CN115282984B - 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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- 239000000463 material Substances 0.000 title claims abstract description 74
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000005941 Thiamethoxam Substances 0.000 claims abstract description 35
- 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 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 8
- 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 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000001035 drying Methods 0.000 claims description 26
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- 238000003756 stirring Methods 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
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- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 8
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- 239000002244 precipitate Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
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- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 abstract description 5
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 10
- 239000000575 pesticide Substances 0.000 description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 240000007643 Phytolacca americana Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
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- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- 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
- B01J37/20—Sulfiding
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- 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
- C02F1/722—Oxidation by peroxides
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a high-efficiency biochar-based catalytic material, wherein the main materials comprise: 0.05 to 0.2g of biochar, 0.05 to 0.2mol/L of potassium ferrate, 0.05 to 0.3mol/L of cadmium acetate, 100 to 500 mu L of thioacetic acid, 0.05 to 0.3mol/L of sodium sulfide and 0.1 to 0.5mol/L of polyvinyl alcohol. The invention also provides a preparation method and application of the efficient 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 thiamethoxam in water under the condition of the invention.
Description
Technical Field
The invention relates to the technical field of photocatalytic oxidation and advanced oxidation of activated persulfate, in particular to a high-efficiency biochar-based catalytic material, a preparation method and application.
Background
The demands of pesticides on domestic and international markets are high, and as agricultural large countries, the pesticide consumption is high and the third world is high, wherein the novel nicotine pesticide is particularly prominent in the global market at present. Thiamethoxam is used as a representative of second generation neonicotinoid pesticides, and is one of the pesticide varieties with the largest development rule, the most successful marketing and the best activity in the whole market due to the characteristics of high efficiency, broad spectrum, good systemic property and the like. Meanwhile, thiamethoxam is frequently detected in various fruits, vegetables, water sources and animal bodies. The harm is that the distribution is wide, the degradation is difficult, the stability is strong, the ecological system is destroyed, the health of human and livestock is influenced, and the like.
Thiamethoxam has stable chemical properties and is difficult to mineralize, so that the conventional adsorption method has poor treatment effect, and the degradation method generates 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 recycling ability of catalytic materials. Therefore, the invention of the high-efficiency and stable catalytic material has important significance.
Although the prior means for removing macromolecular organic pollutants such as thiamethoxam in water are quite abundant, the problems of huge process flow, expensive material equipment, unavoidable secondary pollution and the like of the technologies are undeniably often caused, and the expected quick, efficient and thorough problems are difficult to achieve. Study ofThe key point of the practical application of the semiconductor catalysis technology is that the catalysis material which has stable structure, high light utilization rate, strong photoelectric effect and recycling is prepared. TiO (titanium dioxide) 2 、ZnO、SnO 2 、WO 3 And semiconductor materials such as BiOBr can be used as photocatalytic materials due to the special physicochemical properties of the materials, but the 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 more influencing factors, high difficulty, high cost and the like. The CdS as a photocatalysis material discovered very early has the advantages of narrow band gap, good visible light response, low cost, simple preparation and the like, but has low electron-hole separation efficiency and electron mobility, is easy to agglomerate to form large particles, reduces specific surface area and further influences the photocatalysis efficiency. According to the invention, the CdS@BC composite material with good catalytic performance is prepared, and various characterization means are utilized to evidence the performance and explore the treatment efficacy of the CdS@BC composite material on degrading thiamethoxam in wastewater.
The pokeberry charcoal (BC) is selected as a porous template, and 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 migration efficiency, rich functional groups, sufficient reaction sites and the like, and good catalytic performance and persulfate advanced oxidation activity are achieved. The prepared CdS@BC has good photoresponse capability, the forbidden bandwidth of the CdS@BC is obviously reduced after modification, electrons are easier to transition from a track with lower energy to a track with higher energy under the illumination condition, so that a semi-full band is formed, the conductivity of the material is enhanced, the separation efficiency of photo-generated carriers is improved, and stronger oxidation-reduction capability is provided for the material. The invention is hopeful to synthesize a biochar-based catalyst with excellent separation and catalysis performance, and provides a promising technology for the treatment of thiamethoxam pesticide wastewater.
Disclosure of Invention
The invention aims to provide a high-efficiency biochar-based catalytic material, a preparation method and application, hexagonal-phase and cubic-phase CdS nanocrystals are uniformly loaded on a biochar composite material, and the preparation method has the advantages of high efficiency, good regeneration performance, low cost, simple preparation process, easiness in solid-liquid separation and the like, so that the defects in the background technology are overcome.
In order to achieve the above object, the present invention provides the following technical solutions:
a high-efficiency biochar-based catalytic material, wherein the main materials comprise: 0.05 to 0.2g of biochar, 0.05 to 0.2mol/L of potassium ferrate, 0.05 to 0.3mol/L of cadmium acetate, 100 to 500 mu L of thioacetic acid, 0.05 to 0.3mol/L of sodium sulfide and 0.1 to 0.5mol/L of polyvinyl alcohol.
The invention also provides a preparation method of the efficient biochar-based catalytic material, which comprises the following steps:
step one: collecting radix Phytolaccae plants, pretreating, thoroughly cleaning, removing root, leaf and fruit, only retaining stem, air-drying, oven-drying in a drying oven, pulverizing, grinding, sieving with 50-200 mesh sieve, and bagging to obtain radix Phytolaccae biomass powder;
step two: weighing the product Liu Fenmo obtained in the first step, and immersing into 0.1mol/LK prepared in advance 2 FeO 4 Dispersing in water solution, continuously stirring for 8-12h, drying in vacuum oven at 40-80deg.C for 8-12h, taking out, sieving with 100-200 mesh sieve, and bagging for preservation to obtain porous biomass powder;
step three: weighing the porous biomass powder obtained in the second step, and loosely filling the porous biomass powder in a ceramic square boat of a tube furnace; using a vacuum rotary tube furnace, continuously stabilizing N 2 Setting the target temperature to 300-1000 ℃ under the atmosphere; after the temperature is raised, respectively continuously calcining the biomass at 300-1000 ℃, and then continuously maintaining N 2 Circulating until the tubular furnace is fully cooled to room temperature, repeatedly flushing and centrifuging the obtained pyrolysis product with 0.5-2mol/L dilute nitric acid and ultrapure water in the order of acid and water to remove impurities, and then placing the pyrolysis product in a drying oven for drying and sieving the pyrolysis product with a 50-200-mesh sieve to obtain porous biochar powder;
step four: weighing the porous biochar powder obtained in the step three, immersing the porous biochar powder into a polyvinyl alcohol solution of 0.1mol/L 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 biochar powder with improved stability;
step five: adding the porous biochar powder prepared in the step four into ultrapure water and continuously stirring, after the porous biochar 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 porous biochar powder, 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 temperature of the oven is increased, and 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 step five, 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 and green powder into a vacuum freeze dryer for drying for standby, thus obtaining the biochar-based catalytic material.
Further, in the third step, the vacuum rotary tube furnace is heated to 300-1000 ℃ at a heating rate of 3-7 ℃/min and then calcined for 0.5-5 hours at constant temperature; the rotation speed of the centrifugal machine is 3000-10000rpm, and the centrifugal 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 0.5-2h and 1-2h twice before and after; the hydrothermal temperature of the oven is 120-160 ℃, and the duration of the hydrothermal time is 10-14h.
Further, in the step six, the centrifugal rotational speed of the front and back two times is 3000-8000rpm, and the centrifugal time is 5-10min; the required vacuum freeze dryer temperature 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, which is used for degrading thiamethoxam in water, and specifically comprises the following degradation steps: taking a certain amount of thiamethoxam wastewater, regulating the pH value to be 2.0-10.0, adding a certain amount of 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, the addition amount of potassium hydrogen persulfate is 0.1-1mmol/L, carrying out dark reaction for 0-60min in a magnetic stirrer with the rotating speed of 50-300 rpm, using a xenon lamp with a CUT400 optical filter as a visible light source, adding persulfate, carrying out 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 completed, and completing the degradation of thiamethoxam in water.
Further, the light source conditions required for the reaction were a 300W xenon lamp fitted with a CUT400 (400-780) filter.
Further, the addition amount of the potassium hydrogen persulfate in the reaction system is 0.5-1mmol/L.
Further, it is characterized in that: the pH of the wastewater before the reaction is controlled to be 6.0-8.0.
The method for degrading thiamethoxam in water by utilizing 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, and continuously stirring after light-on, and waiting for complete reaction.
In the technical scheme, the invention has the technical effects and advantages that:
1. by adding potassium ferrate and polyvinyl alcohol on the surface of the biochar, the biochar is more porous, is easy to attach CdS and is not easy to fall off after water is added, so that 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 CdS nanocrystals with biochar, the forbidden bandwidth is obviously reduced because of the presence of the biochar, electrons are easier to transition from a lower-energy track to a higher-energy track under the condition of illumination, so that a half full band is formed, the conductivity of the material is enhanced, and photo-generated electrons e-and photo-generated holes h are more favorable + Separation increases the oxidation and reduction capability of the material to the thiamethoxam pollutant;
3. pi-pi in the biochar-based catalytic material * Is formed by a conjugated system which enhances the visible light of the materialAbsorption efficiency; under the condition that the biochar provides a carrier, cadmium acetate, thioacetic acid and sodium sulfide are deposited on the biochar, so that the morphological characteristics of the biochar are changed, and the synthesized nano CdS with cubic phase and hexagonal phase, high crystallinity and average grain size of 28.9nm greatly improves the response capability to light;
4. the biological carbon-based catalytic material can increase SO-based in the presence of visible light and a catalyst in a photocatalysis coupling persulfate system 4 Number of active species of advanced oxidation technique, while 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 thiamethoxam degradation efficiency is improved. Based on the coupling system, the biochar-based catalytic material can rapidly and efficiently degrade thiamethoxam in pesticide wastewater.
5. The biochar-based catalytic material is recycled for 4 times under a photocatalysis and persulfate coupling system, the degradation rate of thiamethoxam is gradually decreased, but the integral decrease is smaller, so that the biochar-based catalytic material has good stability and is easy to separate solid from liquid and recycle.
Drawings
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.
FIG. 1 is a schematic diagram of a scanning electron microscope of the biochar-based catalytic material of the present invention.
Detailed Description
In order to make the technical scheme of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings.
Example 1:
a high-efficiency biochar-based catalytic material, wherein the main materials comprise: 0.05 to 0.2g of biochar, 0.05 to 0.2mol/L of potassium ferrate, 0.05 to 0.3mol/L of cadmium acetate, 100 to 500 mu L of thioacetic acid, 0.05 to 0.3mol/L of sodium sulfide and 0.1 to 0.5mol/L of polyvinyl alcohol. By uniformly loading CdS nanocrystals on the biochar composite material, the solid-liquid separation and the reutilization are easy,
the preparation method of the efficient biochar-based catalytic material comprises the following steps:
step one: and (5) collecting pokeberry plants for pretreatment. Thoroughly cleaning, removing root, leaf and fruit, only preserving stem, drying in the air, oven drying in a drying oven, pulverizing, grinding, sieving with 50-200 mesh sieve, and bagging to obtain radix Phytolaccae biomass powder.
Step two: weighing the biomass obtained in the first step, and immersing the biomass into 0.1mol/LK prepared in advance 2 FeO 4 Dispersing in water solution, continuously stirring for 8-12h, and drying in a vacuum oven overnight; and then taking out the biomass powder, sieving the biomass powder through a 100-200-mesh sieve, bagging and preserving the biomass powder to obtain the porous biomass powder.
Step three: weighing the product obtained in the second step, and loosely filling the product in a porcelain square boat of a tube furnace; using a vacuum rotary tube furnace, continuously stabilizing N 2 Setting the target temperature to 300-1000 ℃ under the atmosphere; after the temperature is raised, respectively continuously calcining the biomass at 300-1000 ℃, and then continuously maintaining N 2 Circulating until the tubular furnace is fully cooled to room temperature, repeatedly flushing the obtained pyrolysis product with 0.5-2mol/L dilute nitric acid and ultrapure water in the order of acid and water, centrifuging to remove impurities, drying in a drying oven, and sieving with a 50-200-mesh sieve to obtain porous biochar powder.
Step four: and (3) weighing the product obtained in the step (III), immersing the product into a 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 biochar powder with improved stability.
Step five: adding the biochar prepared in the fourth step into ultrapure water and continuously stirring, after the biochar 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 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 an oven, continuously carrying out hydrothermal treatment after the temperature of the oven is increased, and 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 step five, 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 and green powder into a vacuum freeze dryer for drying for standby, thus obtaining the biochar-based catalytic material.
Preferably, the potassium ferrate and the polyvinyl alcohol are both analytically pure, and the purity is 99%.
Preferably, the cadmium acetate, the thioacetic acid and the sodium sulfide are all analytically pure and have a purity of 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 is performed for 12 hours.
Preferably, in the third step, the vacuum rotary tube furnace is heated to 500 ℃, 700 ℃ and 900 ℃ at a heating rate of 5 ℃/min, and then the furnace is calcined for 2 hours at constant temperature; the rotation speed of the centrifugal machine is 4000-6000rpm, and the centrifugation 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 0.5-2h and 1-2h twice before and after; the hydrothermal temperature of the oven is 120-160 ℃, and the duration of the hydrothermal time is 10-14h.
Preferably, in the sixth step, the centrifugal rotational speeds of the two times before and after are 4000-8000rpm, and the centrifugal time is 5-10min; the required temperature of the vacuum freeze dryer is set to be minus 30 ℃, the pressure is set to be 20pa, and the drying time is 6-12h.
A method for degrading thiamethoxam in water by utilizing 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 biochar-based catalytic material into thiamethoxam wastewater to be treated, stirring for 30min under dark condition, adding potassium hydrogen persulfate, simultaneously opening light and stirring for 30min, and finally adding 0.1g of material, wherein the degradation rate of the 10mg/L thiamethoxam with the volume of 100mL can reach 100%.
Example 2:
the biological carbon-based catalytic material of the invention is utilized to degrade thiamethoxam in water in a visible light coupling persulfate system, and comprises the following steps:
5 parts of 0.1g of the biochar-based catalytic material prepared in example 1 is weighed and added into 5 100mL of 10mg/L thiamethoxam wastewater to be treated with pH values of 2, 4, 6, 8 and 10 respectively, a reactor is placed in a photocatalytic reaction box, the temperature of the solution is controlled to be 25 ℃ through a water bath, the reactor is stirred for 30min under dark conditions, potassium hydrogen persulfate is added, the reactor is simultaneously lighted and stirred for 30min, the content of residual thiamethoxam in the wastewater is measured through high performance liquid chromatography, and the degradation rate results obtained through calculation are shown in table 1:
table 1: effect of pH value on biological carbon-based catalytic material coupled with persulfate to catalyze and degrade thiamethoxam in water
As can be seen from Table 1, under the condition of too high and too low pH, the properties of the biochar-based catalytic material per se can be influenced, and the degradation of thiamethoxam is unfavorable, so that the weak acidic solution environment with pH=6 is more suitable for the degradation of the biochar-based catalytic material to the thiamethoxam in the system, and the degradation rate can reach 100%.
Example 3:
the invention relates to a research on recycling performance of a biochar-based catalytic material in a visible light coupling activated persulfate system, which comprises the following steps:
the biochar-based catalytic material prepared in example 1 was weighed 0.1g and added to 100mL of prepared thiamethoxam wastewater to be treated at pH 6, the reactor was placed in a photocatalytic reaction tank, the solution temperature was controlled to 25℃by a water bath, stirred for 30 minutes under dark conditions, then potassium hydrogen persulfate was added while turning on light and stirring for 30 minutes, and the biochar-based catalytic material used in the set of experiments was recorded as 1st. Subsequently, the 1st material was centrifuged to separate the wastewater suspension from solid and liquid, and then repeatedly washed with absolute ethanol and ultrapure water and vacuum-dried. And putting the dried and reground sieved material into a new experiment under the same condition. Each round of experiment controls the initial concentration, the initial pH, the solution temperature, the material addition amount and other conditions of thiamethoxam wastewater to be unchanged, and 4 rounds of circulating experiments are repeated. The recovered biochar-based catalytic materials used in the last 3 recycling experiments were recorded as 2nd, 3rd and 4th, respectively. The content of the residual thiamethoxam in the wastewater is measured by high performance liquid chromatography after each experiment, and the degradation rate obtained by final calculation is shown in table 2:
table 2: the recycling performance of the biochar-based catalytic material
As shown in Table 2, the material is recycled for 4 times under the coupling system of photocatalysis and persulfate, the degradation rate of thiamethoxam is gradually decreased, the degradation rate is reduced to 85.2% from 100% at 30min after light is turned on, but the whole degradation is smaller, which indicates that the biochar-based catalytic material has good photocatalysis stability and is easy for solid-liquid separation and recycling.
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 modifications may be made to the described embodiments in various different ways without departing from the spirit and scope of the invention. Accordingly, the foregoing drawings and description are illustrative in nature and are not to be construed as limiting the scope of the invention as claimed, but any modifications, equivalent arrangements, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The preparation method of the efficient biochar-based catalytic material is characterized by comprising the following steps of: step one: collecting radix Phytolaccae plants, pretreating, thoroughly cleaning, removing root, leaf and fruit, only retaining stem, air-drying, oven-drying in a drying oven, pulverizing, grinding, sieving with 50-200 mesh sieve, and bagging to obtain radix Phytolaccae biomass powder;
step two: weighing the product Liu Fenmo obtained in the first step, and immersing into 0.1mol/LK prepared in advance 2 FeO 4 Dispersing in water solution, continuously stirring for 8-12h, drying in vacuum oven at 40-80deg.C for 8-12h, taking out, sieving with 100-200 mesh sieve, and bagging for preservation to obtain porous biomass powder;
step three: weighing the porous biomass powder obtained in the second step, and loosely filling the porous biomass powder in a ceramic square boat of a tube furnace; using a vacuum rotary tube furnace, continuously stabilizing N 2 Setting the target temperature to 300-1000 ℃ under the atmosphere; after the temperature is raised, respectively continuously calcining the biomass at 300-1000 ℃, and then continuously maintaining N 2 Circulating until the tubular furnace is fully cooled to room temperature, repeatedly flushing and centrifuging the obtained pyrolysis product with 0.5-2mol/L dilute nitric acid and ultrapure water in the order of acid and water to remove impurities, and then placing the pyrolysis product in a drying oven for drying and sieving the pyrolysis product with a 50-200-mesh sieve to obtain porous biochar powder;
step four: weighing the porous biochar powder obtained in the step three, immersing the porous biochar powder into a polyvinyl alcohol solution of 0.1mol/L 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 biochar powder with improved stability;
step five: adding the porous biochar powder prepared in the step four into ultrapure water and continuously stirring, after the porous biochar 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 porous biochar powder, 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 temperature of the oven is increased, and 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 step five, 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 and green powder into a vacuum freeze dryer for drying for standby, thus obtaining the biochar-based catalytic material.
2. The method for preparing the efficient biochar-based catalytic material according to claim 1, which is characterized in that: in the third step, the vacuum rotary tube furnace is heated to 300-1000 ℃ at a heating rate of 3-7 ℃/min and then calcined for 0.5-5h at constant temperature; the rotation speed of the centrifugal machine is 3000-10000rpm, and the centrifugal time is 5-30min; setting the temperature of the oven at 30-95 ℃ and drying for 5-24h.
3. The method for preparing the efficient biochar-based catalytic material according to claim 1, which is characterized in that: in the fifth step, the solution is stirred for 0.5-2h and 1-2h in front and back twice; the hydrothermal temperature of the oven is 120-160 ℃, and the duration of the hydrothermal time is 10-14h.
4. The method for preparing the efficient biochar-based catalytic material according to claim 1, which is characterized in that: in the step six, the centrifugal rotational speed of the front and back two times is 3000-8000rpm, and the centrifugal time is 5-10min; the required vacuum freeze dryer temperature is set to be-60 to-30 ℃, the pressure is set to be 5-20pa, and the drying time is 6-12h.
5. The application of the efficient biochar-based catalytic material prepared by the preparation method of the efficient biochar-based catalytic material according to any one of claims 1 to 4, wherein thiamethoxam in water is degraded by using the efficient biochar-based catalytic material, and the method specifically comprises the following degradation steps: taking a certain amount of thiamethoxam wastewater, regulating the pH value to be 2.0-10.0, adding a certain amount of 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, the addition amount of potassium hydrogen persulfate is 0.1-1mmol/L, carrying out dark reaction for 0-60min in a magnetic stirrer with the rotating speed of 50-300 rpm, using a xenon lamp with a CUT400 optical filter as a visible light source, adding potassium hydrogen persulfate, carrying out photoreaction for 0-60min, controlling the reaction temperature to be 25-45 ℃, separating the biochar-based catalytic material from the solution after the reaction is completed, and completing the degradation of thiamethoxam in water.
6. The use according to claim 5, characterized in that: the light source conditions required for the reaction were a 300W xenon lamp fitted with a CUT400 filter.
7. The use according to claim 5, characterized in that: the adding amount of the potassium hydrogen persulfate in the reaction system is 0.5-1mmol/L.
8. The use according to claim 5, characterized in that: the pH of the wastewater before the reaction is controlled to be 6.0-8.0.
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