CN116002842B - Method for degrading carbamazepine by activating peracetic acid with carbon nanotube-supported catalyst - Google Patents
Method for degrading carbamazepine by activating peracetic acid with carbon nanotube-supported catalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
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Abstract
本发明涉及一种碳纳米管负载型催化剂活化过氧乙酸降解卡马西平的方法，以碳纳米管为载体，通过化学共沉淀结合水热法制备得到CNTs@CoFe2O4载体型催化剂，用于催化活化过氧乙酸降解去除水中卡马西平。本发明首次构建CNTs@CoFe2O4/过氧乙酸高级氧化体系，CNTs@CoFe2O4对卡马西平具有一定吸附作用的同时，通过活化过氧乙酸产生氧化性物种，实现卡马西平的彻底矿化。本发明的催化剂制备方法简单，降解体系pH适用范围广，降解条件温和，为水中卡马西平的去除提供了一个新的思路。
The present invention relates to a method for degrading carbamazepine by activating peracetic acid using a carbon nanotube- supported catalyst. The CNTs@ CoFe2O4 supported catalyst is prepared by chemical coprecipitation combined with a hydrothermal method using carbon nanotubes as a carrier, and is used for catalytic activation of peracetic acid to degrade and remove carbamazepine in water. The present invention constructs a CNTs@ CoFe2O4 /peracetic acid advanced oxidation system for the first time. While CNTs @ CoFe2O4 has a certain adsorption effect on carbamazepine, it generates oxidizing species by activating peracetic acid to achieve complete mineralization of carbamazepine. The catalyst preparation method of the present invention is simple, the pH application range of the degradation system is wide, and the degradation conditions are mild, which provides a new idea for removing carbamazepine in water.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst.
Background
Carbamazepine (CBZ), a typical drug used for treating epileptic diseases and relieving neuralgia, has been frequently detected in water environments in recent years and has a high concentration. CBZ is toxic to aquatic organisms such as bacteria, algae, invertebrates and fish, while CBZ has bioaccumulation and weak biodegradability, making it easy to enrich in humans, and carbamazepine pollution poses a great threat to human health and ecological safety. The existing sewage treatment technology is not ideal in effect of removing CBZ, and cannot meet the requirements of related risk treatment. Therefore, there is an urgent need to develop a rapid and efficient method to remove CBZ in water environments.
In recent years, for CBZ pollution treatment, the traditional methods such as adsorption, biological treatment and the like cannot completely remove CBZ in water, and the risk of secondary pollution is caused, and Advanced Oxidation Processes (AOPs) can generate substances with high activity, such as OH and SO in situ 4 ·- And the like, can efficiently oxidize and remove CBZ, and fully mineralize or convert the CBZ into a low-toxicity substance. Common oxidants include Peroxomonosulphate (PMS), peroxodisulphate (PDS), ozone (O) 3 ) Hydrogen peroxide (H) 2 O 2 ) And peracetic acid (PAA), etc. PAA is used as a disinfectant at the same time, compared with other peroxides, the PAA has little dependence on pH value change, and can generate a large number of small molecular carbon sources while generating a large amount of active substances after being activated, so that the PAA has higher bioavailability, low toxicity and few byproducts. In addition, the O-O bond energy in PAA is lower than PMS and H 2 O 2 Making PAA more susceptible to activation. PAA can be coated withThe external heat source or the ultraviolet light source is activated to generate active substances, however, the external energy increases the cost of large-scale application of PAA in the advanced oxidation process, and the representative transition metal catalyst has the defects of poor stability, difficult recovery, poor reusability and the like, and is difficult to apply in large scale in the actual wastewater treatment.
CoFe 2 O 4 Belongs to a bimetallic transition metal oxide, is an ideal PAA activator and can utilize Co 2+ And Fe (Fe) 3+ The oxidation-reduction and electron transfer reaction between the active substances and the PAA activates and decomposes the PAA to produce active substances such as organic free radicals, hydroxyl free radicals, singlet oxygen, superoxide free radicals and the like so as to deoxidize and decompose the organic substances, but the active substances are independent CoFe 2 O 4 The nano particles can generate serious agglomeration phenomenon in water environment, so that the utilization rate of active sites is reduced. At the same time, individual nano CoFe 2 O 4 The leaching problem of metals can be accompanied in the process of activating PAA, and secondary pollution is generated.
In order to solve the problems, the invention provides a method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst.
Disclosure of Invention
The invention aims to provide a method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst, which is nontoxic and environment-friendly and prepares the supported catalyst CNTs@CoFe by a simple hydrothermal method 2 O 4 The catalyst is used for catalyzing and activating the peroxyacetic acid to efficiently degrade carbamazepine, and the degradation rate of the carbamazepine in water can reach 98.2% under mild conditions.
In order to achieve the technical purpose, the invention adopts the following technical scheme: a method for degrading carbamazepine by activating peroxyacetic acid with a carbon nanotube supported catalyst, which is characterized by comprising the following steps:
s1: carbon Nanotubes (CNTs) and Co (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Uniformly mixing the O solution, adding a NaOH solution with a certain concentration to adjust the pH value to 12.4-12.6, and stirring at room temperature until coprecipitation is complete to obtain a mixed solution;
s2: transferring the obtained mixed solution into a hydrothermal reaction kettle, and transferring the hydrothermal reaction kettle into an oven for heating;
s3: cleaning the product obtained in S2, transferring into a baking oven, and drying to obtain CNTs@CoFe 2 O 4 A catalyst;
s4: adding a certain amount of catalyst and a certain amount of peracetic acid (PAA) into a certain amount of solution containing Carbamazepine (CBZ) to perform catalytic degradation reaction;
s5: sampling the solution at different reaction times, filtering, adding a proper amount of sodium thiosulfate solution to terminate the reaction, and measuring the residual CBZ concentration by using a high performance liquid chromatography;
further, in S1, co (NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 The molar ratio of O was 1:2 and the concentration of NaOH added was 2M.
Further, in S2, the oven heating temperature is 200 ℃ and the time is 12 hours.
Further, in S3, the drying temperature is 60 ℃ and the drying time is 20 hours, and the carbon nano tube and CoFe 2 O 4 The mass ratio of (2) is 10:1.
Further, in the step S4, the concentration of the carbamazepine solution is 5mg/L, the volume is 100mL, the pH value of the solution is 7.0, the reaction temperature is 25 ℃, the adding amount of the catalyst is 0.02g, and the adding amount of the peroxyacetic acid is 0.8mmol.
Further, in the above step S5, the concentration of the sodium thiosulfate solution was 0.1M and the volume was 0.02mL.
The invention has the following beneficial effects:
1. the invention is nontoxic and environment-friendly, and prepares the supported catalyst CNTs@CoFe by combining simple and easy-to-operate chemical coprecipitation with a hydrothermal method 2 O 4 ；
2. The supported catalyst CNTs@CoFe obtained by the invention 2 O 4 Has rapid and efficient catalytic degradation effect on carbamazepine, and can be used for preparing 1 by only adding 20mg of catalyst and 0.8mmol of peracetic acid under the condition that the initial solution pH value is 7.0 at 25 DEG C00mL,5mg/L carbamazepine solution degraded 94% in 60 min, 98.2% in 180 min.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the supported catalyst CNTs@CoFe obtained by the preparation method of the invention 2 O 4 And CNTs, nano-sized CoFe 2 O 4 A comparative transmission electron micrograph;
FIG. 2 shows the CNTs and CoFe of the present invention 2 O 4 CNTs@CoFe in mass ratio 2 O 4 A comparative graph of carbamazepine removal in water;
FIG. 3 is a graph comparing removal of carbamazepine from water at various initial pH values of the solution;
FIG. 4 is a graph comparing various initial peroxyacetic acid concentrations versus carbamazepine removal in water;
FIG. 5 is a graph comparing various initial carbamazepine concentrations versus removal of carbamazepine from water;
FIG. 6 is a graph comparing removal of carbamazepine in water at various temperatures.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Referring to fig. 1, a method for preparing a catalyst in a method for degrading carbamazepine by activating peroxyacetic acid with a carbon nanotube supported catalyst comprises the following steps:
step one, 100mg of Carbon Nanotubes (CNTs) and Co (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Mixing the O solution, adding a NaOH solution with a certain concentration to adjust the pH value to 12.4-12.6, and stirring at room temperature until coprecipitation is complete to obtain a mixed solution;
transferring the obtained mixed solution into a 100mL hydrothermal reaction kettle; transferring the hydrothermal reaction kettle into an oven for heating;
step three, cleaning the product obtained in the step two, and transferring the product into an oven for drying to obtain CNTs@CoFe 2 O 4 A catalyst;
experimental results show that the CNTs@CoFe related to the invention 2 O 4 The catalyst was successfully prepared.
Example 2
A method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst, which comprises the following steps:
exploration of CNTs and CoFe 2 O 4 The influence of the mass ratio on the degradation performance of carbamazepine comprises the following steps:
(1) And (3) preparing materials: 100mg of Carbon Nanotubes (CNTs) were separated with different mass ratios of Co (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Mixing O, adding NaOH solution with a certain concentration to adjust the pH value to 12.4-12.6, and stirring at room temperature until coprecipitation is complete to obtain mixed solution; transferring the obtained mixed solution into a 100mL hydrothermal reaction kettle; transferring the hydrothermal reaction kettle into an oven for heating; washing the obtained product, transferring into an oven, and drying to obtain CNTs and CoFe 2 O 4 CNTs@CoFe with mass ratios of 3:1, 7:1, 8:1, 10:1 and 20:1 respectively 2 O 4 A catalyst;
(2) The experimental process comprises the following steps: preparing CBZ concentration of 10mg/L, regulating pH value to 7.0, pouring 100mL of CBZ solution into a 200mL beaker, adding 0.01g of catalyst and 42.6 mu L of peroxyacetic acid; the solution was sampled at 25℃and 300r/min with mechanical stirring at 0, 5, 10, 15, 20, 30, 45, 60, 180 minutes from the start of the reaction, filtered and quenched by the addition of 0.02mL of 0.1M sodium thiosulfate solution, and the remaining CBZ concentration was determined.
(3) The experimental results show that: when CNTs and CoFe 2 O 4 When the mass ratio is 10:1, the degradation effect is better.
(4) The residual concentration measuring method comprises the following steps of measuring CBZ, wherein the specific measuring content is as follows: the resulting solution was subjected to measurement of CBZ concentration using a high performance liquid chromatography-ultraviolet detector at a wavelength of 285nm, wherein the mobile phase was acetonitrile (0.1% trifluoroacetic acid): water (0.1% formic acid) =50:50, the sample injection amount was 40 μl, the column temperature was 30 ℃, and the flow rate was 0.8mL/min.
Example 3
A method for removing carbamazepine by activating peroxyacetic acid degradation with a carbon nano tube supported catalyst comprises the following steps:
the effect of different initial pH values of the solutions on the degradation performance of carbamazepine was investigated, comprising the following steps:
(1) And (3) preparing materials: 100mg of Carbon Nanotubes (CNTs) were mixed with Co (NO) at a mass ratio of 10:1, respectively 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Mixing O, regulating the pH value of the mixture to 12.4-12.6 by using 2M NaOH solution, and stirring the mixture at room temperature until coprecipitation is complete to obtain mixed solution; transferring the obtained mixed solution into a 100mL hydrothermal reaction kettle; transferring the hydrothermal reaction kettle into an oven for heating; cleaning the obtained product, transferring into a baking oven, and drying to obtain CNTs@CoFe 2 O 4 A catalyst;
(2) The experimental process comprises the following steps: preparing CBZ concentration of 10mg/L, and regulating pH value to 3.0, 5.0, 7.0, 9.0 and 11.0 by using 0.1M NaOH solution or 0.1M nitric acid solution; 100mL of CBZ solution is poured into a 200mL beaker, and 0.01g of catalyst and 42.6 mu L of peracetic acid are added; the solution was sampled at 25℃and 300r/min with mechanical stirring at 0, 5, 10, 15, 20, 30, 45, 60, 180 minutes from the start of the reaction, filtered and quenched by the addition of 0.02mL of 0.1M sodium thiosulfate solution, and the remaining CBZ concentration was determined.
(3) The experimental results show that: when the pH value is 7.0, the degradation effect is good.
(4) The residual concentration measuring method comprises the following steps of measuring CBZ, wherein the specific measuring content is as follows: the resulting solution was subjected to measurement of CBZ concentration using a high performance liquid chromatography-ultraviolet detector at a wavelength of 285nm, wherein the mobile phase was acetonitrile (0.1% trifluoroacetic acid): water (0.1% formic acid) =50:50, the sample injection amount was 40 μl, the column temperature was 30 ℃, and the flow rate was 0.8mL/min.
Example 4
A method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst, which comprises the following steps:
the effect of different initial peroxyacetic acid concentrations on carbamazepine degradation performance was investigated, comprising the steps of:
(1) And (3) preparing materials: 100mg of Carbon Nanotubes (CNTs) were mixed with Co (NO) at a mass ratio of 10:1, respectively 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Mixing O, adding 2M NaOH solution to adjust the pH value to 12.4-12.6, and stirring at room temperature until coprecipitation is complete to obtain mixed solution; transferring the obtained mixed solution into a 100mL hydrothermal reaction kettle; transferring the hydrothermal reaction kettle into an oven for heating; cleaning the obtained product, transferring into a baking oven, and drying to obtain CNTs@CoFe 2 O 4 A catalyst;
(2) The experimental process comprises the following steps: preparing CBZ concentration of 10mg/L, and regulating pH value to 7.0 by using 0.1M NaOH solution or 0.1M nitric acid solution; 100mL of CBZ solution was poured into a 200mL beaker, 0.01g of catalyst was added, and different volumes of peracetic acid (8.52, 21.3, 42.6, 85.2, 213, 426. Mu.L) were added respectively; the solution was sampled at 25℃under mechanical stirring at 300r/min for 0, 5, 10, 15, 20, 30, 45, 60, 180 minutes, respectively, and the reaction was terminated by filtering and adding 0.02mL of a 0.1M sodium thiosulfate solution, and the remaining CBZ concentration was determined.
(3) The experimental results show that: the degradation effect is better when the initial concentration of the peroxyacetic acid is 8 mM.
(4) The residual concentration measuring method comprises the following steps of measuring CBZ, wherein the specific measuring content is as follows: the resulting solution was subjected to measurement of CBZ concentration using a high performance liquid chromatography-ultraviolet detector at a wavelength of 285nm, wherein the mobile phase was acetonitrile (0.1% trifluoroacetic acid): water (0.1% formic acid) =50:50, the sample injection amount was 40 μl, the column temperature was 30 ℃, and the flow rate was 0.8mL/min. Example 5
A method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst, which comprises the following steps:
the effect of different initial carbamazepine concentrations on carbamazepine removal performance was investigated, including the following steps:
(1) And (3) preparing materials: 100mg of Carbon Nanotubes (CNTs) were mixed with Co (NO) at a mass ratio of 10:1, respectively 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Mixing O, adding 2M NaOH solution to adjust the pH value to 12.4-12.6, and stirring at room temperature until coprecipitation is complete to obtain mixed solution; transferring the obtained mixed solution into a 100mL hydrothermal reaction kettle; transferring the hydrothermal reaction kettle into an oven for heating; cleaning the obtained product, transferring into a baking oven, and drying to obtain CNTs@CoFe 2 O 4 A catalyst;
(2) The experimental process comprises the following steps: preparing CBZ concentrations of 2, 5, 10, 15 and 20mg/L respectively, and regulating the pH value to 7.0 by using a 0.1M NaOH solution or a 0.1M nitric acid solution; 100mL of CBZ solution was poured into a 200mL beaker, 0.02g of catalyst was added, and 426. Mu.L of peracetic acid was added; the solution was sampled at 25℃and 300r/min with mechanical stirring at 0, 5, 10, 15, 20, 30, 45, 60, 180 minutes from the start of the reaction, filtered and quenched by the addition of 0.02mL of 0.1M sodium thiosulfate solution, and the remaining CBZ concentration was determined.
(3) The experimental results show that: when the initial carbamazepine concentration is 2mg/L, the degradation effect is good.
(4) The residual concentration measuring method comprises the following steps of measuring CBZ, wherein the specific measuring content is as follows: the resulting solution was subjected to measurement of CBZ concentration using a high performance liquid chromatography-ultraviolet detector at a wavelength of 285nm, wherein the mobile phase was acetonitrile (0.1% trifluoroacetic acid): water (0.1% formic acid) =50:50, the sample injection amount was 40 μl, the column temperature was 30 ℃, and the flow rate was 0.8mL/min.
Example 6
A method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst, which comprises the following steps:
the effect of different temperatures on the removal of carbamazepine was investigated, comprising the following steps:
(1) And (3) preparing materials: 100mg of Carbon Nanotubes (CNTs) were mixed with Co (NO) at a mass ratio of 10:1, respectively 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Mixing the O solution, adding 2M NaOH solution to adjust the pH value to 12.4-12.6, and stirring at room temperature until coprecipitation is complete to obtain mixed solution; transferring the obtained mixed solution into a 100mL hydrothermal reaction kettle; transferring the hydrothermal reaction kettle into an oven for heating; cleaning the obtained product, transferring into a baking oven, and drying to obtain CNTs@CoFe 2 O 4 A catalyst;
(2) The experimental process comprises the following steps: preparing CBZ concentration of 5mg/L, and regulating pH value to 7.0 by using 0.1M NaOH solution or 0.1M nitric acid solution; 100mL of CBZ solution was poured into a 200mL beaker, 0.02g of catalyst was added, and 426. Mu.L of peracetic acid was added; the solution was sampled at 0, 5, 10, 15, 20, 30, 45, 60, 180 minutes from the start of the reaction with mechanical stirring at 15, 20, 25, 30, 35 ℃ and 300r/min, respectively, filtered and quenched by the addition of 0.02mL of 0.1M sodium thiosulfate solution, and the remaining CBZ concentration was determined.
(3) The experimental results show that: the degradation effect is better when the temperature is 35 ℃.
(4) The residual concentration measuring method comprises the following steps of measuring CBZ, wherein the specific measuring content is as follows: the resulting solution was subjected to measurement of CBZ concentration using a high performance liquid chromatography-ultraviolet detector at a wavelength of 285nm, wherein the mobile phase was acetonitrile (0.1% trifluoroacetic acid): water (0.1% formic acid) =50:50, the sample injection amount was 40 μl, the column temperature was 30 ℃, and the flow rate was 0.8mL/min. To further describe CNTs@CoFe 2 O 4 The activation capacity of activated PAA was further calculated by linear fitting the data by Arrhenius' formula. The equation for the model is as follows:
arrhenius formula:
wherein k is the reaction rate constant, ea (kJ. Mol) -1 ) Is thatThe reaction activation energy, R is the gas constant, and the value is 8.314J (mol. K) -1 T (K) is the reaction temperature, A is a dimensionless constant.
Example 7
As can be seen from fig. 1 (a): the pure carbon nano tube has smooth surface and large length-diameter ratio, and is an ideal catalyst carrier; FIG. 1 (b) clearly shows the nano-scale CoFe 2 O 4 The agglomeration phenomenon is obvious, and active sites are covered, so that the catalytic activity is reduced; it can be seen from FIG. 1 (c) that the catalyst prepared according to the present invention has CoFe uniformly supported on the surface 2 O 4 A double transition metal oxide. From fig. 1, it can be seen that the structure of the material completely accords with the design thought of the initial catalyst, the metal active sites are well fixed and dispersed on the surface of the carbon nano tube, the agglomeration of the active nano metal sites in the catalytic process is effectively reduced, and the catalytic activity and stability of the material are improved.
As can be seen from fig. 2: the concentration of metal ions plays a key role in the catalytic performance of the material, and the proportion of transition metals is too low, so that active sites on the surface of the material are insufficient, and the catalytic activity of the material is reduced; and excessive metal ions can be aggregated on the surface of the material, so that effective active sites are reduced, the catalytic activity is reduced, the metal leaching is increased, the risk of secondary pollution is caused, and the sewage treatment cost is also increased. Thus controlling the total amount of metal ions of the material is a critical factor. According to different CNTs and CoFe 2 O 4 The mass ratio can be seen to be a good ratio of 10:1.
As can be seen from fig. 3: the change in pH can affect the surface charge of the material, which in turn affects the formation of free radicals and the contaminant degradation process. The material shows higher degradation efficiency in the pH value range of 3-9, which indicates that the catalyst can be widely applied to acidic, neutral and weak alkaline water bodies.
As can be seen from fig. 4: in this system, the amount of oxidant that is involved in the reaction per unit time is limited, limited by the number of metal active sites of the material, and there is a threshold for the amount added. Experimental results show that 0.8mM peracetic acid shows similar degradation efficiency to that of higher concentration peracetic acid after 180 minutes, and that the use of 0.8mM peracetic acid in the system can reduce cost investment while ensuring degradation efficiency.
As can be seen from fig. 5: the initial concentration of carbamazepine in water has a certain effect on its removal efficiency, it can be seen that the higher the concentration of carbamazepine, the lower the degradation rate, when the concentration of carbamazepine is in the range of 2-20 mg/L. CNTs@CoFe in system 2 O 4 The oxidation capacity is stable under the condition that the addition amount of PAA is unchanged, so as to increase the concentration of carbamazepine, more active substances are consumed, the degradation effect of the carbamazepine with high concentration is reduced, and the degradation effect can be possibly also matched with CNTs@CoFe 2 O 4 Adsorption to carbamazepine.
As can be seen from fig. 6: the temperature is an important factor for accelerating the advanced oxidation reaction rate, the reaction rate of the system is accelerated along with the temperature rise in the range of 15-35 ℃, the reaction rate is obtained through linear fitting, the reaction rate constants are 0.02084,0.0385,0.04056,0.07122,0.09065 at 15, 20, 25, 30 and 35 ℃, and the apparent activation energy of the reaction is 52.54kJ/mol.
The above phenomenon shows that: the invention is nontoxic and environment-friendly, and prepares CNTs@CoFe by a simple hydrothermal synthesis method 2 O 4 The catalyst has rapid and efficient degradation effect on the degradation of carbamazepine by activating peracetic acid.
Claims (6)
1. A method for degrading carbamazepine by activating peroxyacetic acid with a carbon nanotube supported catalyst, which is characterized by comprising the following steps:
s1: carbon Nanotubes (CNTs) and Co (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 Mixing the O solution uniformly, adding the NaOH solution to adjust the pH value to 12.4-12.6, and stirring at room temperature until coprecipitation is complete to obtain a mixed solution;
s2: transferring the obtained mixed solution into a hydrothermal reaction kettle, and transferring the hydrothermal reaction kettle into an oven for heating;
s3: cleaning the product obtained in the step S2, transferring into a baking oven, and drying to obtain CNTs@CoFe 2 O 4 A catalyst;
s4: and adding the catalyst and peracetic acid (PAA) into a solution containing Carbamazepine (CBZ) to perform catalytic degradation reaction, so that the carbamazepine can be degraded.
2. The method for degrading carbamazepine by activating peroxyacetic acid with a carbon nanotube-supported catalyst according to claim 1, wherein in S1, co (NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The molar ratio of O is 1:2.
3. the method for degrading carbamazepine by activating peroxyacetic acid with a carbon nanotube supported catalyst according to claim 1, wherein the concentration of the added NaOH of S1 is 1-3M.
4. The method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst according to claim 1, wherein the hydrothermal reaction temperature in the drying oven in the step S2 is 200-220 ℃ and the reaction time is 10-12 hours.
5. The method for degrading carbamazepine by activating peroxyacetic acid with a carbon nano tube supported catalyst according to claim 1, wherein the drying temperature in S3 is 60-80 ℃ and the drying time is 20-24 hours; carbon nanotubes and CoFe 2 O 4 The mass ratio of (2) is 10:1.
6. the method for degrading carbamazepine by activating a carbon nano tube supported catalyst according to claim 1, wherein in S4, the pH value of the carbamazepine solution is 7, the reaction temperature is 25-30 ℃, the adding amount of the catalyst is 0.01-0.03 g/100ml, and the adding amount of the peroxyacetic acid is 0.6-0.9 mmol/100ml.
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