Composite phosphorite collecting agent and preparation process thereof

Abstract

The invention belongs to the technical field of beneficiation reagents, and particularly relates to a composite phosphorite collecting agent and a preparation process thereof. The invention discloses a preparation method of a composite phosphorite collector, which comprises the following steps: dispersing sensitized quartz sand in an organic acid solution, adding a silane coupling agent, and stirring for reaction to obtain modified quartz sand; adding the obtained modified quartz sand and a polymer pore-forming agent into a sodium alginate solution, dropwise adding an alkaline amino acid solution while stirring until the pH value of the solution is 8-12, and then cooling the obtained solution to room temperature to obtain a sodium alginate copolymer coated with the modified quartz sand; and dissolving sodium oleate and small molecule amine in ethanol together, heating the obtained solution, adding the sodium alginate copolymer coated with the modified quartz sand, uniformly stirring, cooling to room temperature, adding a synergist, and uniformly stirring. The collecting agent can be used for carrying out flotation treatment on phosphorite, high-grade phosphate concentrate can be obtained, and meanwhile the collecting efficiency is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of ore dressing agents, and in particular, relates to a composite phosphate ore collector and a preparation process thereof. Background Art

[0002] Phosphate rock is a general term for phosphate minerals, the main chemical components of which are Ca 5 (PO 4 ) 3 X(X:F,Cl,OH), usually contains fluoroapatite, chloroapatite, hydroxyapatite, and carbon fluoroapatite. As the main chemical raw material of phosphorus, phosphate rock is used to manufacture phosphate fertilizer, yellow phosphorus, phosphoric acid, various phosphorus-containing additives and dyes and other industrial basic products. It is widely used in chemical, agricultural, textile, metallurgical, ceramic and other industries. It is an indispensable raw material for the development of science and technology today. Most phosphate ores need to be separated and enriched by mineral processing technology to meet the requirements of the phosphorus chemical industry. Flotation is the most commonly used and effective process technology in phosphate ore beneficiation, and collectors play a key role in the flotation process of phosphate ore, which determines the final effect of phosphate ore flotation enrichment.

[0003] At present, there are many types of collectors used in phosphate ore flotation, including anionic collectors, cationic collectors, amphoteric collectors and combined collectors. Anionic phosphorus collectors mainly include carboxylic acids, poly=O, -OH oxygen-containing acid collectors and hydroxamic acid collectors. Among them, sulfonic acid, sulfuric acid, arsenic acid and phosphoric acid oxygen-containing acid collectors have large water solubility and ionization, good water solubility and low temperature resistance, but such oxygen-containing acid collectors have poor collection properties and are generally used as compound enhancers. Hydroxamic acid has good selectivity and collection capacity in phosphate ore flotation, but hydroxamic acid collectors are expensive and have certain toxicity. Cationic collectors mainly include fatty amines, amides, ether amines and quaternary ammonium salts. Cationic collectors in phosphate ore flotation are mainly used for reverse flotation and desiliconization of phosphate ore. In the flotation pulp, amine groups can form ammonium ions, which can interact electrostatically with the mineral surface of electronegative minerals. In addition, the nitrogen atoms in the amine groups have strong hydrogen bond forming ability, so amine collectors can show multiple activities. However, amine collectors generally have poor selectivity, difficult defoaming and are only applicable to weakly alkaline pulps, making them difficult to put into practical application. Amphoteric collectors are heteropolar surfactants that contain both anionic and cationic functional groups in the molecular structure of the agent. Common types include aminocarboxylic acid type, aminosulfonic acid type, aminophosphonic acid type and aminoester type. Amphoteric collectors usually have a high dipole moment and are easy to coordinate with metal atoms on the surface of minerals to form hydrophobic and strong chelates, so they often have excellent collection performance, but their synthesis process is complicated and the production cost is high, which limits their industrial application. Summary of the invention

[0004] The primary purpose of the present invention is to provide a composite phosphate rock collector and a preparation process thereof, so as to achieve efficient collection of phosphate rock.

[0005] To this end, the present invention provides the following technical solutions.

[0006] One aspect of the present invention provides a method for preparing a composite phosphate rock collector, the method comprising the following steps:

[0007] Take 80-120 mesh sensitized quartz sand and disperse it in a 5-10wt% organic acid solution, add a silane coupling agent, and stir and react at 50-70°C for 1-3h to obtain modified quartz sand;

[0008] The modified quartz sand and the polymer pore-forming agent are added to a 10-20wt% sodium alginate solution in a mass volume ratio of 1g: 0.1-0.5g: 10-30mL, and the alkaline amino acid solution is added dropwise while stirring until the pH of the solution reaches 8-12, and then the solution is cooled to room temperature to obtain a sodium alginate copolymer coated with the modified quartz sand;

[0009] Sodium oleate and small molecular amine are dissolved in ethanol in a mass ratio of 1:0.05-0.2:10-20, and the resulting solution is heated to 40-60°C, and the obtained sodium alginate copolymer coated with modified quartz sand is added and stirred evenly. After cooling to room temperature, a synergist is added and stirred evenly.

[0010] In a preferred embodiment of the present invention, the sensitized quartz sand is made of quartz sand placed in SnCl 2 -HCl aqueous solution for 4 to 6 hours, followed by washing and drying; wherein the SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1 g:1-5 mL:50-100 mL.

[0011] In a preferred embodiment of the present invention, the organic acid is selected from any one of tartaric acid, acetic acid, oxalic acid, malic acid and citric acid.

[0012] In a preferred embodiment of the present invention, the silane coupling agent is selected from any one of 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane; and the amount of the silane coupling agent added is 1 to 3% of the mass of the sensitized quartz sand.

[0013] In a preferred embodiment of the present invention, the polymer pore-forming agent is amino-terminated hyperbranched polyamide.

[0014] In a preferred embodiment of the present invention, the basic amino acid is selected from any one of lysine, arginine, and histidine, or a mixture of two or more thereof.

[0015] In a preferred embodiment of the present invention, the small molecule amine is selected from any one of 1,2'-dinaphthylamine, diphenylamine, triphenylamine, 4,4'4"-tricarboxylic acid triphenylamine, 2-methyldiphenylamine, and 3-methyldiphenylamine.

[0016] In a preferred embodiment of the present invention, the amount of the sodium alginate copolymer coated with the modified quartz sand is 0.3 to 0.6 times the mass of sodium oleate.

[0017] In a preferred embodiment of the present invention, the synergist is selected from any one of sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dodecylbenzene sulfonate, sodium tetradecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, sodium octadecylbenzene sulfonate, or a mixture of two or more thereof.

[0018] In a preferred embodiment of the present invention, the added amount of the synergist is 0.1 to 0.2 times the mass of sodium oleate.

[0019] By means of the above technical scheme, the present invention has at least the following advantages: the present invention uses modified sodium alginate and sodium oleate as the main active substances, supplemented by a compound such as alkyl sodium sulfate or alkyl benzene sulfonate as a collector, and this type of collector is a combined amphoteric collector, which has both anionic and cationic functional groups, and can obtain high-grade phosphate concentrate, while improving the collection efficiency of phosphate ore. The present invention also forms the collector by adding quartz sand during the preparation process of the collector, so that the effective active ingredients are coated on the surface of the quartz sand particles. In addition, through the action of the polymer pore-forming agent, the final product also has a porous property, thereby giving the product adsorption properties, further improving the collection of phosphate ore. The composite collector of the present invention has good selectivity for phosphate ore and strong collection capacity. In addition, the composite collector of the present invention has good stability, a simple production route, a safe production process, and reduces the cost of mineral processing.

[0020] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the preferred embodiments of the present invention are described in detail as follows. DETAILED DESCRIPTION

[0021] In order to make the technical means, creative features, objectives and effects of the present invention easy to understand, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Unless otherwise specified, the percentage content involved in the present invention refers to mass percentage for solid-liquid mixing and solid-solid mixing, and refers to volume percentage for liquid-liquid mixing.

[0023] Unless otherwise specified, the percentage concentrations referred to in the present invention all refer to final concentrations, which refer to the percentage of the added component in the system after the addition of the component.

[0024] The temperature parameters in the present invention, if not specifically limited, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the precision range controlled by the instrument.

[0025] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.

[0026] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0027] Embodiment 1:

[0028] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0029] 80 mesh sensitized quartz sand was dispersed in 7.5 wt% acetic acid solution, 3-(meth)acryloxypropylmethyldimethoxysilane (the amount added was 2% of the mass of the sensitized quartz sand) was added, and the mixture was stirred at 60°C for 2 h to obtain modified quartz sand;

[0030] The obtained modified quartz sand and the amino-terminated hyperbranched polyamide were added to a 15wt% sodium alginate solution in a mass volume ratio of 1g:0.3g:20mL, and the lysine solution was added dropwise while stirring until the pH of the solution reached 10, and then the obtained solution was cooled to room temperature to obtain a sodium alginate copolymer coated with the modified quartz sand;

[0031] Sodium oleate and 1,2'-dinaphthylamine are dissolved in ethanol in a mass ratio of 1:0.1:15 and the resulting solution is heated to 50°C, the resulting sodium alginate copolymer coated with modified quartz sand (the added amount is 0.45 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium dodecyl sulfate (the added amount is 0.15 times the mass of sodium oleate) is added and stirred evenly.

[0032] Embodiment 2:

[0033] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0034] 90 mesh sensitized quartz sand was dispersed in a 5 wt% oxalic acid solution, 3-(meth)acryloxypropyltrimethoxysilane (the amount added was 1% of the mass of the sensitized quartz sand) was added, and the mixture was stirred at 70°C for 1 h to obtain modified quartz sand;

[0035] The obtained modified quartz sand and the amino-terminated hyperbranched polyamide were added to a 20wt% sodium alginate solution in a mass volume ratio of 1g:0.5g:30mL, and the arginine solution was added dropwise while stirring until the pH of the solution reached 8, and then the obtained solution was cooled to room temperature to obtain a sodium alginate copolymer coated with modified quartz sand;

[0036] Sodium oleate and diphenylamine are dissolved in ethanol in a mass ratio of 1:0.05:20 and the resulting solution is heated to 60°C, the resulting sodium alginate copolymer coated with modified quartz sand (the added amount is 0.3 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium tetradecyl sulfate (the added amount is 0.1 times the mass of sodium oleate) is added and stirred evenly.

[0037] Embodiment 3:

[0038] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0039] 100 mesh sensitized quartz sand was dispersed in a 10 wt % malic acid solution, 3-(meth)acryloxypropylmethyldiethoxysilane (the amount added was 3% of the mass of the sensitized quartz sand) was added, and the mixture was stirred at 50° C. for 3 h to obtain modified quartz sand;

[0040] The obtained modified quartz sand and the amino-terminated hyperbranched polyamide were added to a 10 wt% sodium alginate solution in a mass volume ratio of 1 g: 0.1 g: 10 mL, and the histidine solution was added dropwise while stirring until the pH of the solution reached 12, and then the obtained solution was cooled to room temperature to obtain a sodium alginate copolymer coated with the modified quartz sand;

[0041] Sodium oleate and triphenylamine are dissolved in ethanol in a mass ratio of 1:0.2:10 and the resulting solution is heated to 40°C, the resulting sodium alginate copolymer coated with modified quartz sand (the added amount is 0.6 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium hexadecyl sulfate (the added amount is 0.2 times the mass of sodium oleate) is added and stirred evenly.

[0042] Embodiment 4:

[0043] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0044] 110 mesh sensitized quartz sand was dispersed in a 6 wt % citric acid solution, 3-(meth)acryloxypropyltriethoxysilane (the amount added was 2% of the mass of the sensitized quartz sand) was added, and the mixture was stirred at 60° C. for 2 h to obtain modified quartz sand;

[0045] The obtained modified quartz sand and the amino-terminated hyperbranched polyamide were added to a 10 wt% sodium alginate solution in a mass volume ratio of 1 g: 0.4 g: 25 mL, and the lysine solution was added dropwise while stirring until the pH of the solution reached 9, and then the obtained solution was cooled to room temperature to obtain a sodium alginate copolymer coated with the modified quartz sand;

[0046] Sodium oleate and 2-methyldiphenylamine are dissolved in ethanol in a mass ratio of 1:0.15:15 and the resulting solution is heated to 50°C, the resulting sodium alginate copolymer coated with modified quartz sand (the added amount is 0.4 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium dodecylbenzene sulfonate (the added amount is 0.1 times the mass of sodium oleate) is added and stirred evenly.

[0047] Embodiment 5:

[0048] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0049] 120 mesh sensitized quartz sand was dispersed in a 9 wt% tartaric acid solution, 3-(meth)acryloxypropylmethyldimethoxysilane (the amount added was 3% of the mass of the sensitized quartz sand) was added, and the mixture was stirred at 50°C for 3 h to obtain modified quartz sand;

[0050] The obtained modified quartz sand and the amino-terminated hyperbranched polyamide were added to a 20wt% sodium alginate solution in a mass volume ratio of 1g:0.2g:15mL, and the arginine solution was added dropwise while stirring until the pH of the solution reached 11, and then the obtained solution was cooled to room temperature to obtain a sodium alginate copolymer coated with modified quartz sand;

[0051] Sodium oleate and 3-methyldiphenylamine are dissolved in ethanol in a mass ratio of 1:0.1:20 and the resulting solution is heated to 40°C, the obtained sodium alginate copolymer coated with modified quartz sand (the added amount is 0.5 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium tetradecylbenzene sulfonate (the added amount is 0.2 times the mass of sodium oleate) is added and stirred evenly.

[0052] Embodiment 6:

[0053] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0054] Take 80-120 mesh sensitized quartz sand and disperse it in 8wt% citric acid solution, add 3-(meth)acryloxypropyltrimethoxysilane (the addition amount is 1% of the mass of sensitized quartz sand), stir and react at 70°C for 1h to obtain modified quartz sand;

[0055] The obtained modified quartz sand and the amino-terminated hyperbranched polyamide are added to a 10-20wt% sodium alginate solution in a mass volume ratio of 1g:0.3g:20mL, and the histidine solution is added dropwise while stirring until the pH of the solution reaches 10, and then the addition is stopped, and the obtained solution is cooled to room temperature to obtain a sodium alginate copolymer coated with modified quartz sand;

[0056] Sodium oleate and 4,4'4"-triphenylamine tricarboxylate are dissolved in ethanol in a mass ratio of 1:0.15:20 and the resulting solution is heated to 60°C, and the obtained sodium alginate copolymer coated with modified quartz sand (the added amount is 0.4 times the mass of sodium oleate) is added and stirred evenly. After cooling to room temperature, sodium hexadecylbenzene sulfonate (the added amount is 0.15 times the mass of sodium oleate) is added and stirred evenly.

[0057] Comparative Example 1:

[0058] 80 mesh quartz sand was dispersed in 7.5 wt% acetic acid solution, 3-(meth)acryloxypropylmethyldimethoxysilane (the amount added was 2% of the mass of sensitized quartz sand) was added, and the mixture was stirred at 60°C for 2 h to obtain modified quartz sand;

[0059] The obtained modified quartz sand and the amino-terminated hyperbranched polyamide were added to a 15wt% sodium alginate solution in a mass volume ratio of 1g:0.3g:20mL, and the lysine solution was added dropwise while stirring until the pH of the solution reached 10, and then the obtained solution was cooled to room temperature to obtain a sodium alginate copolymer coated with the modified quartz sand;

[0060] Sodium oleate and 1,2'-dinaphthylamine are dissolved in ethanol in a mass ratio of 1:0.1:15 and the resulting solution is heated to 50°C, the resulting sodium alginate copolymer coated with modified quartz sand (the added amount is 0.45 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium dodecyl sulfate (the added amount is 0.15 times the mass of sodium oleate) is added and stirred evenly.

[0061] Comparative Example 2:

[0062] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl 2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0063] The obtained sensitized quartz sand and the amino-terminated hyperbranched polyamide were added to a 15wt% sodium alginate solution in a mass volume ratio of 1g:0.3g:20mL, and the lysine solution was added dropwise while stirring until the pH of the solution reached 10, and then the addition was stopped, and the obtained solution was cooled to room temperature to obtain a sodium alginate copolymer coated with modified quartz sand;

[0064] Sodium oleate and 1,2'-dinaphthylamine are dissolved in ethanol in a mass ratio of 1:0.1:15 and the resulting solution is heated to 50°C, the resulting sodium alginate copolymer coated with modified quartz sand (the added amount is 0.45 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium dodecyl sulfate (the added amount is 0.15 times the mass of sodium oleate) is added and stirred evenly.

[0065] Comparative Example 3:

[0066] 80 mesh quartz sand and amino-terminated hyperbranched polyamide were added to a 15 wt% sodium alginate solution in a mass volume ratio of 1 g: 0.3 g: 20 mL, and lysine solution was added dropwise while stirring until the pH of the solution reached 10, and then the solution was cooled to room temperature to obtain a sodium alginate copolymer coated with modified quartz sand;

[0067] Sodium oleate and 1,2'-dinaphthylamine are dissolved in ethanol in a mass ratio of 1:0.1:15 and the resulting solution is heated to 50°C, the resulting sodium alginate copolymer coated with modified quartz sand (the added amount is 0.45 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium dodecyl sulfate (the added amount is 0.15 times the mass of sodium oleate) is added and stirred evenly.

[0068] Comparative Example 4:

[0069] In a 15 wt % sodium alginate solution, lysine solution was added dropwise while stirring until the pH of the solution reached 10, and then the resulting solution was cooled to room temperature to obtain modified sodium alginate;

[0070] Sodium oleate and 1,2'-dinaphthylamine are dissolved in ethanol in a mass ratio of 1:0.1:15 and the resulting solution is heated to 50°C, the resulting modified sodium alginate is added (the amount added is 0.45 times the mass of sodium oleate) and stirred evenly, after cooling to room temperature, sodium dodecyl sulfate is added (the amount added is 0.15 times the mass of sodium oleate) and stirred evenly.

[0071] Comparative Example 5:

[0072] Place quartz sand in SnCl 2 -HCl aqueous solution for 5 hours, then taken out, washed and dried to obtain sensitized quartz sand; wherein the above SnCl 2 -HCl aqueous solution from SnCl2 , HCl and water are mixed in a mass volume ratio of 1g:3mL:80mL.

[0073] 80 mesh sensitized quartz sand was dispersed in 7.5 wt% acetic acid solution, 3-(meth)acryloxypropylmethyldimethoxysilane (the amount added was 2% of the mass of the sensitized quartz sand) was added, and the mixture was stirred at 60°C for 2 h to obtain modified quartz sand;

[0074] Sodium oleate and 1,2'-dinaphthylamine are dissolved in ethanol in a mass ratio of 1:0.1:15 and the resulting solution is heated to 50°C, the resulting modified quartz sand (the amount added is 0.45 times the mass of sodium oleate) is added and stirred evenly, after cooling to room temperature, sodium dodecyl sulfate (the amount added is 0.15 times the mass of sodium oleate) is added and stirred evenly.

[0075] Test example: Evaluation of the flotation effect of different collectors on phosphate ore

[0076] The collectors of Examples 1-6 and Comparative Examples 1-5 were used to 2 O 5 Phosphate ore with a content of 10.98% was subjected to froth flotation at a temperature of 20°C, with a grinding fineness of -0.074mm and a mass fraction of 65.32%. Each collector was added to the slurry at a dosage of 1.5 kg / ton of raw ore for roughing and 0.5 kg / ton of raw ore for scavenging. After a closed-circuit test of one roughing, one scavenging, and two concentrating, the final phosphate concentrate and phosphate tailings are shown in Table 1:

[0077] Table 1 Phosphate concentrate and phosphate tailings obtained with different collectors

[0078]

[0079]

[0080] It can be seen from the results in Table 1 that, compared with Comparative Examples 1-5, the collectors of Examples 1-6 of the present invention can significantly improve the capture of P in phosphate rock. 2 O 5 recovery, while increasing the P content in phosphate rock 2 O 5 grade and yield.

[0081] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes by using the methods and technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a composite phosphate rock collector, characterized in that: The method comprises the following steps: Take 80-120 mesh sensitized quartz sand and disperse it in a 5-10wt% organic acid solution, add a silane coupling agent, and stir and react at 50-70°C for 1-3h to obtain modified quartz sand; The modified quartz sand and the polymer pore-forming agent are added to a 10-20wt% sodium alginate solution in a mass volume ratio of 1g: 0.1-0.5g: 10-30mL, and the alkaline amino acid solution is added dropwise while stirring until the pH of the solution is 8-12, and then the addition is stopped, and the obtained solution is cooled to room temperature to obtain a sodium alginate copolymer coated with the modified quartz sand; Sodium oleate and small molecular amine are dissolved in ethanol in a mass ratio of 1:0.05-0.2:10-20, and the resulting solution is heated to 40-60°C, and the obtained sodium alginate copolymer coated with modified quartz sand is added and stirred evenly. After cooling to room temperature, a synergist is added and stirred evenly.

2. The method for preparing the composite phosphate rock collector according to claim 1, characterized in that: The sensitized quartz sand is obtained by soaking quartz sand in a SnCl2-HCl aqueous solution for 4 to 6 hours, followed by washing and drying; wherein the SnCl2-HCl aqueous solution is a mixture of SnCl2, HCl and water in a mass volume ratio of 1 g: 1 to 5 mL: 50 to 100 mL.

3. The method for preparing the composite phosphate rock collector according to claim 1, characterized in that: The organic acid is selected from any one of tartaric acid, acetic acid, oxalic acid, malic acid and citric acid.

4. The method for preparing the composite phosphate rock collector according to claim 1, characterized in that: The silane coupling agent is selected from any one of 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane and 3-(meth)acryloxypropyltriethoxysilane; and the added amount of the silane coupling agent is 1 to 3% of the mass of the sensitized quartz sand.

5. The method for preparing the composite phosphate rock collector according to claim 1, characterized in that: The polymer pore-forming agent is amino-terminated hyperbranched polyamide.

6. The method for preparing a composite phosphate rock collector according to claim 1, characterized in that: The basic amino acid is selected from any one of lysine, arginine and histidine or a mixture of two or more thereof.

7. The method for preparing a composite phosphate rock collector according to claim 1, characterized in that: The small molecule amine is selected from any one of 1,2'-dinaphthylamine, diphenylamine, triphenylamine, 4,4'4''-tricarboxylic acid triphenylamine, 2-methyldiphenylamine, and 3-methyldiphenylamine.

8. The method for preparing a composite phosphate rock collector according to claim 1, characterized in that: The added amount of the sodium alginate copolymer coating the modified quartz sand is 0.3 to 0.6 times the mass of the sodium oleate.

9. The method for preparing a composite phosphate rock collector according to claim 1, characterized in that: The synergist is selected from any one of sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dodecylbenzene sulfonate, sodium tetradecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, sodium octadecylbenzene sulfonate, or a mixture of two or more thereof.

10. The method for preparing a composite phosphate rock collector according to claim 1, characterized in that: The added amount of the synergist is 0.1 to 0.2 times the mass of sodium oleate.

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