Production process of an efficient polyaluminum chloride-based composite flocculant

Abstract

The invention discloses a production process of an efficient polyaluminum chloride-based composite flocculant, which includes adding tourmaline into ethanol for low-temperature ball milling treatment to obtain tourmaline fine powder; performing low-temperature grinding treatment on vermiculite, then successively adding tourmaline, aluminum isopropoxide and trichloromethylsilane and stirring, and obtaining a prefabricated vermiculite carrier after dispersion and granulation; standing the prefabricated vermiculite carrier for 1-2 h, then standing at a constant temperature for 3-5 h, then soaking it in an alkali solution for 20-30 min, performing ultrasonic treatment for 5-10 min, filtering and sintering to obtain porous mixed vermiculite; mixing dimethyldiallylammonium chloride and polyaluminum chloride evenly, then putting them into the porous mixed vermiculite and stirring evenly, then performing microwave oscillation treatment for 1-2 h, taking out the porous mixed vermiculite particles, which are the prefabricated flocculant; standing the prefabricated flocculant for 1-2 h, and obtaining an efficient flocculant after freeze-drying. The invention utilizes vermiculite to improve the sedimentation characteristics of the flocculant, combines with the negative ion adsorption of tourmaline, aggregates the flocs of dimethyldiallylammonium chloride and polyaluminum chloride, reduces the dispersion problem of the flocs, and achieves the balance of adsorption, sedimentation and flocculation.

Description

Technical Field

[0001] The present invention belongs to the technical field of water treatment agents, and particularly relates to a production process of a high-efficiency polyaluminum chloride-based composite flocculant. Background Art

[0002] The flocculation precipitation method is a relatively widely used method in water treatment applications. It has the advantages of economy, high efficiency, simple process, and convenient operation, and is widely used in fields such as seawater desalination, drinking water, aquaculture wastewater, fermentation wastewater, food processing, and civil dredging projects. Currently, the widely used flocculants are polyaluminum chloride and. Polyaluminum chloride itself has good net trapping ability and adsorption ability, but its electro-neutralization ability is weak, the formed flocculation structure is relatively loose, and part of it is extremely likely to float, with poor sedimentation performance, which affects the subsequent process. Therefore, there is a need in the current market for a flocculant that combines deflocculation, flocculation, precipitation, and adsorption. Summary of the Invention

[0003] Aiming at the problems in the prior art, the present invention provides a production process of a high-efficiency polyaluminum chloride-based composite flocculant, which solves the problem that the existing flocculants are easy to float. It uses vermiculite to improve the sedimentation characteristics of the flocculant, combines with the negative ion adsorption of tourmaline, aggregates the flocs of dimethyldiallylammonium chloride and polyaluminum chloride, reduces the dispersion problem of the flocs, and achieves the balance of adsorption, sedimentation, and flocculation.

[0004] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0005] A production process of a high-efficiency polyaluminum chloride-based composite flocculant includes the following steps:

[0006] Step 1: Add tourmaline to ethanol and perform low-temperature ball milling treatment to form fine particles, and obtain tourmaline fine powder through spray drying. The mass ratio of tourmaline to ethanol is 20 - 30:1, the temperature of the low-temperature ball milling treatment is 5 - 10°C, the ball milling uses zirconia balls with a diameter of 2 - 3 mm, and the ball-to-material ratio is 20 - 25:1. The self-rotation speed of the ball milling is 500 - 800 r / min, the revolution rate is 100 - 200 r / min, and the ball milling time is 2 - 3 h. The temperature of the spray drying is 80 - 90°C, and the spray rate is 10 - 20 g / min. This step uses tourmaline to form a wet ball milling system in ethanol, grinds tourmaline into fine powder particles using the firmness of zirconia balls themselves, and forms a flowing ball milling effect using the fluidity of ethanol itself to ensure the homogenization of the fine powder particles. Finally, ethanol is removed in the spray drying to achieve the drying effect.

[0007] Step 2, placing vermiculite in ether for low-temperature ball milling to obtain vermiculite fine powder, then adding tourmaline, aluminum isopropoxide and trichloromethylsilane in sequence for stirring, and dissolving and dispersing at low temperature for 20-30 minutes, and obtaining a prefabricated vermiculite carrier after granulation, wherein the mass ratio of vermiculite to ether is 2-3:1, the temperature of low-temperature ball milling is 5-10°C, the ball milling uses zirconium dioxide balls with a diameter of 2-3mm, and the ball-to-material ratio is 10-15:1, and the ball milling speed is 200-3000rpm. The speed is 500-800r / min, the rotation speed is 100-200r / min, the ball milling time is 1-2h, the amount of tourmaline added is 5-8% of the mass of vermiculite, the amount of aluminum isopropoxide added is 20-30% of the mass of vermiculite fine powder, the amount of trichloromethylsilane added is 3-5% of the mass of vermiculite, the stirring speed is 200-500r / min, the dissolution adopts a mixed solution of ether and isopropanol, and the volume of ether and isopropanol is 20-30%. The ratio is 10-15:1, and the concentration of the vermiculite after dissolution is 200-500g / L, the temperature of the low-temperature ultrasonic dispersion is 5-10°C, the ultrasonic frequency is 40-80kHz, the temperature of the granulation is 40-50°C, and the pressure is 0.4-0.6MPa. This step utilizes low-temperature wet ball milling of vermiculite in ether to finely pulverize the vermiculite and form a particle size structure similar to that of tourmaline, thereby achieving homogenized dispersion; utilizing the solubility of isopropyl alcohol and ether to and the solubility of aluminum isopropoxide and trichloromethylsilane in the solvent, respectively, to form a homogenized system, and with the tourmaline fully mixed in the vermiculite, a homogenous structural system is formed. During the granulation process, the volatility of isopropanol and the low boiling point of ether can quickly remove the solvent to form a homogenous dispersion effect. At this time, in the particles formed by granulation, the vermiculite uniformly wraps the tourmaline, and the surrounding is doped with aluminum isopropoxide and trichloromethylsilane; the vermiculite is calcined vermiculite;

[0008] Step 3: Let the prefabricated vermiculite carrier stand for 1 - 2 h, then keep it standing at a constant temperature for 3 - 5 h, then soak it in an alkali solution for 20 - 30 min, perform ultrasonic treatment for 5 - 10 min, filter and then sinter to obtain porous mixed vermiculite; the atmosphere for the standing treatment is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:20 - 25, the temperature for the standing treatment is 30 - 40 °C, the pressure is 110 - 120% of the atmospheric pressure, the pressure for the constant-temperature standing is 110 - 120% of the atmospheric pressure, the temperature is 110 - 130 °C, and the heating rate is 10 - 20 °C / min; the alkali solution is a sodium hydroxide solution with a pH of 8, the soaking temperature is 10 - 20 °C, the ultrasonic frequency for the ultrasonic treatment is 50 - 80 kHz, the temperature is 20 - 30 °C, and the sintering temperature is 500 - 550 °C; in this step, the prefabricated vermiculite particles are placed in an atmosphere containing water vapor by the standing treatment method, the water molecules are aggregated by the water absorption characteristics of vermiculite itself, and the water molecules are promoted to form an in-situ hydrolysis reaction with trichloromethylsilane and aluminum isopropoxide, and the condensation reaction of the silane hydrolyzate is ensured by the constant-temperature standing and gradual heating methods, forming a certain supportability, ensuring a certain connectivity of the vermiculite, and ensuring the stability of its own structure in the subsequent process. When aluminum hydroxide reacts during soaking in the alkali solution, it is converted into soluble meta-aluminate. At this time, the vermiculite absorbs water and expands, opening the pores, promoting the inward penetration of sodium hydroxide to directly contact aluminum hydroxide, and releasing it after dissolution and cooperation with ultrasonic waves; after sintering treatment, the water is removed to obtain vermiculite particles with a porous structure;

[0009] Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into the porous mixed vermiculite and stir evenly, then perform microwave oscillation treatment for 1 - 2 h, take out the porous mixed vermiculite particles, which are the prefabricated flocculant. The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride is 1:8 - 10, the addition amount of the porous mixed vermiculite is 10 - 40% of the mass of polyaluminum chloride, the stirring speed is 200 - 400 r / min, and the microwave power for the microwave oscillation treatment is 300 - 500 W, and the temperature is 30 - 40 °C; in this step, dimethyldiallylammonium chloride and polyaluminum chloride are mixed, and after being mixed with the porous mixed vermiculite, microwave oscillation is performed to penetrate the mixed dimethyldiallylammonium chloride and polyaluminum chloride into the porous mixed vermiculite, achieving excellent penetration and filling properties, completely blocking the porous mixed vermiculite. At this time, tourmaline can release negative ions and has a certain charge adsorption on dimethyldiallylammonium chloride and polyaluminum chloride, realizing the fixation effect of this structure;

[0010] Step 5: Let the prefabricated flocculant stand for 1 - 2 h, and then obtain the high - efficiency flocculant through freeze - drying. The atmosphere for the standing treatment is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor, with the volume ratio of nitrogen to water vapor being 20 - 25:1. The temperature for the standing treatment is 20 - 30 °C, and the pressure is atmospheric pressure. The temperature for the freeze - drying treatment is - 20 °C. In this step, a stable atmosphere is formed by water vapor and nitrogen, and vermiculite can absorb the water vapor in the air and form a certain absorption and expansion. The dimethyldiallylammonium chloride and polyaluminum chloride in the porous structure are clamped and solidified, and water molecules are also absorbed by dimethyldiallylammonium chloride and polyaluminum chloride. Therefore, after absorbing water molecules, some of the properties of dimethyldiallylammonium chloride and polyaluminum chloride are revealed and fixed in the porous vermiculite, forming an excellent fixing effect. During the freeze - drying process, some of the exposed water molecules are removed to ensure a stable balance of water molecules in the prefabricated flocculant.

[0011] The high - efficiency flocculant contains flocculation and adsorption materials such as vermiculite, dimethyldiallylammonium chloride, and polyaluminum chloride. When treating wastewater, vermiculite forms softening and expansion after absorbing water. At the same time, based on the framework structure of silane, it ensures that the expanded vermiculite does not loosen and maintains its own stability, improving the particle connectivity inside the vermiculite. Dimethyldiallylammonium chloride and polyaluminum chloride themselves are fast - flocculating materials and form an outward expansion. Their own charge characteristics cooperate with the tourmaline molecules in the vermiculite to form charge polymerization, effectively improving the phenomenon of loose flocs of dimethyldiallylammonium chloride and polyaluminum chloride and realizing an aggregated floc structure. It should be particularly noted that after vermiculite absorbs water, it will quickly form a dense void structure, which does not affect its adsorption in water and ensures that the charge adsorption of tourmaline to metal ions is affected by the electrical insulation of vermiculite.

[0012] Furthermore, vermiculite itself has certain water absorption and swelling characteristics, which will bring about a void structure. This structure can ensure the normal entry of metal ions and ensure its good metal ion removal effect. However, the negative ion release range of tourmaline itself is relatively limited, and it can only capture metal ions in a local area, which is only within the vermiculite and cannot extend outward, resulting in poor effects. At the same time, based on the electrical insulation of vermiculite, the charge system has a certain effect on the electro-neutralization adsorption of dimethyldiallylammonium chloride and polyaluminum chloride, but the effective radiation range is relatively limited. Therefore, modified vermiculite is used, and the modified vermiculite is titanium dioxide-modified vermiculite. Titanium dioxide itself has good electrical transfer effects, which can ensure the rotation of negative ions on the surface of tourmaline. Combining with the formation of surface hydroxyl structures by titanium dioxide in water can effectively improve its surface activity, increase the hydroxyl activity on the surface of vermiculite, and greatly expand the radiation range of tourmaline. From another perspective, titanium dioxide, as a charge extension material, forms a rapid surface charge rotation, enhancing the charge influence range. The preparation method of the titanium dioxide-modified vermiculite includes the following steps: a1, put vermiculite into ethanol, stir evenly, and carry out ball milling for 2 - 3 h, then carry out dilution stirring for 0.5 - 1 h, and filter to obtain vermiculite particles adsorbed with ethanol. The mass ratio of vermiculite to ethanol is 5 - 8:1, the stirring speed is 400 - 600 r / min. The ball milling uses zirconia balls with a diameter of 2 - 3 mm, and the ball-to-material ratio is 10 - 15:1. The self-rotation speed of ball milling is 500 - 800 r / min, and the revolution rate is 100 - 200 r / min. The solvent for dilution is ethanol, the stirring speed is 500 - 1000 r / min, and the concentration of vermiculite after dilution is 200 - 400 g / L. This step uses ball milling of vermiculite in ethanol to achieve the refinement of vermiculite, and at the same time uses the dilution method to promote the saturation of vermiculite's adsorption of ethanol. The vermiculite at this time is commercially available expanded vermiculite;a2. Add tetrabutyl titanate to diethyl ether and stir evenly to form a homogeneous solution. Then spray the homogeneous solution onto the surface of vermiculite particles, let it stand at a low temperature for 20 - 30 min, and then raise the temperature and let it stand for 1 - 2 h to obtain prefabricated vermiculite particles. The concentration of tetrabutyl titanate in diethyl ether is 200 - 500 g / L, the stirring speed is 200 - 500 r / min, the spraying speed is 1 - 2 mL / min, and the spraying weight is 10 - 30% of the mass of vermiculite particles. The temperature of the low-temperature standing is 5 - 10 °C, the temperature of the temperature-raising standing is 40 - 50 °C, and the temperature-raising speed is 3 - 5 °C / min. In this step, a homogeneous solution is formed by the solubility of diethyl ether in tetrabutyl titanate, and the diethyl ether solution carrying tetrabutyl titanate is evenly dispersed on the surface of vermiculite particles by spraying. Considering the compatibility of ethanol and diethyl ether in vermiculite and the solubility of tetrabutyl titanate in ethanol, a dissolution and penetration system of tetrabutyl titanate is formed. When diethyl ether volatilizes due to heat, tetrabutyl titanate penetrates into vermiculite as diethyl ether decreases and ethanol dissolves, achieving an excellent transfer effect. At this time, tetrabutyl titanate transfers into vermiculite and dissolves in ethanol. a3. Put the prefabricated vermiculite particles into a reaction kettle and let them stand and react at a constant temperature for 20 - 30 min, and then perform a constant-temperature sintering treatment for 1 - 2 h. After secondary temperature-raising sintering, modified vermiculite is obtained. The atmosphere of the constant-temperature standing is a mixed atmosphere of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 10 - 15:1. The temperature of the constant-temperature standing is 30 - 50 °C, and the pressure is 120 - 150% of the atmospheric pressure. The temperature of the constant-temperature sintering treatment is 200 - 300 °C, and the temperature of the secondary temperature-raising sintering is 500 - 520 °C, and the sintering time is 10 - 20 min. In this step, the water vapor in the atmosphere is absorbed into vermiculite by using the water vapor environment and the absorbency of vermiculite and ethanol to water, promoting the hydrolysis reaction of tetrabutyl titanate in vermiculite. At the same time, ethanol is removed during the constant-temperature sintering, and the hydrolysis product of tetrabutyl titanate is polycondensed to form active titanium dioxide. With the adsorption property of vermiculite itself, a tight binding effect is achieved. During the secondary temperature-raising sintering, the water molecules in vermiculite are completely removed, and at the same time, the structural stability of titanium dioxide is achieved, that is, not only the shrinkage and solidification of vermiculite after losing water but also the charge attraction between the inner layers of vermiculite result in chemical bond solidification between titanium dioxide and vermiculite. The titanium dioxide-modified vermiculite prepared by this scheme shows good attractiveness to titanium dioxide by the negative ions of tourmaline when stirred with tourmaline, promoting the aggregation of titanium dioxide-modified vermiculite towards tourmaline, thus achieving a high-quality and tight aggregate structure. At the same time, as a negative ion conduction material, titanium dioxide can accelerate the transmission speed and range of negative ions, making the entire vermiculite exhibit negative ion characteristics and improving the electroadsorption characteristics.

[0013] Further, the dimethyldiallylammonium chloride and the polyaluminum chloride are ground before mixing to make the dimethyldiallylammonium chloride and the polyaluminum chloride reach the micron level. This micron-level powder can have excellent void permeability and achieve a stable penetration effect during microwave treatment, which helps to completely seal the porous mixed vermiculite.

[0014] The dosage of the flocculant in the wastewater is 0.2-0.5% of the wastewater quality.

[0015] As can be seen from the above description, the present invention has the following advantages:

[0016] 1. The present invention solves the problem that the existing flocculants are prone to floating, uses vermiculite to improve the sedimentation characteristics of the flocculant, and combines with the negative ion adsorption of tourmaline to aggregate the flocs of dimethyldiallylammonium chloride and polyaluminum chloride, reducing the dispersion problem of the flocs, and achieving the balance of adsorption, sedimentation and flocculation.

[0017] 2. The present invention improves the electrical insulation characteristics of vermiculite by means of titanium dioxide modification, effectively improves the electrical adsorption characteristics of negative ions, and greatly improves the efficiency of the flocculant.

[0018] 3. The present invention uses aluminum isopropoxide as a pore-forming material, combines with its alkaline dissolution characteristics to form a stable pore-forming system, and the produced aluminum ion-containing waste liquid can be used in the preparation process of alumina materials. Specific Embodiments

[0019] The present invention will be described in detail in conjunction with the embodiments, but no limitations will be made to the claims of the present invention.

[0020] Embodiment 1

[0021] A production process of a high-efficiency polyaluminum chloride-based composite flocculant includes the following steps:

[0022] Step 1, adding tourmaline into ethanol for low-temperature ball milling treatment to form fine particles, and obtaining tourmaline fine powder through spray drying; the mass ratio of the tourmaline to ethanol is 20:1, the temperature of the low-temperature ball milling treatment is 5°C, the zirconia balls with a diameter of 2 mm are used for ball milling, and the ball-to-material ratio is 20:1, the rotation speed of the ball milling is 500 r / min, the revolution rate is 100 r / min, and the ball milling time is 2 h; the temperature of the spray drying is 80°C, and the spray amount is 10 g / min;

[0023] Step 2: Put vermiculite into ether for low-temperature ball milling to obtain vermiculite fine powder. Then, successively add tourmaline, aluminum isopropoxide, and trichloromethylsilane, stir, and after dilution, disperse by low-temperature ultrasonic wave for 20 min. After granulation, a prefabricated vermiculite carrier is obtained. The mass ratio of vermiculite to ether is 2:1. The temperature of the low-temperature ball milling treatment is 5°C. The zirconia balls with a diameter of 2 mm are used for ball milling, and the ball-to-material ratio is 10:1. The rotation speed of the ball milling is 500 r / min, the revolution rate is 100 r / min, and the ball milling time is 1 h. The addition amount of tourmaline is 5-8% of the mass of vermiculite. The addition amount of aluminum isopropoxide is 20% of the mass of vermiculite fine powder. The addition amount of trichloromethylsilane is 3% of the mass of vermiculite. The stirring speed is 200 r / min. The dilution uses a mixed solution of ether and isopropanol. The volume ratio of ether to isopropanol is 10:1, and the concentration of vermiculite after dilution is 200 g / L. The temperature of the low-temperature ultrasonic dispersion is 5°C, and the ultrasonic frequency is 40 kHz. The temperature of the granulation is 40°C, and the pressure is 0.4 MPa;

[0024] Step 3: Let the prefabricated vermiculite carrier stand for 1 h, then stand at a constant temperature for 3-5 h, and then soak it in an alkali solution for 20 min, perform ultrasonic treatment for 5 min, filter, and sinter to obtain porous mixed vermiculite. The atmosphere of the standing treatment is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:20. The temperature of the standing treatment is 30°C, and the pressure is 110% of the atmospheric pressure. The pressure of the constant-temperature standing is 110% of the atmospheric pressure, and the temperature is 110°C. The heating rate is 10°C / min. The alkali solution uses a sodium hydroxide solution with a pH of 8. The soaking temperature is 10°C. The ultrasonic frequency of the ultrasonic treatment is 50 kHz, and the temperature is 20°C. The sintering temperature is 500°C;

[0025] Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into the porous mixed vermiculite and stir evenly, and then perform microwave oscillation treatment for 1 h. Take out the porous mixed vermiculite particles, which are the prefabricated flocculant. The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride is 1:8. The addition amount of the porous mixed vermiculite is 10% of the mass of polyaluminum chloride. The stirring speed is 200 r / min. The microwave power of the microwave oscillation treatment is 300 W, and the temperature is 30°C. Dimethyldiallylammonium chloride and polyaluminum chloride are ground before mixing to make dimethyldiallylammonium chloride and polyaluminum chloride reach the micron level;

[0026] Step 5: Let the prefabricated flocculant stand for 1 h, and obtain a high-efficiency flocculant after freeze-drying. The atmosphere of the standing treatment is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor. The volume ratio of nitrogen to water vapor is 20:1. The temperature of the standing treatment is 20°C, and the pressure is the atmospheric pressure. The temperature of the freeze-drying treatment is -20°C.

[0027] Example 2

[0028] A production process of an efficient polyaluminum chloride-based composite flocculant includes the following steps:

[0029] Step 1: Add tourmaline into ethanol and conduct low-temperature ball milling treatment to form fine particles, and then obtain tourmaline fine powder through spray drying. The mass ratio of tourmaline to ethanol is 30:1, the temperature of the low-temperature ball milling treatment is 10°C, the zirconia balls with a diameter of 3 mm are used for ball milling, and the ball-to-material ratio is 25:1. The self-rotation speed of the ball milling is 800 r / min, the revolution rate is 200 r / min, and the ball milling time is 3 h. The temperature of the spray drying is 90, and the spray rate is 20 g / min;

[0030] Step 2: Put vermiculite into ether for low-temperature ball milling treatment to obtain vermiculite fine powder, then successively add tourmaline, aluminum isopropoxide, and trichloromethylsilane and stir. After expansion and dissolution, conduct low-temperature ultrasonic dispersion for 30 min, and then obtain a prefabricated vermiculite carrier through granulation. The mass ratio of vermiculite to ether is 3:1, the temperature of the low-temperature ball milling treatment is 10°C, the zirconia balls with a diameter of 3 mm are used for ball milling, and the ball-to-material ratio is 15:1. The self-rotation speed of the ball milling is 800 r / min, the revolution rate is 200 r / min, and the ball milling time is 2 h. The addition amount of tourmaline is 8% of the mass of vermiculite, the addition amount of aluminum isopropoxide is 30% of the mass of vermiculite fine powder, the addition amount of trichloromethylsilane is 3 - 5% of the mass of vermiculite, the stirring speed is 500 r / min, the expansion and dissolution adopt a mixed solution of ether and isopropanol, the volume ratio of ether to isopropanol is 15:1, and the concentration of vermiculite after expansion and dissolution is 500 g / L. The temperature of the low-temperature ultrasonic dispersion is 10°C, the ultrasonic frequency is 80 kHz, the temperature of the granulation is 50°C, and the pressure is 0.4 - 0.6 MPa;

[0031] Step 3: Let the prefabricated vermiculite carrier stand for 2 h, then stand at a constant temperature for 5 h, then soak it in an alkali solution for 30 min, conduct ultrasonic treatment for 10 min, filter and then sinter to obtain porous mixed vermiculite. The atmosphere of the standing treatment is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:25. The temperature of the standing treatment is 40°C, and the pressure is 120% of the atmospheric pressure. The pressure of the constant-temperature standing is 120% of the atmospheric pressure, and the temperature is 130°C, and the heating rate is 20°C / min. The alkali solution uses a sodium hydroxide solution with a pH of 8, the soaking temperature is 20°C, the ultrasonic frequency of the ultrasonic treatment is 80 kHz, and the temperature is 30°C. The sintering temperature is 550°C;

[0032] Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into porous mixed vermiculite and stir evenly. Then, perform microwave oscillation treatment for 2 h. Take out the porous mixed vermiculite particles, which are the prefabricated flocculant. The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride is 1:10. The addition amount of the porous mixed vermiculite is 40% of the mass of polyaluminum chloride. The stirring speed is 400 r / min. The microwave power of the microwave oscillation treatment is 500 W, and the temperature is 40 °C. Before mixing, dimethyldiallylammonium chloride and polyaluminum chloride are ground to reach the micron level.

[0033] Step 5: Let the prefabricated flocculant stand for 2 h, and then obtain the high-efficiency flocculant after freeze-drying. The atmosphere for the standing treatment is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor. The volume ratio of nitrogen to water vapor is 25:1. The temperature for the standing treatment is 30 °C, and the pressure is atmospheric pressure. The temperature for the freeze-drying treatment is -20 °C.

[0034] Example 3

[0035] A production process of a high-efficiency polyaluminum chloride-based composite flocculant includes the following steps:

[0036] Step 1: Add tourmaline to ethanol and perform low-temperature ball milling treatment to form fine particles. After spray drying, obtain tourmaline fine powder. The mass ratio of tourmaline to ethanol is 25:1. The temperature for the low-temperature ball milling treatment is 8 °C. Zirconia balls with a diameter of 3 mm are used for ball milling, and the ball-to-material ratio is 22:1. The rotation speed of the ball milling is 700 r / min, and the revolution rate is 150 r / min. The ball milling time is 3 h. The temperature for the spray drying is 85, and the spray rate is 15 g / min.

[0037] Step 2: Put vermiculite into ether and perform low-temperature ball milling treatment to obtain vermiculite fine powder. Then, successively add tourmaline, aluminum isopropoxide, and trichloromethylsilane and stir. After expansion and dissolution, perform low-temperature ultrasonic dispersion for 25 min. After granulation, obtain the prefabricated vermiculite carrier. The mass ratio of vermiculite to ether is 3:1. The temperature for the low-temperature ball milling treatment is 8 °C. Zirconia balls with a diameter of 3 mm are used for ball milling, and the ball-to-material ratio is 13:1. The rotation speed of the ball milling is 700 r / min, and the revolution rate is 200 r / min. The ball milling time is 2 h. The addition amount of tourmaline is 5-8% of the mass of vermiculite. The addition amount of aluminum isopropoxide is 25% of the mass of vermiculite fine powder. The addition amount of trichloromethylsilane is 4% of the mass of vermiculite. The stirring speed is 400 r / min. The expansion and dissolution use a mixed solution of ether and isopropanol. The volume ratio of ether to isopropanol is 13:1, and the concentration of vermiculite after expansion and dissolution is 400 g / L. The temperature for the low-temperature ultrasonic dispersion is 8 °C, and the ultrasonic frequency is 60 kHz. The temperature for the granulation is 45 °C, and the pressure is 0.5 MPa.

[0038] Step 3: Let the prefabricated vermiculite carrier stand for 2 h, then stand at a constant temperature for 4 h, then soak it in an alkali solution for 25 min, perform ultrasonic treatment for 8 min, filter and sinter it to obtain porous mixed vermiculite; the atmosphere for the standing treatment is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:23, the temperature for the standing treatment is 35°C, and the pressure is 115% of the atmospheric pressure. The pressure for the constant-temperature standing is 115% of the atmospheric pressure, the temperature is 120°C, and the heating rate is 15°C / min; the alkali solution is a sodium hydroxide solution with a pH of 8, the soaking temperature is 15°C, the ultrasonic frequency for the ultrasonic treatment is 70 kHz, and the temperature is 25°C. The sintering temperature is 530°C;

[0039] Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into the porous mixed vermiculite and stir evenly, then perform microwave oscillation treatment for 2 h, take out the porous mixed vermiculite particles, which are the prefabricated flocculant. The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride is 1:9, the addition amount of the porous mixed vermiculite is 30% of the mass of polyaluminum chloride, the stirring speed is 300 r / min, the microwave power for the microwave oscillation treatment is 400 W, and the temperature is 35°C; dimethyldiallylammonium chloride and polyaluminum chloride are ground before mixing to make dimethyldiallylammonium chloride and polyaluminum chloride reach the micron level;

[0040] Step 5: Let the prefabricated flocculant stand for 2 h, and obtain a high-efficiency flocculant after freeze-drying; the atmosphere for the standing treatment is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 23:1. The temperature for the standing treatment is 25°C, and the pressure is the atmospheric pressure. The temperature for the freeze-drying treatment is -20°C.

[0041] Example 4

[0042] A production process of a high-efficiency polyaluminum chloride-based composite flocculant includes the following steps:

[0043] Step 1: Add tourmaline to ethanol and perform low-temperature ball milling treatment to form fine particles, and obtain tourmaline fine powder through spray drying; the mass ratio of tourmaline to ethanol is 25:1, the temperature for the low-temperature ball milling treatment is 8°C, the ball milling uses zirconia balls with a diameter of 3 mm, and the ball-to-material ratio is 22:1. The self-rotation speed of the ball milling is 700 r / min, the revolution rate is 150 r / min, and the ball milling time is 3 h; the temperature for the spray drying is 85, and the spray amount is 15 g / min;

[0044] Step 2: Put vermiculite into ether for cryogenic ball milling to obtain vermiculite fine powder. Then, successively add tourmaline, aluminum isopropoxide, and trichloromethylsilane and stir. After dilution, perform low-temperature ultrasonic dispersion for 25 min. After granulation, a prefabricated vermiculite carrier is obtained. The mass ratio of vermiculite to ether is 3:1. The temperature of the cryogenic ball milling treatment is 8°C. Zirconia balls with a diameter of 3 mm are used for ball milling, and the ball-to-material ratio is 13:1. The self-rotation speed of the ball milling is 700 r / min, the revolution rate is 200 r / min, and the ball milling time is 2 h. The addition amount of tourmaline is 5-8% of the mass of vermiculite. The addition amount of aluminum isopropoxide is 25% of the mass of vermiculite fine powder. The addition amount of trichloromethylsilane is 4% of the mass of vermiculite. The stirring speed is 400 r / min. The dilution uses a mixed solution of ether and isopropanol. The volume ratio of ether to isopropanol is 13:1, and the concentration of vermiculite after dilution is 400 g / L. The temperature of the low-temperature ultrasonic dispersion is 8°C, and the ultrasonic frequency is 60 kHz. The temperature of the granulation is 45°C, and the pressure is 0.5 MPa;

[0045] Step 3: Let the prefabricated vermiculite carrier stand for 2 h, then keep it standing at a constant temperature for 4 h, and then soak it in an alkali solution for 25 min, perform ultrasonic treatment for 8 min, filter, and sinter to obtain porous mixed vermiculite. The atmosphere for the standing treatment is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:23. The temperature of the standing treatment is 35°C, and the pressure is 115% of the atmospheric pressure. The pressure for the constant-temperature standing is 115% of the atmospheric pressure, and the temperature is 120°C. The heating rate is 15°C / min. The alkali solution uses a sodium hydroxide solution with a pH of 8. The soaking temperature is 15°C. The ultrasonic frequency of the ultrasonic treatment is 70 kHz, and the temperature is 25°C. The sintering temperature is 530°C;

[0046] Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into the porous mixed vermiculite and stir evenly, and then perform microwave oscillation treatment for 2 h. Take out the porous mixed vermiculite particles, which are the prefabricated flocculant. The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride is 1:9. The addition amount of the porous mixed vermiculite is 30% of the mass of polyaluminum chloride. The stirring speed is 300 r / min. The microwave power of the microwave oscillation treatment is 400 W, and the temperature is 35°C. Dimethyldiallylammonium chloride and polyaluminum chloride are ground before mixing to make them reach the micron level;

[0047] Step 5: Let the prefabricated flocculant stand for 2 h, and obtain a high-efficiency flocculant after freeze-drying. The atmosphere for the standing treatment is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor. The volume ratio of nitrogen to water vapor is 23:1. The temperature of the standing treatment is 25°C, and the pressure is the atmospheric pressure. The temperature of the freeze-drying treatment is -20°C.

[0048] Further, the vermiculite is modified vermiculite, and the modified vermiculite is titanium dioxide modified vermiculite. The preparation method of the titanium dioxide modified vermiculite includes the following steps: a1. Put the vermiculite into ethanol, stir evenly, and perform ball milling for 2 h, then perform swelling stirring for 0.5 h, and filter to obtain vermiculite particles adsorbed with ethanol. The mass ratio of the vermiculite to ethanol is 5:1, the stirring speed is 400 r / min, the ball milling uses zirconia balls with a diameter of 2 mm, and the ball-to-material ratio is 10:1, the self-rotation speed of the ball milling is 500 r / min, and the revolution rate is 100 r / min. The swelling solvent is ethanol, the stirring speed is 500 r / min, and the concentration of the vermiculite after swelling is 200 g / L; a2. Add tetrabutyl titanate to ether and stir evenly to form a homogeneous solution, then spray the homogeneous solution onto the surface of the vermiculite particles, stand still at a low temperature for 20 min, and then stand still at an elevated temperature for 1 h to obtain prefabricated vermiculite particles. The concentration of tetrabutyl titanate in ether is 200 g / L, the stirring speed is 200 r / min, the spraying speed is 1 mL / min, and the spraying weight is 10% of the mass of the vermiculite particles. The low-temperature standing temperature is 5 °C, the elevated-temperature standing temperature is 40 °C, and the heating rate is 3 °C / min; a3. Put the prefabricated vermiculite particles into a reaction kettle, stand still and react at a constant temperature for 20 min, then perform sintering treatment at a constant temperature for 1 h, and perform secondary heating sintering to obtain modified vermiculite. The atmosphere of the constant-temperature standing is a mixed atmosphere of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 10:1. The constant-temperature standing temperature is 30 °C, the pressure is 120% of the atmospheric pressure. The temperature of the constant-temperature sintering treatment is 200 °C, and the temperature of the secondary heating sintering is 500 °C, and the sintering time is 10 - 20 min.

[0049] Example 5

[0050] A production process of a high-efficiency polyaluminum chloride-based composite flocculant includes the following steps:

[0051] Step 1. Add tourmaline to ethanol and perform low-temperature ball milling treatment to form fine particles, and obtain tourmaline fine powder through spray drying. The mass ratio of the tourmaline to ethanol is 25:1, the temperature of the low-temperature ball milling treatment is 8 °C, the ball milling uses zirconia balls with a diameter of 3 mm, and the ball-to-material ratio is 22:1, the self-rotation speed of the ball milling is 700 r / min, the revolution rate is 150 r / min, and the ball milling time is 3 h; the temperature of the spray drying is 85, and the spray amount is 15 g / min;

[0052] Step 2: Put vermiculite into ether and conduct cryogenic ball milling treatment to obtain vermiculite fine powder. Then, successively add tourmaline, aluminum isopropoxide, and trichloromethylsilane, stir, and after dilution, conduct cryogenic ultrasonic dispersion for 25 min. After granulation, a prefabricated vermiculite carrier is obtained. The mass ratio of vermiculite to ether is 3:1. The temperature of the cryogenic ball milling treatment is 8 °C. Zirconia balls with a diameter of 3 mm are used for ball milling, and the ball-to-material ratio is 13:1. The self-rotation speed of the ball milling is 700 r / min, the revolution rate is 200 r / min, and the ball milling time is 2 h. The addition amount of tourmaline is 5-8% of the mass of vermiculite. The addition amount of aluminum isopropoxide is 25% of the mass of vermiculite fine powder. The addition amount of trichloromethylsilane is 4% of the mass of vermiculite. The stirring speed is 400 r / min. The dilution uses a mixed solution of ether and isopropanol. The volume ratio of ether to isopropanol is 13:1, and the concentration of vermiculite after dilution is 400 g / L. The temperature of the cryogenic ultrasonic dispersion is 8 °C, and the ultrasonic frequency is 60 kHz. The temperature of the granulation is 45 °C, and the pressure is 0.5 MPa;

[0053] Step 3: Let the prefabricated vermiculite carrier stand for 2 h, then stand at a constant temperature for 4 h, and then soak it in an alkali solution for 25 min, conduct ultrasonic treatment for 8 min, filter, and sinter to obtain porous mixed vermiculite. The atmosphere of the standing treatment is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:23. The temperature of the standing treatment is 35 °C, and the pressure is 115% of the atmospheric pressure. The pressure of the constant-temperature standing is 115% of the atmospheric pressure, and the temperature is 120 °C. The heating rate is 15 °C / min. The alkali solution uses a sodium hydroxide solution with a pH of 8. The soaking temperature is 15 °C. The ultrasonic frequency of the ultrasonic treatment is 70 kHz, and the temperature is 25 °C. The sintering temperature is 530 °C;

[0054] Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into the porous mixed vermiculite and stir evenly, and then conduct microwave oscillation treatment for 2 h. Take out the porous mixed vermiculite particles, which are the prefabricated flocculant. The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride is 1:9. The addition amount of the porous mixed vermiculite is 30% of the mass of polyaluminum chloride. The stirring speed is 300 r / min. The microwave power of the microwave oscillation treatment is 400 W, and the temperature is 35 °C. Dimethyldiallylammonium chloride and polyaluminum chloride are ground before mixing to make them reach the micron level;

[0055] Step 5: Let the prefabricated flocculant stand for 2 h, and obtain a high-efficiency flocculant after freeze-drying. The atmosphere of the standing treatment is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor. The volume ratio of nitrogen to water vapor is 23:1. The temperature of the standing treatment is 25 °C, and the pressure is the atmospheric pressure. The temperature of the freeze-drying treatment is -20 °C.

[0056] Furthermore, the vermiculite used is modified vermiculite, and the modified vermiculite is titanium dioxide modified vermiculite. The preparation method of the titanium dioxide modified vermiculite includes the following steps: a1. Put the vermiculite into ethanol, stir evenly, and perform ball milling for 3 h, then perform dilatation stirring for 1 h, and filter to obtain vermiculite particles adsorbed with ethanol; the mass ratio of the vermiculite to ethanol is 8:1, the stirring speed is 600 r / min, the ball milling uses zirconia balls with a diameter of 3 mm, and the ball-to-material ratio is 10 - 15:1, the self-rotation speed of the ball milling is 800 r / min, the revolution rate is 200 r / min, the solvent for dilatation is ethanol, the stirring speed is 1000 r / min, and the concentration of vermiculite after dilatation is 400 g / L; a2. Add tetrabutyl titanate to ether and stir evenly to form a homogeneous solution, then spray the homogeneous solution onto the surface of the vermiculite particles, stand still at a low temperature for 30 min, and then stand still at an elevated temperature for 2 h to obtain prefabricated vermiculite particles. The concentration of tetrabutyl titanate in ether is 500 g / L, the stirring speed is 500 r / min, the spraying speed is 2 mL / min, and the spraying weight is 30% of the mass of the vermiculite particles. The temperature for standing still at a low temperature is 10°C, the temperature for standing still at an elevated temperature is 50°C, and the heating rate is 5°C / min; a3. Put the prefabricated vermiculite particles into a reaction kettle, stand still and react at a constant temperature for 30 min, then perform constant temperature sintering treatment for 2 h, and perform secondary heating sintering to obtain modified vermiculite. The atmosphere for standing still at a constant temperature is a mixed atmosphere of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 15:1. The temperature for standing still at a constant temperature is 50°C, the pressure is 120 - 150% of the atmospheric pressure. The temperature for the constant temperature sintering treatment is 300°C, and the temperature for the secondary heating sintering is 520°C, and the sintering time is 20 min.

[0057] Example 6

[0058] A production process of a highly efficient polyaluminum chloride-based composite flocculant includes the following steps:

[0059] Step 1. Add tourmaline to ethanol and perform low-temperature ball milling treatment to form fine particles, and obtain tourmaline fine powder through spray drying; the mass ratio of the tourmaline to ethanol is 25:1, the temperature for the low-temperature ball milling treatment is 8°C, the ball milling uses zirconia balls with a diameter of 3 mm, and the ball-to-material ratio is 22:1, the self-rotation speed of the ball milling is 700 r / min, the revolution rate is 150 r / min, and the ball milling time is 3 h; the temperature for the spray drying is 85, and the spraying amount is 15 g / min;

[0060] Step 2: Put vermiculite into ether for cryogenic ball milling to obtain vermiculite fine powder. Then, successively add tourmaline, aluminum isopropoxide, and trichloromethylsilane, stir, and after dilution, perform low-temperature ultrasonic dispersion for 25 min. After granulation, a prefabricated vermiculite carrier is obtained. The mass ratio of vermiculite to ether is 3:1. The temperature of the cryogenic ball milling treatment is 8°C. Zirconia balls with a diameter of 3 mm are used for ball milling, and the ball-to-material ratio is 13:1. The rotation speed of the ball milling is 700 r / min, the revolution rate is 200 r / min, and the ball milling time is 2 h. The addition amount of tourmaline is 5-8% of the mass of vermiculite. The addition amount of aluminum isopropoxide is 25% of the mass of vermiculite fine powder. The addition amount of trichloromethylsilane is 4% of the mass of vermiculite. The stirring speed is 400 r / min. The dilution is carried out using a mixed solution of ether and isopropanol. The volume ratio of ether to isopropanol is 13:1, and the concentration of vermiculite after dilution is 400 g / L. The temperature of the low-temperature ultrasonic dispersion is 8°C, and the ultrasonic frequency is 60 kHz. The temperature of the granulation is 45°C, and the pressure is 0.5 MPa;

[0061] Step 3: Let the prefabricated vermiculite carrier stand for 2 h, then stand at a constant temperature for 4 h, and then soak it in an alkali solution for 25 min, perform ultrasonic treatment for 8 min, filter, and sinter to obtain porous mixed vermiculite. The atmosphere for the standing treatment is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:23. The temperature of the standing treatment is 35°C, and the pressure is 115% of the atmospheric pressure. The pressure for the constant-temperature standing is 115% of the atmospheric pressure, and the temperature is 120°C. The heating rate is 15°C / min. The alkali solution used is a sodium hydroxide solution with a pH of 8. The soaking temperature is 15°C. The ultrasonic frequency for the ultrasonic treatment is 70 kHz, and the temperature is 25°C. The sintering temperature is 530°C;

[0062] Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into the porous mixed vermiculite and stir evenly, and then perform microwave oscillation treatment for 2 h. Take out the porous mixed vermiculite particles, which are the prefabricated flocculant. The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride is 1:9. The addition amount of the porous mixed vermiculite is 30% of the mass of polyaluminum chloride. The stirring speed is 300 r / min. The microwave power for the microwave oscillation treatment is 400 W, and the temperature is 35°C. Dimethyldiallylammonium chloride and polyaluminum chloride are ground before mixing to make them reach the micron level;

[0063] Step 5: Let the prefabricated flocculant stand for 2 h, and obtain a high-efficiency flocculant after freeze-drying. The atmosphere for the standing treatment is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor. The volume ratio of nitrogen to water vapor is 23:1. The temperature of the standing treatment is 25°C, and the pressure is the atmospheric pressure. The temperature of the freeze-drying treatment is -20°C.

[0064] Furthermore, the vermiculite used is modified vermiculite, and the modified vermiculite is titanium dioxide modified vermiculite. The preparation method of the titanium dioxide modified vermiculite includes the following steps: a1. Put the vermiculite into ethanol, stir evenly, and perform ball milling for 3 h, then carry out swelling and stirring for 1 h, and filter to obtain vermiculite particles adsorbed with ethanol; the mass ratio of the vermiculite to ethanol is 5 - 8:1, the stirring speed is 500 r / min, the ball milling uses zirconia balls with a diameter of 3 mm, and the ball-to-material ratio is 13:1, the self-rotation speed of the ball milling is 700 r / min, the revolution rate is 150 r / min, the solvent for swelling is ethanol, the stirring speed is 800 r / min, and the concentration of vermiculite after swelling is 300 g / L; a2. Add tetrabutyl titanate to ether and stir evenly to form a homogeneous solution, then spray the homogeneous solution onto the surface of the vermiculite particles, stand still at a low temperature for 25 min, and stand still after heating for 2 h to obtain prefabricated vermiculite particles. The concentration of tetrabutyl titanate in ether is 400 g / L, the stirring speed is 400 r / min, the spraying speed is 2 mL / min, and the spraying weight is 20% of the mass of the vermiculite particles. The temperature for standing still at a low temperature is 8 °C, the temperature for standing still after heating is 45 °C, and the heating rate is 4 °C / min; a3. Put the prefabricated vermiculite particles into a reaction kettle, stand still and react at a constant temperature for 25 min, then carry out sintering treatment at a constant temperature for 2 h, and carry out secondary heating and sintering to obtain modified vermiculite. The atmosphere for standing still at a constant temperature is a mixed atmosphere of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 13:1. The temperature for standing still at a constant temperature is 40 °C, the pressure is 130% of the atmospheric pressure. The temperature for sintering treatment at a constant temperature is 250 °C, and the temperature for secondary heating and sintering is 510 °C, and the sintering time is 15 min.

[0065] Test Example

[0066] Simulated wastewater 1: The concentration of copper ion wastewater is 50 mg / mL, and the pH is 6.5. Using the flocculants of Examples 1 - 6 as test examples, the addition amount is 0.3% of the mass of the wastewater. After adding the flocculant, stir for 10 min, and take the supernatant for detection after standing and sedimentation. The data is as follows:

[0067] Concentration before treatment pH Concentration before treatment pH Example 1 50mg / mL 6.5 0.09mg / mL 7.2 Example 2 50mg / mL 6.5 0.07mg / mL 7.3 Example 3 50mg / mL 6.5 0.07mg / mL 7.4 Example 4 50mg / mL 6.5 0.06mg / mL 7.3 Example 5 50mg / mL 6.5 0.05mg / mL 7.5 Example 6 50mg / mL 6.5 0.05mg / mL 7.3

[0068] The above tests show that the high-efficiency flocculant has good adsorption properties for heavy metal ions, can achieve the effect of rapid removal, and shows excellent sedimentation performance in the treatment of copper ion waste liquid; synchronously conducting experiments on iron ions and zinc ions still shows excellent flocculation and sedimentation effects.

[0069] Wastewater 2: COD is 5000 mg / L, heavy metals (including iron ions, copper ions and zinc ions) are 500 mg / L, turbid water-based paint wastewater. The dosage of the flocculant is 0.5% of the wastewater mass. Using commercially available polyaluminum chloride as the comparative example, stir for 5 minutes and let stand for 10 minutes. After complete precipitation, take the supernatant for testing. The data is as follows:

[0070] Water quality after treatment COD Heavy metals SS removal rate Decolorization rate Example 1 Clear 657 19.2 98.9 100 Example 2 Clear 548 18.4 99.3 100 Example 3 Clear 598 18.7 99.1 100 Example 4 Clear 534 18.3 99.3 100 Example 5 Clear 476 17.5 99.4 100 Example 6 Clear 504 17.9 99.4 100 Control example Slightly turbid 1742 43.7 90.2 85

[0071] In the above simulated wastewater, the flocculant in the technical solution of the present invention has good flocculation and sedimentation effects, can effectively reduce the contents of COD, SS and heavy metal ions, and has excellent decolorization effects, meeting the response requirements of current industrial wastewater and domestic wastewater.

[0072] It can be understood that the above specific description of the present invention is only for explaining the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced to achieve the same technical effects; as long as it meets the usage requirements, it is within the protection scope of the present invention.

Claims

1. A production process of an efficient polyaluminum chloride-based composite flocculant, characterized in that: It includes the following steps: Step 1: Add tourmaline into ethanol and conduct low-temperature ball milling treatment to form fine particles, and then obtain tourmaline fine powder through spray drying; Step 2: Put vermiculite into ether and conduct low-temperature ball milling treatment to obtain vermiculite fine powder. Then, successively add tourmaline, aluminum isopropoxide and trichloromethylsilane and stir. After expansion and dissolution, conduct low-temperature ultrasonic dispersion for 20 - 30 min, and obtain a prefabricated vermiculite carrier after granulation; Step 3: Let the prefabricated vermiculite carrier stand for 1 - 2 h, then stand at a constant temperature for 3 - 5 h, then soak it in an alkali solution for 20 - 30 min, conduct ultrasonic treatment for 5 - 10 min, filter and sinter to obtain porous mixed vermiculite; Step 4: Mix dimethyldiallylammonium chloride and polyaluminum chloride evenly, then put them into the porous mixed vermiculite and stir evenly. Then conduct microwave oscillation treatment for 1 - 2 h, take out the porous mixed vermiculite particles, which are the prefabricated flocculant; Step 5: Let the prefabricated flocculant stand for 1 - 2 h, and obtain a high-efficiency flocculant after freeze drying; The vermiculite in Step 2 is titanium dioxide modified vermiculite, and the preparation method of the titanium dioxide modified vermiculite includes the following steps: a1, put vermiculite into ethanol, stir evenly, and conduct ball milling treatment for 2 - 3 h. Then expand and dissolve and stir for 0.5 - 1 h, and filter to obtain vermiculite particles adsorbed with ethanol; the mass ratio of the vermiculite to ethanol is 5 - 8:1, the stirring speed is 400 - 600 r / min, the ball milling uses zirconia balls with a diameter of 2 - 3 mm, and the ball-to-material ratio is 10 - 15:

1. The self-rotation speed of the ball milling is 500 - 800 r / min, the revolution rate is 100 - 200 r / min, the solvent for expansion and dissolution is ethanol, the stirring speed is 500 - 1000 r / min, and the concentration of vermiculite after expansion and dissolution is 200 - 400 g / L; a2, add tetrabutyl titanate into ether and stir evenly to form a homogeneous solution, then spray the homogeneous solution onto the surface of the vermiculite particles, conduct low-temperature standing for 20 - 30 min, and conduct heating standing for 1 - 2 h to obtain prefabricated vermiculite particles. The concentration of tetrabutyl titanate in ether is 200 - 500 g / L, the stirring speed is 200 - 500 r / min, the spraying speed is 1 - 2 mL / min, and the spraying weight is 10 - 30% of the mass of the vermiculite particles. The temperature of the low-temperature standing is 5 - 10 °C, the temperature of the heating standing is 40 - 50 °C, and the heating rate is 3 - 5 °C / min; a3, put the prefabricated vermiculite particles into a reaction kettle and conduct constant-temperature standing reaction for 20 - 30 min, then conduct constant-temperature sintering treatment for 1 - 2 h, and conduct secondary heating sintering to obtain modified vermiculite. The atmosphere of the constant-temperature standing is a mixed atmosphere of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 10 - 15:

1. The temperature of the constant-temperature standing is 30 - 50 °C, the pressure is 120 - 150% of the atmospheric pressure, the temperature of the constant-temperature sintering treatment is 200 - 300 °C, the temperature of the secondary heating sintering is 500 - 520 °C, and the sintering time is 10 - 20 min.

2. The production process of the high-efficiency polyaluminum chloride-based composite flocculant according to claim 1, characterized in that: The mass ratio of tourmaline to ethanol in the step 1 is 20 - 30:1, the temperature of cryogenic ball milling treatment is 5 - 10 °C, zirconia balls with a diameter of 2 - 3 mm are used for ball milling, and the ball-to-material ratio is 20 - 25:1, the rotation speed of the ball mill is 500 - 800 r / min, the revolution rate is 100 - 200 r / min, and the ball milling time is 2 - 3 h; the temperature of spray drying is 80 - 90 °C, and the spray rate is 10 - 20 g / min.

3. The production process of the high-efficiency polyaluminum chloride-based composite flocculant according to claim 1, characterized in that: The mass ratio of vermiculite to ether in the step 2 is 2 - 3:1, the temperature of cryogenic ball milling treatment is 5 - 10 °C, zirconia balls with a diameter of 2 - 3 mm are used for ball milling, and the ball-to-material ratio is 10 - 15:1, the rotation speed of the ball mill is 500 - 800 r / min, the revolution rate is 100 - 200 r / min, and the ball milling time is 1 - 2 h. The addition amount of tourmaline is 5 - 8% of the mass of vermiculite, the addition amount of aluminum isopropoxide is 20 - 30% of the mass of vermiculite fine powder, the addition amount of trichloromethylsilane is 3 - 5% of the mass of vermiculite, the stirring speed is 200 - 500 r / min. The expansion is carried out with a mixed solution of ether and isopropanol, the volume ratio of ether to isopropanol is 10 - 15:1, and the concentration of vermiculite after expansion is 200 - 500 g / L. The temperature of cryogenic ultrasonic dispersion is 5 - 10 °C, the ultrasonic frequency is 40 - 80 kHz, the temperature of granulation is 40 - 50 °C, and the pressure is 0.4 - 0.6 MPa.

4. The production process of the high-efficiency polyaluminum chloride-based composite flocculant according to claim 1, characterized in that: The atmosphere for static treatment in the step 3 is a mixed atmosphere composed of water vapor and dry air, and the volume ratio of water vapor to dry air is 1:20 - 25. The temperature of static treatment is 30 - 40 °C, and the pressure is 110 - 120% of the atmospheric pressure. The pressure for isothermal static treatment is 110 - 120% of the atmospheric pressure, the temperature is 110 - 130 °C, and the heating rate is 10 - 20 °C / min; the alkaline solution is a sodium hydroxide solution with a pH of 8, the soaking temperature is 10 - 20 °C, the ultrasonic frequency for ultrasonic treatment is 50 - 80 kHz, the temperature is 20 - 30 °C, and the sintering temperature is 500 - 550 °C.

5. The production process of the high-efficiency polyaluminum chloride-based composite flocculant according to claim 1, characterized in that: The mass ratio of dimethyldiallylammonium chloride to polyaluminum chloride in the step 4 is 1:8 - 10, the addition amount of porous mixed vermiculite is 10 - 40% of the mass of polyaluminum chloride, the stirring speed is 200 - 400 r / min, the microwave power for microwave oscillation treatment is 300 - 500 W, and the temperature is 30 - 40 °C.

6. The production process of the high-efficiency polyaluminum chloride-based composite flocculant according to claim 5, characterized in that: Dimethyldiallylammonium chloride and polyaluminum chloride are ground before mixing to make them reach the micron level.

7. The production process of the high-efficiency polyaluminum chloride-based composite flocculant according to claim 1, characterized in that: The atmosphere for static treatment in the step 5 is a humid atmosphere, and the humid atmosphere is a mixed atmosphere of nitrogen and water vapor, the volume ratio of nitrogen to water vapor is 20 - 25:1, the temperature of static treatment is 20 - 30 °C, and the pressure is the atmospheric pressure. The temperature of freeze-drying treatment is -20 °C.