CN112759157A - Method for removing antibiotics in wastewater through catalysis of ionizing radiation and ozone - Google Patents
Method for removing antibiotics in wastewater through catalysis of ionizing radiation and ozone Download PDFInfo
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000005865 ionizing radiation Effects 0.000 title claims abstract description 52
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 43
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 43
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 21
- 239000002351 wastewater Substances 0.000 title claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
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- 230000003647 oxidation Effects 0.000 claims abstract description 35
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- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 11
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 11
- 238000010894 electron beam technology Methods 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052598 goethite Inorganic materials 0.000 claims description 3
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 230000002285 radioactive effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
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- 238000005516 engineering process Methods 0.000 abstract description 17
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- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 229960005404 sulfamethoxazole Drugs 0.000 description 54
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 54
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- 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
- 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
- C02F1/72—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention provides a method for removing antibiotics by combining ozone catalysis and ionizing radiation, which utilizes an iron-based catalyst to respectively improve the degradation and mineralization effects of an ionizing radiation technology and ozone oxidation on organic matters, and simultaneously utilizes the synergistic effect of ozone oxidation and ionizing radiation on the removal of antibiotic organic pollutants in water to improve the removal and mineralization efficiency of the antibiotics in water, shorten the treatment time and simplify the requirements of treatment conditions.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for degrading antibiotics in wastewater by enhancing ozone oxidation and ionizing radiation.
Background
The widespread use of antibiotics has resulted in their widespread contamination in the environment. Antibiotics themselves have biological toxicity and potential risks of inducing microbes to develop resistance and resistance genes, posing a threat to ecological safety and human health. The prior technology for treating antibiotic wastewater mainly comprises biotechnology, physical technology and chemical technology. Due to the characteristics of antibiotics, the biodegradability is poor, and the antibiotics are difficult to be effectively degraded by the traditional biological treatment method (such as an activated sludge method, a membrane bioreactor and the like). Physical methods (e.g., coagulation sedimentation, membrane filtration, etc.) do not completely remove the antibiotic from the environment. Some chemical methods (e.g., photochemical, electrochemical oxidation, etc.) are effective at oxidizing or degrading antibiotics in water, but generally have a low mineralization rate and risk of increased biotoxicity of the oxidation products. How to improve the mineralization rate of antibiotics becomes the research focus of the industry.
In the prior art, a method for treating organic matters and antibiotics in wastewater by adopting ozone oxidation and ionizing radiation technologies exists, for example, CN201310355422.6 discloses a method for treating organic wastewater by utilizing ozone oxidation and ionizing radiation, but when the method is used for treating organic wastewater, the method is kept stand for 6 to 24 hours after being pretreated by ozone, and then the ionizing radiation is carried out after ozone is automatically exhausted, so that the wastewater treatment time is longer, and in addition, the method is used for irradiating after ozone is exhausted, so that the synergistic effect between ozone molecules and radicals generated by ionizing radiation is difficult to utilize; CN201811229606.7 discloses a method for degrading antibiotics in biogas slurry in a farm by using micro-electrolysis-ozone, wherein ferromagnetic ore is used as a catalyst, but the method is greatly influenced by pH conditions, the pH of a reaction solution needs to be adjusted to acidity (pH 3-5), the treatment cost is increased, the preparation of a composite microsphere material is complex, and in addition, micro-electrolysis and ozone are two independent treatment process sections; CN201910362654.1 discloses that the iron-based catalyst is used for strengthening ozone oxidation treatment of organic pollutants, only a single ozone catalysis technology is adopted, a combined process is still necessarily developed aiming at the mineralization efficiency of certain specific pollutants, and the process mineralization capacity is further enhanced, in addition, high-efficiency oxidants such as ferrate and hydrogen peroxide are consumed during the synthesis of the iron-based catalytic material in the technology, and the catalyst manufacturing cost is not very economic; patent CN200810223013.X reports a method for removing cyanide in wastewater by combining ionizing radiation with ozone, but the method is also greatly limited by pH, and the pH of wastewater to be treated needs to be adjusted to be alkaline or acidic according to the form of cyanide in wastewater to be treated, and then ozone and radiation treatment are carried out, so that a synergistic effect can be generated.
Technical scheme
The invention aims to solve the technical problems of low mineralization rate, complex treatment procedure and the like in the existing technology for treating antibiotics in wastewater, and provides a method for removing antibiotics by combining ozone catalysis and ionizing radiation.
Based on the above, the invention provides a method for removing antibiotics in wastewater by ozone catalysis in cooperation with ionizing radiation, which specifically comprises the following steps:
firstly, adding a certain amount of iron-based catalyst into wastewater containing antibiotics, and uniformly stirring;
and secondly, introducing ozone into the wastewater to be treated, performing ozone oxidation treatment and ionizing radiation simultaneously, and keeping the ozone oxidation treatment and the ionizing radiation treatment synchronously.
Wherein, the ozone treatment adopts an iron-based catalyst which can be natural or synthetic materials such as magnetite, iron oxyhydroxide, goethite, ferrite, ferrihydrite and the like with wide sources.
Wherein the addition amount of the iron-based catalyst in the wastewater is 0.05-1.0 g/L.
Wherein the pH application range of the antibiotic wastewater is 2.5-11.
Wherein the ionizing radiation is performed using gamma rays or a high-energy electron beam.
Wherein the gamma-rays are generated from radioisotopes60Co or137Cs decay, and the high energy electron beam is generated by an electron accelerator.
Wherein the irradiation dose of the ionizing radiation is 0.2-5.0 kGy.
Wherein the concentration of the antibiotics in the waste liquid is 1.0-100 mg/L.
Wherein the ozone is generated by an ozone generator, and the addition amount is 0.1-2.8 mol/L.
Wherein the ionizing radiation duration is less than 30 min.
The method simultaneously acts ozone oxidation, iron-based catalyst and ionizing radiation on the wastewater containing antibiotics, and simultaneously makes full use of the ozone dissolved in the water and generates more hydroxyl radicals by utilizing the reinforcing effect of the iron-based catalyst on the ozone oxidation, the reinforcing effect of the iron-based catalyst on the ionizing radiation and the synergistic effect between the ionizing radiation and the ozone oxidation, thereby improving the removal and mineralization effects of the antibiotics. The process can greatly improve the removal and mineralization efficiency of pollutants, reduce the emission of ozone tail gas, reduce the treatment cost of the ozone tail gas and improve the utilization rate of ozone.
Advantageous effects
The method can realize the high-efficiency removal and mineralization of the antibiotic organic pollutants in the water. The method can improve the utilization rate of ozone, reduce the cost of tail gas treatment in the ozone oxidation process, and effectively improve the removal rate and the mineralization rate of organic pollutants by utilizing the catalytic action of the iron-based catalyst on the two technologies and the synergistic effect of ozone oxidation and ionizing radiation. The treatment method can be carried out at normal temperature under the condition of relatively wide pH adjustment, is simple and convenient to operate, has short treatment time, has no selectivity on organic pollutants, can be widely applied to treatment of one or more antibiotics, and has wide application prospect in the field of environmental protection.
Drawings
FIG. 1 comparison of the effect on TOC of Sulfamethoxazole (SMX) solutions treated in different ways;
FIG. 2 shows the effect of ozone-enhanced co-irradiation treatment of Sulfamethoxazole (SMX) with iron oxyhydroxide and ferrihydrite;
FIG. 3 shows the effect of ozone co-irradiation and iron oxyhydroxide enhanced ozone co-irradiation on SMX at different pH.
Detailed Description
The invention provides a method for removing antibiotics in wastewater by ozone catalytic oxidation and ionizing radiation, and aims to promote mineralization of antibiotics and realize harmless treatment of the antibiotics. The method can be applied to the antibiotic treatment in refractory wastewater such as pharmaceutical wastewater, medical wastewater, effluent of sewage plants and the like containing antibiotics.
The invention provides a method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation, which comprises the following steps:
firstly, adding a certain amount of iron-based catalyst into wastewater containing antibiotics, and uniformly stirring;
and secondly, introducing ozone into the wastewater to be treated, performing ozone oxidation treatment and ionizing radiation simultaneously, and keeping the ozone oxidation treatment and the ionizing radiation treatment synchronously.
The treatment of pollutants by ozone oxidation technology can be generally divided into direct oxidation reaction and indirect oxidation reaction. The direct oxidation reaction is that ozone molecules directly act on pollutants, and can be divided into the following steps according to the principle: redox reactions, cycloaddition reactions, electrophilic substitution reactions, nucleophilic reactions, and the like. Because the oxidation of ozone molecules has selectivity, direct oxidation reactions can only act on specific molecular structures, so that ozone oxidation only plays a role in removing part of organic pollutants, and the application of ozone oxidation is limited. The indirect oxidation reaction is that ozone dissolved in water generates particles (such as hydroxyl radical (. OH), E) with higher reactivity in the decomposition process02.80V) and OH is not selective and oxidizes almost all organic pollutants. In this regard, indirect oxidation reactions are more advantageous in treating organic pollutants than direct oxidation reactions.
Due to the limited solubility of ozone and the relatively stable nature of ozone under acidic and neutral conditions, the amount of hydroxyl radicals produced is relatively small, affecting the efficiency of the indirect oxidation reaction. The promoting effect of the transition metal catalyst on the indirect oxidation of ozone has been confirmed in previous studies, and the principle is as follows:
2O3+Me-OH→Me-O2 -·+HO3·+O2 (1)
O3+Me-O2 -·+H2O→Me-OH+HO3·+O2 (2)
O3+Me-OH2 +→Me-OH+·+HO3· (3)
Me-OH+·+H2O→Me-OH2 ++·OH (4)
HO3·→·OH+O2 (5)
the addition of transition metal can effectively increase O3The utilization rate of the organic pollutants can lead more OH to be generated in the system, thereby promoting the removal and mineralization of the organic pollutants.
On the other hand, water molecules, when exposed to ionizing radiation (gamma rays or electron beams), form a series of active species, mainly comprising eaq -，H·，·OH，H2，H2O2And H3O+。
H2O→·OH(2.8)+eaq -(2.7)+H·(0.6)+H2(0.45)+H2O2(0.72)+H3O+(2.7)(6)
The number in parentheses in the formula (6) represents the yield (G value) of each active particle, and represents the number of particles released per 100eV of energy absorbed, in units of. mu. mol. J-1。
In Fe2+In the presence of H2O2Will be partially converted into OH to form Fenton effect.
Fe2++H2O2→·OH+Fe3++OH- (7)
2·OH→H2O2 (8)
·OH+H2O2→·HO2+H2O (9)
In addition, in the presence of ozone, ozone molecules also react with active particles generated by radiation, thereby promoting the generation of OH, and forming a synergistic effect.
eaq -+O3→O3 -· (10)
O3 -·+H+→HO3· (11)
H·+O3→HO3· (12)
HO3·→·OH+O2 (13)
By adopting the method for treating by combining ionizing radiation with ozone oxidation catalysis, the whole treatment time is no more than 30min at most, the effect of promoting the generation of free radicals by the synergistic reaction of ozone and irradiation is fully utilized, and the added catalysis strengthens the indirect oxidation effect of ozone and the Fenton effect in an irradiation system, thereby obviously shortening the treatment time of the existing treatment method.
The ozone treatment adopts an iron-based catalyst which can be natural or synthetic materials such as magnetite, iron oxyhydroxide, goethite, ferrite, ferrihydrite and the like, wherein the addition amount of the iron-based catalyst in the wastewater is 0.05-1.0g/L, and the addition amount of ozone is 0.1-2.8 mol/L.
Different from the existing method, in the method provided by the invention, the pH of the antibiotic wastewater is not required to be regulated usually, the pH is within the application range of 2.5-11, acid and alkali are not required to be added generally, the method is more economical and convenient, and the catalytic material is natural minerals with wide sources.
Ionizing radiation is carried out using gamma rays or high-energy electron beams, the gamma rays being derived from radioisotopes60Co or137Cs decays, the high-energy electron beam is generated by an electron accelerator, and the irradiation dose of the ionizing radiation is 0.2-5.0 kGy.
The concentration of the antibiotics in the waste liquid is 1.0-100 mg/L.
The following embodiments are described in detail to solve the technical problems by applying technical means to the present invention, and the implementation process of achieving the technical effects can be fully understood and implemented.
Comparative example 1 Oxidation treatment with ozone alone
The treatment in this example was 20mg/L Sulfamethoxazole (SMX), and the solution was prepared from deionized water and analytically pure reagents and had an initial pH of 5.2. Ozone is generated by an ozone generator, and the ozone generation concentration is 4.5 mg/min. The experimental results were determined using a high performance liquid chromatograph (Agilent1200Series, Agilent, USA). The mineralizing effect of antibiotics was quantified as the removal rate of Total Organic Carbon (TOC) in aqueous solution, and the TOC content was determined by TOC/TN 2100 analyzer (Analytik Jena AG Corporation). The pH of the reaction solution was measured using a Mettler S220-K desk type pH meter.
The effect of ozone oxidation treatment of SMX on SMX and TOC removal for different treatment times is shown in Table 1.
TABLE 1 Effect of ozone Oxidation treatment of SMX
The result shows that the simple ozone oxidation system has good degradation performance on SMX, and the removal rate of SMX can reach 100% within 15 minutes. In contrast, the mineralization effect of ozone oxidation on SMX is unsatisfactory, the removal rate of TOC is less than 13% after 30 minutes of ozone system treatment, and TOC is removed relatively obviously only in the first 30 minutes of reaction, and the change of TOC is relatively weak after 30 minutes of reaction.
Comparative example 2 treatment with ionizing radiation alone
The treatment in this example was 20mg/L Sulfamethoxazole (SMX), and the solution was prepared from deionized water and analytically pure reagents and had an initial pH of 5.2. The experimental results were determined using a high performance liquid chromatograph (Agilent1200Series, Agilent, USA). The Total Organic Carbon (TOC) content in the aqueous solution was determined by TOC/TN 2100 analyzer (Analytik Jena AG Corporation). The pH of the reaction solution was measured using a Mettler S220-K desk type pH meter.
The radiation source adopts a 60Co radiation device of the nuclear energy and new energy technology research institute of Qinghua university, and the central pore canal dosage rate is 320 Gy/min. In the experiment, 30mL of SMX solution is taken each time and put into a 50mL irradiation-resistant tube and placed in a central hole for irradiation. Experiments examined the effect of ion irradiation on SMX removal at different absorbed doses.
The results of the irradiation treatment of SMX at different doses for the concentration of SMX and the removal of TOC are shown in Table 2.
TABLE 2 Effect of irradiation treatment SMX
The irradiation treatment result shows that the SMX in the water body can be well removed by simply adopting the ionizing radiation technology, and the SMX can be completely removed when the absorbed dose reaches more than 2.0 kGy. Irradiation treatment gave higher TOC removal, 14.9%, than when SMX was completely degraded (15min) as in example 1. Moreover, the removal rate of TOC was gradually increased as the absorbed dose increased, and the removal rate of TOC reached 24.4% when the absorbed dose was 5 kGy.
Comparative example 3 ozone oxidation and ionizing radiation synergy
The treatment in this example was 20mg/L Sulfamethoxazole (SMX), and the solution was prepared from deionized water and analytically pure reagents and had an initial pH of 5.2. Ozone is generated by an ozone generator, the ozone generation rate is 4.5mg/min, and the ozone introduction time and the irradiation duration time are equal. The detection method was the same as in comparative example 1.
The radiation source adopts a 60Co radiation device of the nuclear energy and new energy technology research institute of Qinghua university, and the central pore canal dosage rate is 320 Gy/min. In the experiment, 30mL of SMX solution is taken each time and put into a 50mL irradiation-resistant tube and placed in a central hole for irradiation. Experiments examined the effect of ion irradiation on SMX removal at different absorbed doses.
The results of treating SMX with ozone in combination with irradiation at different doses for SMX concentration and TOC removal are shown in Table 3.
TABLE 3 effect of ozonation in conjunction with irradiation treatment of SMX
The sum of the removal rate of TOC (22.0%) obtained by (13.2%) and 1.0kGy (8.8%) of the single irradiation treatment is high, which indicates that the synergistic effect of 1+1>2 is obvious in the combined system.
EXAMPLE 1 iron-based catalyst synergized with ozone oxidation and ionizing radiation
The treatment in this example was 20mg/L Sulfamethoxazole (SMX), and the solution was prepared from deionized water and analytically pure reagents and had an initial pH of 5.2. Ozone is generated by an ozone generator, the ozone generation rate is 4.5mg/min, and the ozone introduction time and the irradiation duration time are equal. The detection method was the same as in example 1.
The radiation source adopts a 60Co radiation device of the nuclear energy and new energy technology research institute of Qinghua university, and the central pore canal dosage rate is 320 Gy/min. In the experiment, 30mL of SMX solution is taken each time and put into a 50mL irradiation-resistant tube and placed in a central hole for irradiation. Experiments examined the effect of ion irradiation on SMX removal at different absorbed doses. The dosage of the iron-based catalyst is 0.1 g/L.
The removal effects of different doses of SMX on the concentration of SMX and TOC are shown in Table 4 by using an iron-based catalyst, namely magnetite enhanced ozone and irradiation.
TABLE 4 Magnetite-enhanced ozone oxidation synergistic irradiation treatment effect on SMX
As can be seen by comparing Table 3 and Table 4, the addition of the iron-based catalyst oxidatively degrades SMX at a lower absorbed dose (0.5 kGy). Under the condition of the same irradiation dose and ozone adding amount, the removal rate of TOC after the iron-based catalyst is added is improved by 9.9-15.4%, which shows that the iron-based catalyst has obvious promotion effect on the mineralization effect of sulfamethoxazole.
Comparative example 4 comparison of catalytic ozonation, catalytic ionizing radiation, ozone in cooperation with ionizing radiation and iron-based catalyst enhanced ozone catalytic in cooperation with ionizing radiation
The treatment in this example was 20mg/L Sulfamethoxazole (SMX), and the solution was prepared from deionized water and analytically pure reagents and had an initial pH of 5.2. Ozone is generated by an ozone generator, the ozone generation rate is 4.5mg/min, and the ozone introduction time and the irradiation duration time are equal. The detection method was the same as in comparative example 1.
The radiation source adopts a 60Co radiation device of the nuclear energy and new energy technology research institute of Qinghua university, and the central pore canal dosage rate is 320 Gy/min. In the experiment, 30mL of SMX solution is taken each time and put into a 50mL irradiation-resistant tube and placed in a central hole for irradiation. Experiments examined the effect of ion irradiation on SMX removal at different absorbed doses. The dosage of the iron-based catalyst is 0.1 g/L.
The effect of using iron-based catalyst magnetite to enhance ozone in conjunction with irradiation to treat SMX at a dose of 1.0kGy (reaction time of about 3.2min) on the removal of TOC from SMX solution is shown in FIG. 1.
As can be seen from fig. 1, comparing the data in tables 1 and 2, when the irradiation dose is 1.0kGy, the addition of the catalyst can promote the removal of TOC in the antibiotic solution by the system, but under this condition (reaction time about 3.2min), the improvement effect is very limited (TOC increase rate is not enough 4%), the ozone synergistic irradiation has a better synergistic response, and the removal rate of TOC can be significantly improved, and when the catalyst is added, the synergistic effect is further improved obviously, and the improvement (increase of TOC removal rate by about 11%) is not the simple addition (about 6%) of the improvement effect when the catalyst is added to the ozone system (increase by about 4%) and the irradiation system (increase by about 2%) alone, which indicates that the ozone catalysis synergistic irradiation system has a better synergistic effect.
Example 2 comparison of different iron-based catalysts
The treatment in this example was 20mg/L Sulfadimidine (SMT), and the solution was formulated with deionized water and analytical reagents and an initial pH of 5.2. Ozone is generated by an ozone generator, the ozone generation rate is 4.5mg/min, and the ozone introduction time and the irradiation duration time are equal. The detection method was the same as in example 1.
The radiation source adopts a 60Co radiation device of the nuclear energy and new energy technology research institute of Qinghua university, and the central pore canal dosage rate is 320 Gy/min. In the experiment, 30mL of SMX solution is taken each time and put into a 50mL irradiation-resistant tube and placed in a central hole for irradiation. Experiments examined the effect of ion irradiation on SMX removal at different absorbed doses. The iron-based catalyst selects iron oxyhydroxide and ferrihydrite, and the adding amount is 0.1 g/L.
The removal effect of the iron-based catalyst iron oxyhydroxide and ferrihydrite enhanced ozone on TOC under the irradiation dose of 1.0kGy of SMX is shown in figure 2.
As can be seen from FIG. 2, when SMX is treated by ozone combined irradiation of 1.0kGy, the removal rate of TOC is about 30.3%, while the removal rates of TOC by adding 0.1g/L iron oxyhydroxide and ferrihydrite are 49.2% and 53.5%, respectively, and the removal rates of TOC are improved by nearly 20% and 24%, respectively. The result shows that the iron-based catalyst, namely the iron oxyhydroxide and the ferrihydrite, can greatly promote the mineralization and removal effect of the combined system on the antibiotics.
Example 3 comparison of enhanced systems with non-enhanced systems at different pH conditions
The treatment target in this example was 20mg/L Sulfadimidine (SMT), and the solution was formulated with deionized water and analytical reagents, with initial pH adjusted to 2.5, 4.5, 7.0, 9.0, 11.0, respectively. Ozone is generated by an ozone generator, the ozone generation rate is 4.5mg/min, and the ozone introduction time and the irradiation duration time are equal. The detection method was the same as in example 1.
The radiation source adopts a 60Co radiation device of the nuclear energy and new energy technology research institute of Qinghua university, and the central pore canal dosage rate is 320 Gy/min. In the experiment, 30mL of SMX solution is taken each time and put into a 50mL irradiation-resistant tube and placed in a central hole for irradiation. Experiments examined the effect of ion irradiation on SMX removal at different pH conditions. The amount of the iron-based catalyst (iron oxyhydroxide) added was 0.1 g/L.
Under different pH values, the removal effect of adding iron-based catalyst to strengthen ozone synergistic irradiation and processing SMX (irradiation dose of 1.0kGy) on TOC during adding catalysis is shown in figure 3.
As can be seen from FIG. 3, when the solutions to be treated have different pH values, the removal rate of TOC of the combined system (strengthened system) is increased by 21-24% when 0.1g/L of iron oxyhydroxide is added, compared with the case that SMX is treated by ozone combined irradiation of 1.0kGy (non-strengthened system). The result shows that the iron-based catalyst can greatly promote the mineralization and removal effect of the combined system on the antibiotics under different pH conditions, and the iron-based material reinforced ozone synergistic irradiation treatment antibiotics have good applicability under extremely wide pH conditions.
All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are based on the new products of the invention and belong to the reserved rights.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for removing antibiotics in wastewater by using ozone catalysis and ionizing radiation is characterized by comprising the following steps:
firstly, adding a certain amount of iron-based catalyst into wastewater containing antibiotics, and uniformly stirring;
and secondly, introducing ozone into the wastewater to be treated, performing ozone oxidation treatment and ionizing radiation simultaneously, and keeping the ozone oxidation treatment and the ionizing radiation treatment synchronously.
2. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: an iron-based catalyst is used in the ozone treatment.
3. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 2, wherein the method comprises the following steps: the iron-based catalyst is magnetite, iron oxyhydroxide, goethite, ferrite and ferrihydrite.
4. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 2 or 3, wherein: the addition amount of the iron-based catalyst in the wastewater is 0.05-1.0 g/L.
5. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: the pH application range of the antibiotic wastewater is 2.5-11.
6. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: ionizing radiation is carried out using gamma rays or a high-energy electron beam.
7. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 6, wherein the method comprises the following steps: gamma rays from radioactive isotopes60Co or137Cs decay, and the high energy electron beam is generated by an electron accelerator.
8. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 6 or 7, wherein: the irradiation dose of the ionizing radiation is 0.2-5.0 kGy.
9. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: ozone is generated by an ozone generator, and the addition amount is 0.1-2.8 mol/L.
10. The method for removing antibiotics in wastewater by using ozone catalysis in cooperation with ionizing radiation as claimed in claim 1, wherein the method comprises the following steps: the ionizing radiation duration is <30 min.
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