A collector for low-grade phosphate rock, its preparation method and application

Abstract

This invention provides a low-grade phosphate rock collector, its preparation method, and its application. The low-grade phosphate rock collector comprises modified oleic acid, sodium oleate, and sodium dodecyl sulfonate. The components in the low-grade phosphate rock collector, by mass percentage, include: 60-80% modified oleic acid, 20-30% sodium oleate, and 5-10% sodium dodecyl sulfonate. The preparation method of this invention is simple, uses widely available raw materials, requires no complex chemical reactions or high-temperature and high-pressure conditions, requires minimal equipment investment, has low production costs, and all components are environmentally friendly agents with good biodegradability, minimizing impact on water and soil environments, thus conforming to the green and low-carbon mining development concept.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation and separation technology, and in particular to a collector for low-grade phosphate rock, its preparation method, and its application. Background Technology

[0002] Phosphate rock, as an important strategic resource, has wide applications in agriculture, chemical industry, and other fields. With the gradual depletion of high-grade phosphate rock resources, the development and utilization of low-grade phosphate rock has become a key focus of the industry. However, these types of phosphate rock generally exhibit characteristics such as fine-grained disseminated particles and complex gangue mineral composition, making traditional beneficiation processes insufficient to meet the demands of economical and efficient development. Against this backdrop, flotation technology has become the core component of phosphate rock beneficiation, and the performance of the collector directly determines the separation efficiency and production costs.

[0003] Currently, the most widely used phosphate rock collectors in industry are fatty acid compounds. While these collectors have readily available raw materials and strong collecting ability, they still have significant shortcomings in practical applications: poor selectivity, making it difficult to improve concentrate grade; weak low-temperature performance, with significantly reduced dispersibility and collecting ability at low temperatures; and sensitivity to hard water, easily forming precipitates in pulps with high calcium and magnesium ion content, affecting flotation efficiency. To overcome these defects, the industry has gradually developed compounding techniques based on synergistic effects, combining fatty acid-based main collectors with nonionic or anionic surfactants to enhance adsorption efficiency at the solid-liquid interface and optimize foam stability. However, these methods fail to fundamentally solve the problems of poor selectivity and weak low-temperature adaptability. Therefore, this invention provides a low-grade phosphate rock collector, its preparation method, and its application to address the problem of poor collecting performance of existing phosphate rock collectors at low temperatures. Summary of the Invention

[0004] The main objective of this invention is to provide a low-grade phosphate rock collector, its preparation method, and its application, aiming to solve the problem of poor collection performance of existing phosphate rock collectors under low-temperature conditions.

[0005] To achieve the above objectives, the present invention provides a low-grade phosphate rock collector, wherein the low-grade phosphate rock collector comprises modified oleic acid, sodium oleate and sodium dodecyl sulfonate.

[0006] The components of the low-grade phosphate rock collector, by mass percentage, include: 60-80% modified oleic acid, 20-30% sodium oleate, and 5-10% sodium dodecyl sulfonate.

[0007] According to an embodiment of this application, the modified oleic acid is prepared by reacting oleic acid with an aminocarboxylic acid compound.

[0008] The aminocarboxylic acid compounds include 2-(2-aminoethoxy)acetic acid.

[0009] The molar ratio of oleic acid to the aminocarboxylic acid compound is 1:1.1~1.2.

[0010] According to an embodiment of this application, the method for preparing the modified oleic acid includes: The oleic acid and the aminocarboxylic acid compound were dissolved in an organic solvent, and then a catalyst and a dehydrating agent were added to carry out an amidation reaction. After the reaction was completed, the mixture was filtered and dried to obtain the modified oleic acid.

[0011] According to embodiments of this application, the catalyst comprises 4-dimethylaminopyridine.

[0012] The dehydrating agent includes dicyclohexylcarbodiimide.

[0013] According to embodiments of this application, the organic solvent includes one or more of dichloromethane, chloroform, and ethyl acetate.

[0014] The amount of the organic solvent used is: the mass ratio of the oleic acid to the total mass of the aminocarboxylic acid compound is (3~5):1.

[0015] According to embodiments of this application, the amidation reaction step includes: The oleic acid and the aminocarboxylic acid compound are dissolved in the organic solvent, the catalyst is added, and the dehydrating agent is added dropwise under ice-water bath conditions to carry out the first reaction, and then the temperature is raised to 20~30℃ to carry out the second reaction.

[0016] The temperature of the first reaction is 0~5℃.

[0017] The duration of the first reaction is 0.5 to 1 hour.

[0018] The duration of the second reaction is 4 to 6 hours.

[0019] The dripping time is 20-30 minutes.

[0020] This invention also provides a method for preparing a collector for low-grade phosphate rock, comprising the following steps: After dissolving the modified oleic acid, sodium oleate and sodium dodecyl sulfonate are added sequentially and stirred to obtain the low-grade phosphate rock collector.

[0021] The present invention also provides an application of a low-grade phosphate rock collector, wherein the low-grade phosphate rock collector is used for the flotation of low-grade phosphate rock.

[0022] According to the embodiments of this application, the low-grade phosphate rock collector is added to the low-grade phosphate rock rough and processed using a one-roughing and two-cleaning flotation process.

[0023] 800-1500g of the low-grade phosphate rock collector is added to each ton of the low-grade phosphate rock rough.

[0024] The pH value of the flotation pulp is 9.0~10.0.

[0025] The flotation temperature is 15~35℃.

[0026] According to the embodiments of this application, concentrate, middlings and tailings are obtained after the flotation process.

[0027] The yield of the concentrate is 4.0-5.0%.

[0028] The P2O5 grade is 35.0~35.5%.

[0029] The P2O5 recovery rate was 75.0–80.0%.

[0030] Compared with the prior art, the beneficial effects of the present invention are: The aforementioned low-grade phosphate rock collector, its preparation method, and its application effectively address the technical bottleneck of the sharp decline in collection efficiency of traditional phosphate rock collectors at low temperatures through the synergistic compounding of modified oleic acid with sodium oleate and sodium dodecyl sulfonate. Specifically, the polar groups in the modified oleic acid molecular structure enhance the chemical adsorption between the reagent and the phosphate rock surface, maintaining good selectivity and collection ability even at lower temperatures, thus achieving efficient flotation recovery of low-grade phosphate rock at low temperatures. The introduction of sodium oleate regulates the hydrophilic-hydrophobic balance of the collector, enhancing bubble mineralization efficiency and improving the dispersion performance of the reagent in the aqueous phase. Sodium dodecyl sulfonate, as a surfactant component, effectively reduces the gas-liquid interfacial tension, promotes the generation and stabilization of microbubbles, and strengthens the carrying capacity and selectivity of the foam layer. This invention, through the compounding of the three components in a specific ratio, produces a significant synergistic effect, greatly improving overall collection performance. This provides effective technical support for the industrial development and utilization of large quantities of low-grade phosphate rock resources and has significant strategic resource importance.

[0031] Moreover, the preparation method of the present invention is simple, the raw materials are widely available, no complex chemical reactions and high temperature and high pressure conditions are required, the equipment investment is small, the production cost is low, and all components are environmentally friendly agents with good biodegradability and little impact on water and soil environment, which is in line with the concept of green and low-carbon mining development. Detailed Implementation

[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] The technical solutions of the various embodiments of the present invention can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0034] To achieve the above objectives, the present invention provides a low-grade phosphate rock collector, wherein the low-grade phosphate rock collector comprises modified oleic acid, sodium oleate and sodium dodecyl sulfonate.

[0035] The components of the low-grade phosphate rock collector, by mass percentage, include: 60-80% modified oleic acid, 20-30% sodium oleate, and 5-10% sodium dodecyl sulfonate.

[0036] In some embodiments, the components in the low-grade phosphate rock collector, by mass percentage, include: 60-70% modified oleic acid, 25-30% sodium oleate, and 8-10% sodium dodecyl sulfonate.

[0037] In some embodiments, the components in the low-grade phosphate rock collector, by mass percentage, include: 60-65% modified oleic acid, 28-30% sodium oleate, and 5-10% sodium dodecyl sulfonate.

[0038] In some embodiments, modified oleic acid is used as the main collector, and its selective adsorption capacity for phosphate minerals in low-grade phosphate rock is significantly enhanced through molecular structure optimization. Compared with conventional oleic acid, modified oleic acid has a stronger ability to orient its hydrophobic groups and better pulp dispersion stability, which can effectively overcome the interference of gangue minerals (such as quartz, calcite, dolomite, etc.) in low-grade phosphate rock, achieving efficient recovery of phosphate minerals and simultaneously improving concentrate grade and recovery rate.

[0039] In some embodiments, by combining modified oleic acid, sodium oleate, and sodium dodecyl sulfonate in a specific percentage ternary compound, the three components produce a significant synergistic collecting effect. Modified oleic acid provides the main collecting activity by forming stable chemical adsorption with metal ions on the surface of phosphorus minerals through its carboxyl groups. Sodium oleate, as an auxiliary collector, enhances the solubility and dispersibility of the agent in alkaline slurry and expands the effective contact area between the collector and the mineral surface. Sodium dodecyl sulfonate, as a surfactant component, reduces the surface tension of the agent solution, improves the stability and selectivity of the foam structure, and also has certain foaming properties. The synergistic effect of the three components makes the overall performance of the collector better than the simple superposition effect of a single component.

[0040] In some embodiments, modified oleic acid has a low freezing point and good low-temperature fluidity. Combined with the solubilizing effect of sodium oleate, this collector can maintain good dispersion and collecting activity at low temperatures, thus solving the technical bottleneck of traditional fatty acid collectors being prone to solidification at low temperatures and having significantly reduced efficacy.

[0041] The aforementioned low-grade phosphate rock collector, its preparation method, and its application effectively address the technical bottleneck of the sharp decline in collection efficiency of traditional phosphate rock collectors at low temperatures through the synergistic compounding of modified oleic acid with sodium oleate and sodium dodecyl sulfonate. Specifically, the polar groups in the modified oleic acid molecular structure enhance the chemical adsorption between the reagent and the phosphate rock surface, maintaining good selectivity and collection ability even at lower temperatures, thus achieving efficient flotation recovery of low-grade phosphate rock at low temperatures. The introduction of sodium oleate regulates the hydrophilic-hydrophobic balance of the collector, enhancing bubble mineralization efficiency and improving the dispersion performance of the reagent in the aqueous phase. Sodium dodecyl sulfonate, as a surfactant component, effectively reduces the gas-liquid interfacial tension, promotes the generation and stabilization of microbubbles, and strengthens the carrying capacity and selectivity of the foam layer. This invention, through the compounding of the three components in a specific ratio, produces a significant synergistic effect, greatly improving overall collection performance. This provides effective technical support for the industrial development and utilization of large quantities of low-grade phosphate rock resources and has significant strategic resource importance.

[0042] In some embodiments, the modified oleic acid is prepared by reacting oleic acid with an aminocarboxylic acid compound.

[0043] The aminocarboxylic acid compounds include 2-(2-aminoethoxy)acetic acid.

[0044] The molar ratio of oleic acid to the aminocarboxylic acid compound is 1:1.1~1.2.

[0045] In some embodiments, the molar ratio of oleic acid to the aminocarboxylic acid compound is 1:1.1~1.15.

[0046] In some embodiments, modified oleic acid is prepared by reacting oleic acid with 2-(2-aminoethoxy)acetic acid, and a bifunctional group containing ether bonds and carboxyl groups is introduced into the oleic acid molecule through an amidation / condensation reaction; wherein, the amide group and ether oxygen atom in the modified molecule can react with Ca on the surface of phosphate minerals. 2+ Mg 2+ The formation of multi-point coordination of metal ions significantly enhances the binding strength and selectivity between the agent and the phosphate mineral; the introduction of ethoxyacetic acid side chains regulates the spatial configuration of hydrophobic groups, making the agent molecules more tightly and orderly arranged on the surface of the phosphate mineral, thus improving the hydrophobic effect.

[0047] In some embodiments, precise control of the molar ratio of oleic acid to aminocarboxylic acid compounds can ensure sufficient modification of oleic acid and avoid excessive aminocarboxylic acid residue, thus balancing modification efficiency and product purity.

[0048] In some embodiments, the ethoxy structure introduced into the modified oleic acid disrupts the regular arrangement of the original oleic acid molecules, reduces the freezing point and viscosity of the product, and enables the collector to maintain good fluidity and dispersing activity at low temperatures (15℃~20℃). This solves the technical problem of low-temperature solidification and sudden drop in efficacy of traditional fatty acid collectors, extends the mineral processing cycle, and reduces the cost of heat preservation energy consumption.

[0049] In some embodiments, the method for preparing the modified oleic acid includes: The oleic acid and the aminocarboxylic acid compound were dissolved in an organic solvent, and then a catalyst and a dehydrating agent were added to carry out an amidation reaction. After the reaction was completed, the mixture was filtered and dried to obtain the modified oleic acid.

[0050] In some embodiments, the catalyst comprises 4-dimethylaminopyridine.

[0051] The dehydrating agent includes dicyclohexylcarbodiimide.

[0052] The molar ratio of the oleic acid, the aminocarboxylic acid compound, the dehydrating agent, and the catalyst is 1:1.1~1.2:1.1~1.2:0.1~0.2.

[0053] In some embodiments, the molar ratio of oleic acid: aminocarboxylic acid compound: dehydrating agent: catalyst is 1:1.1~1.15:1.1~1.2:0.15~0.2.

[0054] In some embodiments, the organic solvent includes one or more of dichloromethane, chloroform, and ethyl acetate.

[0055] The amount of the organic solvent used is: the mass ratio of the oleic acid to the total mass of the aminocarboxylic acid compound is (3~5):1.

[0056] In some embodiments, the organic solvent includes one of dichloromethane, chloroform, and ethyl acetate.

[0057] In some embodiments, the organic solvent includes dichloromethane.

[0058] In some embodiments, the amount of organic solvent used is: the mass ratio of the oleic acid to the total mass of the aminocarboxylic acid compound is (3~4):1.

[0059] In some embodiments, the amount of organic solvent used is: the mass ratio of the total mass of oleic acid to the total mass of the aminocarboxylic acid compound is (3.5~4):1.

[0060] In some embodiments, the amidation reaction step includes: The oleic acid and the 2-(2-aminoethoxy)acetic acid are dissolved in the organic solvent, the catalyst is added, and the dehydrating agent is added dropwise under ice-water bath conditions to carry out the first reaction, and then the temperature is raised to 20~30℃ to carry out the second reaction.

[0061] The temperature of the first reaction is 0~5℃.

[0062] The duration of the first reaction is 0.5 to 1 hour.

[0063] The duration of the second reaction is 4 to 6 hours.

[0064] The dripping time is 20-30 minutes.

[0065] In some embodiments, the temperature of the ice water bath is 0~5°C.

[0066] In some embodiments, the temperature of the first reaction is 0~3°C.

[0067] The duration of the first reaction is 0.5 to 1 hour.

[0068] The duration of the second reaction is 5-6 hours.

[0069] The dripping time is 25-30 minutes.

[0070] This invention also provides a method for preparing a collector for low-grade phosphate rock, comprising the following steps: After dissolving the modified oleic acid, sodium oleate and sodium dodecyl sulfonate are added sequentially and stirred to obtain the low-grade phosphate rock collector.

[0071] In some embodiments, the modified oleic acid is dissolved at 40°C to 50°C, and then sodium oleate and sodium dodecyl sulfonate are added sequentially and stirred to obtain the low-grade phosphate rock collector.

[0072] In some embodiments, the stirring rate is 150~200 r / min.

[0073] The stirring time is 20-40 minutes.

[0074] In some embodiments, the modified oleic acid is dissolved at 40°C to 45°C.

[0075] In some embodiments, the stirring rate is 180~200 r / min; the stirring time is 25~35 min.

[0076] The flotation results of the low-grade phosphate rock collector prepared in Example 1 are shown in Table 1. It should be noted that the roughing-cleansing flotation process involves one roughing and two cleaning stages. In this invention, middlings 1 refers to the tailings after the first cleaning, and middlings 2 refers to the tailings after the second cleaning.

[0077] The preparation method of this invention is simple, the raw materials are widely available, and there is no need for complex chemical reactions and high temperature and high pressure conditions. The equipment investment is small, the production cost is low, and all components are environmentally friendly agents with good biodegradability and little impact on water and soil environments, which is in line with the concept of green and low-carbon mining development.

[0078] The present invention also provides an application of the above-mentioned low-grade phosphate rock collector or the low-grade phosphate rock collector obtained by the above preparation method, wherein the low-grade phosphate rock collector is used for the flotation of low-grade phosphate rock.

[0079] In some embodiments, the low-grade phosphate rock collector is added to the low-grade phosphate rock rough and processed using a one-roughing-two-cleaning flotation process.

[0080] 800-1500g of the low-grade phosphate rock collector is added to each ton of the low-grade phosphate rock rough.

[0081] The pH value of the flotation pulp is 9.0~10.0.

[0082] The flotation temperature is 15~35℃.

[0083] In some embodiments, 800-1000g of the low-grade phosphate rock collector is added to each ton of the low-grade phosphate rock rough.

[0084] The pH value of the flotation pulp is 9.0~9.5.

[0085] The flotation temperature is 15~20℃.

[0086] In some embodiments, 900-1200g of the low-grade phosphate rock collector is added to each ton of the low-grade phosphate rock rough.

[0087] The pH value of the flotation pulp is 9.0~9.5.

[0088] The flotation temperature is 25~35℃.

[0089] In some embodiments, the flotation process yields concentrate, middlings, and tailings.

[0090] The yield of the concentrate is 4.0-5.0%.

[0091] The P2O5 grade is 35.0~35.5%.

[0092] The P2O5 recovery rate was 75.0–80.0%.

[0093] In some embodiments, the yield of the concentrate is 4.0 to 4.5%.

[0094] The P2O5 grade is 35.0~35.3%.

[0095] The P2O5 recovery rate was 77.0%–80.0%.

[0096] In some embodiments, the yield of the concentrate is 4.0 to 4.2%.

[0097] The P2O5 grade is 35.0~35.3%.

[0098] The P2O5 recovery rate was 77.0%–80.0%.

[0099] To further illustrate the present invention, the following examples are provided: Example 1 A low-grade phosphate rock collector, wherein the components of the low-grade phosphate rock collector, by mass percentage, are: 60% modified oleic acid, 30% sodium oleate, and 10% sodium dodecyl sulfonate.

[0100] Modified oleic acid was prepared by reacting oleic acid with 2-(2-aminoethoxy)acetic acid (an aminocarboxylic acid compound) in a molar ratio of 1:1.1.

[0101] The modified oleic acid was prepared as follows: oleic acid and 2-(2-aminoethoxy)acetic acid were dissolved in an organic solvent. First, 4-dimethylaminopyridine (catalyst) was added, followed by dropwise addition of dicyclohexylcarbodiimide (dehydrating agent) under ice-water bath conditions for the first reaction. Then, the temperature was raised to 25°C for the second reaction. After the reaction was completed, the mixture was filtered and dried to obtain the modified oleic acid. The temperature of the first reaction was 0°C; the duration of the first reaction was 1 h; the duration of the second reaction was 5 h; and the dropwise addition time was 30 min. The molar ratio of oleic acid:2-(2-aminoethoxy)acetic acid:dehydrating agent:catalyst was 1:1.1:1.1:0.2. The organic solvent was dichloromethane; the mass ratio of the organic solvent to the total mass of oleic acid and 2-(2-aminoethoxy)acetic acid was 4:1.

[0102] A method for preparing a collector for low-grade phosphate rock, comprising the following steps: Modified oleic acid was dissolved at 45°C, and then sodium oleate and sodium dodecyl sulfonate were added sequentially and stirred to obtain a low-grade phosphate rock collector. The stirring rate was 200 r / min and the stirring time was 30 min.

[0103] The low-grade phosphate rock collector prepared in Example 1 was added to the low-grade phosphate rock rough, and the process was carried out using a one-roughing and two-cleaning flotation process; 1000g of low-grade phosphate rock collector was added to each ton of low-grade phosphate rock rough; the pH value of the flotation pulp was 9.5; and the flotation temperature was 30℃.

[0104] The flotation results of the low-grade phosphate rock collector prepared in Example 1 are shown in Table 1. It should be noted that the roughing-cleansing flotation process involves one roughing and two cleaning stages. In this invention, middlings 1 refers to the tailings after the first cleaning, and middlings 2 refers to the tailings after the second cleaning.

[0105] Table 1. Flotation results of the low-grade phosphate rock collector prepared in Example 1 Example 2 Compared to Example 1, the mass percentages of each component in the low-grade phosphate rock collector were changed.

[0106] In Example 2, the components of the low-grade phosphate rock collector, by mass percentage, are: 70% modified oleic acid, 20% sodium oleate, and 10% sodium dodecyl sulfonate. Other steps are the same as in Example 1.

[0107] The flotation results of the low-grade phosphate rock collector prepared in Example 2 are shown in Table 2.

[0108] Table 2. Flotation results of the low-grade phosphate rock collector prepared in Example 2 Example 3 Compared to Example 1, the mass percentages of each component in the low-grade phosphate rock collector were changed.

[0109] In Example 3, the components of the low-grade phosphate rock collector, by mass percentage, are: 75% modified oleic acid, 20% sodium oleate, and 5% sodium dodecyl sulfonate. Other steps are the same as in Example 1.

[0110] The flotation results of the low-grade phosphate rock collector prepared in Example 3 are shown in Table 3.

[0111] Table 3. Flotation results of the low-grade phosphate rock collector prepared in Example 3 Comparative Example 1 Compared to Example 1, the composition of the collector for low-grade phosphate rock was changed.

[0112] In Comparative Example 1, the collector for low-grade phosphate rock was only oleic acid, and the other steps were the same as in Example 1.

[0113] The flotation results of the low-grade phosphate rock collector prepared in Comparative Example 1 are shown in Table 4.

[0114] Table 4. Flotation results of the low-grade phosphate rock collector prepared in Comparative Example 1 Comparative Example 2 Compared to Example 1, the composition of the collector for low-grade phosphate rock was changed.

[0115] In Comparative Example 2, the only low-grade phosphate rock collector used was modified oleic acid. Other steps were the same as in Example 1.

[0116] The flotation results of the low-grade phosphate rock collector prepared in Comparative Example 2 are shown in Table 5.

[0117] Table 5. Flotation results of the low-grade phosphate rock collector prepared in Comparative Example 2 The aforementioned low-grade phosphate rock collector, its preparation method, and its application effectively address the technical bottleneck of the sharp decline in collection efficiency of traditional phosphate rock collectors at low temperatures through the synergistic compounding of modified oleic acid with sodium oleate and sodium dodecyl sulfonate. Specifically, the polar groups in the modified oleic acid molecular structure enhance the chemical adsorption between the reagent and the phosphate rock surface, maintaining good selectivity and collection ability even at lower temperatures, thus achieving efficient flotation recovery of low-grade phosphate rock at low temperatures. The introduction of sodium oleate regulates the hydrophilic-hydrophobic balance of the collector, enhancing bubble mineralization efficiency and improving the dispersion performance of the reagent in the aqueous phase. Sodium dodecyl sulfonate, as a surfactant component, effectively reduces the gas-liquid interfacial tension, promotes the generation and stabilization of microbubbles, and strengthens the carrying capacity and selectivity of the foam layer. This invention, through the compounding of the three components in a specific ratio, produces a significant synergistic effect, greatly improving overall collection performance. This provides effective technical support for the industrial development and utilization of large quantities of low-grade phosphate rock resources and has significant strategic resource importance.

[0118] Moreover, the preparation method of the present invention is simple, the raw materials are widely available, no complex chemical reactions and high temperature and high pressure conditions are required, the equipment investment is small, the production cost is low, and all components are environmentally friendly agents with good biodegradability and little impact on water and soil environment, which is in line with the concept of green and low-carbon mining development.

[0119] In summary, the above technical solutions of the present invention are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made using the contents of the present invention under the technical concept of the present invention, or direct / indirect applications in other related technical fields, are included in the patent protection scope of the present invention.

Claims

1. A collector for low-grade phosphate rock, characterized in that, The low-grade phosphate rock collector includes modified oleic acid, sodium oleate, and sodium dodecyl sulfonate. The components of the low-grade phosphate rock collector, by mass percentage, include: 60-80% modified oleic acid, 20-30% sodium oleate, and 5-10% sodium dodecyl sulfonate.

2. The low-grade phosphate rock collector according to claim 1, characterized in that, The modified oleic acid was prepared by reacting oleic acid with aminocarboxylic acid compounds; The aminocarboxylic acid compounds include 2-(2-aminoethoxy)acetic acid; The molar ratio of oleic acid to the aminocarboxylic acid compound is 1:1.1~1.

2.

3. The low-grade phosphate rock collector according to claim 1 or 2, characterized in that, The method for preparing the modified oleic acid includes: The oleic acid and the aminocarboxylic acid compound were dissolved in an organic solvent, and then a catalyst and a dehydrating agent were added to carry out an amidation reaction. After the reaction was completed, the mixture was filtered and dried to obtain the modified oleic acid.

4. The low-grade phosphate rock collector according to claim 3, characterized in that, The catalyst includes 4-dimethylaminopyridine; The dehydrating agent includes dicyclohexylcarbodiimide; The molar ratio of the oleic acid, the aminocarboxylic acid compound, the dehydrating agent, and the catalyst is 1:1.1~1.2:1.1~1.2:0.1~0.

2.

5. The low-grade phosphate rock collector according to claim 3, characterized in that, The organic solvent includes one or more of dichloromethane, chloroform, and ethyl acetate; The amount of the organic solvent used is: the mass ratio of the oleic acid to the total mass of the aminocarboxylic acid compound is (3~5):

1.

6. The low-grade phosphate rock collector according to claim 3, characterized in that, The amidation reaction step includes: The oleic acid and the aminocarboxylic acid compound are dissolved in the organic solvent, the catalyst is added, and the dehydrating agent is added dropwise under ice-water bath conditions to carry out the first reaction, and then the temperature is raised to 20~30℃ to carry out the second reaction; The temperature of the first reaction is 0~5℃; The duration of the first reaction is 0.5~1h; The duration of the second reaction is 4-6 hours; The dripping time is 20-30 minutes.

7. A method for preparing a low-grade phosphate rock collector as described in any one of claims 1 to 6, characterized in that, Includes the following steps: After dissolving the modified oleic acid, sodium oleate and sodium dodecyl sulfonate are added sequentially and stirred to obtain the low-grade phosphate rock collector.

8. The application of a low-grade phosphate rock collector as described in any one of claims 1 to 6, characterized in that, The low-grade phosphate rock collector is used for the flotation of low-grade phosphate rock.

9. The application of the low-grade phosphate rock collector according to claim 8, characterized in that, The low-grade phosphate rock collector is added to the low-grade phosphate rock rough, and then processed using a one-roughing and two-cleaning flotation process. Add 800-1500g of the low-grade phosphate rock collector to each ton of the low-grade phosphate rock rough; The pH value of the flotation pulp is 9.0~10.0; The flotation temperature is 15~35℃.

10. The application of the low-grade phosphate rock collector according to claim 9, characterized in that, The flotation process yields concentrate, middlings, and tailings. The yield of the concentrate is 4.0-5.0%; The P2O5 grade is 35.0~35.5%; The P2O5 recovery rate was 75.0–80.0%.

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