Phosphorite low-temperature flotation collecting agent and preparation method and application thereof

Abstract

The invention discloses a phosphorite low-temperature flotation collecting agent and a preparation method and application thereof. The phosphorite low-temperature flotation collecting agent is prepared from the following components in percentage by mass: 5-25% of vegetable oil, 1-5% of a chlorinating agent, 1-5% of an alkaline compound, 1-10% of a foaming agent and the balance of water. The prepared low-temperature collecting agent has good water solubility and is convenient to use. When the collecting agent is applied to flotation of low-grade phosphorite, the phosphorite can be effectively floated in the temperature range lower than 20 DEG C, the collecting agent has the advantages of being uniform in foam size and low in viscosity, and the flotation recovery rate is remarkably increased.

Description

Technical Field

[0001] The invention belongs to the technical field of phosphate ore flotation, and in particular relates to a phosphate ore low-temperature flotation collector and a preparation method and application thereof. Background Art

[0002] Phosphate resources are abundant, but high-grade and easy-to-select phosphate ores are mainly concentrated in Hubei, Hunan, Yunnan and Guizhou. The north and northeast regions are mostly medium- and low-grade phosphate ores, and the low ambient temperature increases the difficulty of mining and selection. Positive flotation technology is one of the most effective methods to directly float high-grade phosphate concentrate from the pulp. At present, the research directions of phosphate flotation agents mainly include: fatty acid anionic collectors, amine cationic collectors, amphoteric collectors, and non-ionic collectors of hydrocarbon oils and esters. Among them, fatty acid collectors are still widely used because of their wide source of raw materials, low price and strong adaptability. However, most of the existing fatty acid positive flotation collectors have the problem of complex preparation process, not only poor solubility, but also inconvenient operation during on-site dissolution and dilution, and low mineral recovery rate. In addition, in order to ensure the effective activation of phosphate ore by the flotation agent, it is usually necessary to heat the slurry, which increases energy consumption and increases the flotation cost.

[0003] In the existing patent literature, many technical solutions for phosphate flotation collectors have been disclosed. For example, Chinese patent CN107029894A discloses a low-temperature resistant medium- and low-grade colloidal phosphate flotation collector prepared from malic acid and a preparation method thereof, which comprises the following steps: first, under the action of a solid acid catalyst, malic acid and methanol undergo an esterification reaction; then, the product reacts with ethanolamine to form malic acid alkanolamide; then, 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, the derivative is mixed with sodium alkyl sulfonate and other components to obtain the final positive flotation collector. This collector can effectively float phosphate within a temperature range of 5 to 35°C, and the recovery rate of P2O5 can reach 93 to 96%. Although the patent significantly improves the flotation recovery rate of medium- and low-grade phosphate ores under low temperature conditions, its preparation process is relatively complex, involving a variety of raw materials, and some reactions require higher temperatures, which increases the difficulty of product quality control and the safety risks of the production process, which is not conducive to large-scale production and popularization. Summary of the invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a low-temperature flotation collector for phosphate ore and a preparation method and application thereof. The low-temperature collector prepared by the present invention has good water solubility and is easy to use. When it is applied to the flotation of low-grade phosphate ore, it exhibits the characteristics of uniform foam size and low viscosity, and the flotation recovery rate is high. In addition, the comprehensive use cost of the collector is low, and the production process is simple, safe and efficient.

[0005] The purpose of the present invention is achieved through the following technical solutions: A phosphate rock low-temperature flotation collector is prepared from the following components in percentage by mass: 5-25% vegetable oil, 1-5% chlorinating agent, 1-5% alkaline compound, 1-10% frother, and the balance is water.

[0006] Preferably, it is prepared from the following components in percentage by weight: 15-20% vegetable oil, 2.2-2.5% chlorinating agent, 3.4-3.8% alkaline compound, 7-8.5% foaming agent, and the remainder is water.

[0007] Preferably, the vegetable oil is at least one of soybean oil, corn oil, sunflower oil, linseed oil and corresponding acidified oils thereof.

[0008] Preferably, the chlorinating agent is at least one of phosphorus trichloride, chloroacetic acid, thionyl chloride and trichloroisocyanuric acid.

[0009] Preferably, the alkaline compound is at least one of sodium hydroxide, potassium hydroxide and ammonia water.

[0010] Preferably, the foaming agent is at least one of dodecylbenzenesulfonic acid, sodium lauryl sulfate, pine oil, methyl isobutyl carbinol and polyol.

[0011] Preferably, the polyol is at least one of ethylene glycol, polyethylene glycol and butanediol.

[0012] The preparation method of the above-mentioned phosphate rock low-temperature flotation collector comprises the following steps: First, vegetable oil and water in a component ratio are mixed evenly, and then a chlorinating agent is added to carry out a chlorination reaction at 70-120°C. After the chlorination reaction is completed, an alkaline compound is added at 70-100°C 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 heat preservation and stirring, a phosphate rock low-temperature flotation collector is obtained.

[0013] Preferably, the vegetable oil and water are mixed evenly by stirring.

[0014] In some embodiments, stirring is performed at a rotation speed of 120 r / min to fully mix the vegetable oil and water.

[0015] Preferably, the chlorination reaction time is 0.5 to 3 hours; the saponification reaction time is 0.5 to 3 hours.

[0016] Preferably, the temperature of the chlorination reaction is 75-80° C., and the time of the chlorination reaction is 2-2.5 h; the temperature of the saponification reaction is 90-95° C., and the time of the saponification reaction is 2.5 h.

[0017] Preferably, the specific operation of heat preservation and stirring is: heat preservation and stirring at 90° C. for 1 to 1.5 hours.

[0018] The application of the phosphate rock low-temperature flotation collector as a low-grade phosphate rock positive flotation collector comprises the following steps: preparing the ground phosphate rock into a slurry with a concentration of 25-35wt%, adding the phosphate rock low-temperature flotation collector at a dosage of 0.3-1.0kg / t to the slurry at a temperature below 20°C, stirring evenly and then flotation, and obtaining the refined phosphate rock after solid-liquid separation of the obtained flotation foam.

[0019] Preferably, the phosphorus content of the low-grade phosphate rock is 2-5%.

[0020] Preferably, the phosphate rock low temperature flotation collector is added to the slurry at a temperature of 15-17°C at a dosage of 0.3-1.0 kg / t.

[0021] Preferably, the portion of the phosphate rock ground to a particle size of -0.074 mm accounts for 25-35% of the total mass of the phosphate rock, and then is prepared into a slurry with a concentration of 25-35wt%.

[0022] The reaction mechanism involved in the present invention is as follows: the molecular structure of the vegetable oil is changed by adding a chlorinating agent to enhance its water solubility and dispersibility and adsorption performance on the surface of the mineral powder. Subsequently, the modified vegetable oil is converted into fatty acid salts by treating with alkaline compounds. These fatty acid salts, as the main collector components, can be more effectively attached to the surface of the phosphate ore. In addition, in order to ensure normal foaming and adjust the foam state during the flotation process, a foaming agent is added. This series of steps significantly improves the flotation effect.

[0023] Compared with the prior art, the beneficial effects of the present invention include: (1) The phosphate rock low-temperature flotation collector prepared by the present invention can significantly improve the flotation recovery rate of phosphate rock. The flotation foam has uniform size and low viscosity, which is convenient for on-site operation and control, and effectively avoids the phenomenon of foam overflowing or overflowing the flotation tank during the flotation process.

[0024] (2) The collector prepared by the present invention has good water solubility, is easy to use on site, reduces the amount of hot water required for dissolving the agent, and reduces the comprehensive use cost. In addition, the product is environmentally friendly, has little harm to the human body, and meets the requirements of green environmental protection.

[0025] (3) The collector prepared by the present invention is suitable for slurry flotation at a temperature below 20°C, which greatly reduces the ore dressing cost caused by slurry heating and improves economic benefits. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0027] Examples 1 to 3 use the same flotation equipment, and all flotation parameters and conditions not specifically explained remain the same.

[0028] Example 1 A low-temperature flotation collector for phosphate rock is prepared from the following components in percentage by mass: 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 carbinol, and the balance is water.

[0029] The preparation method of the above-mentioned phosphate rock low-temperature flotation collector comprises the following specific steps: First, weighed water is added to the reactor according to the component ratio, and the stirrer is started for stirring. The speed of the stirrer is set to 120r / min. Then, corn oil and soybean oil are added to the reactor and stirred evenly. Then, phosphorus trichloride and thionyl chloride are slowly added to the reactor through a dropper. A chlorination reaction is carried out at a constant temperature of 75°C for 2.5 hours. After the chlorination reaction is completed, the system temperature is increased to 90°C, and sodium hydroxide is added while stirring. A saponification reaction is carried out at a constant temperature of 90°C for 2.5 hours. After the saponification reaction is completed, sodium dodecyl sulfate and methyl isobutyl carbinol are added. After stirring evenly, the mixture is kept warm at 90°C for 1 hour to obtain a uniform and stable liquid, i.e., the phosphate rock low-temperature flotation collector.

[0030] The above-mentioned phosphate rock low-temperature flotation collector is used for the flotation of low-grade phosphate rock. The specific operation steps are as follows: (1) grinding phosphate rock with a phosphorus content of 2.8% to a particle size of -0.074 mm, which accounts for 25-35% of the total mass of the phosphate rock, and then pouring it into a flotation tank, adding water to prepare a slurry with a concentration of 30wt%; (2) The slurry in step (1) is cooled to 15° C., and the phosphate rock flotation collector is added at a dosage of 0.35 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a dosage of 0.15 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and the solid-liquid separation is performed to obtain refined phosphate rock.

[0031] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 18.89%, and the phosphorus recovery rate is 75.92%.

[0032] Example 2 A low-temperature flotation collector for phosphate rock is prepared from the following components in percentage by mass: 12% soybean oil, 4% sunflower 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 carbinol, 2% ethylene glycol, and the balance is water.

[0033] The preparation method of the above-mentioned phosphate rock low-temperature flotation collector comprises the following specific steps: First, weighed water is added to a reactor according to the component ratio, and an agitator is started for stirring, and the speed of the agitator is set to 120 r / min. Then, sunflower oil and soybean oil are added to the reactor and stirred evenly. Chloroacetic acid, thionyl chloride and trichloroisocyanuric acid are slowly added to the reactor through a dropper, and a chlorination reaction is carried out at a constant temperature of 75° C. for 2 hours. After the chlorination reaction is completed, the system temperature is increased to 95° C., and sodium hydroxide is added while stirring. A saponification reaction is carried out at a constant temperature of 95° C. for 2.5 hours. After the saponification reaction is completed, dodecylbenzenesulfonic acid, methyl isobutyl carbinol and polyol are added, and after stirring evenly, the mixture is kept warm and stirred at 90° C. for 1 hour to obtain a uniform and stable liquid, i.e., the phosphate rock low-temperature flotation collector.

[0034] The above-mentioned phosphate rock low-temperature flotation collector is used for the flotation of low-grade phosphate rock. The specific operation steps are as follows: (1) grinding phosphate rock with a phosphorus content of 2.8% to a particle size of -0.074 mm, which accounts for 25-35% of the total mass of the phosphate rock, and then pouring it into a flotation tank, adding water to prepare a slurry with a concentration of 30wt%; (2) The slurry in step (1) is cooled to 17° C., and the phosphate rock flotation collector is added at a dosage of 0.35 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a dosage of 0.15 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and the solid-liquid separation is performed to obtain refined phosphate rock.

[0035] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 19.37%, and the recovery rate of phosphorus is 82.64%.

[0036] Example 3 A low-temperature flotation collector for phosphate rock is prepared from the following components in percentage by mass: 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, and the balance is water.

[0037] The preparation method of the above-mentioned phosphate rock low-temperature flotation collector comprises the following specific steps: First, weighed water is added to a reactor according to the component ratio, and an agitator is started for stirring. The speed of the agitator is set to 120 r / min. Then, linseed oil, corn oil and soybean oil are added to the reactor and stirred evenly. Then, phosphorus trichloride and chloroacetic acid are slowly added to the reactor through a dropper. A chlorination reaction is carried out at a constant temperature of 80° C. for 2.5 hours. After the chlorination reaction is completed, the system temperature is increased to 95° C., and sodium hydroxide is added while stirring. A saponification reaction is carried out at a constant temperature of 95° C. for 2.5 hours. After the saponification reaction is completed, dodecylbenzenesulfonic acid, pine oil and polyol are added. After stirring evenly, the mixture is kept warm at 90° C. and stirred for 1.5 hours to obtain a uniform and stable liquid, i.e., the phosphate rock low-temperature flotation collector.

[0038] The above-mentioned phosphate rock low-temperature flotation collector is used for the flotation of low-grade phosphate rock. The specific operation steps are as follows: (1) grinding phosphate rock with a phosphorus content of 2.8% to a particle size of -0.074 mm, which accounts for 25-35% of the total mass of the phosphate rock, and then pouring it into a flotation tank, adding water to prepare a slurry with a concentration of 28wt%; (2) The slurry in step (1) is cooled to 15° C., and the phosphate rock flotation collector is added at a dosage of 0.4 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a dosage of 0.2 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and the solid-liquid separation is performed to obtain refined phosphate rock.

[0039] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 17.43%, and the phosphorus recovery rate is 83.25%.

[0040] The specific implementation of the present invention is described, which does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A low-temperature flotation collector for phosphate rock, characterized in that: The invention is prepared from the following components in percentage by weight: 5-25% vegetable oil, 1-5% chlorinating agent, 1-5% alkaline compound, 1-10% foaming agent, and the balance is water.

2. The phosphate rock low temperature flotation collector according to claim 1, characterized in that: The invention is prepared from the following components in percentage by weight: 15-20% of vegetable oil, 2.2-2.5% of chlorinating agent, 3.4-3.8% of alkaline compound, 7-8.5% of foaming agent, and the balance of 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 oil, linseed oil and their corresponding acidified oils; The chlorinating agent is at least one of phosphorus trichloride, chloroacetic acid, thionyl chloride and trichloroisocyanuric acid.

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 dodecylbenzene sulfonic acid, sodium dodecyl sulfate, pine oil, methyl isobutyl carbinol and polyol.

5. The method for preparing the phosphate rock low-temperature flotation collector according to any one of claims 1 to 4, characterized in that: The steps include: First, vegetable oil and water in a component ratio are mixed evenly, and then a chlorinating agent is added to carry out a chlorination reaction at 70-120° C.; after the chlorination reaction is completed, an alkaline compound is added at 70-100° C. and a saponification reaction is carried out at a constant temperature, and after the saponification reaction is completed, a foaming agent is added and stirred evenly, and after heat preservation and stirring, the phosphate rock low-temperature flotation collector is obtained.

6. The method for preparing the phosphate rock low-temperature flotation collector according to claim 5, characterized in that: The chlorination reaction time is 0.5 to 3 hours; the saponification reaction time is 0.5 to 3 hours.

7. The method for preparing the phosphate rock low-temperature flotation collector according to claim 6, characterized in that: The temperature of the chlorination reaction is 75-80°C, and the time of the chlorination reaction is 2-2.5h; the temperature of the saponification reaction is 90-95°C, and the time of the saponification reaction is 2.5h; The specific operation of the heat preservation and stirring is: heat preservation and stirring at 90° C. for 1 to 1.5 hours.

8. Use of the phosphate rock low-temperature flotation collector according to any one of claims 1 to 4 as a low-grade phosphate rock positive flotation collector, characterized in that: The method comprises the following steps: preparing the ground phosphate rock into a slurry with a concentration of 25-35wt%, adding the phosphate rock low-temperature flotation collector in a dosage of 0.3-1.0kg / t to the slurry at a temperature below 20°C, stirring the slurry evenly and performing flotation, and obtaining the refined phosphate rock after solid-liquid separation of the obtained flotation foam.

9. The use according to claim 8, characterized in that: The phosphorus content of the low-grade phosphate rock is 2-5%.

10. The use according to claim 8, characterized in that: The slurry is added with the phosphate rock low temperature flotation collector at a dosage of 0.3-1.0 kg / t at a temperature of 15-17°C; The portion of the phosphate rock ground to a particle size of -0.074 mm accounts for 25-35% of the total mass of the phosphate rock, and then is prepared into a slurry with a concentration of 25-35wt%.