CN114044554A - Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst - Google Patents
Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst Download PDFInfo
- Publication number
- CN114044554A CN114044554A CN202111172307.6A CN202111172307A CN114044554A CN 114044554 A CN114044554 A CN 114044554A CN 202111172307 A CN202111172307 A CN 202111172307A CN 114044554 A CN114044554 A CN 114044554A
- Authority
- CN
- China
- Prior art keywords
- iron
- solution
- antibiotics
- persulfate
- degrading
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C02F1/30—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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- 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)
- Catalysts (AREA)
Abstract
The invention discloses a method for degrading antibiotics by activating persulfate through a photoelectric synergistic reinforced iron-based catalyst, which is a method for generating active oxygen by activating persulfate through an iron-based oxide and degrading the antibiotics through the active oxygen. Under the synergistic enhancement of visible light and an electric field, the catalytic activation performance of the iron-based oxidant on persulfate is further improved, the degradation efficiency of the iron-based oxidant on organic antibiotics is enhanced, the excellent removal efficiency on organic antibiotic wastewater in high-concentration inorganic anions and wide pH ranges is realized, the iron-based catalyst has a wide application prospect in the field of antibiotic wastewater treatment, and the iron-based catalyst has an important significance in promoting the iron-based catalyst to be used for antibiotic wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of antibiotic degradation treatment, and particularly relates to a method for degrading antibiotics by activating persulfate through a photoelectric synergistic reinforced iron-based catalyst.
Background
The antibiotic can interfere the metabolic process of pathogenic microorganisms, so that the antibiotic has the bacteriostatic or bactericidal effect and is widely applied to the fields of medicine, agriculture and animal husbandry and the like. Most antibiotics are of great interest due to their biodegradability, tendency to accumulate, high toxicity, environmental persistence and long-distance migratory properties. The antibiotic has the characteristics of toxicity, difficult biodegradation, easy biological accumulation and the like, so that the antibiotic poses serious threats to public health, but the antibiotic discharge requirements which are increasingly strict are difficult to achieve by adopting the traditional methods of adsorption, precipitation, biodegradation and the like. Therefore, there is an urgent need to search for a technique having a good treatment effect.
In recent years, SO is a radical of Sulfate radical4 ·-) The basic advanced oxidation processes (SR-AOPs) are a technology for efficiently removing organic matters difficult to degrade in water, and are receiving increasing attention from researchers. The persulfate has certain oxidizing capacity and low activity when acting alone, and can be used for removing pollutants only by activating the persulfate in a physical and chemical way under certain conditions, so that the activating way of the persulfate is very critical to the practical application of the persulfate. Currently, the activation of persulfate can be achieved by different methods, including thermal activation, alkali activation, ultraviolet activation, transition metal activation, and ultrasonic activation, as well as other novel activation techniques. Wherein the persulfate may pass through Fe2 +、Fe3+、Mn2+、Ni2+、Co2+、Ag+The single electron transfer of the plasma metal ion is activated to form SO4 ·-However, homogeneous transition metal ions are difficult to recycle, and pollution caused by residual metal ions in water is not negligible. Therefore, in recent years, heterogeneous catalysts have been activated using transition metal oxides as persulfatesThe research field of SR-AOPs is concerned. Among them, the iron-based catalyst is one of the most promising heterogeneous catalysts in SR-AOPs due to its advantages of relative non-toxicity, environmental friendliness, low cost, etc. However, a great deal of research shows that the activation performance of the pure iron-based catalyst on persulfate is low, so a new technical means for improving the performance of the iron-based catalyst on catalytically activating Persulfate (PMS) still needs to be explored.
Electrochemical (EC) is a new wastewater treatment technology due to low cost and good environmental compatibility, but the efficiency of a single electrochemical process is low, and the degradation effect can be improved only by improving the current density or prolonging the reaction time, but the use cost is greatly increased. Therefore, a good treatment technology capable of improving the performance of degrading antibiotic wastewater is urgently needed to be explored.
Chinese patent CN112973739A discloses a composite catalyst for catalytic oxidation treatment of antibiotic wastewater, and the invention uses a cocatalyst MoS2Introduction into Fe3+In the catalyst, when the catalyst is used for catalytic oxidation treatment of antibiotic wastewater, Fe can be expanded by generating surface complex state ferric iron and accelerating the circulation of iron among different valence states in the reaction process3+The high pH value applicability of the method promotes the generation of free radicals of strong oxidizing species, thereby improving the removal effect of antibiotic pollutants under neutral conditions and reducing the generation of iron mud. The comparison documents although Fe is also used3+The catalyst does not adopt the synergy of visible light and an electric field.
Disclosure of Invention
In order to overcome the problems in the prior art, the application provides a method for degrading antibiotics by activating persulfate through photoelectric cooperative reinforcement iron-based catalyst, under the cooperative reinforcement of visible light and an electric field, the catalytic activation performance of iron-based oxidant to persulfate is further improved, the degradation efficiency of iron-based oxidant to organic antibiotics is enhanced, the excellent removal efficiency of organic antibiotic wastewater is achieved in high-concentration inorganic anions and wide pH, the wide application prospect is achieved in the field of antibiotic wastewater treatment, and the method has important significance for promoting the iron-based catalyst to be used for antibiotic wastewater treatment.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention provides a method for degrading antibiotics by activating persulfate through a photoelectric synergistic reinforced iron-based catalyst, which is a method for generating active oxygen by activating persulfate through an iron-based oxide and degrading the antibiotics through the active oxygen.
As an alternative embodiment, the method for degrading antibiotics provided by the present invention specifically includes the following steps:
s1, taking a solution to be treated containing organic antibiotics for later use;
s2, adding an iron-based oxide into the organic antibiotic solution prepared in the step S1, wherein the mass ratio of the iron-based oxide to the organic antibiotic is 1: 5-15, uniformly stirring until the adsorption and desorption are balanced;
s3, adding persulfate solution into the solution prepared in the step S2, wherein 25-40 mmol of persulfate solution is added into each gram of organic antibiotics, and the pH value of the solution is adjusted and maintained to be 1-11;
and S4, arranging a visible light source above the solution for catalytic reaction, and simultaneously adding an electric field into the solution to stir the solution for degrading the organic antibiotics in the solution.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, the iron-based oxide is ferric oxide or ferroferric oxide having visible light catalytic performance.
As an alternative embodiment, in the method for degrading an antibiotic provided by the present invention, the antibiotic is one or more of tetracycline, oxytetracycline, levofloxacin, or ciprofloxacin.
As an alternative embodiment, in the method for degrading an antibiotic provided by the present invention, the antibiotic is one or more of tetracycline, oxytetracycline, levofloxacin, ciprofloxacin, or sulfamethoxazole.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, interfering ions are further added in step S3, and the concentration of the interfering ions is less than or equal to 200 mM.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, the interfering ion includes one of a sulfate ion, a chloride ion, a carbonate ion, a nitrate ion, or a dihydrogen phosphate ion.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, the pH of the solution in step S3 is 3.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, the acid and base used for adjusting the pH of the solution in step S3 are hydrochloric acid and sodium hydroxide, respectively.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, the persulfate solution in step S3 is potassium monopersulfate or sodium monopersulfate.
As an optional implementation mode, in the method for degrading antibiotics provided by the invention, the stirring speed in the step S4 is 160 r/min-200 r/min, and the reaction temperature is 20-30 ℃.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, the reaction temperature in step S4 is 25 ℃.
As an optional implementation mode, in the method for degrading antibiotics provided by the invention, the current density of the applied electric field in the step S4 is 6.25-18.75 mA/cm2。
As an optional implementation mode, in the method for degrading antibiotics provided by the invention, the distance between the visible light source and the reaction solution in the step S4 is 10-20 cm.
As an alternative embodiment, in the method for degrading antibiotics provided by the present invention, the distance between the visible light source and the reaction solution in step S3 is 14 cm.
The reaction mechanism of the present invention:
an iron-based oxide (ferric oxide or ferroferric oxide) with visible light catalytic performance is used as a persulfate activation catalyst in the processThe persulfate is activated under the synergistic enhancement of visible light and an electric field, so that the quantity and the speed of active oxygen species generated by activating the persulfate by the iron-based oxide are obviously improved, and the degradation efficiency of the persulfate on antibiotics is enhanced. In the technology of the invention, an external electric field is applied to improve Fe on one hand3+/Fe2+Circulation rate, promoting Fe2+The single electron transfer activates persulfate to generate SO4 ·-. On the other hand, after the electric field is introduced, the surface of the iron-based oxide is electrically polarized to form electrode particles, which is equivalent to enlarging the electrode reaction area, thereby enhancing the electrochemical reaction efficiency. And after the surface of the iron-based oxide is electrically polarized, the surface potential of the iron-based oxide can be increased, so that more persulfate is attracted to be adsorbed on the surface of the iron-based oxide to be activated. In addition, the persulfate can capture electrons generated in the photocatalysis process and activate the electrons to generate active oxygen, and can play a role in inhibiting the recombination of photo-generated electrons and holes of the iron-based oxide, so that the photocatalysis efficiency of the iron-based oxide is indirectly promoted. Therefore, under the synergistic effect of visible light and an electric field, the degradation efficiency of the iron-based oxide to the antibiotics can be obviously improved.
The invention has the following beneficial effects:
(1) according to the invention, the photocatalysis and the external electric field are utilized to cooperate with the iron-based oxide to activate persulfate, so that the photocatalysis efficiency can be improved, and the Fe can be promoted3+/Fe2+The circulation rate is increased, the electrochemical reaction area is increased by the iron-based oxide which is electrically polarized, and the adsorption capacity of persulfate on the surface of the iron-based oxide is enhanced, so that more persulfate is activated to generate active oxygen species, and the photocatalytic efficiency of the iron-based oxide is indirectly promoted, so that the generation amount of hydroxyl radicals, sulfate radicals, singlet oxygen, superoxide radicals and the like in a visible light + electric field system is far greater than that in a single visible light + iron-based oxide, electric field + iron-based oxide and pure iron-based oxide system. The active oxygen generated by the method is abundant and abundant in species, and has high utilization rate of persulfate, stronger oxidizing power and wider action range.
(2) The invention has excellent removal efficiency on the organic antibiotic wastewater in high-concentration inorganic anions and wide pH, has unique anti-interference capability and wide pH adaptability, has wide application prospect in the field of antibiotic wastewater treatment, and can adapt to the inherent defect of high salinity of wastewater in the environment.
(3) The persulfate is low in cost, is solid particles and is convenient to transport, so that the operability is high in practical engineering application; the iron-based oxide as a novel catalyst has the advantages of relative innocuity, environmental protection, low price, good physical and chemical stability, repeated and repeated utilization and the like, thereby having wide application prospect.
Drawings
FIG. 1 is a graph of tetracycline removal under different conditions in example 1;
FIG. 2 shows the different concentrations of Fe in example 22O3A tetracycline removal rate curve under the conditions;
FIG. 3 is a graph showing the tetracycline removal rate under different concentrations of persulfate in example 3;
FIG. 4 is a graph of tetracycline removal at various pH conditions of example 4;
FIG. 5 is a graph of tetracycline removal at different current densities in example 5;
FIG. 6 is a graph of the removal rate of tetracycline under different interfering ion conditions in example 6;
FIG. 7 is a graph of the removal rate of different antibiotics from example 7.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
A method for degrading antibiotics by activating persulfate through a photoelectric synergistic reinforced iron-based catalyst comprises the following steps:
s1, preparing an organic antibiotic solution with the concentration less than or equal to 20mg/L, and uniformly stirring for later use;
s2, adding iron-based oxide into the organic antibiotic solution prepared in the step S1, wherein 0.1-0.3 g of iron-based oxide is added into each liter of organic antibiotic solution, and stirring uniformly until adsorption and desorption balance is achieved; the iron-based oxide in this application may be ferric oxide or ferroferric oxide, and in this embodiment, ferric oxide is taken as an example for description:
preparation of ferric oxide:
(1) preparation of MOF-Fe precursor solution: 2.703g of FeCl3·6H2O (0.01mol) was dissolved in a mixed solution of DMF (10 ml of 1, 2-dimethylformamide) to give a transparent solution A. 1.66g C8H6O4Dissolved in a mixed solution of DMF (56ml) to give a transparent solution B. Next, solution a and solution B were slowly mixed for 30 minutes under magnetic stirring. The mixture of solution a and solution B was a MOF-Fe precursor solution (solution C). Adding the washed rose petals into MOF-Fe precursor solution, and heating at 20 deg.CAnd soaking for 24 hours to enable the MOF-Fe precursor solution to be completely adsorbed on the MOF-Fe precursor solution. Taking out the rose petals after 24 hours, and naturally drying the rose petals in the sun.
(2) Calcining the sun-dried rose petals adsorbing the MOF-Fe precursor solution in a muffle furnace at 350 ℃ for 2 hours at the heating rate of 2 ℃/min to obtain reddish brown fluffy Fe2O3And (3) powder.
S3, adding persulfate solution into the solution prepared in the step S2, wherein 0.5-0.8 mmol/L persulfate solution is added into each liter of organic antibiotic solution, and the pH value of the solution is adjusted and maintained to be 1-11;
the persulfate solution in this application can be potassium peroxymonosulfate or sodium peroxymonosulfate, and in this example, sodium peroxymonosulfate is described as an example.
S4, arranging a visible light source above the solution for catalytic reaction, simultaneously adding an electric field in the solution, and stirring to degrade the organic antibiotics in the solution;
electrodes such as platinum-plated titanium (Pt/Ti), stainless steel and graphite are respectively used as an anode and a cathode, the size of the electrodes is 4.0cm multiplied by 2.5cm, the distance between the anode and the cathode is fixed to be 5cm, the electrodes are horizontally immersed into 100mL of reaction solution, and the actual effective area of the electrodes is 8.0cm2. Direct Current (DC) source (PS-6403D, Longwei, China) provides constant current for the reaction system. A300 WXe lamp equipped with an ultraviolet wavelength filter (. lamda. gtoreq.420 nm) is the visible light source.
Example 1
Adding 20mL of 100mg/L tetracycline and 80mL of ultrapure water into a reaction vessel, and uniformly stirring the mixture on a stirrer; then adding Fe into the reaction vessel2O3Adding 0.2g of the solution per liter, and stirring the solution on a stirrer for 30min to reach adsorption and desorption balance; adding 50 mmol. L-1Na2SO4、0.65mmol·L-1After the sodium peroxymonosulfate is added, the pH value is adjusted to 3, and the reaction container is respectively placed under the conditions of no illumination and no electric field, visible light xenon light source, direct current power supply, visible light xenon light source and direct current power supply which are simultaneously turned on; uniformly stirring for 10min at room temperature to finish the utilization of Fe in different systems2O3Removal of tetracycline by activation of persulfate, where the concentration of tetracycline is measured using a visible spectrophotometer.
The test results are shown in FIG. 1, and the removal rates of tetracycline in the example at 10min are 67.16%, 78.56%, 81.64% and 100%, respectively, which shows that the removal efficiency of tetracycline is higher under the synergistic effect of the visible light source and the direct current power source.
Example 2
Adding 20mL of 100mg/L tetracycline and 80mL of ultrapure water into a reaction vessel, and uniformly stirring the mixture on a stirrer; then adding Fe into the reaction vessel2O3Adding the solution in an amount of 0.1g, 0.2g and 0.3g per liter of solution, and stirring for 30min on a stirrer to reach adsorption and desorption balance; adding 50 mmol. L-1Na2SO4、0.65mmol·L-1After passing through sodium monopersulfate, the pH was adjusted to 3 at a current density of 12.50mA/cm2Uniformly stirring for 10min at room temperature under the condition that the distance between a light source and the reaction vessel is 14cm, and finishing the process of preparing the Fe with different concentrations2O3Removal of tetracycline by activation of persulfate, where the concentration of tetracycline is measured using a visible spectrophotometer.
The test results are shown in FIG. 2, and the tetracycline removal rate at 10min in this example is 84%, 100%, and 89.3%, respectively.
Example 3
Adding 20mL of 100mg/L tetracycline and 80mL of ultrapure water into a reaction vessel, and uniformly stirring the mixture on a stirrer; then adding Fe into the reaction vessel2O3Adding 0.2g of the solution per liter, and stirring the solution on a stirrer for 30min to reach adsorption and desorption balance; adding 50 mmol. L-1Na2SO4Then, 0.50 mmol. multidot.L was added thereto-1、0.65mmol·L-1、0.8mmol·L-1After passing through sodium monopersulfate, the pH was adjusted to 3 at a current density of 12.50mA/cm2Under the condition that the distance between a light source and the reaction container is 14 cm; stirring evenly for 10min at room temperature, namely using Fe under different persulfate concentrations2O3Removal of tetracycline by activated persulfate, wherein tetracycline is used in concentrationsAnd measuring by a visible spectrophotometer.
The test results are shown in FIG. 3, and the tetracycline removal rates at 10min in this example are 84.8%, 100%, and 91.7%, respectively.
Example 4
Adding 20mL of 100mg/L tetracycline and 80mL of ultrapure water into a reaction vessel, and uniformly stirring the mixture on a stirrer; then adding Fe into the reaction vessel2O3Adding 0.2g of the solution per liter, and stirring the solution on a stirrer for 30min to reach adsorption and desorption balance; adding 50 mmol. L-1Na2SO4Then, 0.65 mmol. multidot.L was added-1After passing through sodium monopersulfate, sodium hydroxide solution and dilute hydrochloric acid solution are added respectively to adjust the pH values to 1, 3, 5, 7, 9 and 11, and the current density is 12.50mA/cm2Uniformly stirring for 10min at room temperature under the condition that the distance between a light source and the reaction container is 14cm, and finishing the reaction under different pH values by utilizing Fe2O3Removal of tetracycline by activation of persulfate, where the concentration of tetracycline is measured using a visible spectrophotometer.
The results are shown in FIG. 4, and the tetracycline removal rates at 10min in this example are 72.84%, 100%, 89.17%, 83.87%, 82.65%, 69.85%, respectively.
Example 5
Adding 20mL of 100mg/L tetracycline and 80mL of ultrapure water into a reaction vessel, and uniformly stirring the mixture on a stirrer; then adding Fe into the reaction vessel2O3Adding 0.2g of the solution per liter, and stirring the solution on a stirrer for 30min to reach adsorption and desorption balance; adding 50 mmol. L-1Na2SO4Then, 0.65 mmol. multidot.L was added-1After passing through sodium monopersulfate, the pH was adjusted to 3 at a current density of 0mA/cm2、6.25mA/cm2、12.50mA/cm2、18.75mA/cm2Uniformly stirring for 10min at room temperature under the condition that the distance between a light source and the reaction vessel is 14cm, and finishing utilizing Fe under the condition of different current densities2O3Removal of tetracycline by activation of persulfate, where the concentration of tetracycline is measured using a visible spectrophotometer.
The results are shown in FIG. 5, where the tetracycline removal rates at 10min are 78.56%, 82.34%, 100%, 81.05% in this example.
Example 6
Adding 20mL of 100mg/L tetracycline and 80mL of ultrapure water into a reaction vessel, and uniformly stirring the mixture on a stirrer; then adding Fe into the reaction vessel2O3Adding 0.2g of the solution per liter, and stirring the solution on a stirrer for 30min to reach adsorption and desorption balance; in different interfering ions Na2SO4、NaCl、NaCO3、NaNO3、NaH2PO4The concentration is 200 mmol.L-1Then, 0.65 mmol. multidot.L was added-1After passing through sodium monopersulfate, the pH was adjusted to 3 at a current density of 12.50mA/cm2Uniformly stirring for 10min at room temperature under the condition that the distance between a light source and the reaction vessel is 14cm, and finishing at different 200 mmol.L-1Using Fe under interfering ion conditions2O3Removal of tetracycline by activation of persulfate, where the concentration of tetracycline is measured using a visible spectrophotometer.
The results are shown in FIG. 6, in which case the tetracycline removal rates at 10min are 99.5%, 88.46%, 90.35%, 83.66%, and 89.13%, respectively.
Example 7
Respectively adding 20mL of 100mg/L Oxytetracycline (OTC), Levofloxacin (LVF), Carbamazepine (CBZ), Sulfamethoxazole (SMX) and 80mL of ultrapure water into a reaction vessel, and placing the reaction vessel on a stirrer to stir uniformly; then adding Fe into the reaction vessel2O3Adding 0.2g of the solution per liter, and stirring the solution on a stirrer for 30min to ensure that the solution reaches adsorption and desorption balance; adding 50 mmol. L-1Na2SO4,0.65mmol·L-1After passing through sodium monopersulfate, the pH was adjusted to 3 at a current density of 12.50mA/cm2And uniformly stirring at room temperature for 30min under the condition that the distance between a light source and the reaction container is 14cm, thus completing the removal of the oxytetracycline, the levofloxacin, the ciprofloxacin and the sulfamethoxazole, wherein the concentrations of the oxytetracycline, the levofloxacin, the ciprofloxacin and the sulfamethoxazole are measured by using a visible spectrophotometerAnd (5) obtaining the product.
The test results are shown in FIG. 7, in which the removal rates of oxytetracycline, levofloxacin, ciprofloxacin, and sulfamethoxazole at 30min are respectively 100%, 90.3%, 85.6%, and 89.7%.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the practice of the invention to these embodiments. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A method for degrading antibiotics by activating persulfate through a photoelectric synergistic reinforced iron-based catalyst is characterized in that an iron-based oxide is adopted to activate persulfate to generate active oxygen, and the antibiotics are degraded by using the active oxygen.
2. The method for degrading antibiotics by activating persulfate according to the photoelectric synergistic strengthening iron-based catalyst, disclosed by claim 1, is characterized by comprising the following steps of:
s1, taking a solution to be treated containing organic antibiotics for later use;
s2, adding an iron-based oxide into the organic antibiotic solution prepared in the step S1, wherein the mass ratio of the iron-based oxide to the organic antibiotic is 1: 5-15, uniformly stirring until the adsorption and desorption are balanced;
s3, adding persulfate solution into the solution prepared in the step S2, wherein 25-40 mmol of persulfate solution is added into each gram of organic antibiotics, and the pH value of the solution is adjusted and maintained to be 1-11;
and S4, arranging a visible light source above the solution for catalytic reaction, simultaneously adding an electric field in the solution, and stirring the solution for degrading the organic antibiotics in the solution.
3. The method for degrading antibiotics by activating persulfate according to photoelectric synergistic strengthening of the iron-based catalyst in accordance with claim 1 or 2, wherein the iron-based oxide is ferric oxide or ferroferric oxide with visible light catalytic performance.
4. The method for degrading the antibiotic by activating the persulfate according to the photoelectric synergistic strengthening iron-based catalyst, which is disclosed by claim 1 or 2, wherein the antibiotic is one or more of tetracycline, oxytetracycline, levofloxacin, ciprofloxacin or sulfamethoxazole.
5. The method for degrading antibiotics by activating persulfate according to claim 2, wherein an interfering ion is further added in the step S3, and the concentration of the interfering ion is less than or equal to 200 mM.
6. The method of claim 5, wherein the interfering ions comprise one of sulfate, chloride, carbonate, nitrate, or dihydrogen phosphate.
7. The method for degrading antibiotics by activating persulfates through the photoelectricity synergistic strengthening iron-based catalyst in accordance with claim 2, wherein the persulfate solution in the step S3 is potassium peroxymonosulfate or sodium peroxymonosulfate.
8. The method for degrading antibiotics by activating persulfate according to the photoelectric synergistic enhancement iron-based catalyst of claim 2, wherein the stirring speed in the step S4 is 160-200 r/min, and the reaction temperature is 20-30 ℃.
9. The method for degrading antibiotics by activating persulfate according to claim 2, wherein the current density of the external electric field in the step S4 is 6.25-18.75mA/cm2。
10. The method for degrading antibiotics by activating persulfate according to the photoelectric synergistic enhancement of the iron-based catalyst, which is disclosed by claim 2, wherein the distance between a visible light source and the reaction solution in the step S4 is 10-20 cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111172307.6A CN114044554A (en) | 2021-10-08 | 2021-10-08 | Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111172307.6A CN114044554A (en) | 2021-10-08 | 2021-10-08 | Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114044554A true CN114044554A (en) | 2022-02-15 |
Family
ID=80204939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111172307.6A Pending CN114044554A (en) | 2021-10-08 | 2021-10-08 | Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114044554A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956194A (en) * | 2022-04-22 | 2022-08-30 | 浙江华源颜料股份有限公司 | Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121746A (en) * | 2013-03-20 | 2013-05-29 | 武汉大学 | Method for treating wastewater by complexly activating persulfate |
| JP2016089250A (en) * | 2014-11-10 | 2016-05-23 | 国立研究開発法人産業技術総合研究所 | Utilization method of light energy and utilization device of light energy |
| CN109950523A (en) * | 2019-03-14 | 2019-06-28 | 常熟理工学院 | Lithium ion battery negative material transition metal oxide/carbon preparation method |
| CN110240221A (en) * | 2019-04-25 | 2019-09-17 | 中国科学院生态环境研究中心 | A kind of method that photoelectrocatalytioxidation oxidation system and degradable organic pollutant recycle noble silver simultaneously |
| CN111054395A (en) * | 2019-12-10 | 2020-04-24 | 中国环境科学研究院 | Visible-light-driven photocatalyst, and preparation method and application thereof |
| CN113023843A (en) * | 2021-03-19 | 2021-06-25 | 重庆大学 | Method for degrading organic matters in water by synergistically activating permanganate-persulfate through cathode and anode |
-
2021
- 2021-10-08 CN CN202111172307.6A patent/CN114044554A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121746A (en) * | 2013-03-20 | 2013-05-29 | 武汉大学 | Method for treating wastewater by complexly activating persulfate |
| JP2016089250A (en) * | 2014-11-10 | 2016-05-23 | 国立研究開発法人産業技術総合研究所 | Utilization method of light energy and utilization device of light energy |
| CN109950523A (en) * | 2019-03-14 | 2019-06-28 | 常熟理工学院 | Lithium ion battery negative material transition metal oxide/carbon preparation method |
| CN110240221A (en) * | 2019-04-25 | 2019-09-17 | 中国科学院生态环境研究中心 | A kind of method that photoelectrocatalytioxidation oxidation system and degradable organic pollutant recycle noble silver simultaneously |
| CN111054395A (en) * | 2019-12-10 | 2020-04-24 | 中国环境科学研究院 | Visible-light-driven photocatalyst, and preparation method and application thereof |
| CN113023843A (en) * | 2021-03-19 | 2021-06-25 | 重庆大学 | Method for degrading organic matters in water by synergistically activating permanganate-persulfate through cathode and anode |
Non-Patent Citations (1)
| Title |
|---|
| 刘希涛: "《活化过硫酸盐在环境污染控制中的应用》", 30 April 2018, 中国环境出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114956194A (en) * | 2022-04-22 | 2022-08-30 | 浙江华源颜料股份有限公司 | Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate |
| WO2023201974A1 (en) * | 2022-04-22 | 2023-10-26 | 浙江华源颜料股份有限公司 | Iron oxyhydroxide and use thereof in synergistic degradation of antibiotic with persulfate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Fenton/Fenton-like processes with in-situ production of hydrogen peroxide/hydroxyl radical for degradation of emerging contaminants: Advances and prospects | |
| CN101187646A (en) | Granule electrode possessing photoelectric catalytic function and its uses | |
| CN104628200A (en) | Method for treating organic wastewater by photoelectric combined technique | |
| CN105481063A (en) | Particle electrode for treatment of refractory organic wastewater and preparation method for particle electrode | |
| CN109721148A (en) | A kind of catalytic ozonation water treatment technology and application method that ability is cut down with bromate of heterojunction boundary electron transmission induction | |
| CN113908835A (en) | Preparation and application of active composite material based on non-free-radical efficient mineralization sulfonamide antibiotics | |
| Xiao et al. | Efficient degradation of tetracycline hydrochloride by peroxymonosulfate activated by composite materials FeSe2/Fe3O4 under visible light | |
| Wu et al. | Heterogeneous catalytic system of photocatalytic persulfate activation by novel Bi2WO6 coupled magnetic biochar for degradation of ciprofloxacin | |
| Huang et al. | Effective and continuous degradation of levofloxacin via the graphite felt electrode loaded with Fe3O4 | |
| CN113998758A (en) | Method for degrading antibiotics by activating persulfate through photoelectric synergistic graphite-phase carbon nitride | |
| CN109626513B (en) | Method for degrading pollutants and improving electricity generation by coupling photocatalytic fuel cell and persulfate | |
| Chen et al. | The preparation of MoS2/δ-FeOOH and degradation of RhB under visible light | |
| CN114044554A (en) | Method for degrading antibiotics by activating persulfate through photoelectric synergistic strengthening iron-based catalyst | |
| CN113083369B (en) | electro-Fenton catalyst derived based on iron-based metal organic framework and preparation method and application thereof | |
| CN111545211B (en) | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof | |
| Yi et al. | Highly efficient degradation of antibiotic metronidazole by an environmental-friendly metal-free dual-cathode electro-Fenton system | |
| CN113600205B (en) | Copper-based Cu-Al 2 O 3 Catalyst and application thereof in treatment of estrogen-containing wastewater | |
| CN115888823A (en) | Visible light photocatalyst for in-situ synthesis of hydrogen peroxide and preparation method and application thereof | |
| CN109876816A (en) | A kind of micro ware auxiliary catalysis wet oxidation nanocatalyst and its application | |
| CN113171777B (en) | Iron/cerium bimetallic heterogeneous electro-Fenton catalyst and preparation method and application thereof | |
| CN110526484B (en) | Process for treating industrial wastewater of organophosphorus pesticide | |
| CN111569890B (en) | Graphene oxide-terbium oxide-ferric oxide composite material, synthetic method and application thereof in catalytic degradation | |
| CN112759060A (en) | Hydroxylamine hydrochloride heterogeneous Fenton-like system and application thereof | |
| CN111957320B (en) | Supported catalyst filter fiber for catalytic degradation of pollutants in water, and preparation and application thereof | |
| CN116002842B (en) | Method for degrading carbamazepine by activating peroxyacetic acid with carbon nano tube supported catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |