CN-121988288-A - Preparation method and application of efficient thallium removal adsorption material

CN121988288ACN 121988288 ACN121988288 ACN 121988288ACN-121988288-A

Abstract

The invention discloses a preparation method and application of an efficient thallium removal adsorption material, and relates to the technical field of wastewater treatment, wherein the preparation method comprises the following steps of respectively preprocessing precipitated sludge containing ferromanganese and agricultural biomass waste to obtain sludge powder and biomass-based raw material powder; uniformly mixing sludge powder and biomass-based raw material powder to obtain a mixed raw material, heating the mixed raw material to 550-700 ℃ in an inert atmosphere for pyrolysis to obtain biochar containing magnetic components, carrying out acid washing modification treatment on the biochar containing the magnetic components to obtain surface modified magnetic biochar, dispersing the surface modified magnetic biochar in constant-temperature ultrapure water, adding ferricyanide, ferrous salt and a high-molecular polymer, reacting under stirring, cooling, washing and drying to obtain the magnetic biochar. The preparation method provided by the invention has the effects of low cost, resource utilization, natural magnetism, easiness in recovery, high selectivity, high-efficiency adsorption and the like.

Inventors

CHEN YING
SUN CHENYANG
TIAN SHIQIANG
FU GUANGYI
TIAN JUNKAI
ZHAO YAOHUI
LI YAOYU
SHI YANG
MAO ZHAOZHI
ZHANG JUN

Assignees

湖南省环境保护科学研究院
中冶京诚工程技术有限公司

Dates

Publication Date: 20260508
Application Date: 20260320

Claims (10)

1. The preparation method of the efficient thallium removal adsorption material is characterized by comprising the following steps of: s1, respectively preprocessing the precipitated sludge containing ferro-manganese and agricultural biomass waste to obtain sludge powder and biomass-based raw material powder; s2, uniformly mixing the sludge powder and biomass-based raw material powder according to a mass ratio of 1 (0.5-1.5) to obtain a mixed raw material; S3, heating the mixed raw materials to 550-700 ℃ in an inert atmosphere for pyrolysis to obtain biochar containing magnetic components; S4, carrying out acid washing modification treatment on the biochar containing the magnetic component to obtain surface modified magnetic biochar; S5, dispersing the surface-modified magnetic biochar in constant-temperature ultrapure water, adding ferricyanide, ferrous salt and high-molecular polymer, reacting under stirring to enable Prussian blue compounds to be generated on the surface of the surface-modified magnetic biochar in situ, and cooling, washing and drying to obtain the Prussian blue-loaded magnetic biochar-based thallium removal adsorption material.
2. The method for preparing the efficient thallium removal adsorbing material according to claim 1, wherein in step S1: in the precipitated sludge containing ferromanganese, the iron content is 40% -65%, the calcium content is 8% -12%, and the manganese content is 0.5% -3.5%; The agricultural biomass waste is at least one selected from rice straw, corn straw and wheat straw; the pretreatment comprises drying, grinding and sieving treatment; the particle diameter of the sludge powder and the biomass-based raw material powder is not more than 150 μm.
3. The method for preparing the efficient thallium removal adsorbing material according to claim 1, wherein in step S3: The inert atmosphere is nitrogen atmosphere, and the flow rate of the nitrogen is not lower than 1.0L/min; the temperature rising rate is not higher than 15 ℃ per minute, and the pyrolysis time is 2-3 hours.
4. The method for preparing the efficient thallium removal adsorbing material according to claim 1, wherein in step S4: the pickling modification treatment adopts hydrochloric acid with the mass fraction of 2% -5%, and pickling is carried out for 20-40 min under the ultrasonic condition; Washing with ultrapure water for many times until the washing liquid is neutral, and drying at a temperature of not more than 65 ℃ for not more than 24 hours.
5. The method for preparing a thallium-removing adsorbent according to claim 1, wherein in step S5, the ferricyanide is potassium ferricyanide, the ferrous salt is ferrous sulfate, and the mass ratio of potassium ferricyanide to ferrous sulfate is 2:3.
6. The method for preparing a highly efficient thallium-removing adsorption material according to claim 5, wherein in step S5, the high molecular polymer is at least one selected from polyvinylpyrrolidone, polyethylene oxide and polyvinyl alcohol, and the mass ratio of the surface-modified magnetic biochar to the high molecular polymer is 1 (2-5).
7. The method for preparing the efficient thallium removal adsorbing material according to claim 6, wherein the step S5 specifically comprises the following sub-steps: s51, dispersing the surface-modified magnetic biochar in constant-temperature ultrapure water to obtain a magnetic biochar suspension, wherein the temperature of the ultrapure water is not lower than 80 ℃, and the mass ratio of the surface-modified magnetic biochar to water is 1 (0.01-0.05); S52, adding potassium ferricyanide and a high molecular polymer into the magnetic biochar suspension, and reacting for 25-30 min under the stirring condition of not less than 400 r/min; S53, adding ferrous sulfate solution into the reaction system, and continuing stirring and reacting for 2-4 hours under the constant temperature condition; S54, after the reaction is finished, naturally cooling to room temperature, carrying out solid-liquid separation, washing a solid product with ultrapure water for multiple times until the washing liquid is clarified, and then drying at a temperature not exceeding 65 ℃ to obtain the Prussian blue-loaded magnetic biochar-based thallium removal adsorption material; And adding the potassium ferricyanide, the high polymer and the ferrous sulfate solution within 3-5 min.
8. The method for preparing the efficient thallium removal adsorbing material according to any one of claims 1 to 7, wherein the steps S4 and S5 further comprise the following steps: Dispersing the surface-modified magnetic biochar in ultrapure water or buffer solution with the pH value of 6.5-8.0, adding an organic bridging agent, dispersing for 10-30 min under ultrasonic conditions, and reacting for 1-3 h under stirring conditions; The dosage of the organic bridging agent is 0.5% -2% of the mass of the surface modified magnetic biochar, and the organic bridging agent is carboxyl-imidazole functionalized diamine bridging agent or phosphoramide-phenolic hydroxyl bridging agent.
9. The method for preparing the efficient thallium removal adsorbing material according to claim 8, characterized in that: the carboxyl-imidazole functionalized diamine bridging agent is prepared by the following steps: Carrying out Michael addition reaction for 2-4 hours at 50-70 ℃ in sodium hydroxide aqueous solution according to the mass ratio of (1.8-2.5) histidine to acrylic acid or maleic anhydride, regulating the pH value to 3-4 by hydrochloric acid after the reaction is finished, precipitating, filtering, washing and drying to obtain the product: the phosphoramide-phenolic hydroxyl bridging agent is prepared by the following steps: And (3) reacting p-hydroxyphenylethylamine with phosphoryl chloride according to a mass ratio of 1 (1.8-2.2) in the presence of triethylamine at 0-5 ℃ in an ice bath for 2-3 hours to generate a phosphoryl chloride intermediate, then adding excessive ammonia water, continuing the amination reaction at room temperature for 3-5 hours, filtering to remove salts after the reaction is finished, evaporating the solvent under reduced pressure, washing the residue with ultrapure water, and drying to obtain the product.
10. The application of the efficient thallium removal adsorbing material prepared by the preparation method of the efficient thallium removal adsorbing material as set forth in any one of claims 1 to 9, characterized in that the efficient thallium removal adsorbing material is used for removing thallium ions in a water body, the water body is selected from industrial thallium containing wastewater, surface water or drinking water source water, the addition amount of the efficient thallium removal adsorbing material is 0.05 to 0.5g/L, and the adsorption time is not less than 15 min.

Description

Preparation method and application of efficient thallium removal adsorption material Technical Field The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method and application of an efficient thallium removal adsorption material. Background Thallium (Tl) is used as a highly toxic heavy metal element, and can enter a human body through the contact of respiratory tract, alimentary canal, skin and the like, so as to cause irreversible damage to central nervous system, myocardial tissues and other key organs, and the high-dose exposure can cause death. In view of the remarkable biotoxicity, thallium is listed as a priority pollutant in China and European and American main countries, and strict drinking water quality standards are established. The limit value of thallium regulated in the current sanitary Standard for Drinking Water in China (GB 5749-2022) is 0.1 mug/L, which belongs to the international strict standard. However, the problem of thallium pollution in the mineral resource development process in China is increasingly prominent, and environmental risks and ecological hazard events caused by the problem are frequent, so that development of a thallium removal material with high adsorption capacity, easiness in solid-liquid separation and controllable cost is needed. Biochar is a highly aromatic, structurally stable, carbon-rich solid material prepared by thermal cracking of biomass under oxygen-limited and medium-low temperature conditions. It has the characteristics of large specific surface area, developed pore structure, rich surface functional groups, good conductivity and the like. Compared with the traditional activated carbon, the biochar has the advantages of wide raw material sources, obvious cost benefit and rich oxygen-containing functional groups (such as carboxyl and hydroxyl) on the surface, and can effectively enhance the adsorption capacity of heavy metal ions. The resources of crop waste, straw and the like in China are rich, the annual collectable quantity is more than 6 hundred million tons, and the biomass charcoal has the potential of being used as a biochar raw material in a large-scale manner. In order to further improve the adsorption performance of the biochar on heavy metals and realize convenient recovery of the biochar in actual water treatment, magnetic functional modification is often carried out on the biochar by introducing magnetic components such as iron, manganese, cobalt and the like. The magnetic biochar can realize rapid solid-liquid separation by using an external magnetic field, and the supported metal oxide or hydroxide can enhance the thallium removal efficiency through mechanisms such as specific adsorption, coprecipitation, oxidation reduction and the like of thallium. On the other hand, the mine water can generate a large amount of chemical precipitation sludge rich in iron and manganese in the treatment process. At present, the sludge is mostly treated by landfill after dehydration, so that the operation cost is increased, and the risks of heavy metal re-release and soil pollution exist. Therefore, the recycling utilization of the ferromanganese precipitation mud is promoted, and the sustainable development goal of solid waste reduction and recycling is met. Based on the background, the biological carbon is prepared by utilizing crop wastes such as straw and the like and is subjected to composite modification with the ferromanganese precipitation mud, so that the efficient thallium removal adsorption material is developed, an economically feasible technical approach is provided for thallium-containing wastewater treatment, a synergistic solution is provided for high-valued resource utilization of two types of wastes, and the method has remarkable environmental benefit and resource recycling significance. Disclosure of Invention In order to solve the technical problems, the invention provides a preparation method and application of an efficient thallium removal adsorption material, and the specific technical scheme is as follows: the preparation method of the efficient thallium removal adsorption material comprises the following steps: s1, respectively preprocessing the precipitated sludge containing ferro-manganese and agricultural biomass waste to obtain sludge powder and biomass-based raw material powder; S2, uniformly mixing the sludge powder and biomass-based raw material powder according to a mass ratio of 1 (0.5-1.5) to obtain a mixed raw material; s3, heating the mixed raw materials to 550-700 ℃ in an inert atmosphere for pyrolysis to obtain biochar containing magnetic components; S4, carrying out acid washing modification treatment on the biochar containing the magnetic components to obtain surface modified magnetic biochar; S5, dispersing the surface-modified magnetic biochar in constant-temperature ultrapure water, adding ferricyanide, ferrous salt and high-molecular polymer, reacting und