invention.
Claims
1. A low-temperature flotation collector for phosphate rock, characterized in that, It is prepared from the following components in weight percentage: 5-25% vegetable oil, 1-5% chlorinating agent, 1-5% alkaline compound, 1-10% foaming agent, and the balance being water; The chlorinating agent is at least one of phosphorus trichloride, chloroacetic acid, thionyl chloride, and trichloroisocyanuric acid; The preparation method of the phosphate rock low-temperature flotation collector includes the following steps: First, the vegetable oil and water are mixed evenly according to the proportions of the components. Then, a chlorinating agent is added, and a chlorination reaction is carried out at 70~120℃. After the chlorination reaction is completed, an alkaline compound is added at 70~100℃ and a saponification reaction is carried out at a constant temperature. After the saponification reaction is completed, a foaming agent is added and stirred evenly. After stirring at a constant temperature, the low-temperature flotation collector for phosphate rock is obtained.
2. The phosphate rock low-temperature flotation collector according to claim 1, characterized in that, It is prepared from the following components by mass percentage: 15-20% vegetable oil, 2.2-2.5% chlorinating agent, 3.4-3.8% alkaline compound, 7-8.5% foaming agent, and the balance being water.
3. The phosphate rock low-temperature flotation collector according to claim 1 or 2, characterized in that, The vegetable oil is at least one of soybean oil, corn oil, sunflower seed oil, flaxseed oil, and their corresponding acidified oils.
4. The phosphate rock low-temperature flotation collector according to claim 3, characterized in that, The alkaline compound is at least one of sodium hydroxide, potassium hydroxide, and ammonia water; The foaming agent is at least one of dodecylbenzenesulfonic acid, sodium dodecyl sulfate, pine oil, methyl isobutyl methanol, and polyols.
5. The phosphate rock low-temperature flotation collector according to claim 1, characterized in that, The chlorination reaction takes 0.5 to 3 hours; the saponification reaction takes 0.5 to 3 hours.
6. The phosphate rock low-temperature flotation collector according to claim 1, characterized in that, The chlorination reaction is carried out at a temperature of 75-80°C for 2-2.5 hours; the saponification reaction is carried out at a temperature of 90-95°C for 2.5 hours. The specific operation of the heat preservation and stirring is as follows: heat preservation and stirring at 90℃ for 1~1.5h.
7. The application of the phosphate rock low-temperature flotation collector according to any one of claims 1 to 6 as a collector for the positive flotation of low-grade phosphate rock, characterized in that, The process includes the following steps: the ground phosphate ore is prepared into a slurry with a concentration of 25-35 wt%. The slurry is then mixed with a low-temperature flotation collector at a dosage of 0.3-1.0 kg / t at a temperature below 20°C. After stirring evenly, flotation is carried out. The resulting flotation froth is then separated into solid and liquid phases to obtain refined phosphate ore.
8. The application according to claim 7, characterized in that, The phosphorus content of the low-grade phosphate rock is 2-5%.
9. The application according to claim 7, characterized in that, The phosphate rock low-temperature flotation collector is added to the slurry at a temperature of 15~17℃ at a dosage of 0.3~1.0 kg / t. The portion of phosphate rock ground to a particle size of -0.074 mm accounts for 25-35% of the total mass of phosphate rock, and then it is prepared into a slurry with a concentration of 25-35 wt%.