Phosphorite flotation collecting agent and preparation method and application thereof

Abstract

The invention discloses a phosphorite flotation collecting agent and a preparation method and application thereof. The phosphorite flotation collecting agent is prepared from the following components in percentage by mass: 10-30% of vegetable oil, 1-5% of sulfuric acid, 1-5% of an alkaline compound and the balance of water. The preparation method of the phosphorite flotation collecting agent comprises the following steps that vegetable oil and water are evenly mixed according to the component proportion, then a sulfuric acid solution is added, and sulfonation reaction is conducted at the temperature of 70-120 DEG C; and after the sulfonation reaction is completed, an alkaline compound is added under the condition of 70-100 DEG C, saponification is conducted at the constant temperature, and the phosphorite flotation collecting agent is prepared. The collecting agent can be produced in a single reaction kettle in the production process, the production process is simplified, the reaction conditions are mild, and danger is reduced. When the collecting agent is used for flotation, the collecting agent does not need to be dissolved with hot water, meanwhile, foam which is good in state, stable and non-sticky can be generated, and therefore the flotation effect is optimized.

Description

Technical Field

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

[0002] Although phosphate resources are abundant, high-grade, easy-to-select ores are gradually decreasing, and most of them are medium- and low-grade phosphate ores, which increases the difficulty of mining and selection. Direct flotation technology is one of the most effective methods to directly float high-grade phosphate concentrates from slurry. For siliceous or calcium-siliceous phosphate rock, endogenous apatite, and sedimentary phosphate ore, when using collectors that are difficult to dissolve and whose solubility changes with temperature (such as fatty acids and their soap collectors), keeping the slurry temperature at 35~40℃ can ensure good dissolution and dispersion of the reagents and promote the reaction activity between the reagents and the minerals.

[0003] At present, the research on phosphate flotation agents mainly focuses on the following categories: anionic collectors such as fatty acids; cationic collectors such as amines; amphoteric collectors; and non-ionic collectors, including hydrocarbon oils and esters. Fatty acid collectors are still widely used due to their wide range of raw material sources, low prices and strong adaptability. However, most existing fatty acid positive flotation collectors face the problem of poor solubility, which not only makes on-site dissolution and dilution inconvenient to use, but also leads to low phosphorus recovery.

[0004] Many technical solutions for phosphate flotation collectors have been disclosed in existing patent documents. For example, Chinese patent CN101797536A discloses a collophane flotation collector prepared from rubber seed oil and a preparation method thereof. The method uses rubber seeds as raw materials, and performs pressurized hydrolysis at a temperature range of 160±5°C and a pressure condition of 0.7~0.8MPa to obtain mixed fatty acids. After cooling, electrolytes are added and stirred evenly. The separated mixed fatty acids are subjected to alkalinization reaction with substances such as isopentanol and sodium hydroxide at 90~120°C to finally obtain a positive flotation collector. Although this method achieves a flotation recovery rate of 90.8% for ore with a phosphorus grade of 19.26%, its preparation process is relatively complicated and requires high temperature and pressure conditions, which poses certain safety hazards. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a phosphate ore flotation collector and its preparation method and application. The collector prepared by the present invention has good water solubility and is suitable for the flotation of low-grade phosphate ore; when used, the flotation foam has uniform size, low foam viscosity, simple operation, and low comprehensive cost.

[0006] The purpose of the present invention is achieved through the following technical solutions: A phosphate rock flotation collector is prepared from the following components in percentage by mass: 10-30% vegetable oil, 1-5% sulfuric acid, 1-5% alkaline compound, and the balance water.

[0007] Preferably, it is prepared from the following components in percentage by weight: 22-23% vegetable oil, 3.2-3.5% sulfuric acid, 4.5-5% alkaline compound, and the remainder water.

[0008] Preferably, the vegetable oil is at least one of soybean oil, corn oil, sunflower oil, linseed oil and corresponding acidified oils thereof.

[0009] Preferably, the sulfuric acid used is concentrated sulfuric acid.

[0010] Preferably, the alkaline compound is at least one of sodium hydroxide, potassium hydroxide and ammonia water.

[0011] The preparation method of the phosphate rock flotation collector comprises the following steps: first, the vegetable oil and water are mixed evenly according to the component distribution ratio, and then a sulfuric acid solution is added to carry out a sulfonation reaction at 70-120° C.; after the sulfonation 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, the phosphate rock flotation collector is obtained.

[0012] Preferably, the vegetable oil and water are mixed evenly by stirring.

[0013] In some embodiments, stirring is performed at a rotation speed of 120 r / min to fully mix the vegetable oil and water.

[0014] Preferably, the sulfonation reaction time is 0.5 to 3 h; the saponification reaction time is 0.5 to 3 h.

[0015] Preferably, the temperature of the sulfonation reaction is 70-75° C., and the time of the sulfonation reaction is 2.5 h; the temperature of the saponification reaction is 90-95° C., and the time of the saponification reaction is 2.5 h.

[0016] The application of the phosphate rock flotation collector as a positive flotation collector for low-grade phosphate rock comprises the following steps: preparing the ground phosphate rock into a slurry with a concentration of 35-50wt%, heating the slurry to 33-37°C, adding the phosphate rock flotation collector at a ratio of 0.8-1.5kg / t, stirring evenly and then flotating, and obtaining the refined phosphate rock after solid-liquid separation of the obtained flotation foam.

[0017] Preferably, the phosphorus content of the low-grade phosphate rock is 6-12%.

[0018] Preferably, the portion of the phosphate rock ground to a particle size of -0.074 mm accounts for 35-45% of the total mass of the phosphate rock, and then is prepared into a slurry with a concentration of 35-50wt%.

[0019] The reaction mechanism of the present invention: The reaction mechanism of the collector described in the present invention mainly involves two key processes: the first is the sulfonation reaction, in which products with significant foaming effects, such as alkyl sulfonic acid, etc., can be generated; the second is the saponification reaction, which is a key step in the synthesis of the main components of the phosphorus capture agent. Through these two reactions, the present invention can not only complete the entire reaction process in a single reactor, simplifying the production process, but also its reaction conditions are relatively mild: the reaction temperature is lower than that of the traditional process, effectively reducing the steam generated by high temperature, thereby reducing the risk of steam injuring people; at the same time, the reaction time is also greatly shortened, from the traditional 6-8h to only about half the time.

[0020] Compared with the prior art, the beneficial effects of the present invention include: (1) When the collector provided by the present invention is used for the flotation of low-grade phosphate ore, it can achieve the effect of uniform flotation foam size and low foam viscosity, facilitate on-site operation and control, and effectively avoid the phenomenon of foam overflowing and overflowing the flotation tank during the flotation process, showing an excellent flotation effect.

[0021] (2) The collector provided by the present invention has good water solubility at medium temperature (33-37°C), is easy to use on site, reduces the amount of hot water required for dissolving the agent, reduces the overall cost of use, and at the same time causes little harm to the environment and human body, and is green and environmentally friendly.

[0022] (3) The collector prepared by the present invention can promote the formation and stabilization of bubbles during the flotation process without the need to add additional frothers, thereby reducing the flotation cost.

[0023] (4) The preparation method of the collector provided by the present invention is simple and easy, which significantly improves the production efficiency and product qualification rate, and ensures the quality stability of the product. The collector described in the present invention can complete the entire reaction process in a single reactor, thereby significantly optimizing the production process of the agent. DETAILED DESCRIPTION

[0024] 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.

[0025] Examples 1 to 3 and Comparative Examples 1 to 3 used the same flotation equipment, and all flotation parameters and conditions not specifically explained were kept consistent.

[0026] Example 1 A phosphate rock flotation collector is prepared from the following components in percentage by mass: 15% corn oil, 7% linseed oil, 3.5% sulfuric acid, 5% sodium hydroxide, and the balance is water.

[0027] The preparation method of the above-mentioned phosphate rock 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 linseed oil are added to the reactor and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reactor through a dropper. The sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 hours. After the sulfonation reaction is completed, the system temperature is increased to 90°C, and sodium hydroxide is added while stirring. The saponification reaction is carried out at a constant temperature of 90°C for 2.5 hours to obtain a uniform and transparent viscous liquid, which is the phosphate rock flotation collector.

[0028] The above phosphate rock 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 7.3% to a particle size of -0.074 mm, which accounts for 35-45% 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 43wt%; (2) The slurry of step (1) is heated to 33-37° C., and the phosphate rock flotation collector is added at a ratio of 0.95 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a ratio of 0.25 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and after solid-liquid separation, refined phosphate rock is obtained.

[0029] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 23.89%, and the recovery rate of phosphorus is 95.72%.

[0030] Example 2 A phosphate rock flotation collector is prepared from the following components in percentage by mass: 18% of soybean acidified oil, 5% of sunflower oil, 3.2% of sulfuric acid, 4.5% of potassium hydroxide, and the balance is water.

[0031] The preparation method of the above-mentioned phosphate rock flotation collector comprises the following specific steps: First, weighed water is added to the reactor according to the component distribution ratio, and the stirrer is started for stirring. The speed of the stirrer is set to 120r / min. Then, soybean acidified oil and sunflower oil are added to the reactor and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reactor through a dropper, and a sulfonation reaction is carried out at a constant temperature of 70°C for 2.5 hours. After the sulfonation reaction is completed, the system temperature is increased to 95°C, potassium hydroxide is added while stirring, and a saponification reaction is carried out at a constant temperature of 95°C for 2.5 hours to obtain a uniform and transparent viscous liquid, i.e., the phosphate rock flotation collector.

[0032] The above phosphate rock 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 7.3% to a particle size of -0.074 mm, which accounts for 35-45% 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 45wt%; (2) The slurry of step (1) is heated to 33-37° C., and the phosphate rock flotation collector is added at a ratio of 0.95 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a ratio of 0.25 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and after solid-liquid separation, refined phosphate rock is obtained.

[0033] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 25.83%, and the recovery rate of phosphorus is 92.34%.

[0034] Example 3 A phosphate rock flotation collector is prepared from the following components in percentage by mass: 15% of soybean acidified oil, 7% of linseed oil, 3.5% of sulfuric acid, 4.8% of sodium hydroxide, and the balance is water.

[0035] The preparation method of the above-mentioned phosphate rock flotation collector comprises the following specific steps: First, weighed water is added to the reactor according to the component distribution ratio, and the stirrer is started for stirring. The speed of the stirrer is set to 120r / min. Then, soybean acidified oil and linseed oil are added to the reactor and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reactor through a dropper, and a sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 hours. After the sulfonation 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 to obtain a uniform and transparent viscous liquid, i.e., the phosphate rock flotation collector.

[0036] The above phosphate rock 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 7.3% to a particle size of -0.074 mm, which accounts for 35-45% 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 45wt%; (2) The slurry of step (1) is heated to 33-37° C., and the phosphate rock flotation collector is added at a ratio of 0.95 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a ratio of 0.25 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and after solid-liquid separation, refined phosphate rock is obtained.

[0037] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 28.05%, and the recovery rate of phosphorus is 96.06%.

[0038] Comparative Example 1 A phosphate rock flotation collector is prepared from the following components in percentage by mass: 20% oleic acid, 3.5% sulfuric acid, 4.5% sodium hydroxide, and the balance is water.

[0039] The preparation method of the above-mentioned phosphate rock flotation collector comprises the following specific steps: First, weighed water is added to the reactor according to the component distribution ratio, and the stirrer is started for stirring. The speed of the stirrer is set to 120r / min. Then, analytically pure oleic acid is added to the reactor and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reactor through a dropper, and a sulfonation reaction is carried out at a constant temperature of 70°C for 2.5 hours. After the sulfonation 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 to obtain a uniform viscous liquid, namely the phosphate rock flotation collector.

[0040] The above phosphate rock 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 7.3% to a particle size of -0.074 mm, which accounts for 35-45% 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 45wt%; (2) The slurry of step (1) is heated to 33-37° C., and the phosphate rock flotation collector is added at a ratio of 0.95 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a ratio of 0.25 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and after solid-liquid separation, refined phosphate rock is obtained.

[0041] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 22.05%, and the recovery rate of phosphorus is 86.22%.

[0042] Comparative Example 2 A phosphate rock flotation collector is prepared from the following components in percentage by mass: 20% tall oil, 3.3% sulfuric acid, 4.8% potassium hydroxide, and the balance is water.

[0043] The preparation method of the above-mentioned phosphate rock flotation collector comprises the following specific steps: First, weighed water is added to the reactor according to the component distribution ratio, and the stirrer is started for stirring. The speed of the stirrer is set to 120r / min. Then, tall oil is added to the reactor and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reactor through a dropper. The sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 hours. After the sulfonation reaction is completed, the system temperature is increased to 95°C, potassium hydroxide is added while stirring, and a saponification reaction is carried out at a constant temperature of 95°C for 2.5 hours to obtain a uniform viscous liquid, i.e., the phosphate rock flotation collector.

[0044] The above phosphate rock 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 7.3% to a particle size of -0.074 mm, which accounts for 35-45% 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 45wt%; (2) The slurry of step (1) is heated to 33-37° C., and the phosphate rock flotation collector is added at a ratio of 0.95 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a ratio of 0.25 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and after solid-liquid separation, refined phosphate rock is obtained.

[0045] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 25.75%, and the recovery rate of phosphorus is 91.06%.

[0046] Comparative Example 3 A phosphate rock flotation collector is prepared from the following components in percentage by mass: 20% castor oil, 3.2% sulfuric acid, 4.5% sodium hydroxide, and the balance is water.

[0047] The preparation method of the above-mentioned phosphate rock flotation collector comprises the following specific steps: First, weighed water is added to the reactor according to the component distribution ratio, and the stirrer is started for stirring. The speed of the stirrer is set to 120r / min. Then, castor oil is added to the reactor and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reactor through a dropper. The sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 hours. After the sulfonation reaction is completed, the system temperature is increased to 95°C, and sodium hydroxide is added while stirring. The saponification reaction is carried out at a constant temperature of 95°C for 2.5 hours to obtain a uniform viscous liquid, i.e., the phosphate rock flotation collector.

[0048] The above phosphate rock 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 7.3% to a particle size of -0.074 mm, which accounts for 35-45% 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 45wt%; (2) The slurry of step (1) is heated to 33-37° C., and the phosphate rock flotation collector is added at a ratio of 0.95 kg / t, and the mixture is stirred evenly before roughing; then, the phosphate rock flotation collector is added at a ratio of 0.25 kg / t, and the tailings after roughing are scavenged, and the flotation foams of the roughing and scavenging are combined, and after solid-liquid separation, refined phosphate rock is obtained.

[0049] After analysis and calculation, the grade of the refined phosphate ore obtained by the above flotation is 20.79%, and the recovery rate of phosphorus is 81.54%.

[0050] The specific implementation of the present invention described above 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 phosphate ore flotation collector, characterized in that: The invention is prepared from the following components in percentage by weight: 10-30% vegetable oil, 1-5% sulfuric acid, 1-5% alkaline compound, and the balance water.

2. The phosphate rock flotation collector according to claim 1, characterized in that: The invention is prepared from the following components in percentage by weight: 22-23% vegetable oil, 3.2-3.5% sulfuric acid, 4.5-5% alkaline compound, and the balance water.

3. The phosphate rock 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 alkaline compound is at least one of sodium hydroxide, potassium hydroxide and ammonia water.

4. The phosphate rock flotation collector according to claim 1, characterized in that: The sulfuric acid used is concentrated sulfuric acid.

5. The method for preparing the phosphate rock flotation collector according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: firstly, evenly mixing vegetable oil and water in a component distribution ratio, then adding sulfuric acid solution, and carrying out sulfonation reaction at 70-120° C.; after the sulfonation reaction is completed, adding alkaline compounds at 70-100° C. and carrying out saponification reaction at a constant temperature, and after the saponification reaction is completed, the phosphate rock flotation collector is obtained.

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

7. The method for preparing a phosphate rock flotation collector according to claim 6, characterized in that: The temperature of the sulfonation reaction is 70-75° C., and the time of the sulfonation reaction is 2.5 h; the temperature of the saponification reaction is 90-95° C., and the time of the saponification reaction is 2.5 h.

8. Use of the phosphate rock flotation collector according to any one of claims 1 to 4 as a positive flotation collector for low-grade phosphate rock, characterized in that: The method comprises the following steps: preparing the ground phosphate rock into a slurry with a concentration of 35-50wt%, heating the slurry to 33-37°C, adding the phosphate rock flotation collector at a ratio of 0.8-1.5kg / t, stirring evenly and then 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 6-12%.

10. The use according to claim 8, characterized in that: The portion of the phosphate rock ground to a particle size of -0.074 mm accounts for 35-45% of the total mass of the phosphate rock, and then is prepared into a slurry with a concentration of 35-50wt%.