KR100601113B1 - Method of decomposing antibacterial agent by radiation - Google Patents

Abstract

The present invention relates to a method for decomposing various antimicrobial agents present in by-products of natural ecosystems and environmental pollutants through radiation irradiation, natural ecosystem containing antimicrobial agents in the presence of N ₂ O gas, sewage water, sewage sludge, serving, livestock manure Or it is characterized by the method of decomposing the antimicrobial agent through the irradiation of food waste, the decomposition method according to the present invention can remove the toxicity caused by the organism as well as the toxicity of the antimicrobial agent, as a non-degradable organic toxic substance Known antimicrobial agents have the advantage of improving and maximizing biological treatment, composting and feed efficiency by using irradiation technology.

Antibacterial, antibiotics, antimicrobial decomposition, radiation, gamma rays

Description

Method of decomposing antibacterial agent by radiation

1 is a change in gamma radiation dose, O ₂ and N ₂ O gas injection and change of Cefaclor Total Organic Carbon (TOC, mg / L) at pH 2,

2 is a change in gamma-irradiation, O ₂ and N ₂ O gas injection and change of Total Organic Carbon (TOC, mg / L) of Oxytetracycline at pH2.

The present invention relates to a method for decomposing antimicrobial agents including various antibiotics present in natural ecosystems and environmental pollutant treatment by-products through irradiation.

Recently, antimicrobial agents are not only administered to the human body, but are also supplied in large quantities in animal feed, and thus, wastewater containing wastewater, wastewater sludge, servings, livestock manure or food wastes are exposed to natural ecosystems. Antimicrobial resistance genes caused by E. coli are transferred to pathogens, resulting in a deadly threat to humans.

However, the antimicrobial agent that is finally discharged into the natural ecosystem is not included in the standard of discharged water at home and abroad, so the development of the removal technology is very minimal, and the antimicrobial agent is not only difficult to decompose due to its stable chemical structure, but also decomposes. Even if there is a possibility of conversion to various carcinogenic substances there is a difficulty in decomposition.

In particular, there is little research on the treatment of specific antimicrobial agents in Korea, and it is the degree to measure the antimicrobial agent remaining in the natural ecosystem and study the effects on the biodegradation of existing sewage treatment plants and natural photochemical reactions. Livestock manure or food waste is limited in terms of recycling resources because it is difficult to mature biologically due to the toxicity of antimicrobial agents during composting and feed.

In Japanese Laid-Open Patent Publication No. 2004-7419, it is known to a method characterized in that the decomposition treatment of the water contaminated with medicines and quasi-drugs by direct irradiation with ozone in the presence of ozone, the decomposition process of these, Rather than decomposing the antimicrobial agent into a harmless compound, the radical promotes chemical bonds to form oligomers or high molecular weight polymers.

The present invention has been made to solve the above problems, an object of the present invention is to completely inorganicize the antimicrobial agent that may exist in the natural ecosystem or exist after applying the existing environmental treatment technology using an efficient irradiation method It provides a way to maximize the biodegradation efficiency of existing sewage treatment plants by mineralization or removal of toxicity. It also provides a method of biodegradation in the biodegradation process of wastewater, pharmaceutical wastewater and other industrial wastewater and the composting and feeding of livestock manure, phosphate, wastewater sludge, and food waste by decomposing antimicrobial agents by irradiation. will be.

The present invention relates to a method for decomposing antimicrobial agents containing various antibiotics present in natural ecosystems and environmental pollutant by-products by irradiation, to achieve the above object, containing an antimicrobial agent in the presence of N ₂ O gas. The method of decomposing an antimicrobial agent, characterized in that the antimicrobial agent is completely dehydrogenated by removing the toxicity or by removing the toxicity by irradiating the natural ecosystem, wastewater, wastewater sludge, serving, livestock manure or food waste. It is done.

Hereinafter, the present invention will be described in detail, but the following description does not limit the present invention.

In the present invention, the antimicrobial agent decomposed by the method according to the present invention includes Cephalosporins family, one of the β-Lactam family, the most frequently administered antibacterial agent to humans, and the addition of livestock feed and the most commonly administered Tetracycline family. Lamphenicol, macroride-based and aminoglycosides.

In the decomposition method of the antimicrobial agent by irradiating the radiation according to the present invention, the decomposition efficiency has an advantage that it can be applied to various kinds of wastes, since the pH is all in the range of 1 to 13, and preferably in the range of pH1 to pH3. .

On the other hand, when radiation is irradiated to an aqueous solution, ionic substances such as hydroxyl radicals, hydrogen atoms, and hydride electrons are generated by hydration decomposition, and among the ionic substances, hydroxyl radicals are very effective for inorganicizing the material to be treated. It is known.

However, natural ecosystems, wastewater, sewage sludge, servings, livestock manure or food waste, which contain antimicrobial agents, have low concentrations, and there are a wide variety of substances in the treated substances, in addition to antimicrobial agents. Since the hydroxyl radical generated by irradiation reacts very quickly with the hydration electrons as in reaction (1) and part of it disappears, it is necessary to irradiate more than an appropriate amount of radiation to obtain satisfactory decomposition results. Preference is given to adding one or more selected from N ₂ O, Thiourea and EDTA to generate and maintain the appropriate amount of radicals.

^{_{e aq - + · OH → OH}} - (1)

In particular, it is preferable to add a nitrous oxide (N ₂ O) gas, which generates a nitrogen gas and hydroxyl radicals by reacting the generated hydride electrons very rapidly with dissolved nitrous oxide in water as in Scheme (2), The reaction of the hydride electrons with the hydroxyl radical reaction is suppressed, which is due to the presence of a large amount of hydroxy radicals in the material to be treated, thereby increasing the decomposition efficiency of the antimicrobial agent.

^{_{e aq - + N 2 O →}} OH - + · OH + N 2 (2)

In addition, when nitrous oxide is dissolved in the material to be treated, the radicals generated are transferred not only to the antimicrobial agent but also to various organic compounds contained in the material to be treated so that the compounds do not decompose and promote chemical bonds with each other to promote oligomer or high molecular weight. Since the reaction to form the polymer of the reaction is prevented from proceeding more predominantly, high decomposition rate can be obtained even if the irradiation time and irradiation amount of the radiation are kept to a minimum.

In the decomposition method of the antimicrobial agent by radiation according to the present invention, the radiation dose of radiation is preferably 1 Gy to 20 MGy based on the absorbed dose, and the radiation is from Co ⁶⁰ , Co ⁵⁶ , Sc ⁴⁶ , Na ²² , Cs ¹³⁴ . Gamma rays generated, or gamma rays generated from electron beam accelerators, electron beams, or plasma are all possible.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1

Cefaclor, one of the most administered antimicrobial agents, was prepared in an aqueous solution of 30 mg / L concentration, and then the irradiation dose of gamma ray to the aqueous solution was 0 kGy, 0.1 kGy, 0.2 kGy, 0.3 kGy, 0.4 kGy, 0.6 kGy, 0.8 kGy, 1 The change in the degradation rate of Cefaclor was measured as the change in the concentration of Cefaclor (mg / L) in aqueous solution while changing to kGy. In the condition of Example 1, the sample was filled in a 1L glass bottle and sealed without head space, and the irradiation rate was set to 10-100 Gy / min. By adopting a method of adjusting the total dose by varying the irradiation distance. Was fixed at 10 minutes.

Example 2

The same procedure as in Example 1 was carried out except that Oxytetracycline, which is widely used in livestock, was used as a 50 mg / L aqueous solution instead of the aqueous solution of Cefaclor.

[Table 1] Changes in the Degradation Rate of Cefaclor and Oxytetracycline According to the Gamma Irradiation

As can be seen in Table 1, it can be seen that in the case of Cefaclor, gamma-irradiation was completely decomposed when the amount of gamma-irradiation was 0.8 kGy or more, and oxytetracycline was mostly decomposed at 1 kGy.

Example 3

In the irradiation of gamma rays of 0 kGy, 10 kGy, 20 kGy, 30 kGy, 40 kGy, 60 kGy, 100 kGy to a solution of Cefaclor (30 mg / L), the amount of TOC and the amount of TOC that were investigated by adding oxygen or N ₂ O gas The amount of TOC change in the case of irradiating without adding was measured.

In the condition of Example 3, the sample was saturated with oxygen or N ₂ O gas in an aqueous solution using high purity oxygen or high purity N ₂ O gas in a gas washing bottle, and then sealed in a 1L glass bottle without head space. In addition, the irradiation rate was 10 to 100 kGy / hr with different irradiation distances, and the irradiation time was fixed at 10 hours.

Example 4

The same procedure as in Example 3 was carried out except that an aqueous solution of Oxytetracycline (50 mg / L) was used instead of the aqueous solution of Cefaclor (30 mg / L).

[Table 2] TOC Variation of Cefaclor and Oxytetracycline According to Addition of Oxygen or N ₂ O Gas

As shown in Table 2 and FIGS. 1 and 2, when Cefaclor is irradiated with gamma rays of various doses, when only gamma rays are irradiated without a gas additive, approximately 45% of Cefaclor is inorganicized at 40 kGy. _{In the} case of saturating the Cefaclor aqueous solution with ₂ gas and irradiating with gamma rays, the mineralization was about 10% at 10 kGy and more than 90% at 100 kGy. On the other hand, gamma-irradiation after filling with N ₂ O gas as an additive shows nearly 100% mineralization efficiency at 20 kGy. In the case of Oxytetracyline, only 27% of Oxytetracyline was inorganicized at 40 kGy when gamma-irradiation was performed without adding gas additives, and at 30 kGy when it was irradiated with gamma-ray after saturation of O ₂ gas, about 62% was mineralized. Gamma-irradiation after filling N ₂ 0 gas as an additive showed nearly 100% mineralization efficiency above 30 kGy.

Example 5

The aqueous solution of Cefaclor (30 mg / L) was adjusted to pH 2, followed by saturation of oxygen, followed by irradiation with gamma rays, in the same manner as in Example 3.

Example 6

Oxytetracycline (50mg / L) solution was adjusted to pH 2, and the same procedure as in Example 3 except for irradiating gamma rays after saturating oxygen.

TABLE 3 Changes in TOC concentration after irradiation with oxygen gas and irradiation at pH 2

As shown in Table 3, when irradiated with radiation at pH 2, it can be seen that the decomposition rate is increased compared to the case where the pH is not adjusted.

As described above, the antimicrobial decomposition method using radiation according to the present invention has the effect of minimizing the amount emitted to the natural ecosystem by completely decomposing and mineralizing the antimicrobial agent contained in the wastewater using radiation, N ₂ 0 By using gas irradiation as an additive, it is possible to maximize the existing biological treatment efficiency by converting various antibacterial agents that may exist in natural ecosystem and byproducts of environmental pollutants into non-toxic low-molecular substances. Biocomposition is difficult due to the toxicity of antimicrobial agents in composting and feeding wastes, wastewater sludges, and food wastes. Therefore, it is possible to improve and maximize the efficiency of biological composting and feed by using irradiation technology.

Claims (8)

delete A method of decomposing an antimicrobial agent, characterized in that irradiated with radiation by adding one or more selected from N ₂ O, O ₂ , Thiourea and EDTA to sewage water, sewage sludge, serving, livestock manure or food waste containing the antimicrobial agent. The method of claim 2, wherein N ₂ O is added during irradiation. The method of claim 2, wherein the pH of the antimicrobial agent, characterized in that carried out in the range of 1-3. The method for decomposing the antimicrobial agent according to claim 2 or 3, wherein the irradiation dose of radiation is 1 Gy to 20 MGy based on the absorbed dose. The method of claim 5, wherein the radiation is gamma rays generated from Co ⁶⁰ , Co ⁵⁶ , Sc ⁴⁶ , Na ²² , Cs ¹³⁴ , or gamma rays, electron beams or plasma generated from the electron beam accelerator. 6. The method of claim 5, wherein the antimicrobial agent is tetracycline or β-Lactam. A method of treating wastewater, wastewater sludge, servings, livestock manure or food waste by the decomposition method of the antimicrobial agent using irradiation according to claim 3, and composting and feeding by biological treatment.

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