CN111905810B - Method for biologically preparing humic acid-goethite coprecipitation Fenton-like catalyst and application of catalyst in degrading sulfanilamide - Google Patents
Method for biologically preparing humic acid-goethite coprecipitation Fenton-like catalyst and application of catalyst in degrading sulfanilamide Download PDFInfo
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Abstract
The invention provides a method for biologically preparing a humic acid-goethite coprecipitation Fenton-like catalyst and application of the catalyst in degrading sulfanilamide. The biological preparation method comprises the following steps: culturing ferrous iron oxidizing bacteria; preparing humic acid mother liquor; a method for synthesizing humic acid-goethite coprecipitation by utilizing biological oxidizability. The method has the advantages of mild reaction conditions, low cost, simple and convenient operation and environmental friendliness. The synthesized humic acid-goethite coprecipitation can be used as a Fenton-like catalyst to treat wastewater containing the sulfonamide antibiotics, has high catalytic reaction rate, high degradation efficiency and strong reusability, and is favorable for popularization and application in the actual wastewater treatment process.
Description
Technical Field
The invention relates to a biological preparation method and application of a humic acid-goethite coprecipitation Fenton-like catalyst.
Background
As a new micro-polluted organic matter in a water environment, the antibiotic has the characteristics of difficult degradability, high risk, potential unknown toxicity, general residue and the like. Sulfonamides are the most widely used class of antibiotic drugs at present, may damage DNA of bacteria or eukaryotic cells, have high resistance to biodegradation, and have been detected in environmental samples such as wastewater, surface water, and groundwater. At present, many sewage treatment systems do not completely remove sulfonamides, so that sulfonamide compounds remained in effluent or sludge pose great threats to human health and environment. Aiming at the problem of water ecological safety caused by the current discharge of sulfonamide antibiotics to the environment, a new method for treating the refractory organic pollutants more efficiently is urgently needed.
Fenton oxidation, one of the typical advanced oxidation techniques, utilizes Fe2+And H2O2The reaction generates hydroxyl free radical (. OH) to degrade organic pollutants, has low treatment cost and high efficiency, and can realize the complete degradation of the pollutants. However, the traditional Fenton technology has the problems of difficult catalyst recovery, generation of a large amount of iron mud and the like. In order to overcome the above disadvantages, the fenton-like technology mediated by heterogeneous catalysts such as iron-containing minerals attracts much attention of researchers. In general, since Fe (III) and H2O2The reaction rate of (a) is low, which is not beneficial to the Fe (III)/Fe (II) cycle of Fenton-like reaction catalyzed by iron-containing minerals, thereby limiting the pollutant degradation efficiency. In order to solve the problems, researchers find that the Fe (III)/Fe (II) circulation rate of Fenton-like reaction catalyzed by iron-containing minerals can be effectively improved by methods such as ultraviolet/ultrasonic radiation, reducing agent/compounding agent addition, core-shell structure design and the like, and further the degradation efficiency of pollutants is improved. However, the above measures still have the disadvantages of high cost, complicated steps, low catalyst stability, easy secondary pollution and the like in the practical application process.
Humic acid is an organic substance widely distributed in natural environment and having rich oxygen-containing functional groups. In recent years, researchers find that the coprecipitation of humic acid and iron oxide prepared by a chemical method can be applied to the removal of organic pollutants. For example, Niu H et al in Humic acid coated Fe3O4magnetic nanoparticles as a high density effective Fenton-like catalyst for complete simulation of a failure zone, Peng L et al in Modifying Fe3O4nanoparticles with a humic acid for removal of Rhodamine B in water and
n P F et al, in a Humic acid-coated magnetic particles as a high affinity hydrophobic photo-materials for water devices, indicate that at 90 deg.C, N is2Under the environment, by adding Fe2+And Fe3+The solution can be added with ammonia water and humic acid to synthesize humic acid-magnetiteCarrying out ore coprecipitation; the synthesized coprecipitation can be used as a Fenton-like catalyst, an adsorbent and a photo-Fenton catalyst to efficiently remove organic pollutants. However, the above synthesis method requires the use of toxic chemical reagents during the preparation of the coprecipitation, and has the disadvantages of harsh operating conditions, complicated procedures, and possible environmental hazards. The research for applying the humic acid-iron oxide coprecipitation to treat pollutants is focused by finding a green and efficient preparation method.
Compared with the traditional chemical preparation method, the biosynthesis condition is mild, and the preparation process is clean, nontoxic and more environment-friendly. The nitrate-dependent ferrous iron oxidizing bacteria can generate intermediate products with high activity such as nitrite and the like through denitrification, and oxidize ferrous iron into solid-phase iron oxide. Yu H et al, in contaminated Fe (II) oxidation but inhibited polymerization by reduced graphene oxide double-dependent Fe (II) oxidation, using nitrate-dependent ferrous iron oxidizing bacteria can form graphene-iron oxide composites. In addition to this, the present invention is,
in the Formation of the organic-iron-oxide coprecipitates, it is proposed that iron oxide may be associated with organic matter containing carboxylic acid or fatty acid groups during the Formation process under the action of nitrate-dependent ferrous oxidizing bacteria to form an organic matter-iron oxide coprecipitate. Based on the above research progress, there is a possibility of preparing humic acid-iron oxide coprecipitate using nitrate-dependent ferrous oxidizing bacteria. In general, microbially formed coprecipitates have a lower crystallinity and a larger specific surface area than chemically synthesized coprecipitates, and the fe (iii)/fe (ii) cycle of fenton-like reactions is expected to be further improved. At present, no report that humic acid-iron oxide coprecipitation prepared by ferrous iron oxidizing bacteria is used as a fenton-like catalyst is found.
The method for synthesizing the humic acid-iron oxide coprecipitation by using the nitrate-dependent ferrous oxidizing bacteria has the advantages of simple and clean process, low cost and environmental friendliness. The synthesized humic acid-iron oxide coprecipitation can be used as a Fenton-like catalyst to realize the high-efficiency degradation of refractory pollutants such as sulfanilamide and the like.
Disclosure of Invention
The invention provides a method for synthesizing humic acid-goethite coprecipitation by utilizing the oxidizing capability of microorganisms Fe (II), and aims to prepare a novel efficient Fenton-like catalyst which is low in cost and environment-friendly and is used for degrading pollutants such as sulfanilamide in wastewater.
The technical scheme of the invention is as follows:
a method for biologically preparing a humic acid-goethite coprecipitation Fenton-like catalyst comprises the following steps:
step 1: culturing ferrous iron oxidizing bacteria: adopting nitrate-dependent ferrous iron oxidizing bacteria as microbial strains for preparing humic acid-goethite coprecipitation, inoculating the ferrous iron oxidizing bacteria into a culture medium containing a carbonate buffer solution, wherein the volume ratio of the ferrous iron oxidizing bacteria to the culture medium is 1/20-1/10, and culturing for 3-5 days under the anaerobic condition of 28-32 ℃;
step 2: preparing humic acid mother liquor: adding humic acid powder into NaOH solution, and treating in an ultrasonic cleaning instrument for more than 20min to fully dissolve the humic acid; by H2SO4Adjusting the pH value of the dissolved humic acid mother liquor to be neutral to obtain humic acid mother liquor with the concentration of 1-2 g/L;
and step 3: the method for biologically synthesizing the humic acid-goethite coprecipitation comprises the following steps:
(1) culturing the nitrate-dependent ferrous iron oxidizing bacteria in the logarithmic growth phase in the step 1;
(2) FeCl is added2·4H2Dissolving O in oxygen-free ultrapure water to obtain a mother solution containing 1-2MFe (II), sterilizing, placing in an anaerobic glove box, and storing under dark condition;
(3) adding the Fe (II) mother liquor prepared in the step 3(2) to the culture medium to ensure that the initial Fe (II) concentration of the culture medium is 10mM and form a suspension with an off-white precipitate; standing the suspension in the dark, and after the system is completely precipitated, filtering the culture medium through a 0.22 mu m filter membrane under the anaerobic condition to obtain a clarified culture medium containing Fe (II);
(4) adding different volumes of the humic acid mother liquor obtained in the step 2 and the ferrous oxidizing bacteria bacterial liquid in the logarithmic phase obtained in the step 3(1) into the clarified culture medium obtained in the step 3(3), wherein the volume ratio of the bacterial liquid to the culture medium is 1/20-1/10, the final concentration of humic acid is 10-100mg/L, and the content of co-precipitated organic carbon is regulated and controlled by changing the adding concentration of humic acid; the co-precipitation formed has a C/Fe molar ratio of between 0.16 and 0.99; and (3) performing static culture on the system in an anaerobic environment at the temperature of 28-32 ℃ for 14-21d to obtain the biosynthetic humic acid-goethite coprecipitation.
The ferrous iron oxidizing bacteria are Acidovorax sp.
The humic acid-goethite coprecipitation prepared by the method is used as a catalyst for Fenton-like reaction to degrade sulfonamide antibiotics, and the method comprises the following steps:
step 1: and adding the prepared humic acid-goethite coprecipitation into water to obtain a humic acid-goethite coprecipitation suspension. And (3) treating the suspension in an ultrasonic cleaning instrument for more than 20min to improve the dispersibility of the coprecipitation.
Step 2: preparing a sulfanilamide solution with the concentration of 10mg/L, and adjusting the pH value to 3;
and step 3: adding humic acid-goethite coprecipitation mother liquor and H into the sulfanilamide solution2O2The mixture is placed on a magnetic stirrer (200rpm) for reaction, samples are taken at regular time, and the concentration of the residual sulfanilamide in the system is detected by high performance liquid chromatography.
The invention has the beneficial effects that: the humic acid-goethite coprecipitation Fenton-like catalyst can be synthesized by Acidovorax sp. BoFeN1 cells at normal temperature in one step; the synthetic process is simple, the reaction condition is mild, the synthesized material can be used for catalyzing Fenton-like reaction, the catalytic efficiency is high, the recycling rate is good, and the OH generating capacity is strong.
Drawings
Fig. 1 is an X-ray diffraction pattern of the synthesized goethite (C/Fe ═ 0) and humic acid-goethite coprecipitates at different C/Fe ratios (C/Fe ═ 0.16 to 0.99).
Fig. 2(a) is a scanning electron micrograph of the synthesized goethite.
Fig. 2(b) is a scanning electron micrograph of humic acid-goethite coprecipitation (C/Fe ═ 0.30).
FIG. 3 shows the accumulated concentration of OH in the process of humic acid-goethite coprecipitation catalysis Fenton-like reaction.
FIG. 4 shows that humic acid-goethite coprecipitation is used for catalyzing Fenton-like reaction to degrade sulfanilamide.
Figure 5 is a comparison of the reusability of goethite and humic acid-goethite co-precipitates to catalyze fenton-like reactions to degrade sulfanilamide.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Biological preparation of humic acid-goethite coprecipitation:
(1) culture of Acidovorax sp. BoFeN1: using Acidovorax sp.BoFeN1 as a strain for biologically synthesizing humic acid-goethite coprecipitation; the culture medium for culturing the strain comprises the following specific components: NaHCO 23 2g/L,NaNO30.85g，CH3COONa 0.50g，MgSO4·7H2O 0.50g/L，NH4Cl 0.30g/L，NaCl 0.20g/L，NaH2PO40.15g/L, 1mL/L MEM vitamin solution (100X), and 1mL/L trace element solution. Before culturing, the vessel and pipette tip required for the culturing process are sterilized by an autoclave at 121 ℃ for 20 min. Aerating the prepared culture medium (99.999% N)2)30min, sealed, and placed in an anaerobic glove box (99.999% N) after UV sterilization2) In (1). The medium was sterilized in an anaerobic glove box over a 0.22 μm water film and inoculated with BoFeN1 strain at a 6% inoculum volume. Sealing the inoculated culture medium, and performing static culture in a dark anaerobic incubator at 28-32 ℃ for 3-5d to logarithmic phase for later use.
Wherein, the formula of the microelement solution is as follows: NaCl 2.00g/L, MgSO4·7H2O 2.00g/L，MnSO4·H2O 0.50g/L，NH4Cl 0.20g/L，CoSO4·7H2O 0.18g/L，ZnCl20.15 g/L，FeSO4·7H2O 0.10g/L，CuSO4·5H2O 0.01g/L，NiCl2·6H2O 0.03g/L，AgNO3 0.01g/L，H3BO3 0.01g/L。
(2) Preparing humic acid mother liquor: adding 0.1g humic acid powder into 100mL sterile 1M NaOH solution to obtain 1g/L humic acid mother liquor, treating the mother liquor in an ultrasonic cleaning instrument (100W) for more than 20min, and dissolving humic acid sufficiently, and then using 0.5M H2SO4Adjusting the pH value of the humic acid mother liquor to be neutral, sealing, and placing in an anaerobic glove box for later use.
(3) The method for biologically synthesizing the humic acid-goethite coprecipitation comprises the following steps:
step 1: 39.6g FeCl was weighed2·4H2Dissolving O in sterile and oxygen-free ultrapure water, and adding dissolved FeCl2·4H2Sterilizing the O mother liquor at 121 deg.C for 20min to obtain FeCl with concentration of 2M2·4H2And (4) placing the O mother liquor in an anaerobic glove box for sealed storage under the dark condition.
Step 2: preparing the culture medium in the step (1), and aerating the culture medium (99.999% N)2) Sealing and placing in an anaerobic glove box after 30min, adding FeCl described in step (1) of step (3) into the culture medium in the anaerobic glove box2·4H2Mother liquor, the initial Fe (II) concentration of the medium was 10mM, and a suspension with an off-white precipitate was formed. The medium was allowed to stand in the dark for more than 30h to allow the insoluble fraction to precipitate completely. Passing the medium through a 0.22 μm water membrane to obtain a clarified, about 3 mfe (ii) -containing medium.
And 3, step 3: adding different volumes of humic acid mother liquor obtained in the step (2) into the clarified culture medium obtained in the step (3) 2 in an anaerobic glove box with the constant temperature of 30 ℃, so as to obtain culture media containing humic acid with different concentrations, wherein the concentration range of the humic acid is 0-100 mg/L.
And 4, step 4: inoculating the BoFeN1 strain cultured to logarithmic growth phase in the step (1) into the culture medium obtained in the step 3 of the step (3) at a volume ratio of 6%. And (3) storing the inoculated culture medium in a sealed manner, and performing static culture for 14d under a dark condition to obtain the biosynthetic humic acid-goethite coprecipitation, wherein the C/Fe ratio of the coprecipitation is between 0 and 0.99.
FIG. 1 is an X-ray diffraction pattern of iron oxide synthesized and humic acid-iron oxide coprecipitates at initial humic acid concentrations of 0, 10mg/L, 25mg/L, 50mg/L and 100mg/L in example 1. The results show that the characteristic diffraction peaks of the formed iron oxide are respectively positioned at 2 theta, namely 18 degrees, 21 degrees, 33 degrees, 35 degrees, 37 degrees, 40 degrees, 41 degrees, 53 degrees, 59 degrees, 61 degrees and 64 degrees, all represent the diffraction peaks of the goethite, and no other characteristic peaks of the iron oxide are detected, so that the iron oxide component in the formed coprecipitate is proved to be the goethite. The C/Fe ratios of the coprecipitates formed at the above initial humic acid concentrations were 0, 0.16, 0.30, 0.55 and 0.99, respectively.
Fig. 2(a) is a scanning electron micrograph of goethite synthesized by biological oxidation in example 1 without addition of humic acid, and (b) is a scanning electron micrograph of humic acid-goethite coprecipitation synthesized at an initial humic acid concentration of 25mg/L (C/Fe ═ 0.30) in example 1. The result shows that the biological oxidation method synthesizes rod-shaped goethite particles and humic acid-goethite coprecipitation particles with nanometer scale, the widths of the rod-shaped goethite particles and the humic acid-goethite coprecipitation particles are both 50-100nm, the length of the synthesized goethite particles is between 155-415nm, and the length of the humic acid-goethite coprecipitation is smaller than that of the goethite particles and is between 95-385 nm.
Example 2
The humic acid-goethite coprecipitation catalysis Fenton-like reaction process generates OH:
(1) humic acid-goethite coprecipitation materials with C/Fe ratios of 0.16, 0.30, 0.55 and 0.99 are added in an amount of 3mg to 2mL of ultrapure water, respectively, to obtain humic acid-goethite coprecipitation suspensions with different C/Fe ratios. The suspension is treated in an ultrasonic cleaner (100W) for more than 20min to improve the dispersibility of the coprecipitation.
(2) 0.0244g of benzoic acid was dissolved in 17.5mL of ultrapure water in an Erlenmeyer flask, and the concentration of. OH in the solution was quantitatively determined by high performance liquid chromatography using benzoic acid as a capture probe for. OH.
(3) Adding the humic acid-goethite coprecipitation suspensions with different C/Fe ratios in the step (1) into a conical flask containing a benzoic acid solution, and using 0.5M H2SO4The solution adjusted the system pH to 3 and 0.5mL of 80mM H was added to the system2O2(final concentration 2)mM), the flask was placed on a magnetic stirrer (200rpm) and the reaction was started.
(4) The other experimental conditions were the same as above with a fenton-like system catalyzed by 3mg goethite particles (C/Fe ═ 0) as a control.
(5) And (5) sampling at fixed time. About 1mL of the sample was aspirated by a syringe, passed through a 0.22 μm water film, and then the OH concentration was measured by high performance liquid chromatography. As shown in FIG. 3, the cumulative concentration of. OH in the Fenton-like system catalyzed by humic acid-goethite coprecipitation having C/Fe ratios of 0.16, 0.30, 0.55 and 0.99 after the reaction was carried out for 2 hours was 20.2, 94.0, 81.7 and 46.5. mu.M, respectively, which were higher than the concentration of. OH produced in the control group of the Fenton-like system catalyzed by goethite (15.7. mu.M). With the increase of the ratio of humic acid to goethite coprecipitation C/Fe, the accumulated concentration of OH increases first and then decreases, and the humic acid-goethite coprecipitation with a C/Fe ratio of 0.30 is most beneficial to the generation of OH. The results indicate that humic acid-goethite co-precipitation can promote the generation of OH in a fenton-like reaction system.
Example 3
The humic acid-goethite coprecipitation catalysis Fenton system is applied to degradation of sulfonamides antibiotics:
(1) 4mg of humic acid-goethite coprecipitation materials with C/Fe ratios of 0.16, 0.30, 0.55 and 0.99 were added to 2mL of ultrapure water, respectively, to obtain humic acid-goethite coprecipitation suspensions with different C/Fe ratios. The suspension is treated in an ultrasonic cleaner (100W) for more than 20min to improve the dispersibility of the coprecipitation.
(2) Adding the humic acid-goethite coprecipitation suspension obtained in the step (1) into conical flasks containing 17.5mL of sulfanilamide solution (10mg/L) respectively, and using 0.5M H2SO4The solution adjusted the system pH to 3 and 0.5mL of 80mM H was added to the system2O2(final concentration: 2mM), the Erlenmeyer flask was placed on a magnetic stirrer (200rpm), and the reaction was started.
(3) The other experimental conditions were the same as above with a fenton-like system catalyzed by 4mg goethite particles (C/Fe ═ 0) as a control.
(4) And (5) sampling at fixed time. About 1mL of the sample was aspirated by a syringe, and the concentration of sulfanilamide in the solution was measured by high performance liquid chromatography after passing through a 0.22 μm water film. The experimental results are shown in fig. 4, and after the reaction is carried out for 2 hours, the degradation rates of sulfanilamide in fenton-like systems catalyzed by humic acid-goethite coprecipitation with C/Fe ratios of 0.16, 0.30, 0.55 and 0.99 are respectively 42%, 91%, 82% and 77%, which are higher than the degradation rate of sulfanilamide in the fenton-like system control group catalyzed by goethite (29%). Along with the improvement of the ratio of humic acid to goethite coprecipitation of C/Fe, the degradation rate of sulfanilamide is increased and then reduced, and the humic acid-goethite coprecipitation with the ratio of C/Fe of 0.30 is most beneficial to the fenton-like degradation of sulfanilamide. The result shows that the humic acid-goethite coprecipitation can promote the degradation of sulfanilamide in a Fenton-like reaction system and can be applied to the treatment of antibiotic pollutants such as sulfanilamide and the like in wastewater.
Example 4
Reusability of humic acid-goethite coprecipitation degradation sulfanilamide:
(1) to 2mL of ultrapure water, 5mg of a humic acid-goethite coprecipitation material having C/Fe of 0.30 was added to obtain a humic acid-goethite coprecipitation suspension. The suspension is treated in an ultrasonic cleaner (100W) for more than 20min to improve the dispersibility of the coprecipitation.
(2) Adding the humic acid-goethite coprecipitation suspension obtained in the step (1) into a conical flask containing 17.5mL of sulfanilamide solution (10mg/L), and using 0.5M H2SO4The solution adjusted the system pH to 3 and 0.5mL of 80mM H was added to the system2O2(final concentration 2mM), the reaction was started by placing the Erlenmeyer flask on a magnetic stirrer (200 rpm).
(3) The same other experimental conditions were used for a fenton-like system catalyzed by 5mg goethite particles (C/Fe ═ 0) as a control.
(4) And (5) sampling at fixed time. About 1mL of the sample was aspirated by a syringe, and the concentration of sulfanilamide in the solution was measured by high performance liquid chromatography after passing through a 0.22 μm water film.
(5) And (3) after 4 hours of reaction, recovering the coprecipitation material in the system by using a suction filtration method, freezing and drying the coprecipitation material into powder, repeating the operations (1) to (4), continuing the next degradation experiment, and repeating the operations for 4 times.
The test results show that: in the goethite-catalyzed fenton-like system, the degradation rate of the sulfonamides decreased to less than 10% after two cycles. In a Fenton-like system catalyzed by humic acid-goethite coprecipitation, the degradation efficiency of sulfanilamide after the first, second, third and fourth cycles is 90%, 88%, 85% and 84% respectively. The effect of humic acid-goethite coprecipitation catalysis sulfanilamide degradation is stable, and the recovered sulfanilamide antibiotics can be repeatedly applied to treatment of sulfanilamide antibiotics in wastewater.
Claims (4)
1. A method for biologically preparing a humic acid-goethite coprecipitation Fenton-like catalyst is characterized by comprising the following steps:
step 1: culturing ferrous iron oxidizing bacteria: adopting nitrate-dependent ferrous iron oxidizing bacteria as microbial strains for preparing humic acid-goethite coprecipitation, inoculating the ferrous iron oxidizing bacteria into a culture medium containing a carbonate buffer solution, wherein the volume ratio of the ferrous iron oxidizing bacteria to the culture medium is 1/20-1/10, and culturing for 3-5 days under the anaerobic condition of 28-32 ℃;
step 2: preparing humic acid mother liquor: adding humic acid powder into NaOH solution, and treating in an ultrasonic cleaning instrument for more than 20min to fully dissolve the humic acid; by H2SO4Adjusting the pH value of the dissolved humic acid mother liquor to be neutral to obtain humic acid mother liquor with the concentration of 1-2 g/L;
and step 3: the method for biologically synthesizing the humic acid-goethite coprecipitation comprises the following steps:
(1) culturing the nitrate-dependent ferrous iron oxidizing bacteria in the logarithmic growth phase in the step 1;
(2) FeCl2·4H2Dissolving O in oxygen-free ultrapure water to obtain a mother solution containing 1-2MFe (II), sterilizing, placing in an anaerobic glove box, and storing under dark condition;
(3) adding the Fe (II) mother liquor prepared in the step 3(2) to the culture medium to ensure that the initial Fe (II) concentration of the culture medium is 10mM and form a suspension with an off-white precipitate; standing the suspension in the dark, and after the system is completely precipitated, filtering the culture medium through a 0.22 mu m filter membrane under the anaerobic condition to obtain a clarified culture medium containing Fe (II);
(4) adding different volumes of the humic acid mother liquor obtained in the step 2 and the ferrous oxidizing bacteria bacterial liquid in the logarithmic phase obtained in the step 3(1) into the clarified culture medium obtained in the step 3(3), wherein the volume ratio of the bacterial liquid to the culture medium is 1/20-1/10, the final concentration of humic acid is 10-100mg/L, and the content of co-precipitated organic carbon is regulated and controlled by changing the adding concentration of humic acid; the co-precipitation formed has a C/Fe molar ratio of between 0.16 and 0.99; and (3) carrying out static culture on the system for 14-21d in an anaerobic environment at the temperature of 28-32 ℃ to obtain the humic acid-goethite coprecipitation Fenton-like catalyst.
2. The method according to claim 1, wherein the ferrous oxidising bacteria is Acidovorax sp.
3. The humic acid-goethite coprecipitation Fenton-like catalyst prepared according to the method of claim 1 or 2 is applied to Fenton-like reaction to degrade sulfonamide antibiotics.
4. Use according to claim 3, characterized in that the steps are as follows:
step 1: adding the humic acid-goethite coprecipitation Fenton-like catalyst into water to obtain a humic acid-goethite coprecipitation suspension, and performing ultrasonic treatment for more than 20min to obtain a humic acid-goethite coprecipitation mother liquor;
step 2: preparing a sulfanilamide solution with the concentration of 10mg/L, and adjusting the pH value to 3;
and step 3: adding humic acid-goethite coprecipitation mother liquor and H into sulfanilamide solution2O2Sampling at fixed time under the condition of stirring, and detecting the concentration of the residual sulfanilamide in the system by using high performance liquid chromatography.
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| CN110508284A (en) * | 2019-08-30 | 2019-11-29 | 中南大学 | A kind of preparation method of two dimension ferroso-ferric oxide class fenton catalyst and its application in wastewater degradation containing aminobenzenesulfonic acid |
| CN110721688A (en) * | 2019-11-15 | 2020-01-24 | 大连理工大学 | Preparation of soluble black carbon-iron oxide coprecipitation Fenton-like catalyst and application of catalyst in catalytic degradation of norfloxacin |
| CN111018084A (en) * | 2019-12-23 | 2020-04-17 | 大连理工大学 | Biochar-goethite heterogeneous Fenton oxidation method applied to ofloxacin wastewater treatment |
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| CN110508284A (en) * | 2019-08-30 | 2019-11-29 | 中南大学 | A kind of preparation method of two dimension ferroso-ferric oxide class fenton catalyst and its application in wastewater degradation containing aminobenzenesulfonic acid |
| CN110721688A (en) * | 2019-11-15 | 2020-01-24 | 大连理工大学 | Preparation of soluble black carbon-iron oxide coprecipitation Fenton-like catalyst and application of catalyst in catalytic degradation of norfloxacin |
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