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CN-121974495-A - Zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland

CN121974495ACN 121974495 ACN121974495 ACN 121974495ACN-121974495-A

Abstract

The invention belongs to the technical field of wastewater treatment, and particularly relates to a zirconium-based composite filler for removing antibiotics in wastewater based on an artificial ecological wetland. The removal efficiency of the traditional constructed wetland on the sulfonamide antibiotics is difficult to reach more than 95 percent. Aiming at the problems, the invention provides a zirconium-based composite filler for removing antibiotics in wastewater based on an artificial ecological wetland, which comprises the chemical components of porous zeolite, amyloid protein fibers and nano ZrO 2 , wherein the porous zeolite is completely coated by the amyloid protein fibers, and the nano ZrO 2 is loaded on the outer surfaces of the amyloid protein fibers. The zirconium-based composite filler successfully overcomes the defects of limited removal efficiency, insufficient stability, poor compatibility with an artificial wetland system and the like of the prior art, and has important significance in guaranteeing the safety of water environment and the healthy development of aquaculture industry.

Inventors

  • TENG JIE
  • ZHANG YUZHEN
  • Zhang Caihan
  • LI PU
  • XUE YABO
  • YANG YONGQIANG
  • PENG MINGGUO

Assignees

  • 常州大学

Dates

Publication Date
20260505
Application Date
20260127

Claims (10)

  1. 1. The zirconium-based composite filler for removing antibiotics in wastewater based on the artificial ecological wetland is characterized by comprising the chemical components of porous zeolite, amyloid protein fibers and nano ZrO 2 , wherein the porous zeolite is completely coated by the amyloid protein fibers, and the nano ZrO 2 is loaded on the outer surface of the amyloid protein fibers.
  2. 2. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 1, wherein the preparation method comprises the following steps: (1) In the aqueous solution, lysozyme undergoes acid-heat reaction on the surface of porous zeolite to form amyloid protein fibers by self-assembly, so as to obtain modified porous zeolite; (2) ZrOCl 2 or a hydrate thereof is uniformly dispersed in the reaction system of the step (1), zirconium-based cations in the solution and the amyloid protein fibers modified on the surface of the porous zeolite are subjected to electrostatic adsorption and dispersed on the surfaces of the protein fibers, the zirconium-based cations on the surfaces of the protein fibers are subjected to acidic reduction reaction to generate nano ZrO 2 in situ, and the nano ZrO 2 -AA@Zeolite is obtained after solid-liquid separation, washing and drying.
  3. 3. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 2, wherein ph=1.8-2.2 of acid thermal reaction.
  4. 4. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 2, wherein the temperature of the acid thermal reaction is 85-95 ℃.
  5. 5. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 2, wherein the mass ratio of lysozyme to porous zeolite is 1.5:10-3:10.
  6. 6. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 2, wherein the mass ratio of ZrOCl 2 or hydrate thereof to lysozyme in the step (1) is 4.5:1-5.5:1.
  7. 7. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 2, wherein pH of acidic reduction reaction is=3.5-4.0.
  8. 8. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 2, wherein the temperature of the acidic reduction reaction is room temperature.
  9. 9. The zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland according to claim 2, wherein the dispersion of zirconium-based cations on the surface of protein fibers through electrostatic adsorption is realized by uniformly stirring on a constant-temperature water bath shaker for at least 24 hours.
  10. 10. An artificial ecological wetland, characterized in that the zirconium-based composite filler according to any one of claims 1 to 9 is used as the filler of the artificial ecological wetland.

Description

Zirconium-based composite filler for removing antibiotics in wastewater based on artificial ecological wetland Technical Field The invention belongs to the technical field of wastewater treatment, and particularly relates to a zirconium-based composite filler for removing antibiotics in wastewater based on an artificial ecological wetland. Background At present, the technology for removing the sulfonamide antibiotics in the water body mainly comprises a chemical method, a biological method and a physical method. Chemical methods (such as advanced oxidation, photocatalytic oxidation, etc.) have high degradation efficiency, but generally have problems of high operation cost, severe reaction conditions, possibility of producing toxic byproducts, etc. Biological methods (such as aerobic/anaerobic biological treatment, artificial wetland and the like) have the advantage of lower cost, but the microbial activity is easily affected by water quality fluctuation and antibiotic toxicity inhibition, so that the treatment effect is unstable. In the physical method (such as membrane separation, adsorption and the like), the equipment investment and maintenance cost of the membrane separation technology is high, the membrane pollution problem is remarkable, while the conventional adsorption method has the defects of limited adsorption capacity, difficult regeneration of an adsorbent, poor selectivity on trace pollutants and the like, and secondary pollution can be caused if the adsorption is improperly treated after saturation. Compared with the prior art, the artificial wetland technology is used as a green treatment process for simulating a natural ecological process, has the advantages of low construction and operation cost, environmental friendliness, capability of simultaneously removing various pollutants, simplicity and convenience in management and maintenance and the like, and is particularly suitable for treating the culture tail water with larger fluctuation of water quality and water quantity. However, the traditional constructed wetland has no good specific selectivity for removing trace emerging pollutants such as sulfonamides. Researches show (for example, chinese patent No. 119083154A) that the protein fiber immobilized zirconium-based activated carbon hybrid membrane has a good adsorption effect on sulfadiazine, but the research team of the invention finds that the protein fiber immobilized zirconium-based activated carbon hybrid membrane prepared by the patent is difficult to be applied to the filler of the artificial ecological wetland because the membrane material is difficult to be stably fixed in the filler layer of the artificial ecological wetland and is easy to deform and shift. According to the invention, a research team tries to carry out solid-liquid separation, water washing and drying on the solution 1 containing the protein-like fiber with the immobilized ZrO 2 nano particles obtained by the patent through a conversion thought, then separates to obtain the protein-like fiber with the immobilized ZrO 2 nano particles, then composites the protein-like fiber with the immobilized ZrO 2 nano particles with activated carbon to obtain the protein-fiber immobilized zirconium-based activated carbon composite filler, and uses the protein-fiber immobilized zirconium-based activated carbon composite filler as the filler of the artificial ecological wetland, and analysis and test show that the adsorption removal effect of the artificial ecological wetland using the protein-fiber immobilized zirconium-based activated carbon composite filler on sulfonamide antibiotics in the cultivation wastewater is difficult to reach more than 90%. The adsorption stability of the protein fiber immobilized zirconium-based active carbon composite filler needs to be further improved. Based on the above problems, the present invention provides a zirconium-based composite filler, the chemical components of which include porous zeolite, amyloid protein fibers and nano ZrO 2, wherein the porous zeolite is completely coated with the amyloid protein fibers, and the nano ZrO 2 is loaded on the outer surface of the amyloid protein fibers. The zirconium-based composite filler is used as the filler of the artificial ecological wetland, and the test research shows that the zirconium-based composite filler has very excellent stability, and the adsorption removal rate of sulfonamide antibiotics is not obviously reduced after the zirconium-based composite filler is recycled for 100 times. However, the adsorption removal rate of the zirconium-based composite filler prepared according to the scheme on the sulfonamide antibiotics can not reach more than 90% or even more than 95%, and the adsorption removal rate of the sulfonamide antibiotics is in a dense and inseparable relationship with the use ratio of the raw materials of porous zeolite, lysozyme, zrOCl 2 or the hydrate thereof in the preparation process of the zirconium-based composit