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CN-117884088-B - Microplastic degradation agent in water body and preparation method and application thereof

CN117884088BCN 117884088 BCN117884088 BCN 117884088BCN-117884088-B

Abstract

The invention discloses a micro-plastic degradation agent in a water body, and a preparation method and application thereof. The microplastic degradation agent comprises a first metal component, a second metal component and a third metal component, wherein the first metal component is selected from one or more of cerium, lanthanum and gadolinium, the second metal component is selected from one or more of iron, titanium and manganese, and the third metal component is selected from one or more of gallium, indium and tin. The microplastic degradation agent can efficiently degrade microplastic in water, has the characteristics of low degradation temperature, high reaction activity, nearly neutral pH of the water and the like, has simple reaction process, and is suitable for industrialized batch operation.

Inventors

  • ZHAO LIANG

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20221008

Claims (20)

  1. 1. The micro plastic degradation agent in the water body comprises a first metal component, a second metal component and a third metal component, wherein the first metal component is one or more of cerium, lanthanum and gadolinium, the second metal component is one or more of iron and titanium, the third metal component is one or more of gallium, indium and tin, the general formula of the micro plastic degradation agent is X a Y b Z c O x , wherein X is the first metal component, Y is the second metal component and Z is the third metal component, b is c=1 (0.05-0.5): (0.01-0.1), and the degradation agent belongs to an orthorhombic crystal system.
  2. 2. The microplastic degradation agent according to claim 1, wherein the first metal component is gadolinium, the second metal component is titanium, and the third metal component is indium.
  3. 3. The microplastic degradation agent according to claim 1, wherein in the general formula of the microplastic degradation agent, a is b, c=1, (0.08-0.35), and (0.03-0.07).
  4. 4. The microplastic degradation agent according to claim 1, wherein the specific surface area of the degradation agent is 53m 2 /g~68m 2 /g and the pore volume is 2.75cm 3 /g~3.56cm 3 /g.
  5. 5. The preparation method of the micro plastic degradation agent in the water body according to any one of claims 1 to 4 comprises the following steps: (1) Preparing a mixed metal salt solution containing a first metal component, a second metal component and a third metal component, and then carrying out precipitation reaction with a sodium hydroxide solution; (2) And (3) carrying out solid-liquid separation, washing, drying and roasting on the mixture obtained after the precipitation reaction in the step (1) to obtain the degradation agent.
  6. 6. The method according to claim 5, wherein the concentration of the mixed metal salt solution in the step (1) is 0.1mol/L to 0.8mol/L.
  7. 7. The method according to claim 6, wherein the concentration of the mixed metal salt solution in the step (1) is 0.35mol/L to 0.65mol/L.
  8. 8. The method according to claim 5, wherein the first metal component precursor in the step (1) is one or more selected from cerium nitrate, lanthanum nitrate and gadolinium nitrate, the second metal component precursor is one or more selected from ferrous sulfate and titanium sulfite, and the third metal component precursor is one or more selected from gallium nitrate, indium nitrate and tin nitrate.
  9. 9. The method of claim 8, wherein the first metal component precursor in step (1) is gadolinium nitrate, the second metal component precursor is titanium sulfite, and the third metal component precursor is indium nitrate.
  10. 10. The preparation method of claim 5, wherein the mass ratio of the mixed metal salt solution to the sodium hydroxide solution in the step (1) is 1 (0.3-2.5).
  11. 11. The preparation method of claim 10, wherein the mass ratio of the mixed metal salt solution to the sodium hydroxide solution in the step (1) is 1 (0.8-1.5).
  12. 12. The method according to claim 5, wherein the concentration of the sodium hydroxide solution in the step (1) is 0.5mol/L to 2.5mol/L.
  13. 13. The method according to claim 12, wherein the concentration of the sodium hydroxide solution in the step (1) is 0.8mol/L to 1.2mol/L.
  14. 14. The preparation method of claim 5, wherein the precipitation reaction temperature in the step (1) is 30-90 ℃, and the precipitation reaction time is 0.5-8 hours.
  15. 15. The method according to claim 14, wherein the precipitation reaction temperature in the step (1) is 50 ℃ to 70 ℃, and the precipitation reaction time is 2h to 5h.
  16. 16. The preparation method of the ceramic material according to claim 5, wherein the drying temperature in the step (2) is 80-150 ℃, the drying time is 10-30 hours, and/or the roasting temperature is 300-700 ℃ and the roasting time is 1-8 hours.
  17. 17. The method according to claim 16, wherein the drying temperature in the step (2) is 100 ℃ to 120 ℃, the drying time is 16h to 25h, and/or the baking temperature is 450 ℃ to 550 ℃, and the baking time is 3h to 5h.
  18. 18. The use of the microplastic degradation agent in a water body according to any one of claims 1 to 4 for degrading microplastic in a water body.
  19. 19. The use according to claim 18, wherein the method for degrading microplastic in a body of water comprises adding the degradation agent and hydrogen peroxide to an aqueous solution of microplastic, and adding an organic acid to adjust the pH of the solution, followed by thermal degradation.
  20. 20. The use according to claim 19, wherein the micro plastic is selected from any one of low density polyethylene plastic, polystyrene plastic, polypropylene plastic and ultra-high molecular weight polyethylene plastic, and/or the water in the micro plastic aqueous solution is selected from one or more of tap water, river water and sea water, and/or the mass concentration of the micro plastic aqueous solution is 1 g/L-5 g/L, and/or the average particle diameter of the micro plastic particles is 0.1 mm-2.5 mm.

Description

Microplastic degradation agent in water body and preparation method and application thereof Technical Field The invention belongs to the technical field of micro-plastic treatment, and particularly relates to a micro-plastic degradation agent in a water body, and a preparation method and application thereof. Background Plastic products are widely used in today's society, and have been grown in annual production over 3 x 10 8 tons and at a rate of 0.2 x 10 8 tons/year. Due to mass production and use, plastic products inevitably enter various water environments. It is estimated that the global ocean surface floats on more than 2.5x 5 tons of plastic waste, which undergoes physical, photodegradation and biodegradation, further decomposing to form microplastic (Microplastic) with a diameter of less than 5 mm. Microplastic is of various kinds and is divided into materials, mainly including Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS) and polyethylene terephthalate (PET). The microplastic can undergo a series of migration and transformation in the water body, and can float or suspend in the water body after entering various water body environments due to the density lower than that of the water, and can be diffused under the action of wind waves and ocean currents. Under the long-term action of the water body environment, the surface characteristics of the micro-plastic with hydrophobicity become complex, so that some organic and metal chemical pollutants are easily adsorbed, and the micro-plastic can be absorbed into the body of the aquatic organism to endanger the health and safety of the aquatic organism. At the same time, a series of adverse physiological reactions can be induced after humans eat these water organisms containing microplastic contaminants. The existing degradation treatment technology for plastic products is mainly aimed at the development of original ecological plastics and compounds thereof, is mainly used for the degradation process of solid plastic products, has no effective means for the degradation technology of secondary microplastic in water body, and is one of key technologies which are urgently needed to be solved. CN111825241a discloses a method for treating microplastic pollutant based on micro-nano motor material. The method comprises the steps of adding a micro-nano motor material into sewage to be treated, then adding hydrogen peroxide into the sewage to start a treatment process, enabling the micro-nano motor material to perform catalytic reaction in the water to be treated, continuously generating micro-nano bubbles, driving pollutants in the water to float to the water surface and concentrate in a bubble foam phase, and separating the foam phase from the sewage to achieve the aim of treating micro-plastic pollutants, wherein the outer diameter of the micro-nano bubbles is 20 nm-5000 mu m. The method utilizes the self-driven motion of the micro-nano motor, self-stirring and the capability of generating micro-bubbles at a high speed to realize the adsorptive bubble separation process of suspended pollutants in water, but the method separates the micro-plastics from sewage through bubble adsorption, then treats the micro-plastics, can not directly degrade the plastics in water, adopts ferroferric oxide powder as a base material, grows manganese dioxide in a hydrothermal mode, has weak binding force between the two, namely limited manganese dioxide load as a catalytic component, is easy to fall off after long-term use, and has more loss of the ferroferric oxide base material, namely limited service life of a degradation agent. CN111514868a discloses a magnetic nano carbon, its preparation method and its application in removing microplastic in water. The method utilizes a method combining chemical deposition and high-temperature calcination to prepare magnetic nano carbon, the synthesized magnetic nano carbon is put into water containing microplastic, after full contact, the magnetic nano carbon is adsorbed on the surface of the microplastic, the microplastic can be removed from the water by utilizing a permanent magnet, then the mixture of the microplastic and the magnetic nano carbon is placed in a tubular furnace, high-temperature treatment is carried out under nitrogen atmosphere, the microplastic is decomposed into gas by heat, and the microplastic is removed. The iron-containing compound attached to the nano carbon material is easy to run off after being recycled for 4 times, the removal rate of the microplastic is reduced by about 15 percent, which is unfavorable for industrial application, and meanwhile, the method needs to be combined with a high-temperature calcination process in the process of removing the microplastic, so that the energy consumption in the treatment process is increased, and the purpose of removing the microplastic by a one-step method cannot be achieved. Disclosure of Invention Aiming at the defects of the prior ar