Phosphate ore flotation collector, and preparation method and application thereof

Abstract

This invention discloses a phosphate rock flotation collector, its preparation method, and its application. The phosphate rock flotation collector is prepared from components comprising the following mass percentages: 10-30% vegetable oil, 1-5% sulfuric acid, 1-5% alkaline compound, and the balance being water. The preparation method of the phosphate rock flotation collector includes the following steps: mixing the vegetable oil and water according to the specified proportions, then adding a sulfuric acid solution, and carrying out a sulfonation reaction at 70-120°C; after the sulfonation reaction is completed, adding an alkaline compound at 70-100°C and carrying out a saponification reaction at a constant temperature to obtain the phosphate rock flotation collector. The collector of this invention can be produced in a single reaction vessel, simplifying the production process, and the reaction conditions are relatively mild, reducing the risk. When used in flotation, the collector does not require hot water for dissolution and can produce well-formed, stable, and non-viscous foam, thereby optimizing the flotation effect.

Description

Technical Field

[0001] This invention belongs to the field of phosphate rock flotation technology, and particularly relates to a phosphate rock flotation collector, its preparation method and application. Background Technology

[0002] Although phosphate resources are abundant, high-grade, easily beneficiated ores are gradually decreasing, with most being medium- to low-grade phosphate ores, increasing 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. For siliceous or calcareous-siliceous phosphate rocks, endogenic apatite, and sedimentary phosphate rocks, when using collectors that are sparingly soluble and whose solubility varies with temperature (such as fatty acids and their soaps), maintaining the pulp temperature at 35–40°C ensures good dissolution and dispersion of the reagents and promotes the reactivity between the reagents and the minerals.

[0003] Currently, research on phosphate rock flotation agents mainly focuses on the following categories: anionic collectors such as fatty acids; cationic collectors such as amines; amphoteric collectors; and nonionic collectors, including hydrocarbon oils and esters. Fatty acid collectors remain widely used due to their wide availability of raw materials, low price, and strong adaptability. However, most existing fatty acid-based positive flotation collectors suffer from poor solubility, which not only makes on-site dissolution and dilution inconvenient but also results in low phosphorus recovery rates.

[0004] Numerous technical solutions for phosphate rock flotation collectors have been disclosed in existing patent literature. For example, Chinese patent CN101797536A discloses a flotation collector for phosphate rock prepared from rubber seed oil and its preparation method. This method uses rubber seeds as raw material, and involves pressurized hydrolysis at a temperature range of 160±5℃ and a pressure of 0.7~0.8MPa to obtain mixed fatty acids. After cooling, electrolytes are added and stirred evenly. The separated mixed fatty acids undergo an alkalization reaction with isoamyl alcohol and sodium hydroxide at 90~120℃, ultimately yielding 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 complex and requires high temperature and pressure conditions, posing certain safety hazards. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a phosphate rock flotation collector, its preparation method, and its application. The collector prepared by this invention exhibits good water solubility, making it suitable for the flotation of low-grade phosphate rock. During use, it produces uniform flotation froth of uniform size and low viscosity, is easy to operate, and has a low overall cost.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A phosphate rock flotation collector is prepared from components comprising the following mass percentages: 10-30% vegetable oil, 1-5% sulfuric acid, 1-5% alkaline compound, and the balance being water.

[0008] Preferably, it is prepared from components comprising the following mass percentages: 22-23% vegetable oil, 3.2-3.5% sulfuric acid, 4.5-5% alkaline compound, with the balance being water.

[0009] Preferably, the vegetable oil is at least one of soybean oil, corn oil, sunflower seed oil, flaxseed oil, and their corresponding acidified oils.

[0010] Preferably, concentrated sulfuric acid is used when applying sulfuric acid.

[0011] Preferably, the alkaline compound is at least one of sodium hydroxide, potassium hydroxide, and ammonia water.

[0012] The preparation method of the above-mentioned phosphate rock flotation collector includes the following steps: First, vegetable oil and water are mixed evenly according to the proportions of the components, and then sulfuric acid solution is added and sulfonation reaction is carried out at 70~120℃; after the sulfonation reaction is completed, an alkaline compound is added at 70~100℃ and saponification reaction is carried out at a constant temperature. After the saponification reaction is completed, the phosphate rock 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 speed of 120 r / min to ensure that the vegetable oil and water are thoroughly mixed.

[0015] Preferably, the sulfonation reaction time is 0.5~3h; the saponification reaction time is 0.5~3h.

[0016] Preferably, the sulfonation reaction temperature is 70~75℃ and the sulfonation reaction time is 2.5h; the saponification reaction temperature is 90~95℃ and the saponification reaction time is 2.5h.

[0017] The application of the above-mentioned phosphate rock flotation collector as a collector for positive flotation of low-grade phosphate rock includes the following steps: the phosphate rock after grinding is prepared into a slurry with a concentration of 35~50wt%, the slurry is heated to 33~37℃, and the phosphate rock flotation collector is added at a ratio of 0.8~1.5kg / t. After stirring evenly, flotation is carried out. The flotation froth obtained is then separated into solid and liquid phases to obtain refined phosphate rock.

[0018] Preferably, the phosphorus content of low-grade phosphate rock is 6-12%.

[0019] Preferably, the portion of phosphate rock ground to a particle size of -0.074 mm accounts for 35-45% of the total mass of phosphate rock, and then a slurry with a concentration of 35-50 wt% is prepared.

[0020] The reaction mechanism involved in this invention mainly involves two key processes: first, a sulfonation reaction, which generates products with significant foaming effects, such as alkyl sulfonic acids; and second, a saponification reaction, a crucial step in the synthesis of the main components of the phosphorus scavenger. Through these two reactions, this invention not only completes the entire reaction process in a single reactor, simplifying the production process, but also provides milder reaction conditions: the reaction temperature is lower than in traditional processes, effectively reducing the steam generated at high temperatures and thus lowering the risk of steam burns; simultaneously, the reaction time is significantly shortened, from the traditional 6-8 hours to only about half the time.

[0021] Compared with the prior art, the beneficial effects of the present invention include:

[0022] (1) When the collector provided by the present invention is used for the flotation of low-grade phosphate rock, it can achieve the effect of uniform flotation foam size and low foam viscosity, which is convenient for on-site operation and control, and effectively avoids the phenomenon of foam overflowing and overflowing during the flotation process, thus showing excellent flotation effect.

[0023] (2) The collector provided by the present invention has good water solubility at medium temperature (33~37℃), which is convenient for on-site use, reduces the amount of hot water required for dissolving the agent, reduces the overall cost of use, and is less harmful to the environment and human body, making it green and environmentally friendly.

[0024] (3) The collector prepared by the present invention can promote the formation and stability of bubbles during the flotation process without the need to add additional frothers, thereby reducing the flotation cost.

[0025] (4) The preparation method of the collector provided by the present invention is simple and easy to implement, significantly improving production efficiency and product qualification rate, and ensuring product quality stability. The collector described in the present invention can complete the entire reaction process in a single reactor, thus significantly optimizing the production process of the reagent. Detailed Implementation

[0026] 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.

[0027] Examples 1-3 and Comparative Examples 1-3 used the same flotation equipment, and all flotation parameters and conditions, unless otherwise specified, remained consistent.

[0028] Example 1

[0029] A phosphate rock flotation collector is prepared from the following components in the indicated mass percentages: 15% corn oil, 7% linseed oil, 3.5% sulfuric acid, 5% sodium hydroxide, and the balance being water.

[0030] The specific steps for preparing the above-mentioned phosphate rock flotation collector are as follows:

[0031] First, the weighed water is added to the reaction vessel according to the proportions, and the stirrer is started and the speed is set to 120 r / min. Then, corn oil and flaxseed oil are added to the reaction vessel and stirred evenly. Then, concentrated sulfuric acid (98% concentration) is slowly added to the reaction vessel through a dropper. The sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 h. After the sulfonation reaction is completed, the system temperature is raised 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 h to obtain a uniform, transparent, viscous liquid, which is the phosphate rock flotation collector.

[0032] The specific operating steps for using the above-mentioned phosphate rock flotation collector for the flotation of low-grade phosphate rock are as follows:

[0033] (1) The portion of phosphate rock with a phosphorus content of 7.3% that is ground to a particle size of -0.074 mm accounts for 35-45% 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 43 wt%.

[0034] (2) Heat the slurry from step (1) to 33~37℃, add the phosphate rock flotation collector at a ratio of 0.95kg / t, stir evenly and then carry out roughing; then add the phosphate rock flotation collector at a ratio of 0.25kg / t, scaveng the tailings after roughing, combine the flotation froth from roughing and scavenging, and after solid-liquid separation, obtain refined phosphate rock.

[0035] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 23.89%, and the phosphorus recovery rate is 95.72%.

[0036] Example 2

[0037] A phosphate rock flotation collector is prepared from the following components in the indicated mass percentages: 18% soybean acidified oil, 5% sunflower seed oil, 3.2% sulfuric acid, 4.5% potassium hydroxide, and the balance being water.

[0038] The specific steps for preparing the above-mentioned phosphate rock flotation collector are as follows:

[0039] First, the weighed water is added to the reaction vessel according to the grouping ratio, and the stirrer is started and the speed of the stirrer is set to 120 r / min. Then, the soybean acidified oil and sunflower seed oil are added to the reaction vessel and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reaction vessel through a dropper. The sulfonation reaction is carried out at a constant temperature of 70℃ for 2.5 h. After the sulfonation reaction is completed, the system temperature is raised to 95℃, and potassium hydroxide is added while stirring. The saponification reaction is carried out at a constant temperature of 95℃ for 2.5 h to obtain a uniform and transparent viscous liquid, which is the phosphate rock flotation collector.

[0040] The specific operating steps for using the above-mentioned phosphate rock flotation collector for the flotation of low-grade phosphate rock are as follows:

[0041] (1) The portion of phosphate rock with a phosphorus content of 7.3% that is ground to a particle size of -0.074 mm accounts for 35~45% 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 45wt%.

[0042] (2) Heat the slurry from step (1) to 33~37℃, add the phosphate rock flotation collector at a ratio of 0.95kg / t, stir evenly and then carry out roughing; then add the phosphate rock flotation collector at a ratio of 0.25kg / t, scaveng the tailings after roughing, combine the flotation froth from roughing and scavenging, and after solid-liquid separation, obtain refined phosphate rock.

[0043] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 25.83%, and the phosphorus recovery rate is 92.34%.

[0044] Example 3

[0045] A phosphate rock flotation collector is prepared from the following components in the indicated mass percentages: 15% soybean acidified oil, 7% linseed oil, 3.5% sulfuric acid, 4.8% sodium hydroxide, and the balance being water.

[0046] The specific steps for preparing the above-mentioned phosphate rock flotation collector are as follows:

[0047] First, the weighed water is added to the reaction vessel according to the grouping ratio, and the stirrer is started and the speed of the stirrer is set to 120 r / min. Then, the soybean acidified oil and flaxseed oil are added to the reaction vessel and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) is slowly added to the reaction vessel through a dropper. The sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 h. After the sulfonation reaction is completed, the system temperature is raised 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 h to obtain a uniform and transparent viscous liquid, which is the phosphate rock flotation collector.

[0048] The specific operating steps for using the above-mentioned phosphate rock flotation collector for the flotation of low-grade phosphate rock are as follows:

[0049] (1) The portion of phosphate rock with a phosphorus content of 7.3% that is ground to a particle size of -0.074 mm accounts for 35~45% 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 45wt%.

[0050] (2) Heat the slurry from step (1) to 33~37℃, add the phosphate rock flotation collector at a ratio of 0.95kg / t, stir evenly and then carry out roughing; then add the phosphate rock flotation collector at a ratio of 0.25kg / t, scaveng the tailings after roughing, combine the flotation froth from roughing and scavenging, and after solid-liquid separation, obtain refined phosphate rock.

[0051] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 28.05%, and the phosphorus recovery rate is 96.06%.

[0052] Comparative Example 1

[0053] A phosphate rock flotation collector is prepared from the following components in the indicated mass percentages: 20% oleic acid, 3.5% sulfuric acid, 4.5% sodium hydroxide, with the balance being water.

[0054] The specific steps for preparing the above-mentioned phosphate rock flotation collector are as follows:

[0055] First, the weighed water was added to the reaction vessel according to the grouping ratio, and the stirrer was started and the stirring speed was set to 120 r / min. Then, analytical grade oleic acid was added to the reaction vessel and stirred evenly. Then, concentrated sulfuric acid (concentration of 98%) was slowly added to the reaction vessel through a dropper. The sulfonation reaction was carried out at a constant temperature of 70°C for 2.5 h. After the sulfonation 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 h to obtain a uniform viscous liquid, which is the phosphate rock flotation collector.

[0056] The specific operating steps for using the above-mentioned phosphate rock flotation collector for the flotation of low-grade phosphate rock are as follows:

[0057] (1) The portion of phosphate rock with a phosphorus content of 7.3% that is ground to a particle size of -0.074 mm accounts for 35~45% 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 45wt%.

[0058] (2) Heat the slurry from step (1) to 33~37℃, add the phosphate rock flotation collector at a ratio of 0.95kg / t, stir evenly and then carry out roughing; then add the phosphate rock flotation collector at a ratio of 0.25kg / t, scaveng the tailings after roughing, combine the flotation froth from roughing and scavenging, and after solid-liquid separation, obtain refined phosphate rock.

[0059] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 22.05%, and the phosphorus recovery rate is 86.22%.

[0060] Comparative Example 2

[0061] A phosphate rock flotation collector is prepared from the following components in the indicated mass percentages: 20% tall oil, 3.3% sulfuric acid, 4.8% potassium hydroxide, with the balance being water.

[0062] The specific steps for preparing the above-mentioned phosphate rock flotation collector are as follows:

[0063] First, add the weighed water to the reaction vessel according to the grouping ratio, start the stirrer and set the stirrer speed to 120 r / min. Then, add tall oil to the reaction vessel and stir evenly. Next, slowly add concentrated sulfuric acid (concentration of 98%) to the reaction vessel through a dropper. The sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 h. After the sulfonation reaction is completed, raise the system temperature to 95°C and add potassium hydroxide while stirring. The saponification reaction is carried out at a constant temperature of 95°C for 2.5 h to obtain a uniform viscous liquid, which is the phosphate rock flotation collector.

[0064] The specific operating steps for using the above-mentioned phosphate rock flotation collector for the flotation of low-grade phosphate rock are as follows:

[0065] (1) The portion of phosphate rock with a phosphorus content of 7.3% that is ground to a particle size of -0.074 mm accounts for 35~45% 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 45wt%.

[0066] (2) Heat the slurry from step (1) to 33~37℃, add the phosphate rock flotation collector at a ratio of 0.95kg / t, stir evenly and then carry out roughing; then add the phosphate rock flotation collector at a ratio of 0.25kg / t, scaveng the tailings after roughing, combine the flotation froth from roughing and scavenging, and after solid-liquid separation, obtain refined phosphate rock.

[0067] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 25.75%, and the phosphorus recovery rate is 91.06%.

[0068] Comparative Example 3

[0069] A phosphate rock flotation collector is prepared from the following components in the indicated mass percentages: 20% castor oil, 3.2% sulfuric acid, 4.5% sodium hydroxide, and the balance being water.

[0070] The specific steps for preparing the above-mentioned phosphate rock flotation collector are as follows:

[0071] First, the weighed water is added to the reaction vessel according to the proportions, and the stirrer is started and the speed is set to 120 r / min. Then, castor oil is added to the reaction vessel and stirred evenly. Next, concentrated sulfuric acid (98% concentration) is slowly added to the reaction vessel through a dropper. The sulfonation reaction is carried out at a constant temperature of 75°C for 2.5 h. After the sulfonation reaction is completed, the system temperature is raised 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 h to obtain a uniform viscous liquid, which is the phosphate rock flotation collector.

[0072] The specific operating steps for using the above-mentioned phosphate rock flotation collector for the flotation of low-grade phosphate rock are as follows:

[0073] (1) The portion of phosphate rock with a phosphorus content of 7.3% that is ground to a particle size of -0.074 mm accounts for 35~45% 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 45wt%.

[0074] (2) Heat the slurry from step (1) to 33~37℃, add the phosphate rock flotation collector at a ratio of 0.95kg / t, stir evenly and then carry out roughing; then add the phosphate rock flotation collector at a ratio of 0.25kg / t, scaveng the tailings after roughing, combine the flotation froth from roughing and scavenging, and after solid-liquid separation, obtain refined phosphate rock.

[0075] Analysis and calculation show that the grade of the refined phosphate rock obtained by the above flotation is 20.79%, and the phosphorus recovery rate is 81.54%.

[0076] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A phosphate ore flotation collector, characterized in that, Prepared from components including the following mass percentages: 10-30% plant oil, 1-5% sulfuric acid, 1-5% basic compound, and the balance being water; The preparation method of the phosphate ore flotation collector comprises the following steps: firstly, uniformly mixing plant oil and water according to component allocation ratios, then adding a sulfuric acid solution, and performing a sulfonation reaction at 70-120 DEG C; after the sulfonation reaction is completed, adding a basic compound at 70-100 DEG C and performing a saponification reaction, and after the saponification reaction is completed, the phosphate ore flotation collector is obtained. The sulfonation reaction time is 0.5-3h, and the saponification reaction time is 0.5-3h.

2. The phosphate ore flotation collector according to claim 1, characterized in that, Prepared from components including the following mass percentages: 22-23% plant oil, 3.2-3.5% sulfuric acid, 4.5-5% basic compound, and the balance being water.

3. The phosphate ore flotation collector according to claim 1 or 2, characterized in that, The plant oil is at least one of soybean oil, corn oil, sunflower seed oil, flaxseed oil, soybean acidified oil, corn acidified oil, sunflower seed acidified oil, and flaxseed acidified oil. The basic compound is at least one of sodium hydroxide, potassium hydroxide, and ammonia water.

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

5. The phosphate ore flotation collector according to claim 1, characterized in that, The sulfonation reaction temperature is 70-75 DEG C, and the sulfonation reaction time is 2.5h; the saponification reaction temperature is 90-95 DEG C, and the saponification reaction time is 2.5h.

6. Use of the phosphate ore flotation collector according to any one of claims 1 to 4 as a direct flotation collector for low-grade phosphate ores, characterized in that, The method comprises the following steps: preparing phosphate ore after grinding into a pulp with a concentration of 35-50wt%, heating the pulp to 33-37 DEG C, adding the phosphate ore flotation collector according to a proportion of 0.8-1.5kg / t, uniformly stirring, and then performing flotation, and obtaining refined phosphate ore after solid-liquid separation of the flotation froth.

7. Use according to claim 6, characterized in that, The low-grade phosphate ore has a phosphorus content of 6-12%.

8. Use according to claim 6, characterized in that, The phosphate ore is ground to a particle size of -0.074mm, and the portion accounts for 35-45% of the total mass of the phosphate ore, and then prepared into a pulp with a concentration of 35-50wt%.