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KR-102963607-B1 - Method of treatment of polluted groundwater using boron doped Undaria pinnatifida derived biochar

KR102963607B1KR 102963607 B1KR102963607 B1KR 102963607B1KR-102963607-B1

Abstract

The present invention relates to a method for treating contaminated groundwater using boron-doped seaweed biochar, wherein the contaminants are treated by activating peroxymonosulfate using boron-doped seaweed-based biochar as a catalyst, and the boron-doped seaweed-based biochar is prepared by including the steps of washing and drying the seaweed (S1), grinding the dried seaweed (S2), mixing the ground seaweed with boric acid and then hydrothermal treatment (S3), and thermally decomposing the hydrothermally treated mixture (S4), wherein in step S2, HTFS (Hydroxyl Terminated Functional Silicone) is mixed with the dried seaweed and then ground.

Inventors

  • 신원식
  • 안나말라 시바산카르
  • 서기웅

Assignees

  • 경북대학교 산학협력단

Dates

Publication Date
20260513
Application Date
20230526

Claims (10)

  1. To treat pollutants through the activation of peroxymonosulfate using boron-doped seaweed-based biochar as a catalyst, The above boron-doped seaweed-based biochar is manufactured by including the steps of washing and drying the seaweed (S1), grinding the dried seaweed (S2), mixing the ground seaweed with boric acid and then hydrothermally treating it (S3), and thermally decomposing the hydrothermally treated mixture (S4). A method for treating contaminated groundwater using boron-doped seaweed-based biochar, characterized in that, in the above S2 step, HTFS (Hydroxyl Terminated Functional silicone) is mixed with dried seaweed and ground.
  2. In Article 1, A method for treating contaminated groundwater using boron-doped seaweed-based biochar , characterized by generating hydroxyl radicals (˙OH), sulfate radicals ( SO₄ - ˙), and singlet oxygen ( ¹O₂ ) through the activation of peroxymonosulfate using boron-doped seaweed-based biochar as a catalyst.
  3. In Article 1, A method for treating contaminated groundwater using boron-doped seaweed-based biochar, characterized in that the above-mentioned peroxymonosulfate is potassium peroxymonosulfate.
  4. In Article 1, A method for treating contaminated groundwater using boron-doped seaweed-based biochar, characterized in that the above-mentioned contaminants include one or more of organic contaminants and diclofenac.
  5. In Paragraph 4, A method for treating contaminated groundwater using boron-doped seaweed-based biochar, characterized in that the above organic pollutants include at least one of phenol, bisphenol A, nitrophenol, dichlorophenol, trichlorophenol, benzene, toluene, ethylbenzene, xylene, TCE, PCE, total petroleum hydrocarbons (TPH), and polycyclic aromatic hydrocarbons (PAHs).
  6. delete
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  8. In Article 1, In the above S2 step, A method for treating contaminated groundwater using boron-doped seaweed-based biochar characterized by the addition of ammonia water.
  9. In Article 1, A method for treating contaminated groundwater using boron-doped seaweed-based biochar, characterized by further including a step (S5) of mixing and stirring lignin sulfonic acid into the pyrolyzed mixture after the above S4 step.
  10. In Article 9, In the above S5 step, A method for treating contaminated groundwater using boron-doped seaweed-based biochar characterized by the additional addition of sodium gluconate.

Description

Method of treatment of polluted groundwater using boron-doped Undaria pinnatifida-derived biochar The present invention relates to a method for treating groundwater contaminated with recalcitrant trace contaminants of the antibiotic class, such as diclofenac, through advanced oxidation, and more specifically, to a groundwater purification method for treating trace contaminants of antibiotics through the catalytic action of peroxymonosulfate and boron-doped seaweed-based biochar. Antibiotics, known as representative trace pollutants, are not removed by general wastewater treatment processes, resulting in high persistence and are known to accumulate in aquatic ecosystems, causing adverse effects. Diclofenac is one of the representative residual antibiotics widely used as a treatment for human rheumatoid arthritis, osteoarthritis, ankylosing spondylitis, and post-traumatic inflammation and pain. Because diclofenac has a low solubility in water of 2.37 ppm and a log Kow of 4.51, it exhibits high bioaccumulation and is resistant to microbial activity. Treatment methods mainly used to purify groundwater contaminated with organic pollutants, including these antibiotics, include pump and treat, air sparging, bioremediation, biodegradation, phytoremediation, reductive dechlorination, and advanced oxidation. Meanwhile, diclofenac, one of the antibiotics cited as a micropollutant, is not completely removed in general water and sewage treatment processes and is being detected in tap water and effluent. The aforementioned technologies for treating organic pollutants in groundwater include methods using microorganisms or plants (Patent No. 1003975400000), Fenton oxidation (Patent No. 1018098880000), permanganate and persulfate oxidation (Application No. 1020140180542), nanobubble and inorganic acid multi-stage washing processes (Patent No. 1017680060000), and steam extraction (Patent No. 1004182800000). However, most of these technologies involve injection methods and injection devices. As with existing methods, the oxidizing agent injected into the ground to treat pollutants reacts with and is consumed not only by the pollutants but also by organic matter, minerals, and ions in the groundwater. Consequently, the amount of oxidizing agent used increases, which can raise the overall purification cost. Furthermore, the persistence of the oxidizing agent within the groundwater acts as a major factor in the oxidation treatment of groundwater; since the contact time with pollutants increases with the duration of the agent's persistence, there is a need for technology capable of efficiently treating groundwater contaminated with organic pollutants over the long term. Figure 1 is a photograph showing a method for manufacturing a boron-doped seaweed-based biochar catalyst, and Figure 2 is a graph showing the oxidation removal efficiency of boron-doped seaweed-based biochar according to thermal decomposition temperatures (600, 700, 800, 900℃) when treated with diclofenac by peroxymonosulfate and a boron-doped seaweed-based biochar catalyst. Figure 3 is a graph showing the removal efficiency according to the concentration of the catalyst (left) and peroxymonosulfate (right) during diclofenac oxidation treatment by a boron-doped seaweed-based biochar catalyst and peroxymonosulfate, and Figure 4 is a graph showing the removal efficiency of diclofenac according to the initial concentration during oxidation treatment of diclofenac by boron-doped seaweed-based biochar catalyst and peroxymonosulfate, and Figure 5 is a graph showing the effect of initial pH on diclofenac oxidation treatment with a boron-doped seaweed-based biochar catalyst and peroxymonosulfate, and Figure 6 is a graph showing the effect of a boron-doped seaweed-based biochar catalyst on the oxidation of diclofenac by peroxymonosulfate, and Figure 7 is a graph showing the results of electron spin resonance spectrophotometry (ESR) analysis for boron-doped seaweed-based biochar catalysts and peroxymonosulfate, and Figure 8 is a graph showing the results of treating diclofenac by reusing a boron-doped seaweed-based biochar catalyst after oxidation treatment with peroxymonosulfate. The structure and effects of the present invention are to be explained more specifically through the following examples; however, these examples are merely exemplary descriptions of the present invention, and the scope of the present invention is not limited to these examples. The method of the present invention is characterized by treating groundwater contaminated with antibiotics such as diclofenac through the activation of peroxymonosulfate using boron-doped seaweed-based biochar as a carbon catalyst. The above-mentioned peroxymonosulfate chemically oxidizes organic pollutants and diclofenac in contaminated groundwater. That is, the above-mentioned peroxymonosulfate oxidizes pollutants by absorbing moisture in contaminated groundwater and releasing persulfate ions. The above persulfate ions are