CN115282984A - Efficient biochar-based catalytic material, preparation method and application - Google Patents
Efficient biochar-based catalytic material, preparation method and application Download PDFInfo
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- CN115282984A CN115282984A CN202210946728.8A CN202210946728A CN115282984A CN 115282984 A CN115282984 A CN 115282984A CN 202210946728 A CN202210946728 A CN 202210946728A CN 115282984 A CN115282984 A CN 115282984A
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 64
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- 239000005941 Thiamethoxam Substances 0.000 claims abstract description 38
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 9
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 6
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- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 5
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/20—Sulfiding
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- 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
- C02F1/722—Oxidation by peroxides
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention discloses a high-efficiency biochar-based catalytic material, wherein the main materials comprise: 0.05-0.2g of biochar, 0.05-0.2mol/L of potassium ferrate, 0.05-0.3mol/L of cadmium acetate, 100-500 mu L of thioacetic acid, 0.05-0.3mol/L of sodium sulfide and 0.1-0.5mol/L of polyvinyl alcohol. The invention also provides a preparation method and application of the high-efficiency biochar-based catalytic material. The product has the advantages of high efficiency, good regeneration performance, low cost, easy solid-liquid separation and the like. The invention can rapidly and efficiently degrade the thiamethoxam in water under the condition of the invention.
Description
Technical Field
The invention relates to the technical field of photocatalytic oxidation and persulfate activation advanced oxidation, and particularly relates to a high-efficiency biochar-based catalytic material, a preparation method and application.
Background
The demand of pesticide in domestic and international markets is high, the pesticide dosage is higher in the third world as the agricultural kingdom, and the novel nicotine pesticide accounts for the most remarkable proportion in the global market at present. Thiamethoxam, as a representative of the second generation neonicotinoid pesticides, has the characteristics of high efficiency, broad spectrum, good systemic property and the like, and becomes one of the pesticide varieties with the largest development scale, the most successful marketing and the best activity in the whole market. Meanwhile, thiamethoxam is frequently detected in various fruits, vegetables, water sources and animal bodies. The harm of the fertilizer is that the fertilizer is widely distributed, difficult to degrade, strong in stability, capable of destroying an ecological system, and influencing the health of people and livestock.
The thiamethoxam has stable chemical properties and is difficult to mineralize, so that the conventional adsorption method has poor treatment effect, and the degradation method has great harm to the environment. Advanced oxidation technology has been widely used in the field of organic wastewater in recent years, but the limiting factor of the technology is focused on the efficiency and the recycling capability of the catalytic material. Therefore, the invention of a high-efficiency and stable catalytic material has important significance.
Although the existing means for removing macromolecular organic pollutants such as thiamethoxam in water are quite abundant, the technologies often have the problems of large process flow, expensive material and equipment, unavoidable secondary pollution and the like, and the expected rapidness, efficiency and thoroughness are difficult to achieve. Researches show that the key of the practicality of the semiconductor catalysis technology is to prepare the catalytic material which has stable structure, high utilization rate of light, strong photoelectric effect and cyclic utilization. TiO 2 2 、ZnO、SnO 2 、WO 3 And semiconductor materials such as BiOBr and the like can be used as photocatalytic materials due to special physicochemical properties, but the semiconductor materials also have limitations of different degrees, such as wide forbidden band width, low visible light utilization rate, small specific surface area, high electron-hole pair recombination rate and the like, and meanwhile, the modification method has the defects of many influencing factors, high difficulty, high cost and the like. The CdS as a photocatalytic material discovered very early has the advantages of narrow band gap, good visible light response, low price, simple preparation and the like, but the electron-hole separation efficiency and the electron mobility are low, and the CdS is easy to agglomerate to form large particles, so that the specific surface area is reduced, and the photocatalytic efficiency is influenced. According to the invention, the CdS @ BC composite material with good catalytic performance is prepared, the performance of the CdS @ BC composite material is proved by utilizing various characterization means, and the treatment efficiency of the CdS @ BC composite material on the thiamethoxam in the degradation wastewater is explored.
Phytolacca acinosa (BC) is selected as a porous template, and the CdS nanocrystals are uniformly loaded on the surface of the BC through a one-step method and a hydrothermal method, so that the composite material has higher electron transfer efficiency, rich functional groups, sufficient reaction sites and the like to achieve good catalytic performance and persulfate advanced oxidation activity. The prepared CdS @ BC has good photoresponse capability, the forbidden bandwidth of the CdS @ BC is obviously reduced after modification, and electrons are easier to jump from a track with lower energy to a track with higher energy under the illumination condition, so that a half-full band is formed, the conductivity of a material is enhanced, the separation efficiency of a photon-generated carrier is improved, and stronger oxidation-reduction capability is provided for the material. The invention is expected to synthesize a charcoal-based catalyst with excellent separation and catalytic performances, and provides a promising technology for treating thiamethoxam pesticide wastewater.
Disclosure of Invention
The invention aims to provide a high-efficiency biochar-based catalytic material, a preparation method and application, which load hexagonal-phase and cubic-phase CdS nanocrystals on a biochar composite material uniformly, have the advantages of high efficiency, good regeneration performance, low cost, simple preparation process, easiness in solid-liquid separation and the like, and further overcome the defects in the background art.
In order to achieve the above purpose, the invention provides the following technical scheme:
a high-efficiency biochar-based catalytic material comprises the following main materials: 0.05-0.2g of biochar, 0.05-0.2mol/L of potassium ferrate, 0.05-0.3mol/L of cadmium acetate, 100-500 mu L of thioacetic acid, 0.05-0.3mol/L of sodium sulfide and 0.1-0.5mol/L of polyvinyl alcohol.
The invention also provides a preparation method of the high-efficiency biochar-based catalytic material, which comprises the following steps:
the method comprises the following steps: collecting phytolacca plants, pretreating, thoroughly cleaning, removing roots, leaves and fruits, only keeping stems, drying in the air, drying in a drying oven, pulverizing, grinding, sieving with a 50-200 mesh sieve, and bagging for storage to obtain phytolacca biomass powder;
step two: weighing the pokeberry root powder obtained in the step one, and soaking the pokeberry root powder into 0.1mol/LK prepared in advance 2 FeO 4 Dispersing in water solution, continuously stirring for 8-12h, drying in vacuum oven at 40-80 deg.C for 8-12h, taking out, sieving with 100-200 mesh sieve, and bagging for storage to obtain porous biomass powder;
step three: weighing the porous biomass powder obtained in the step two, and loosely filling the porous biomass powder in a tubular furnace porcelain ark; using a vacuum rotary tube furnace at a continuously stable N 2 Setting the target temperature to be 300-1000 ℃ in an atmosphere; after the temperature rise is finished, respectively continuously calcining the biomass at 300-1000 ℃, and then continuously maintaining N 2 When the tube furnace is fully cooled to room temperature, the tube furnace is cooledRepeatedly washing the obtained pyrolysis product with 0.5-2mol/L dilute nitric acid and ultrapure water in an acid-water sequence, centrifuging to remove impurities, drying in a drying oven, and sieving with a 50-200 mesh sieve to obtain porous charcoal powder;
step four: weighing the porous charcoal powder obtained in the third step, immersing the porous charcoal powder into 0.1mol/L of polyvinyl alcohol solution prepared in advance for dispersing, continuously stirring for 2-4h, drying in a vacuum freeze dryer, and sieving with a 50-200 mesh sieve to obtain the porous charcoal powder with improved stability;
step five: adding the porous charcoal powder prepared in the fourth step into ultrapure water, continuously stirring, after the powder is uniformly dispersed, sequentially adding 1-20mL of 0.05-0.5mol/L cadmium acetate solution, 10-500 μ L of analytically pure thioacetic acid and 1-20mL of 0.05-0.5mol/L sodium sulfide solution into the suspension, continuously stirring to fully mix the solution, then adding the suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing a kettle cover, putting the kettle cover into a drying oven, continuously carrying out hydrothermal treatment after the temperature of the drying oven is raised, taking the reaction kettle out after the hydrothermal treatment is finished, and cooling the reaction kettle to room temperature;
step six: and D, centrifuging the product obtained after cooling in the fifth step, respectively washing and centrifuging the residual precipitate by using absolute ethyl alcohol and ultrapure water to remove impurities in the precipitate, and finally, placing the obtained black-green powder in a vacuum freeze dryer for drying for later use to obtain the biochar-based catalytic material.
Further, in the third step, the vacuum rotary tube furnace is heated to 300-1000 ℃ at the heating rate of 3-7 ℃/min and then is calcined for 0.5-5h at constant temperature; the rotation speed of the centrifuge is 3000-10000rpm, and the centrifugation time is 5-30min; setting the temperature of the oven at 30-95 ℃ and drying for 5-24h.
Further, in the fifth step, the solution is stirred for 0.5 to 2 hours and 1 to 2 hours in the previous and subsequent steps; the hydrothermal temperature of the oven is 120-160 ℃, and the hydrothermal time lasts 10-14h.
Further, in the sixth step, the rotating speed of the two centrifugations is 3000-8000rpm, and the centrifugation time is 5-10min; the temperature of the vacuum freeze dryer is set to be-60 to-30 ℃, the pressure is set to be 5-20pa, and the drying time is 6-12h.
The invention also provides an application of the high-efficiency biochar-based catalytic material prepared by the preparation method of the high-efficiency biochar-based catalytic material, and the method for degrading thiamethoxam in water by using the high-efficiency biochar-based catalytic material specifically comprises the following degradation steps: taking a certain amount of thiamethoxam wastewater, adjusting the pH value to be 2.0-10.0, adding a certain amount of a biochar-based catalytic material into the thiamethoxam wastewater, putting the thiamethoxam wastewater into a photocatalytic reactor, wherein the addition amount of the biochar-based catalytic material in each 100ml of wastewater is 0.05-0.2g, and the addition amount of potassium hydrogen persulfate is 0.1-1mmol/L, performing dark reaction in a magnetic stirrer with the rotation speed of 50-300 rpm for 0-60min, taking a xenon lamp provided with a CUT400 optical filter as a visible light source, adding persulfate, performing open-light reaction for 0-60min, controlling the reaction temperature to be 25-45 ℃, separating the biochar-based catalytic material from the solution after the reaction is finished, and finishing the degradation of the thiamethoxam in water.
Further, the light source conditions required for the reaction were a 300W xenon lamp equipped with a CUT400 (400-780) filter.
Further, the addition amount of potassium hydrogen persulfate in the reaction system is 0.5-1mmol/L.
Further, it is characterized in that: the pH value of the waste water before reaction is controlled between 6.0 and 8.0.
The method for degrading thiamethoxam in water by using the high-efficiency biochar-based catalytic material prepared by the preparation method of the high-efficiency biochar-based catalytic material comprises the steps of adding a proper amount of biochar-based catalytic material into wastewater to be treated, adjusting the pH value of the solution, controlling the temperature of the solution, adding persulfate after adsorption balance, starting light and continuously stirring, and waiting for complete reaction.
In the technical scheme, the invention provides the following technical effects and advantages:
1. by adding potassium ferrate and polyvinyl alcohol on the surface of the biochar and utilizing the oxidability and stability of the biochar, the biochar is more porous and easy to adhere CdS and is not easy to fall off after entering water, the stability of the material is improved, and the biochar-based catalytic material is better recycled;
2. the problem of high recombination rate of photo-generated carriers of CdS is effectively solved by loading the CdS nano-crystal on the biochar,the forbidden bandwidth is obviously reduced due to the existence of the biochar, and electrons are easier to jump from a track with lower energy to a track with higher energy under the illumination condition, so that a half-full band is formed, the conductivity of the material is enhanced, and the photo-generated electrons e-and photo-generated holes h are facilitated + The material is separated, so that the oxidation and reduction capacity of the material to the pollutant thiamethoxam is improved;
3. pi → Pi in the biochar-based catalytic material * The formation of the conjugated system enhances the absorption efficiency of the material on visible light; under the condition that the biochar provides a carrier, cadmium acetate, thioacetic acid and sodium sulfide are deposited on the biochar, the morphological characteristics of the biochar are changed, and the synthesized cubic-phase and hexagonal-phase nano-CdS with high crystallinity and the average grain size of 28.9nm greatly improves the response capability to light;
4. in a photocatalytic coupling persulfate system, the existence of visible light and a catalyst of the biochar-based catalytic material can be increased based on SO 4 The number of active species of advanced oxidation technique, and SO 4 The generation of the isoactive free radicals can effectively reduce the recombination probability of photo-generated electrons and holes, and the two have a mutual promotion relationship, so that the efficiency of degrading the thiamethoxam is improved. Based on the method, the charcoal-based catalytic material can quickly and efficiently degrade thiamethoxam in pesticide wastewater under the coupling system.
5. The biochar-based catalytic material is recycled for 4 times under a photocatalysis and persulfate coupling system, the degradation rate of the biochar-based catalytic material to the thiamethoxam is gradually decreased, but the overall decrease amplitude is small, so that the biochar-based catalytic material has good stability and is easy to separate solid from liquid and recycle.
Drawings
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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
FIG. 1 is a schematic view of a scanning electron microscope of the biochar-based catalytic material of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the accompanying drawings.
Example 1:
a high-efficiency biochar-based catalytic material comprises main materials as follows: 0.05-0.2g of biochar, 0.05-0.2mol/L of potassium ferrate, 0.05-0.3mol/L of cadmium acetate, 100-500 mu L of thioacetic acid, 0.05-0.3mol/L of sodium sulfide and 0.1-0.5mol/L of polyvinyl alcohol. By uniformly loading the CdS nano-crystals on the biochar composite material, the solid-liquid separation and the reutilization are easy,
a preparation method of a high-efficiency biochar-based catalytic material comprises the following steps:
the method comprises the following steps: collecting phytolacca americana plants for pretreatment. Thoroughly cleaning, removing roots, leaves and fruits, only keeping stems of the roots, fully airing, drying in a drying oven, crushing, fully grinding, sieving with a 50-200 mesh sieve, bagging and storing to obtain the phytolacca acinosa biomass powder.
Step two: weighing the biomass obtained in the step one, and soaking the biomass into 0.1mol/LK prepared in advance 2 FeO 4 Dispersing in the water solution, continuously stirring for 8-12h, and drying in a vacuum oven overnight; then taking out and sieving the biomass powder by a 100-200 mesh sieve, bagging and storing to obtain porous biomass powder.
Step three: weighing the product obtained in the step two, and filling the product in the tube furnace porcelain ark in a loose manner; using a vacuum rotary tube furnace, in a continuously stable N 2 Setting the target temperature to be 300-1000 ℃ in an atmosphere; after the temperature rise is finished, respectively continuously calcining the biomass at 300-1000 ℃, and then continuously maintaining N 2 And (3) after the circulation is completed, fully cooling the tubular furnace to room temperature, repeatedly washing and centrifuging the obtained pyrolysis product by using 0.5-2mol/L dilute nitric acid and ultrapure water in an acid-water sequence to remove impurities, drying the pyrolysis product in a drying box, and sieving the dried pyrolysis product by using a 50-200-mesh sieve to obtain the porous charcoal powder.
Step four: weighing the product obtained in the third step, immersing the product into 0.1mol/L polyvinyl alcohol solution prepared in advance for dispersion, continuously stirring for 2-4h, drying in a vacuum freeze dryer, and sieving with a 50-200 mesh sieve to obtain the porous charcoal powder with improved stability.
Step five: adding the biochar prepared in the fourth step into ultrapure water, continuously stirring, after the biochar is uniformly dispersed, sequentially adding 1-20mL of 0.05-0.5mol/L cadmium acetate solution, 10-500 μ L of analytically pure thioacetic acid and 1-20mL of 0.05-0.5mol/L sodium sulfide solution into the suspension, continuously stirring to fully mix the solutions, then adding the suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing a kettle cover, putting the kettle cover into an oven, continuously carrying out hydrothermal treatment after the oven is heated, and taking the reaction kettle out to cool the reaction kettle to room temperature after the hydrothermal treatment is finished.
Step six: and D, centrifuging the product obtained after cooling in the fifth step, respectively washing and centrifuging the residual precipitate by using absolute ethyl alcohol and ultrapure water to remove impurities in the precipitate, and finally, placing the obtained black-green powder in a vacuum freeze dryer for drying for later use to obtain the biochar-based catalytic material.
Preferably, the potassium ferrate and the polyvinyl alcohol are analytically pure, and the purity is 99%.
Preferably, the cadmium acetate, thioacetic acid and sodium sulfide are analytically pure, and the purity is 99%.
Preferably, the absolute ethanol is analytically pure and has a concentration of 99.7%.
Preferably, the nitric acid is analytically pure at a concentration of 99%.
Preferably, in the second step, the temperature of the vacuum drying oven is 80 ℃, and the drying time is 12h.
Preferably, in the third step, the vacuum rotary tube furnace is heated to 500 ℃, 700 ℃ and 900 ℃ at the heating rate of 5 ℃/min and then is calcined for 2 hours at constant temperature; the rotation speed of the centrifugal machine is 4000-6000rpm, and the centrifugal time is 5-20min; setting the temperature of the oven at 60-80 ℃, and drying for 8-12h.
Preferably, in the fourth step, the temperature of the vacuum freeze dryer is set to-30 ℃, and the pressure is set to 20pa.
Preferably, in the fifth step, the solution is stirred for 0.5 to 2 hours and 1 to 2 hours in the previous and next steps; the hydrothermal temperature of the oven is 120-160 ℃, and the hydrothermal time lasts for 10-14h.
Preferably, in the sixth step, the rotating speed of the two centrifugations is 4000-8000rpm, and the centrifugation time is 5-10min; the required temperature of the vacuum freeze dryer is set to be-30 ℃, the pressure is set to be 20pa, and the drying time is 6-12h.
A method for degrading thiamethoxam in water by using a high-efficiency biochar-based catalytic material prepared by the preparation method of the high-efficiency biochar-based catalytic material comprises the following steps:
adding a proper amount of a biochar-based catalytic material into thiamethoxam wastewater to be treated, stirring for 30min in the dark, adding oxonium persulfate, starting to light, stirring for 30min, and finally adding 0.1g of the material, wherein the degradation rate of 10mg/L thiamethoxam with the volume of 100mL can reach 100%.
Example 2:
the method for degrading thiamethoxam in water by using the biochar-based catalytic material in a visible light coupled persulfate system comprises the following steps:
weighing 5 parts of 0.1g of the biochar-based catalytic material prepared in the example 1, respectively adding 5 100mL of 10mg/L thiamethoxam wastewater to be treated with pH values of 2, 4, 6, 8 and 10, placing a reactor in a photocatalytic reaction box, controlling the temperature of the solution to be 25 ℃ through a water bath, stirring for 30min under a dark condition, adding oxone while starting to light and stirring for 30min, measuring the content of the remaining thiamethoxam in the wastewater by using a high performance liquid chromatography, and finally calculating the degradation rate result to be shown in Table 1:
table 1: effect of pH value on efficiency of biochar-based catalytic material coupled persulfate visible light to catalyze and degrade thiamethoxam in water
As can be seen from table 1, both the case of excessively high pH and the case of excessively low pH may affect the properties of the biochar-based catalytic material itself, and are not favorable for the degradation of thiamethoxam, so that the biochar-based catalytic material under the system is more suitable for the degradation of thiamethoxam in a weak acid solution environment with pH =6, and the degradation rate can reach 100%.
Example 3:
the research on the regeneration and utilization performance of the biochar-based catalytic material in a visible light coupling activation persulfate system comprises the following steps:
0.1g of the biochar-based catalytic material prepared in the example 1 is weighed and added into 100mL of 10mg/L thiamethoxam wastewater to be treated with the pH value of 6, the reactor is placed in a photocatalytic reaction box, the temperature of the solution is controlled to be 25 ℃ through water bath, after stirring for 30min under the dark condition, potassium hydrogen persulfate is added, meanwhile, the light is turned on, the stirring is carried out for 30min, and the biochar-based catalytic material used in the experiment is recorded as 1st. Subsequently, the 1st material was centrifuged to separate a suspension of the wastewater into solid and liquid, and then washed repeatedly with absolute ethanol and ultrapure water and vacuum-dried. The dried and reground sieved material was then put into a new round of experiment under the same conditions. Each round of experiment controls the initial concentration, initial pH, solution temperature, material adding amount and other conditions of the thiamethoxam wastewater to be unchanged, so that 4 rounds of circulation experiments are repeatedly carried out. The recycled biochar-based catalytic materials used in the last 3 recycling experiments are respectively marked as 2nd, 3rd and 4th. The content of the thiamethoxam remained in the wastewater is determined by a high performance liquid chromatography after each round of experiment, and finally, the degradation rate result obtained by calculation is shown in table 2:
table 2: regeneration and utilization performance of charcoal-based catalytic material
As can be seen from Table 2, the material is recycled for 4 times under a photocatalysis and persulfate coupling system, the degradation rate of the material to thiamethoxam is gradually decreased, the degradation rate is reduced to 85.2% from 100% at a position 30min after the start of light, but the overall reduction amplitude is small, and the biochar-based catalytic material has good photocatalysis stability and is easy for solid-liquid separation and reutilization.
While certain exemplary embodiments of the present invention have been described above by way of illustration only, it will be apparent to those of ordinary skill in the art that the described embodiments may be modified in various different ways without departing from the spirit and scope of the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive on the scope of the appended claims, and any changes, substitutions of equivalents, modifications, etc. that come within the spirit and scope of the invention are intended to be embraced therein.
Claims (9)
1. The high-efficiency biochar-based catalytic material is characterized in that the main materials comprise: 0.05-0.2g of biochar, 0.05-0.2mol/L of potassium ferrate, 0.05-0.3mol/L of cadmium acetate, 100-500 mu L of thioacetic acid, 0.05-0.3mol/L of sodium sulfide and 0.1-0.5mol/L of polyvinyl alcohol.
2. A preparation method of a high-efficiency biochar-based catalytic material is characterized by comprising the following steps:
the method comprises the following steps: collecting phytolacca americana plants, pretreating, thoroughly cleaning, removing roots, leaves and fruits, only keeping stems of the phytolacca americana plants, fully airing, drying in a drying box, crushing, fully grinding, sieving with a 50-200-mesh sieve, bagging and storing to obtain phytolacca americana biomass powder;
step two: weighing the pokeberry root powder obtained in the step one, and soaking the pokeberry root powder into 0.1mol/LK prepared in advance 2 FeO 4 Dispersing in water solution, continuously stirring for 8-12h, drying in vacuum oven at 40-80 deg.C for 8-12h, taking out, sieving with 100-200 mesh sieve, and bagging for storage to obtain porous biomass powder;
step three: weighing the porous biomass powder obtained in the step two, and loosely filling the porous biomass powder in a tubular furnace porcelain ark; using a vacuum rotary tube furnace at a continuously stable N 2 Setting the target temperature to be 300-1000 ℃ in an atmosphere; after the temperature rise is finished, respectively continuously calcining the biomass at 300-1000 ℃, and then continuously maintaining N 2 When the circulation is cooled to room temperature, the obtained pyrolysis product is treated with 0.5-2mol/L dilute nitric acid and ultrapure waterWashing and centrifuging the water repeatedly in sequence to remove impurities, drying the washed and centrifuged water in a drying oven, and sieving the dried and centrifuged water with a 50-200-mesh sieve to obtain porous charcoal powder;
step four: weighing the porous charcoal powder obtained in the third step, immersing the porous charcoal powder into 0.1mol/L of polyvinyl alcohol solution prepared in advance for dispersing, continuously stirring for 2-4h, drying in a vacuum freeze dryer, and sieving with a 50-200 mesh sieve to obtain the porous charcoal powder with improved stability;
step five: adding the porous charcoal powder prepared in the fourth step into ultrapure water, continuously stirring, after the porous charcoal powder is uniformly dispersed, sequentially adding 1-20mL of 0.05-0.5mol/L cadmium acetate solution, 10-500 mu L of analytically pure thioacetic acid and 1-20mL of 0.05-0.5mol/L sodium sulfide solution into the suspension, continuously stirring to fully mix the solutions, then adding the suspension into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing a kettle cover, putting the kettle into a drying oven, continuously carrying out hydrothermal treatment after the drying oven is heated, taking out the reaction kettle after the hydrothermal treatment is finished, and cooling the reaction kettle to room temperature;
step six: and D, centrifuging the product obtained after cooling in the fifth step, respectively washing and centrifuging the residual precipitate by using absolute ethyl alcohol and ultrapure water to remove impurities in the precipitate, and finally, placing the obtained black-green powder in a vacuum freeze dryer for drying for later use to obtain the biochar-based catalytic material.
3. The preparation method of the high-efficiency biochar-based catalytic material as claimed in claim 2, characterized in that: in the third step, the vacuum rotary tube furnace is heated to 300-1000 ℃ at the heating rate of 3-7 ℃/min and then is calcined for 0.5-5h at constant temperature; the rotation speed of the centrifuge is 3000-10000rpm, and the centrifugation time is 5-30min; setting the temperature of the oven at 30-95 ℃ and drying for 5-24h.
4. The method for preparing the high-efficiency biochar-based catalytic material according to claim 2, which is characterized by comprising the following steps of: in the fifth step, the solution is stirred for 0.5-2h and 1-2h in the two times; the hydrothermal temperature of the oven is 120-160 ℃, and the hydrothermal time lasts 10-14h.
5. The method for preparing the high-efficiency biochar-based catalytic material according to claim 2, which is characterized by comprising the following steps of: in the sixth step, the rotating speed of the two centrifugations is 3000-8000rpm, and the centrifuging time is 5-10min; the temperature of the vacuum freeze dryer is set to be-60 to-30 ℃, the pressure is set to be 5-20pa, and the drying time is 6-12h.
6. The application of the high-efficiency biochar-based catalytic material prepared by the preparation method of the high-efficiency biochar-based catalytic material as claimed in any one of claims 2 to 5, which is characterized in that the high-efficiency biochar-based catalytic material is used for degrading thiamethoxam in water, and the method specifically comprises the following degradation steps: taking a certain amount of thiamethoxam wastewater, adjusting the pH value to be 2.0-10.0, adding a certain amount of a biochar-based catalytic material into the thiamethoxam wastewater, putting the thiamethoxam wastewater into a photocatalytic reactor, wherein the addition amount of the biochar-based catalytic material in each 100ml of wastewater is 0.05-0.2g, and the addition amount of potassium hydrogen persulfate is 0.1-1mmol/L, performing dark reaction in a magnetic stirrer with the rotation speed of 50-300 rpm for 0-60min, taking a xenon lamp provided with a CUT400 optical filter as a visible light source, adding persulfate, performing open-light reaction for 0-60min, controlling the reaction temperature to be 25-45 ℃, separating the biochar-based catalytic material from the solution after the reaction is finished, and finishing the degradation of the thiamethoxam in water.
7. The method for degrading thiamethoxam in water by using high-efficiency biochar-based catalytic material according to claim 6, wherein the method comprises the following steps: the light source condition required by the reaction is a 300W xenon lamp provided with a CUT400 filter.
8. The method for degrading thiamethoxam in water by using high-efficiency biochar-based catalytic material according to claim 6, wherein the method comprises the following steps: the adding amount of the potassium hydrogen persulfate in the reaction system is 0.5-1mmol/L.
9. The method for degrading thiamethoxam in water by using high-efficiency biochar-based catalytic material as claimed in claim 6, wherein the method comprises the following steps: the method is characterized in that: the pH value of the waste water before reaction is controlled between 6.0 and 8.0.
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