CN113880225A - Degradation agent and method for degrading florfenicol in culture wastewater - Google Patents

Degradation agent and method for degrading florfenicol in culture wastewater Download PDF

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CN113880225A
CN113880225A CN202111354634.3A CN202111354634A CN113880225A CN 113880225 A CN113880225 A CN 113880225A CN 202111354634 A CN202111354634 A CN 202111354634A CN 113880225 A CN113880225 A CN 113880225A
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florfenicol
degradation
potassium ferrate
degrading
hydrogen peroxide
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王�忠
王立琦
吕世明
程振涛
宋旭琴
郑寅
彭佳英
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Guizhou University
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
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    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/36Organic compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/40Organic compounds containing sulfur
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2103/20Nature of the water, waste water, sewage or sludge to be treated from animal husbandry

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Abstract

The invention discloses a degrading agent and a method for degrading florfenicol in culture wastewater. The degrading agent comprises potassium ferrate and hydrogen peroxide; the degradation agent is added into the culture wastewater, and the florfenicol in the culture wastewater can be degraded after standing for 40-50 min. When the degradation agent is used for treating florfenicol in culture wastewater, the degradation agent has the advantages of low cost, easiness in operation, good degradation effect and the like, and avoids the generation of drug-resistant bacteria.

Description

Degradation agent and method for degrading florfenicol in culture wastewater
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a degrading agent and a method for degrading florfenicol in aquaculture wastewater.
Background
Florfenicol is also called florfenicol, which is a special amidol broad-spectrum antibacterial drug developed in the late stage of the last eighties. The color is white or off-white, is a crystalline powder, is bitter and odorless, is easily soluble in methanol, and is slightly soluble in water. Can be used for treating bacterial diseases of pig, chicken and aquatic animals, especially bacterial infection of intestinal tract and respiratory system.
A large amount of florfenicol is used for farms every year in China and finally enters culture wastewater along with excrement. The florfenicol residue in the breeding wastewater can cause the immune toxicity and liver toxicity of animals, and simultaneously can induce a plurality of drug-resistant strains coexisting with human and livestock, such as haemophilus influenzae, golden yellow bacillus and the like, to begin to appear and become more serious. Human beings may ingest the florfenicol left in the environment by means of the food chain, and the florfenicol is damaged by direct toxicity and the probability of tolerance of pathogenic bacteria of the human bodies is increased. At present, multiple drug-resistant genes cfr induced by florfenicol can generate drug resistance to five types of drugs, and pose great threat to treatment of human infectious diseases. If the florfenicol-containing aquaculture wastewater is discharged to the ecological environment without special treatment, the florfenicol-containing aquaculture wastewater may enter surface water and underground water environments, and has great harm to the health of animals and human beings. Therefore, how to treat florfenicol in the aquaculture wastewater is very critical.
At present, the treatment methods mainly comprise biological treatment, chlorine disinfection treatment, physical treatment, membrane treatment and ozone treatment, and the treatment methods have the problems of easy generation of drug-resistant bacteria, high economic cost, poor safety, easy blockage of pore diameters and the like. Therefore, the method for degrading florfenicol is very significant.
Disclosure of Invention
In order to solve the defects of the prior art, the inventor provides a degrading agent for degrading florfenicol in aquaculture wastewater through a large amount of researches, and specifically adopts the following technical scheme:
a degrading agent for degrading florfenicol in culture wastewater comprises potassium ferrate and hydrogen peroxide.
In some preferred embodiments, the molar ratio of potassium ferrate to hydrogen peroxide is 1: 0.5-4. Preferably 1: 1.
The inventor finds that florfenicol in the culture wastewater can be effectively degraded by adopting the synergistic cooperation of potassium ferrate and hydrogen peroxide, and the degradation efficiency can reach 80%.
On the basis of the above, the inventor also provides a method for degrading florfenicol in aquaculture wastewater, which comprises the following steps: adding the degradation agent of any one of claims 1 to 3 into the culture wastewater, and standing for 40 to 50 min.
In some preferred implementation cases, after the potassium ferrate in the degradation agent is added to the culture wastewater, the pH value of the culture wastewater is adjusted to 6.5-7.5, and then hydrogen peroxide is added. Preferably, the pH of the aquaculture wastewater is adjusted to 7.
Preferably, the molar ratio of the potassium ferrate in the degradation agent to the florfenicol in the culture wastewater is 40-60: 1. Preferably 45: 1.
The invention has the beneficial effects that: when the degradation agent is used for treating florfenicol in culture wastewater, the degradation agent has the advantages of low cost, easiness in operation, good degradation effect and the like, and avoids the generation of drug-resistant bacteria.
Drawings
FIG. 1 shows a chromatogram of a 75. mu. mol/L florfenicol solution;
FIG. 2 shows a standard curve for a florfenicol solution;
FIG. 3 is a graph showing the effect of potassium ferrate dosage on florfenicol degradation;
FIG. 4 is a graph showing the effect of hydrogen peroxide to potassium ferrate ratio on florfenicol degradation;
FIG. 5 is a graph showing the results of pH effects on florfenicol degradation;
FIG. 6 is a graph showing the results of the effect of reaction time on florfenicol degradation.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present invention.
The main reagents used in the following examples are shown in Table 1 and the main apparatus is shown in Table 2.
TABLE 1
Figure BDA0003357017300000021
TABLE 2
Figure BDA0003357017300000022
Figure BDA0003357017300000031
Example 1:
(1) preparing a solution:
preparing a florfenicol solution: weighing 0.0537g of florfenicol, and dissolving the florfenicol in a 500mL volumetric flask by using absolute ethyl alcohol to prepare 300 mu mol/L of florfenicol.
Preparing a buffer solution: 1mmol/L borax and 5mmol/L sodium dihydrogen phosphate, and adjusting the pH value to 9.
Preparing potassium ferrate: weighing a certain mass of potassium ferrate, and performing constant volume by using a prepared buffer solution.
Preparing hydrogen peroxide: calculating the concentration of hydrogen peroxide according to the molar ratio of the potassium ferrate to the hydrogen peroxide, weighing the hydrogen peroxide with corresponding mass, and performing constant volume by using pure water.
Preparing sodium thiosulfate: sodium thiosulfate was prepared at a concentration of 0.1mol/L for terminating the reaction after reaching a predetermined time point, and the ratio to the reaction solution was 4: 1.
(2) Drawing a standard curve:
using high performance liquid chromatograph (chromatographic column is S mu nfireC)18Column, mobile phase acetonitrile and pH 4 sodium sulfate solution, flow rate 1.0mL/min, detection wavelength 230nm, using 0.22 μm filter) 300, 75, 37 pairs5, 18.75 and 9.375 mu mol/L of florfenicol, and the obvious absorption peak of the sample at about 220nm can be effectively observed (the chromatogram of 75 mu mol/L is shown in figure 1). A corresponding standard curve was made based on the measured peak areas and the corresponding solution concentrations (as shown in table 3), as shown in figure 2. As can be seen, the linear relation between the concentration of the florfenicol and the peak area within the concentration range of 0-300 mu mol/L is good, and the correlation coefficient>0.999。
TABLE 3
Figure BDA0003357017300000032
After the sample is detected by the high performance liquid chromatography, the content of the residual florfenicol in the system after the reaction is finished is calculated by using a standard curve, so that the degradation rate can be calculated.
Example 2:
the specific degradation process is as follows:
the reaction is carried out in a 50mL centrifuge tube, 10mL florfenicol solution (300. mu. mol/L) is added into the centrifuge tube, a magnetic stirrer is used for stirring at the rotating speed of 500rpm, potassium ferrate solution prepared by borax and sodium dihydrogen phosphate mixed solution is added while stirring, then the pH of the reaction system is adjusted (adjusted by 0.1mol/L sodium hydroxide and 0.1mol/L hydrochloric acid), hydrogen peroxide is added as an experimental group, purified water with the same volume is added as a control group, after a period of reaction, sampling is carried out, and 1/4 volume of sodium thiosulfate solution (0.1mol/L) is added into the reaction system to stop the reaction.
The sample was vortexed, filtered through a 0.22 μm microfiltration membrane (aqueous system), and then analyzed and detected by a high performance liquid chromatograph. Chromatographic conditions are as follows: the chromatographic column is S mu nfireC18The column was filled with acetonitrile and a solution of sodium sulfate at pH 4, flow rate 1.0mL/min, detection wavelength 230nm, and filtered through a 0.22 μm filter. Specific experimental conditions and results are shown in table 4.
TABLE 4
Figure BDA0003357017300000041
Figure BDA0003357017300000051
A is the molar ratio of potassium ferrate to florfenicol; b is the molar ratio of hydrogen peroxide to potassium ferrate; c is pH; d is the reaction time (min).
Wherein the maximum ratio of the molar ratio of the potassium ferrate to the florfenicol is 45:1, and the degradation rate can reach 77.55%; the largest molar ratio of the hydrogen peroxide to the potassium ferrate is 1:1, and the degradation rate can reach 86.62%; the maximum pH value is Ph-7, and the degradation rate reaches 70.84%; the average reaction time is 45min at most, and the degradation rate reaches 73.57%. The most influencing factor of the reaction can be obtained by comparing the range of the difference of the two levels, namely the molar ratio of hydrogen peroxide to potassium ferrate, the molar ratio of potassium ferrate to florfenicol and the least influencing factor of the two levels is the pH value of the reaction system. The optimal level combination of all factors is B3A4D3C3
As can be seen from the table 5 of orthogonal variance analysis, the molar ratio of potassium ferrate to florfenicol and the molar ratio of hydrogen peroxide to potassium ferrate have significant differences, and the results show that the two factors have the greatest influence on the experimental results, and the degradation rate difference between the levels is significant.
TABLE 5
Figure BDA0003357017300000052
As can be seen from an orthogonal variance analysis table, the molar ratio of potassium ferrate to florfenicol and the molar ratio of hydrogen peroxide to potassium ferrate have obvious differences, and the results show that the two factors have the greatest influence on the experimental results, and the degradation rate difference between the levels is obvious.
(1) Influence of potassium ferrate dosage on florfenicol degradation:
the effect of potassium ferrate dosage on florfenicol degradation is shown in figure 3. When the ratio of the potassium ferrate to the florfenicol is 45:1, the content of the florfenicol drug left after the reaction is the lowest, and the degradation rate can reach 78%. When the proportion is increased to 60:1, the degradation rate can reach 80 percent, and the adding amount of the additive is not in direct proportion to the increase of the degradation rate. In the experiment, the concentration of the florfenicol in the system is 300 mu mol/L, and when the ratio of the potassium ferrate to the florfenicol is 60:1, the potassium ferrate in the system is 18000 mu mol/L, a saturated state is reached, and the excessive potassium ferrate cannot be dissolved.
(2) The influence of the ratio of hydrogen peroxide to potassium ferrate on the degradation of florfenicol:
as can be seen from FIG. 4, when the ratio of hydrogen peroxide to potassium ferrate is 1:1, the degradation effect of the reaction is the best, and the degradation ratio can reach 86%. With the increase of the proportion of hydrogen peroxide to potassium ferrate, the degradation efficiency is firstly increased and then reduced.
(3) Effect of pH on florfenicol degradation: as can be seen from fig. 5, the degradation effect was the best at pH 7.
(4) Effect of reaction time on florfenicol degradation: as can be seen from FIG. 6, the potassium ferrate was most degraded when the reaction time was 45 min.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiment, and the present invention shall fall within the protection scope of the present invention as long as the technical effects of the present invention are achieved by the same means. The invention is capable of other modifications and variations in its technical solution and/or its implementation, within the scope of protection of the invention.

Claims (8)

1. A degrading agent for degrading florfenicol in culture wastewater is characterized by comprising potassium ferrate and hydrogen peroxide.
2. The degradation agent according to claim 1, wherein the molar ratio of potassium ferrate to hydrogen peroxide is 1: 0.5-4.
3. The degradation agent according to claim 2, wherein the molar ratio of potassium ferrate to hydrogen peroxide is 1: 1.
4. A method for degrading florfenicol in aquaculture wastewater is characterized by comprising the following steps: adding the degradation agent of any one of claims 1 to 3 into the culture wastewater, and standing for 40 to 50 min.
5. The method according to claim 4, wherein the potassium ferrate in the degradation agent is added to the aquaculture wastewater, the pH of the aquaculture wastewater is adjusted to 6.5-7.5, and then hydrogen peroxide is added.
6. The method of claim 5, wherein the pH of the aquaculture wastewater is adjusted to 7.
7. The method of claim 4, wherein the molar ratio of potassium ferrate in the degradation agent to florfenicol in the wastewater from the culture is 40-60: 1.
8. The method of claim 7, wherein the molar ratio of potassium ferrate to florfenicol is 45: 1.
CN202111354634.3A 2021-11-16 2021-11-16 Degradation agent and method for degrading florfenicol in culture wastewater Pending CN113880225A (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1430896A (en) * 2003-01-28 2003-07-23 王永东 Combination of disinfectors and its applications used in aquiculture
CN103011526A (en) * 2012-12-23 2013-04-03 山东新时代药业有限公司 Method for treating erythromycin thiocyanate wastewater
CN106882866A (en) * 2017-02-24 2017-06-23 河北科技大学 The method that hydrogen peroxide synergy ozone heterogeneous catalytic oxidation processes waste water
KR20210090758A (en) * 2020-01-10 2021-07-21 부경대학교 산학협력단 Prb-aop linking process apparatus and water treatment method using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1430896A (en) * 2003-01-28 2003-07-23 王永东 Combination of disinfectors and its applications used in aquiculture
CN103011526A (en) * 2012-12-23 2013-04-03 山东新时代药业有限公司 Method for treating erythromycin thiocyanate wastewater
CN106882866A (en) * 2017-02-24 2017-06-23 河北科技大学 The method that hydrogen peroxide synergy ozone heterogeneous catalytic oxidation processes waste water
KR20210090758A (en) * 2020-01-10 2021-07-21 부경대학교 산학협력단 Prb-aop linking process apparatus and water treatment method using the same

Non-Patent Citations (1)

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Title
仇丽君等: "《高铁酸钾与H2O2联用处理高浓度环丙沙星废水》", 《广州化工》 *

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Application publication date: 20220104