CN113716673A - Method for removing antibiotics - Google Patents
Method for removing antibiotics Download PDFInfo
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- CN113716673A CN113716673A CN202111089515.XA CN202111089515A CN113716673A CN 113716673 A CN113716673 A CN 113716673A CN 202111089515 A CN202111089515 A CN 202111089515A CN 113716673 A CN113716673 A CN 113716673A
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 53
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000011028 pyrite Substances 0.000 claims abstract description 75
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 74
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000002351 wastewater Substances 0.000 claims abstract description 52
- 229930194936 Tylosin Natural products 0.000 claims description 44
- 239000004182 Tylosin Substances 0.000 claims description 44
- WBPYTXDJUQJLPQ-VMXQISHHSA-N tylosin Chemical compound O([C@@H]1[C@@H](C)O[C@H]([C@@H]([C@H]1N(C)C)O)O[C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)CO[C@H]1[C@@H]([C@H](OC)[C@H](O)[C@@H](C)O1)OC)CC)[C@H]1C[C@@](C)(O)[C@@H](O)[C@H](C)O1 WBPYTXDJUQJLPQ-VMXQISHHSA-N 0.000 claims description 44
- 229960004059 tylosin Drugs 0.000 claims description 44
- 235000019375 tylosin Nutrition 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 39
- 230000015556 catabolic process Effects 0.000 abstract description 38
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 description 5
- 239000008363 phosphate buffer Substances 0.000 description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003120 macrolide antibiotic agent Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002634 lipophilic molecules Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
Abstract
The application relates to a method for removing antibiotics, which comprises the following steps: adding pyrite powder into the wastewater to be treated, so that the concentration of the pyrite powder in the obtained mixed wastewater is more than or equal to 0.5g/L, wherein the wastewater to be treated contains antibiotics; and carrying out plasma jet treatment on the mixed wastewater. Pyrite powder capable of reacting with plasma generated H2O2And the like, generate Fenton (Fenton) reaction to generate a large amount of hydroxyl radicals (. OH), so that the degradation effect of the antibiotics is obviously improved. Simultaneously, combining the plasma jet with the pyrite powder utilizes light H2O2And O3Hair waiting deviceThe biological catalytic reaction generates OH, the degradation of organic matters is accelerated, the energy efficiency is improved, and therefore the antibiotics are degraded, and the degradation rate is far higher than that of the antibiotics by independently using plasma or pyrite under the same experimental condition. The method for removing the antibiotics has the advantages of low cost, simple and convenient operation and no secondary pollution, and can efficiently degrade the residual antibiotics in the environment.
Description
Technical Field
The invention relates to the field of ecological environment protection, in particular to a method for removing antibiotics.
Background
At present, antibiotics are widely applied to animal husbandry and aquaculture industry besides being applied to clinical antibacterial treatment. However, antibiotics and derivatives thereof are continuously discharged into the external environment as trace pollutants, and the pollution caused to the environment and the environmental effect caused by the pollution, particularly the pollution to the water body, are not negligible.
The degradation method of antibiotics mainly comprises a traditional treatment method, an advanced oxidation method and the like. Conventional treatment methods include physical, chemical and biological methods.
The physical treatment method is to remove pollutants in water by technologies such as coagulation, adsorption and membrane separation. Although the method of partial adsorption treatment also achieves higher removal rate, antibiotics still exist in the adsorbent and cannot be completely removed, so that secondary pollution is easily caused; and part of the adsorbent is expensive and difficult to regenerate, so that the expected effect is difficult to achieve in practical application. Chemical oxidation is the removal of contaminants by chemical reaction of the oxidizing agent itself with a chemical agent. But is not suitable for large-area use due to higher cost, large energy consumption, more byproducts and the like. The biological removal method mainly comprises the technologies of a biomembrane method, an artificial wetland and the like, mainly depends on the adsorption action of microorganisms, and antibiotic molecules are not completely degraded and can be released into a water environment again to bring secondary pollution. The advanced oxidation method can oxidize and degrade most of organic pollutants which are difficult to degrade into low-toxicity or non-toxic small molecular substances until carbon dioxide (CO)2) And water (H)2O), the degradation efficiency is better, but the treatment cost is higher, and the reaction condition is too harsh. Therefore, how to develop a technology for efficiently degrading residual antibiotics in the environment with low cost, simple operation and no secondary pollution is one of the important issues to be solved at present.
Disclosure of Invention
The embodiment of the invention provides a method for removing residual antibiotics in an environment, which has the advantages of low cost, simple and convenient operation, no secondary pollution and high efficiency.
The embodiment of the application provides an antibiotic removal method, which comprises the following steps:
adding pyrite powder into the wastewater to be treated, so that the concentration of the pyrite powder in the obtained mixed wastewater is more than or equal to 0.5g/L, wherein the wastewater to be treated contains antibiotics;
and carrying out plasma jet treatment on the mixed wastewater.
According to some embodiments, the concentration of pyrite powder in the mixed wastewater is 0.5g/L or less and 5g/L or less.
According to some embodiments, the pyrite powder has a particle size within 100 mesh.
According to some embodiments, the step of subjecting the mixed wastewater to plasma jet treatment comprises:
and carrying out plasma jet treatment on the mixed wastewater for 1-30 min under the conditions that the temperature is 25 +/-2 ℃ and the current intensity of plasma jet is 30-130 muA.
According to some embodiments, the mixed wastewater is subjected to plasma jet treatment for 10-30 min under the conditions that the temperature is 25 +/-2 ℃ and the current intensity of the plasma jet is 110 muA.
According to some embodiments, the method further comprises adjusting the pH of the wastewater to be treated to 3 to 9 or adjusting the pH of the mixed wastewater to 3 to 9 before adding the pyrite powder.
According to some embodiments, the method further comprises adjusting the pH of the wastewater to be treated to 3 to 6 or adjusting the pH of the mixed wastewater to 3 to 6 before adding the pyrite powder.
According to some embodiments, the concentration ratio of the antibiotics to the pyrite of the wastewater to be treated is 1: 50-500.
According to some embodiments, the concentration of the antibiotics in the wastewater to be treated is 8-12 mg/L.
According to some embodiments, the antibiotic is tylosin.
According to the antibiotic removal method provided by the embodiment of the invention, the plasma jet is used for treating the aqueous solution, and H can be generated in water2O2、HNO3、HNO2And O3Etc. oxygen-containing reactive species (ROS), nitrogen-containing reactive species (RNS), and may also generate a dose of ultraviolet light (UV), etc. Pyrite powder capable of reacting with plasma generated H2O2Fenton reaction is carried out to generate a large amount of OH, so that the degradation effect of the antibiotics is obviously improved. Simultaneously, combining the plasma jet with the pyrite powder utilizes light H2O2And O3And the degradation rate is far higher than that of the antibiotic by independently using the plasma and the pyrite under the same experimental condition. The method for removing the antibiotics has the advantages of low cost, simple and convenient operation and no secondary pollution, and can efficiently degrade the residual antibiotics in the environment.
Drawings
Features, advantages and technical effects of exemplary embodiments of the present application will be described below with reference to the accompanying drawings.
FIG. 1 is a graph showing the relationship between the current value and the degradation rate of tylosin in example 1;
FIG. 2 is a graph showing the relationship between the amount of pyrite added and the degradation rate of tylosin in example 2;
FIG. 3 is a graph showing the relationship between the pH of example 3 and the degradation rate of tylosin;
FIG. 4 is a graphical representation of the relationship between the effect of example 4 on the degradation rate of tylosin after addition of the OH inhibitor isopropanol;
FIG. 5 is a graph showing the relationship between the different degradation methods of comparative example 1 and the degradation rate of tylosin.
Detailed Description
Embodiments of the present application will be described in further detail below with reference to the drawings and examples. The following detailed description of the embodiments and the accompanying drawings are provided to illustrate the principles of the application and are not intended to limit the scope of the application, i.e., the application is not limited to the described embodiments.
For a better understanding of the present application, embodiments of the present application are described below with reference to fig. 1 to 5.
The embodiment of the application provides an antibiotic removal method, which comprises the following steps:
adding pyrite powder into the wastewater to be treated, so that the concentration of the pyrite powder in the obtained mixed wastewater is more than or equal to 0.5g/L, wherein the wastewater to be treated contains antibiotics.
And carrying out plasma jet treatment on the mixed wastewater.
Pyrite (FeS)2Pyrite) is widely present in anaerobic environments and is the most widely distributed sulfide in the crust. The oxidation-reduction activity of the pyrite is obviously lower than that of ROS and RNS generated by plasma, and the pyrite cannot degrade and remove antibiotics. Adding pyrite powder into wastewater to be treated, namely wastewater containing antibiotics, so as to obtain mixed wastewater. And the addition amount of the pyrite powder is required to ensure that the concentration of the pyrite powder in the mixed wastewater is greater than or equal to 0.5 g/L. The pyrite powder used may be self-made in the laboratory or purchased commercially.
And then treating the mixed wastewater by using a plasma jet device. Plasma is a non-coherent system consisting of a large number of charged particles, such as electrons, ions, radicals, and neutral particles, and in which the number of positive and negative charges are substantially equal and macroscopically quasi-electroneutrality is exhibited. The plasma jet device can generate plasma jet, namely, a slender plasma with a certain flow speed is generated.
Plasma jet treatment of aqueous solutions to generate H in water2O2、HNO3、HNO2And O3And RON, RNS, and in addition, UV, and the like, may be generated at a certain dose. The ROS and RNS have strong oxidizing property, can treat organic wastewater, nitroaromatic compounds, polymers and the like, and have the advantages of simple operation and capability of being carried out at normal temperature. Research shows that in the plasma jet, a large amount of H can be generated2O2The active substances with equal length and long service life can convert carbon on benzene ring of organic matter into inorganic carbon and finally into CO2And H 20, andand is discharged to the external environment. And when the reaction environment contains OH, the reaction process can be accelerated, and the time cost can be saved.
Although plasma jet devices can theoretically produce OH, the half-life of OH is very short in practice, and the amount produced under the jet of the device is small (without excluding the possibility that the time for measuring its content has exceeded its half-life and is thus deactivated), the possibility of participating in the above reaction is not great.
The applicant found that when the plasma acts in synergy with pyrite, the light generated by the plasma jet can induce the main component FeS of pyrite2Is separated from the H, the photogenerated electrons and holes can be separated from H2O or OH-OH is generated; in addition, due to Fe in pyrite2+Presence of H, which can be generated with the plasma during the plasma jet2O2Fenton reaction is carried out to generate a large amount of OH (see formula 1 and formula 2), which can accelerate the conversion of carbon on the benzene ring of the organic matter into inorganic carbon and finally into CO2And H2And O, and the conversion rate of the reaction is improved. And Fe on the surface of the pyrite2+Can be reacted with H2O2Generation of OH and Fe3+Generation of Fe3+And can be reduced to Fe by electrons2+(ii) a Thereby recycling the above reaction process. Plasma self-generated O3、H2O2OH, etc. with FeS2OH generated by catalysis acts on antibiotics together, so that the antibiotics are decomposed into intermediate products, and then are further decomposed into micromolecular organic acid and inorganic acid, and the micromolecular inorganic acid is finally mineralized into CO2And H2And O. The plasma technology is combined with pyrite to fully utilize light H2O2And O3And the like, generate OH through catalytic reaction, accelerate the degradation of organic matters and improve the energy efficiency of the organic matters. Most antibiotics are organic substances containing benzene rings. Therefore, when the plasma is cooperated with the pyrite to degrade the antibiotic, the antibiotic degradation effect can be obviously improved, and the degradation rate is far higher than that of the antibiotic when the plasma and the pyrite are used alone under the same condition.
Fe2++H2O2→Fe3++OH-+·OH (1)
Fe2++H2O2→Fe2++·OOH+·H+ (2)
According to the antibiotic removal method provided by the embodiment of the invention, the plasma jet is used for treating the aqueous solution, and H can be generated in water2O2、HNO3、HNO2And O3And the like ROS, RNS, and in addition, UV, and the like, may be generated at a certain dose. Pyrite powder capable of reacting with plasma generated H2O2Fenton reaction is carried out to generate a large amount of OH, so that the degradation effect of the antibiotics is obviously improved. Simultaneously, combining the plasma jet with the pyrite powder utilizes light H2O2And O3And the degradation rate is far higher than that of the antibiotic by independently using the plasma and the pyrite under the same experimental condition. The method for removing the antibiotics has the advantages of low cost, simple and convenient operation and no secondary pollution, and can efficiently degrade the residual antibiotics in the environment.
According to some embodiments, the concentration of pyrite powder in the mixed wastewater is 0.5g/L or less and 5g/L or less. At this concentration, the antibiotic can be effectively removed while the amount of pyrite powder is reduced.
According to some embodiments, the pyrite powder with a particle size of 100 meshes has a large specific surface area, and OH and H can be increased2O2And O3And the contact area is equal, so that the reaction rate and efficiency are improved.
According to some embodiments, the step of subjecting the mixed wastewater to plasma jet treatment comprises:
and carrying out plasma jet treatment on the mixed wastewater for 1-30 min under the conditions that the temperature is 25 +/-2 ℃ and the current intensity of plasma jet is 30-130 muA.
The reaction condition is mild, and the degradation rate of the antibiotics is relatively high.
According to some embodiments, the mixed wastewater is subjected to plasma jet treatment for 10-30 min under the conditions that the temperature is 25 +/-2 ℃ and the current intensity of the plasma jet is 110 muA.
According to some embodiments, the method further comprises adjusting the pH of the wastewater to be treated to 3 to 9 or adjusting the pH of the mixed wastewater to 3 to 9 before adding the pyrite powder. Under the condition, the antibiotic is easy to chemically react, so that the original structure of the antibiotic is damaged, and meanwhile, the antibiotic is finally mineralized into a small molecular substance CO under the synergistic action of plasma jet and pyrite2And H2And O. Therefore, the degradation of tylosin is favored under such conditions.
According to some embodiments, the method further comprises adjusting the pH of the wastewater to be treated to 3 to 6 or adjusting the pH of the mixed wastewater to 3 to 6 before adding the pyrite powder. Under the condition, the degradation rate of tylosin can be further improved.
According to some embodiments, the wastewater to be treated has a mass ratio of antibiotics to the pyrite of 1:50 to 500.
According to some embodiments, the concentration of the antibiotics in the wastewater to be treated is 8-12 mg/L.
According to some embodiments, the antibiotic is tylosin.
Examples
Example 1
The method for removing the antibiotics comprises the following steps:
(1) the pyrite powder prepared in the laboratory has the approximate size and the particle size within 100 meshes.
(2) 0.01g of the pyrite powder in step (1) was weighed and added to 10mL of ultrapure water containing tylosin and mixed. Wherein the concentration of the antibiotic is 10 mg/L.
(3) The mixed liquid was treated for a certain period of time in a plasma jet apparatus with current values set to 30 μ A, 40 μ A, 50 μ A, 70 μ A, 90 μ A, 110 μ A and 130 μ A, respectively.
(4) After the completion of the treatment, the sample was filtered through a 0.45 μm filter membrane, and the concentration of residual tylosin in the sample was measured by liquid chromatography (mobile phase acetonitrile: potassium dihydrogen phosphate buffer mobile phase 35:65, measurement wavelength 287nm, flow rate 0.5 mL/min).
(5) Referring to fig. 1, the results show that the current has an effect on the degradation of tylosin, and that a higher current contributes to the degradation of tylosin. Under the current of 30 muA, 40 muA, 50 muA, 70 muA, 90 muA, 110 muA and 130 muA, the degradation rate of tylosin after reaction for 30min can reach 72.42%, 76.905%, 94.75%, 98.73%, 99.025%, 99.71% and 99.45% respectively. The degradation rate of tylosin reaches a maximum at a current of 110 muA. It is presumed that the synergistic effect of the physicochemical effect (high-energy electrons, strong electric field, light, chemically active particles, etc.) and pyrite at this time becomes stronger, thereby promoting the degradation of tylosin. It is to be noted that when the current value is increased from 110. mu.A to 130. mu.A, the degradation efficiency of tylosin is not only not increased but also slightly decreased, and therefore, it is uneconomical to increase the current excessively for the purpose of increasing the degradation rate of tylosin. The current values of the following examples are all set to 110 μ a.
Example 2
The method for removing the antibiotics comprises the following steps:
(1) the pyrite powder prepared in the laboratory has the approximate size and the particle size within 100 meshes.
(2) Weighing 0g, 0.005g, 0.01g, 0.02g, 0.03g, 0.04g and 0.05g of pyrite powder with different masses in the step (1), respectively adding the weighed materials into 10mL of ultra-pure water containing tylosin, and mixing. Wherein the concentration of the antibiotic is 10 mg/L.
(3) The mixed liquid was treated for a certain period of time in a plasma jet apparatus with a set current value of 110 μ A.
(4) After the completion of the treatment, the sample was filtered through a 0.45 μm filter membrane, and the concentration of residual tylosin in the sample was measured by liquid chromatography (mobile phase acetonitrile: potassium dihydrogen phosphate buffer mobile phase 35:65, measurement wavelength 287nm, flow rate 0.5 mL/min).
(5) Referring to FIG. 2, the results show that the degradation rate of tylosin tends to increase and decrease as the amount of pyrite powder added increases, and when the amount is 0.01g, the degradation rate is increasedA maximum of 99.88% was achieved. It is presumed that an increase in the amount of addition promotes the rapid progress of the photo-Fenton reaction, and more OH is produced. However, too much amount of addition causes the catalyst to be accumulated with each other to cause mixing with light and H2O2The contact area of the active particles decreases, and the OH formation rate decreases. Furthermore, the treatment liquid becomes more and more impermeable to UV-Vis light, H2O2The rate of generation of OH by itself undergoing photon decomposition is reduced, resulting in a reduced rate of degradation of tylosin. Therefore, the amount of the pyrite powder added in the following examples was set to 0.01 g.
Example 3
The method for removing the antibiotics comprises the following steps:
(1) the pyrite powder prepared in the laboratory has the approximate size and the particle size within 100 meshes.
(2) Weighing 0.01g of pyrite powder in the step (1), adding the pyrite powder into 10mL of ultra-pure water containing tylosin, and mixing, wherein the concentration of the antibiotic is 10 mg/L. The pH values in the ultra-pure water to which tylosin was added were set to 3, 5.8, 7 and 9, respectively.
(3) The mixed liquid was treated for a certain period of time in a plasma jet apparatus with a set current value of 110 μ A.
(4) After the completion of the treatment, the sample was filtered through a 0.45 μm filter membrane, and the concentration of residual tylosin in the sample was measured by liquid chromatography (mobile phase acetonitrile: potassium dihydrogen phosphate buffer mobile phase 35:65, measurement wavelength 287nm, flow rate 0.5 mL/min).
(5) Referring to fig. 3, the results show that the highest tylosin degradation rate can reach 99.99% at pH 3, and the degradation rate gradually decreases with increasing pH. Presumably, most of macrolide antibiotics are basic lipophilic compounds, and are easy to generate chemical reaction under acidic conditions, so that the original structure of the macrolide antibiotics is damaged, and simultaneously, under the synergistic effect of plasma jet and pyrite powder, the macrolide antibiotics are finally mineralized into small molecular substances CO2And H2And O. Therefore, the degradation of tylosin is favored under acidic conditions.
From the results of the above examples, it can be seen that: the effect of the plasma in cooperation with the treatment of the tylosin with the pyrite powder is better than the degradation effect of the plasma and the pyrite powder on the tylosin, and the optimal experimental conditions that the current value is 110 muA, the adding amount of the pyrite powder is 0.01g and the pH value is 3 are determined. Therefore, the following examples were conducted under the optimum conditions obtained in the above experiments.
Example 4
The method for removing the antibiotics comprises the following steps:
(1) the pyrite powder prepared in the laboratory has the approximate size and the particle size within 100 meshes.
(2) 0.01g of pyrite powder and 5mL of isopropanol in the step (1) were weighed and added to 10mL of ultrapure water containing tylosin and mixed. Wherein the concentration of the antibiotic is 10 mg/L.
(3) And respectively treating the mixed liquid under a plasma jet device for 1min, 2min, 4min, 7min, 10min, 20min and 30min, wherein the current value of the device is set to be 110 muA.
(4) After the completion of the treatment, the sample was filtered through a 0.45 μm filter membrane, and the concentration of residual tylosin in the sample was measured by liquid chromatography (mobile phase acetonitrile: potassium dihydrogen phosphate buffer mobile phase 35:65, measurement wavelength 287nm, flow rate 0.5 mL/min).
(5) Referring to fig. 4, the results show that the degradation efficiency of tylosin is significantly reduced with the addition of isopropanol. The tendency became clear as the plasma treatment time increased, and when a certain time was reached, the curves of the degradation of tylosin with the addition of isopropanol (the curve labeled with isopropanol in the figure) and the degradation of tylosin without the addition of isopropanol (the curve labeled with blank control in the figure) tended to be approximately parallel, and it was presumed that the inhibition of OH generated by the plasma jet apparatus by isopropanol had reached saturation. From this it can be concluded that: OH is directly involved in the degradation process of tylosin.
Comparative example 1
The removal of tylosin (pyrite powder content 0.01g, current 110 muA) by mixing plasma/pyrite powder, plasma and pyrite powder (pyrite) was carried out as follows:
(1) the pyrite powder prepared in the laboratory has the approximate size and the particle size within 100 meshes.
(2) 0.01g of the pyrite powder in step (1) was weighed and added to 10mL of ultrapure water containing tylosin and mixed. Wherein the concentration of the antibiotic is 10 mg/L.
(3) And respectively treating the mixed liquid under a plasma jet device for 1min, 2min, 4min, 7min, 10min, 20min and 30min, wherein the current value of the device is set to be 110 muA.
(4) After the completion of the treatment, the sample was filtered through a 0.45 μm filter membrane, and the concentration of residual tylosin in the sample was measured by liquid chromatography (mobile phase acetonitrile: potassium dihydrogen phosphate buffer mobile phase 35:65, measurement wavelength 287nm, flow rate 0.5 mL/min).
(5) Referring to fig. 5, the results show that after 30min of reaction, the removal rate of tylosin by using plasma alone is within 80%, and the removal rate of tylosin by using pyrite powder alone is close to 10% (actually, adsorption effect, and no degradable antibiotics). Compared with the prior art, the removal rate of the tylosin by the plasma/pyrite powder is obviously accelerated, the tylosin can be removed by 99.7% after the reaction is carried out for 30min, the removal efficiency is higher than the sum of the removal rates of the plasma and the pyrite powder to the tylosin, and a good synergistic effect is shown.
While the present application has been described with reference to preferred embodiments, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the present application, and in particular, features shown in the various embodiments may be combined in any manner as long as there is no structural conflict. The present application is not intended to be limited to the particular embodiments disclosed herein but is to cover all embodiments that may fall within the scope of the appended claims.
Claims (10)
1. A method for removing antibiotics, comprising the steps of:
adding pyrite powder into the wastewater to be treated, so that the concentration of the pyrite powder in the obtained mixed wastewater is more than or equal to 0.5g/L, wherein the wastewater to be treated contains antibiotics;
and carrying out plasma jet treatment on the mixed wastewater.
2. The method for removing antibiotics according to claim 1, wherein the concentration of pyrite powder in the mixed wastewater is 0.5g/L or less and 5g/L or less.
3. The method of claim 1, wherein the pyrite powder has a particle size of 100 mesh or less.
4. The method of claim 1, wherein the step of subjecting the mixed wastewater to plasma jet treatment comprises:
and carrying out plasma jet treatment on the mixed wastewater for 1-30 min under the conditions that the temperature is 25 +/-2 ℃ and the current value of the plasma jet is 30-130 muA.
5. The method for removing antibiotics according to claim 4, wherein the mixed wastewater is subjected to plasma jet treatment for 10 to 30min at a temperature of 25 ± 2 ℃ and a current value of a plasma jet of 110 μ A.
6. The method for removing antibiotics according to claim 1, further comprising adjusting the pH of the wastewater to be treated to 3 to 9 or adjusting the pH of the mixed wastewater to 3 to 9 before adding pyrite powder.
7. The method for removing antibiotics according to claim 6, further comprising adjusting the pH of the wastewater to be treated to 3 to 6 or adjusting the pH of the mixed wastewater to 3 to 6 before adding pyrite powder.
8. The method for removing antibiotics according to claim 1, wherein the concentration ratio of the antibiotics to the pyrite in the wastewater to be treated is 1: 50-500.
9. The method for removing antibiotics according to claim 8, wherein the concentration of antibiotics in the wastewater to be treated is 8-12 mg/L.
10. The method for removing antibiotics according to any one of claims 1 to 9, wherein the antibiotics are tylosin.
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| CN112142158A (en) * | 2020-10-23 | 2020-12-29 | 大连海洋大学 | Method for removing antibiotic residues in aquaculture tail water |
| CN113044951A (en) * | 2021-03-19 | 2021-06-29 | 西安交通大学 | Method for degrading antibiotics in water by plasma in cooperation with sulfite and ferric salt |
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| CN104961222A (en) * | 2015-06-08 | 2015-10-07 | 浙江大学 | Method for degrading organic pollutants in water under synergetic catalysis of plasma and pyrite |
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