CN118237050A - MoS (MoS)2Sludge biochar and preparation method and application thereof - Google Patents
MoS (MoS)2Sludge biochar and preparation method and application thereof Download PDFInfo
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- CN118237050A CN118237050A CN202410640630.9A CN202410640630A CN118237050A CN 118237050 A CN118237050 A CN 118237050A CN 202410640630 A CN202410640630 A CN 202410640630A CN 118237050 A CN118237050 A CN 118237050A
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- sludge biochar
- sludge
- biochar
- imidacloprid
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- 239000010802 sludge Substances 0.000 claims abstract description 138
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 90
- 238000000498 ball milling Methods 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 20
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
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- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 description 16
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 7
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
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Landscapes
- Treatment Of Sludge (AREA)
Abstract
The invention relates to MoS 2 sludge biochar, a preparation method and application thereof, comprising the following steps: washing and drying the residual sludge, and then carrying out pyrolysis, acid leaching, washing, drying, grinding and sieving to obtain sludge biochar; uniformly mixing the sludge biochar with a molybdenum source, a sulfur source, a dispersing agent and a solvent, and obtaining the hydro-thermal synthesis MoS 2 sludge biochar through hydro-thermal synthesis reaction; and/or, further comprising: performing ball milling on the sludge biochar obtained by the hydro-thermal synthesis of the MoS 2 to obtain the sludge biochar obtained by the ball milling hydro-thermal synthesis of the MoS 2. The invention can effectively reduce the energy and the synthesis cost consumed in the synthesis process by a one-pot hydrothermal synthesis method; the particle size is reduced through ball milling treatment, and MoS 2 can be dispersed more uniformly on the surface of the biochar; the MoS 2 sludge biochar has high catalytic activity, particularly the MoS 2 sludge biochar synthesized by ball milling and hydrothermal method, and can activate the removal rate of the peroxymonosulfate to the neonicotinoid compounds in water to reach more than 95%.
Description
Technical Field
The invention relates to the technical field of biochar preparation and water treatment, in particular to MoS 2 sludge biochar, a preparation method and application thereof.
Background
In recent years, the problem of water pollution is more and more serious. The neonicotinoid insecticide has become the fastest-growing type of insecticide in modern crop protection due to the advantages of broad insecticidal spectrum, high efficiency, low acute toxicity to mammals and the like, and is widely used for preventing and controlling various pests. Of the neonicotinoid insecticides, imidacloprid is the most well known and most widely used representative of the neonicotinoid insecticide, and has been applied to 140 more than 140 crops to control pests. However, the widespread use of imidacloprid has become a serious problem due to its toxicity, bioaccumulation and persistence. Studies have demonstrated that prolonged exposure to imidacloprid, even at ambient concentrations, can cause inflammation of the rat liver and central nervous system, induce oxidative stress and DNA damage in zebra fish, and reduce survival of large invertebrates in surface waters. Imidacloprid may be exposed to aquatic ecosystems for a long period of time under poor lighting conditions, and may have a harmful effect on human health and the environment. Therefore, development of an effective technique capable of effectively removing neonicotinoid compounds in water is of great importance, and has become a hot spot in water treatment research.
Previous studies have shown that various techniques have been used to treat imidacloprid in water, such as adsorption, biodegradation, and membrane filtration. Although the adsorption method has the advantages of simple operation and low cost, the thorough removal of pollutants can not be realized; the microbial growth period in the biodegradation method is longer, the environment for culturing the microorganisms is more severe, the operation is complex, and the cost is higher. Imidacloprid is difficult to eliminate by conventional treatment processes due to its high water solubility and biotoxicity. In contrast, advanced oxidation processes are effective tools for completely decomposing imidacloprid in wastewater by generating active oxygen having a strong oxidizing ability. In particular, advanced sulfate-based oxidation processes, in which Peroxodisulfate (PDS) or Peroxomonosulfate (PMS) is used to generate sulfate radicals and hydroxyl radicals, are of considerable interest due to the long half-life and strong oxidizing power of SO 4·-. Among them, peroxymonosulfate is more easily activated due to its asymmetric molecular structure.
Currently, various methods have been employed to activate peroxymonosulfates. Carbon-based materials are expected to be potential materials for activating persulfate due to low cost, easy availability and environmental friendliness. Carbon-based materials are commonly derived from agricultural, industrial and municipal waste. Among them, sewage sludge is a main byproduct of urban sewage treatment plants, and improper sewage sludge management may cause secondary pollution. The sludge biochar obtained through pyrolysis has stable chemical properties, so that the sludge becomes a potential material for preparing the biochar. However, the smaller specific surface area and fewer oxygen-containing functional groups of the raw sludge biochar still limit their activation efficiency. Accordingly, various modification methods have been developed to enhance the performance of biochar activated peroxymonosulfate. In heterogeneous catalysts, moS 2 acts as a nanocrystalline material because of its unique layered structure, a large surface area, and is a very potential material.
Conventional methods for synthesizing MoS 2 composite materials include a hydrothermal synthesis method, a secondary pyrolysis method, a mechanical stripping method and an in-situ oxidation polymerization method, but each method has certain disadvantages. Secondary pyrolysis processes typically involve multiple steps and high energy consumption, can result in structural failure and reduced performance of the MoS 2, and are costly. The mechanical stripping method is complicated in the synthesis process, and cannot control the size of the sheet, so that it is not suitable for mass production. In-situ oxidation polymerization method, although MoS 2 composite materials with special structures can be obtained, the method relies on a large amount of chemical reagents, often accompanies high cost, environmental pollution and potential safety hazard, and has harsh reaction conditions and complex operation. In contrast, the one-pot hydrothermal synthesis method can effectively reduce the energy and the synthesis cost consumed in the synthesis process, has more stable physicochemical properties, and needs further treatment to improve the catalytic activity.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides MoS 2 sludge biochar, a preparation method and application thereof, and the technical problem that the sludge biochar has low catalytic activity on peroxymonosulfate in the prior art is solved.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:
In a first aspect, the invention provides a method for preparing MoS 2 sludge biochar, which comprises the following steps:
(1) Washing and drying the residual sludge, and then carrying out pyrolysis, acid leaching, washing, drying, grinding and sieving to obtain sludge biochar;
(2) Uniformly mixing the sludge biochar with a molybdenum source, a sulfur source, a dispersing agent and a solvent, and obtaining the hydro-thermal synthesis MoS 2 sludge biochar through hydro-thermal synthesis reaction; and/or, further comprising:
(3) Performing ball milling on the sludge biochar obtained by the hydro-thermal synthesis of the MoS 2 to obtain the sludge biochar obtained by the ball milling hydro-thermal synthesis of the MoS 2.
In a second aspect, the invention provides MoS 2 sludge biochar prepared by the preparation method; the MoS 2 sludge biochar comprises hydro-thermal synthesis of MoS 2 sludge biochar and/or ball-milling hydro-thermal synthesis of MoS 2 sludge biochar.
In a third aspect, the invention provides an application of MoS 2 sludge biochar in removing neonicotinoid compounds in water by activating peroxymonosulfate.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, the hydrothermal synthesis MoS 2 sludge biochar is prepared by one-pot hydrothermal synthesis, so that the energy consumed in the synthesis process and the synthesis cost can be effectively reduced, wherein the soluble ash in the sludge biochar is removed by acid leaching, the physicochemical property of the sludge biochar can be effectively improved, and the catalytic performance of the obtained hydrothermal synthesis MoS 2 sludge biochar is improved; the ball milling treatment is carried out on the sludge biochar of the hydro-thermal synthesis MoS 2, so that the biochar of the hydro-thermal synthesis MoS 2 is more stable, the particle size is reduced, and MoS 2 can be more uniformly dispersed on the surface of the biochar; the hydrothermal synthesis MoS 2 sludge biochar and the ball-milling hydrothermal synthesis MoS 2 sludge biochar prepared by the method have high catalytic activity, have the potential of efficiently activating the peroxymonosulfate to remove the neonicotinoid compound, have stable physicochemical properties, can ensure the quick recovery of the activated peroxymonosulfate of the biochar after removing the neonicotinoid compound, realize the recycling of the catalyst, and realize better removal effect when different ions exist in water and in a wider pH range; in particular to ball milling hydrothermal synthesis of MoS 2 sludge biochar, which can activate peroxymonosulfate to degrade pollutants, and the removal rate of neonicotinoid compounds such as imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid in water reaches more than 95%.
Drawings
FIG. 1 shows the removal of imidacloprid at doses of 0.1 g/L for SBC, MSBC and BMSBC at PMS concentrations of 1 mmol/L at 0-60 min vs. 10 mg/L;
FIG. 2 shows the removal rate of imidacloprid at a concentration of 10 mg/L for BMSBC (5 mg), PMS (concentration of 1mmol/L in the removal system) single or combined system (BMSBC (5 mg) +PMS (concentration of 1mmol/L in the removal system)) at 0-60 min;
FIG. 3 is a graph showing the effect of BMSBC dosage (0.05-0.2 g/L) in BMSBC/PMS system on the removal of imidacloprid at a concentration of 10 mg/L at 0-60 min;
FIG. 4 is a graph showing the effect of PMS concentration (0.1-5 mmol/L) in BMSBC/PMS system on removal of imidacloprid at a concentration of 10 mg/L at 0-60 min;
FIG. 5 is a graph showing the effect of pH (3-11) on the removal of imidacloprid at a concentration of 10 mg/L in BMSBC/PMS system at 0-60 min;
FIG. 6 is the effect of humic acid (1-10 mg/L) on the removal of imidacloprid at a concentration of 10 mg/L in BMSBC/PMS system at 0-60 min;
FIG. 7 is a graph showing the effect of Na 2CO3 at concentrations of 1, 10, and 100 mmol/L on imidacloprid removal at concentrations of 10 mg/L at 0-60 min in a BMSBC/PMS system;
FIG. 8 is a graph showing the effect of NaHCO 3 at concentrations of 1, 10 and 100 mmol/L on the removal of imidacloprid at concentrations of 10 mg/L in a BMSBC/PMS system at 0-60 min;
FIG. 9 is the effect of NaNO 3 at concentrations of 1, 10 and 100 mmol/L on the removal of imidacloprid at concentrations of 10 mg/L in a BMSBC/PMS system at 0-60 min;
FIG. 10 is the effect of NaCl concentration of 1, 10 and 100 mmol/L on imidacloprid removal at a concentration of 10 mg/L in BMSBC/PMS system at 0-60 min;
FIG. 11 is a graph showing the effect of Na 2SO4 at concentrations of 1, 10, and 100 mmol/L on imidacloprid removal at concentrations of 10 mg/L at 0-60 min in a BMSBC/PMS system;
FIG. 12 is BMSBC's ability to regenerate imidacloprid;
FIG. 13 shows the removal rates of imidacloprid (IMI), thiamethoxam (THX), clothianidin (CLO), thiacloprid (THI) and Acetamiprid (ACE) at a dose of 0.1 g/L BMSBC at a PMS concentration of 1mmol/L of 0-60min vs. 10 mg/L;
FIG. 14 mineralization rates of 10 mg/L imidacloprid (IMI), thiamethoxam (THX), clothianidin (CLO), thiacloprid (THI) and Acetamiprid (ACE) at 60 min in a BMSBC dose of 0.1 g/L at a PMS concentration of 1mmol/L in a BMSBC/PMS system;
FIG. 15 is the effect of synthesis temperature (160 ℃,180 ℃ and 200 ℃) on removal rate of imidacloprid from 0-60 min to 10 mg/L for hydrothermally synthesized MoS 2 sludge biochar;
FIG. 16 is the effect of the synthetic material element mass ratio (mass of Mo element: mass of C element = 1:0.5, 1:1 and 1:2) on the removal rate of imidacloprid of 10 mg/L at 0-60 min for the hydrothermal synthesis of MoS 2 sludge biochar;
FIG. 17 is the effect of ball milling speeds (300 r, 500r and 700 r) on removal of imidacloprid at 0-60 min to 10 mg/L for ball milling hydrothermal synthesis of MoS 2 sludge biochar;
FIG. 18 is the effect of ball mass ratio (10:1, 20:1 and 50:1) on removal rate of imidacloprid from 0-60 min to 10 mg/L for ball-milled hydrothermal synthesis of MoS 2 sludge biochar;
FIG. 19 is the effect of ball milling time (1 h, 2h and 4 h) on removal of imidacloprid at 0-60 min to 10 mg/L for ball milling hydrothermal synthesis of MoS 2 sludge biochar.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The residual sludge is used as a byproduct of sewage treatment of a sewage treatment plant, is an extremely complex non-uniform mass composed of organic residues, inorganic particles, colloid and the like, and contains abundant organic substances and wide sources of raw materials.
Conventional methods for synthesizing MoS 2 composite materials include a hydrothermal synthesis method, a secondary pyrolysis method, a mechanical stripping method and an in-situ oxidation polymerization method, but each method has certain disadvantages. Secondary pyrolysis processes typically involve multiple steps and high energy consumption, can result in structural failure and reduced performance of the MoS 2, and are costly. The mechanical stripping method is complicated in the synthesis process, and cannot control the size of the sheet, so that it is not suitable for mass production. In-situ oxidation polymerization method, although MoS 2 composite materials with special structures can be obtained, the method relies on a large amount of chemical reagents, often accompanies high cost, environmental pollution and potential safety hazard, and has harsh reaction conditions and complex operation. In contrast, the one-pot hydrothermal synthesis method can effectively reduce the energy and the synthesis cost consumed in the synthesis process, has more stable physicochemical properties, but needs further treatment to improve the catalytic activity, and the synthesis condition has an influence on the catalytic performance, so that the one-pot hydrothermal synthesis method has yet to be explored.
The invention provides a ball-milling hydrothermal synthesis MoS 2 sludge biochar, a preparation method and application thereof, wherein the MoS 2 sludge biochar is synthesized by one-pot hydrothermal synthesis, and then ball-milling is carried out to obtain the ball-milling hydrothermal synthesis MoS 2 sludge biochar; the ball milling treatment can make the MoS 2 biochar synthesized by hydrothermal method more stable, reduce the particle size and make MoS 2 more uniformly dispersed on the surface of the biochar; according to the invention, the MoS 2 sludge biochar (BMSBC) is synthesized by ball milling hydrothermal synthesis through optimizing the hydrothermal synthesis parameters and the ball milling parameters in the synthesis process, so that the novel nicotine compound in water can be removed by efficiently activating the peroxymonosulfate. The invention can realize the resource utilization of the main byproduct sewage sludge of the urban sewage treatment plant, and can also realize the efficient removal of the neonicotinoid compound in the water, thereby achieving the purpose of preparing sewage by waste; according to the invention, moS 2 sludge biochar is synthesized by adopting a ball milling and hydrothermal method, and the influence of hydrothermal synthesis parameters and ball milling parameters on the catalytic performance of the modified sludge biochar in the synthesis process is explored, so that the method has important research value and significance in realizing sustainable removal of the neonicotinoid compound in water.
In a first aspect, the invention provides a method for preparing MoS 2 sludge biochar, which comprises the following steps:
(1) Preparation of Sludge Biochar (SBC): washing and drying the residual sludge, and then pyrolyzing, pickling, washing, drying, grinding and sieving to obtain sludge biochar SBC;
(2) Preparation of MoS 2 sludge biochar (MSBC) by hydrothermal synthesis: uniformly mixing the sludge biochar SBC with a molybdenum source, a sulfur source, a dispersing agent and a solvent, and obtaining a hydrothermal synthesis MoS 2 sludge biochar MSBC through a hydrothermal synthesis reaction; and/or, further comprising:
(3) Preparation of ball-milling hydro-thermal synthesis MoS 2 sludge biochar (BMSBC), wherein the hydro-thermal synthesis MoS 2 sludge biochar is subjected to ball milling to obtain ball-milling hydro-thermal synthesis MoS 2 sludge biochar BMSBC.
Preferably, the step (1) specifically includes: washing the residual sludge with ultrapure water, drying to constant weight, pyrolyzing in protective atmosphere (nitrogen atmosphere), immersing in HCl to remove soluble ash, alternately flushing with ethanol and ultrapure water until the pH of the filtrate is neutral, drying to constant weight, grinding and sieving to obtain sludge biochar SBC.
As an improvement of the above embodiment, in the step (1), the drying temperature is 60 to 120 ℃, further 60 ℃, 70 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, more preferably 105 ℃.
As an improvement to the above embodiment, in the step (1), the pyrolysis condition is that the nitrogen flow rate is 0.2-0.6L/min, further 0.2L/min, 0.3L/min, 0.35L/min, 0.4L/min, 0.45L/min, 0.5L/min, 0.6L/min, more preferably 0.4L/min; the heating rate is 5-20 ℃/min, further 5 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, 18 ℃/min, 20 ℃/min, more preferably 10 ℃/min; continuously pyrolyzing 60-120 min at 400-800 ℃ at a pyrolysis temperature of 400 ℃ and 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, more preferably 600 ℃ for 60 min, 65 min, 70 min, 80 min, 90 min, 100 min, 105 min, 110 min, 115 min, 120 min, more preferably 120 min; grinding, sieving with 50-200 mesh sieve, and further sieving with 100 mesh sieve.
Preferably, the step (2) specifically includes: placing the sludge biochar SBC obtained in the step (1) into a solution containing sodium molybdate (NaMoO 4·2H2 O), thioacetamide (CH 3CSNH2) and polyethylene glycol (PEG 10000) for ultrasonic mixing uniformly, transferring into a reaction kettle, performing hydrothermal synthesis under optimized hydrothermal synthesis conditions, filtering to obtain solid, washing ultrapure water until filtrate is colorless, drying, grinding and sieving to obtain the sludge biochar MSBC for the hydrothermal synthesis MoS 2;
As an improvement of the above embodiment, in the step (2), the mass ratio of the molybdenum source, the sulfur source and the sludge biochar is (1.15 to 4.6): (4.6-13.8): (1-3), further (1.15-4.6): (4.6-13.8): 1, more preferably 2.3:4.6:1.
As an improvement of the above embodiment, in the step (2), the ratio of the sludge biochar to the solvent is (1 to 3) g: (40-80) mL, further 1 g: (40-80) mL, more preferably 1 g:60 mL; the solvent is ultrapure water.
As an improvement of the above embodiment, in the step (2), a polyethylene glycol solution, more preferably an aqueous polyethylene glycol 10000 solution is used as the dispersant. The concentration of the polyethylene glycol (PEG 10000) solution is 0.1-0.5 mol/L, further 0.1 mol/L, 0.15 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L, more preferably 0.1 mol/L; the mass ratio of the dispersant to the sludge biochar is (0.1-0.4) 1; further 0.26:1.
In the invention, polyethylene glycol (PEG) is used as a dispersing agent, and the polyethylene glycol is used as a high molecular polymer, so that the high molecular polymer has good dispersibility and stability. In the ultrasonic treatment process, PEG can effectively disperse the biochar particles, prevent agglomeration and precipitation of the biochar particles, and further ensure that the biochar particles are fully contacted and mixed with raw materials. The addition of PEG can increase the viscosity of the solution, which helps to slow the rising rate of bubbles generated during the sonication process, allowing the bubbles to contact the biochar particles for a longer period of time, thereby improving the mixing effect. PEG itself may also interact with the surface of biochar to form a coating, changing the surface properties and structure of biochar. Such a coating may help to further improve the catalytic performance of the biochar. In the process of preparing the nano molybdenum disulfide, the addition of polyethylene glycol is beneficial to regulating the physical and chemical environment of a reaction system, so that the growth and crystallization process of molybdenum disulfide crystals are influenced, the uniform distribution of molybdenum disulfide on the surface of the biochar is facilitated, and the optimized dispersion degree of the synthesized molybdenum disulfide on the surface of the sludge biochar is optimized and improved.
As an improvement of the above embodiment, in the step (2), the hydrothermal synthesis reaction conditions are: the hydrothermal temperature is 160-220 ℃, further 160 ℃, 170 ℃, 180 ℃, 190 ℃,200 ℃, 210 ℃, 220 ℃, more preferably 180 ℃; the hydrothermal synthesis reaction time is 720 min to 1440min, more preferably 720 min、810 min、870 min、900 min、960 min、1020 min、1050 min、1080 min、1140 min、1200 min、1260 min、1320 min、1440 min,, and still more preferably 1440min.
As an improvement of the above embodiment, in the step (2), after the hydrothermal synthesis reaction is completed, the solid obtained by filtration is dried at 60 to 120 ℃, further at 60 ℃, and is ground and then sieved by a 50 to 200 mesh sieve, further by a 105 mesh sieve.
Preferably, the step (3) specifically includes: putting the MSBC of the sludge biomass of the MoS 2 obtained in the step (2) into a planetary ball mill provided with a stainless steel grinding tank, putting zirconia balls into the planetary ball mill, and ball-milling the planetary ball mill into fine particles under the optimized ball milling condition to obtain the MSBC BMSBC of the sludge biomass of the MoS 2 obtained in the ball-milling hydrothermal synthesis.
As a modification of the above example, in the step (3), the ball milling rotation speed is 300 to 700 rpm, further 300 rpm, 400 rpm, 500rpm, 600 rpm, 700 rpm, more preferably 500rpm; the ball milling time is 60-300 min, further 60 min, 90 min, 120min, 150 min, 210 min, 240 min, 300 min, more preferably 120min; the ball-to-material ratio is (10-100): 1, further 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 80:1, 100:1, more preferably 20:1.
In a second aspect, the invention provides MoS 2 sludge biochar prepared by the preparation method; the MoS 2 sludge biochar comprises hydro-thermal synthesis of MoS 2 sludge biochar and/or ball-milling hydro-thermal synthesis of MoS 2 sludge biochar.
In a third aspect, the invention provides an application of MoS 2 sludge biochar in efficiently activating peroxymonosulfate to remove neonicotinoid compounds in water.
Preferably, the application comprises the steps of: adding MoS 2 sludge biochar (MSBC and/or BMSBC) as a catalyst into an aqueous solution containing PMS and neonicotinoid, and filtering after the removal process is finished to obtain a solution after the neonicotinoid is removed.
As an improvement of the above embodiment, the neonicotinoid compound includes imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid; in the aqueous solution of the neonicotinoid compound, the concentration of the neonicotinoid compound is 1-15 mg/L, further 10mg/L, the pH of the system is 3-11, further 3-9; the adding amount of MoS 2 sludge biochar BMSBC in ball milling hydrothermal synthesis is 0.05-1.0 g/L, and further 0.1g/L; the concentration of the peroxymonosulfate is 0.1 to 5mmol/L, and further 1 mmol/L.
The ball-milling hydrothermal synthesis MoS 2 sludge biochar prepared by the method has the potential of efficiently activating the peroxymonosulfate to remove the neonicotinoid, has stable physical and chemical properties, can ensure the quick recovery of the activated peroxymonosulfate by the biochar after removing the neonicotinoid, realizes the recycling of the catalyst, and can achieve better removal effect when different ions exist in water and in a wider pH range.
The invention is further illustrated by the following specific examples.
Example 1
(1) Washing residual sludge (from a sewage treatment plant of Wuhan) with ultrapure water for three times, placing the sludge in a baking oven at 105 ℃ to be dried to constant weight, transferring the sludge into a high-temperature tube furnace (the flow rate of N 2 is 0.4L/min, the heating rate of the sludge is 10 ℃/min), keeping the sludge at 600 ℃ for 120 min, completely immersing the sludge in HCl (1 mol/L) to remove soluble ash in the sludge, alternately washing the sludge with ethanol and ultrapure water until the pH of the filtrate is neutral, drying the filtrate to constant weight, grinding the filtrate, and sieving the filtrate with a 100-mesh sieve (0.15 mm) to obtain the sludge biochar SBC.
(2) Dissolving 2.3 g sodium molybdate (NaMoO 4·2H2 O), 4.6 g thioacetamide (CH 3CSNH2) and 0.26g polyethylene glycol (PEG 10000) solution with the concentration of 0.1 mol/L in 60 mL ultrapure water, adding the solution into a reaction kettle, transferring SBC (with the mass of 1.0 g) into the reaction kettle, performing hydrothermal activation 1440 min at the temperature of 180 ℃, cooling to room temperature, filtering to obtain a solid in the reaction kettle, washing the solid with ultrapure water until the filtrate is colorless, putting the solid into an oven, drying the solid in the oven at the temperature of 60 ℃ until the solid weight is constant, grinding a sample, and sieving the sample with a 100-mesh sieve (0.15 mm) to obtain the MoS 2 sludge biochar MSBC for hydrothermal synthesis.
(3) 3.5G MSBC (ball-to-material ratio is 20:1) is put into a planetary ball mill (Changsha Brilliant power XQM-0.4A) equipped with a stainless steel grinding tank to be ball-milled into fine particles (ball-milling rotation speed 500rpm, ball-milling time 120 min), and the MoS 2 sludge biochar BMSBC is obtained through ball-milling hydrothermal synthesis.
Wherein, the soluble ash in the HCl is removed by immersing the HCl, so that the physicochemical property of the HCl can be effectively improved. Too high soluble ash can affect the catalytic performance of biochar. Inorganic impurities in ash can affect the pore structure and surface properties of biochar, reducing its binding capacity to neonicotinoid compounds. Heavy metal ions and other harmful substances in the ash can be released and leached into the solution, and metal cations in the ash can react with oxygen-containing functional groups on the surface of the biochar to influence the stability of the biochar. After HCl treatment, the synthesized BMSBC surface energy scattering X-ray spectrum (EDS) shows that the weight percentage of silicon element is reduced to 3.06 percent, and the silicon element content of the sewage sludge is greatly reduced compared with that of the conventional sewage sludge.
Wherein, the MSBC is ball-milled to obtain BMSBC, the specific surface area (increased from 12.5 m to 78.0 m mu/g) and the total pore volume (single-point total pore volume increased from 0.0051 cm 3 to 0.0330 cm 3/g) of the MSBC are obviously improved.
Application example 1
SBC, MSBC and BMSBC (all the products of the steps in example 1) at a dosage of 5mg were added as catalysts to an imidacloprid solution containing 1 mmol/L PMS at a concentration of 10 mg/L (volume 50 mL), at which time the catalyst concentration was 0.1 g/L, stirred on a magnetic stirrer at a rotation speed of 500 rpm, sampled at a set time (0-60 min), the imidacloprid residual concentration was measured by high performance liquid chromatography-mass spectrometry, and the removal rates of imidacloprid were calculated at different times.
As can be seen from fig. 1, the removal capacities of the SBC, MSBC and BMSBC activated PMS systems for imidacloprid are different, wherein the BMSBC/PMS system has the strongest removal capacity for imidacloprid, and the removal rate of imidacloprid is 95.1% at 60 and min; secondly, the removal rate of MSBC/PMS is 74.4% after 60 min; while the removal rate of SBCs varies very slowly. The MSBC after hydrothermal synthesis has stronger catalytic performance than SBC, because the molybdenum disulfide is loaded on the surface of the MSBC after hydrothermal synthesis, has stronger electron transfer capability, and meanwhile, the MSBC after hydrothermal synthesis has larger specific surface area, more defect structures and oxygen-containing functional groups, and stronger activation capability. The BMSBC after ball milling has stronger catalytic performance than MSBC, because ball milling treatment can lead MSBC to have smaller particle size and more defect structures, and partial oxygen-containing functional groups can be introduced and the stability of the MSBC is improved.
Application example 2
Comparing the removal capacities of the mono-component (BMSBC (mg)) and PMS (the concentration in the removal system is1 mmol/L)) and the di-component (BMSBC (5 mg) +PMS (the concentration in the removal system is1 mmol/L)) systems in the range of 0-60 min for the imidacloprid solution with the concentration of 10 mg/L (the volume is 50 mL), stirring the imidacloprid solution on a magnetic stirrer with the rotating speed of 500 rpm, sampling the imidacloprid solution at a set time (0-60 min), measuring the residual concentration of the imidacloprid by utilizing high performance liquid chromatography-mass spectrometry, and calculating the imidacloprid removal rates at different times.
As can be seen from FIG. 2, the removal rate and the removal rate of imidacloprid by the binary system (BMSBC (mg) +PMS (the concentration in the removal system is 1 mmol/L)) are both significantly higher than those of the unitary system, and the removal rate of imidacloprid by the reaction 60 min can reach 95.1%, which indicates that BMSBC can efficiently activate PMS to realize efficient removal of imidacloprid. When there is only BMSBC (5 mg) in the system, the removal rate of imidacloprid by 60 min is only 4.0%, which indicates that the adsorption of imidacloprid by BMSBC in the system is very low, and the degradation effect in the binary system (BMSBC (5 mg) +PMS (the concentration in the removal system is 1 mmol/L)) plays a major role, and the following description of the effect is expressed in degradation.
Application example 3
In the binary system, the PMS concentration is 1mmol/L, the imidacloprid concentration is 10 mg/L, the volume is 50 mL, the dosage of BMSBC is respectively set to be 0.05 g/L, 0.1 g/L, 0.15 g/L and 0.2g/L, the imidacloprid is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at the set time (0-60 min), the residual imidacloprid concentration is measured by utilizing high performance liquid chromatography-mass spectrometry, and the influence of the dosage of BMSBC in the binary system on the removal of the imidacloprid is explored.
As can be seen from fig. 3, the removal rate of imidacloprid by the binary system increases with the dosage of BMSBC. When BMSBC is 0.2g/L, the removal rate of imidacloprid by 60min can reach 97.6% in response, wherein when 60min is in response, the removal rate of BMSBC is 0.1g/L and the removal rate of imidacloprid is 0.2g/L, but when BMSBC is 0.2g/L, the removal rate is very high in response for 30min, which indicates that increasing BMSBC can increase the efficiency of imidacloprid removal by activated PMS; considering the application cost and the removal effect comprehensively, the addition amount of MoS 2 sludge biochar BMSBC for ball-milling hydrothermal synthesis is preferably 0.1g/L.
Application example 4
The dosage of BMSBC in the binary system is 5 mg, the concentration of imidacloprid is 10 mg/L, the volume is 50mL, the PMS concentration is respectively set to be 0.1, 0.5, 1,2 and 5 mmol/L, the mixture is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at the set time (0-60 min), the residual imidacloprid concentration is measured by utilizing high performance liquid chromatography-mass spectrometry, and the influence of the PMS concentration in the binary system on the removal of imidacloprid is explored.
As can be seen from fig. 4, the removal rate of imidacloprid by the binary system increases with the increase of PMS concentration. When the PMS concentration is 5 mmol/L, the reaction is 60min, the removal rate of the binary system to the imidacloprid is about 97.9%, which shows that the improvement of the PMS concentration can improve the imidacloprid removal efficiency of the activated PMS.
Application example 5
The dosage of BMSBC mg in the binary system, the PMS concentration of 1 mmol/L, the imidacloprid concentration of 10 mg/L and the volume of 50 mL, the pH of the solution is regulated by adopting NaOH and H 2SO4 (the existence of Na + and SO 4 2- has no obvious influence on the removal efficiency of the imidacloprid), the pH of the solution is set to be 3, 5, 7, 9 and 11, the solution is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at the set time (0-60 min), the residual imidacloprid concentration is measured by utilizing high performance liquid chromatography-mass spectrometry, and the influence of the pH of the solution in the binary system on the removal capacity of the imidacloprid is explored.
As can be seen from fig. 5, the removal rate of imidacloprid by the binary system is different depending on the change of the pH of the solution. The binary system has higher removal rate of imidacloprid than alkaline condition under the acidic condition, and the highest removal rate of imidacloprid is 97.6% when the pH value of the solution is 3, and has poorer removal effect on imidacloprid when the pH value is 11, because the solution existsWill be associated with/>The interaction produces OH, whose oxidation potential is relatively low. An increase in pH results in PMS (/ >)) Negatively charged, resulting in greater electrostatic repulsion between IMI/PMS and BMSBC, which significantly affects the interaction between BMSBC and PMS, the preferred pH range of the present invention is 3-9.
Application example 6
The dosage of BMSBC mg in the binary system, the PMS concentration of 1mmol/L, the imidacloprid concentration of 10 mg/L, the volume of 50 mL, the Humic Acid (HA) concentration of 0,1, 5 and 10 mg/L respectively, stirring on a magnetic stirrer with the rotating speed of 500 rpm, sampling at the set time (0-60 min), and measuring the imidacloprid residual concentration by utilizing high performance liquid chromatography-mass spectrometry to explore the influence of the HA concentration in the binary system on the imidacloprid removal capacity.
As can be seen from fig. 6, the removal rate of imidacloprid by the binary system decreases with the increase of HA concentration, and when the HA concentration is 10 mg/L, the reaction is 60 min, and the removal rate of imidacloprid is 83.4%, which indicates that the increase of HA concentration can inhibit BMSBC activation of PMS to remove imidacloprid.
Application example 7
The dosage of BMSBC mg in the binary system, the PMS concentration is1 mmol/L, the imidacloprid concentration is 10 mg/L, the volume is 50 mL, the Na 2CO3、NaHCO3、NaNO3, naCl and Na 2SO4 concentrations are 1, 10 and 100 mmol/L respectively, the imidacloprid is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at a set time (0-60 min), the residual imidacloprid concentration is measured by utilizing high performance liquid chromatography-mass spectrometry, and the influence of coexisting inorganic ions on the imidacloprid removal capability of the system is explored.
From fig. 7 to 11, it can be seen that the inhibition effect of Na 2CO3、NaHCO3、NaNO3, naCl on the imidacloprid removal ability of the binary system is enhanced with the increase of the concentration, wherein the inhibition effect of Na 2CO3 is strongest. The inhibition of the imidacloprid-removing ability of the binary system by Na 2SO4 is basically negligible.
Application example 8 (cycle test)
The dosage of BMSBC mg, the PMS concentration of 1mmol/L, the imidacloprid concentration of 10 mg/L and the volume of 50 mL in the binary system are stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at the time of reaction balance (60 min), and the residual imidacloprid concentration is measured by utilizing high performance liquid chromatography-mass spectrometry. Carrying out suction filtration separation on BMSBC after the removal reaction is achieved, washing with ultrapure water for 5-6 times, and freeze-drying BMSBC in a freeze dryer and then carrying out the removal experiment again. The regeneration removal capacity of BMSBC was measured by repeating 5 times.
As can be seen from fig. 12, BMSBC can continuously remove imidacloprid in the binary system, and the removal rate of the binary system to imidacloprid can still reach 71.3% after 5 cycles, wherein the removal rate is reduced because the oxygen-containing functional groups and the defect structures on the surface are consumed, and meanwhile, the generated conversion product masks part of pores, so that the catalytic activity of BMSBC is reduced after use.
Application example 9
The dosage of BMSBC mg in the binary system, the PMS concentration is 1mmol/L, the imidacloprid (IMI), thiamethoxam (THX), clothianidin (CLO), thiacloprid (THI) and Acetamiprid (ACE) concentrations are 10 mg/L, the volume is 50mL, the binary system is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at set time (0-60 min), the residual concentrations of imidacloprid (IMI), thiamethoxam (THX), thiacloprid (CLO), thiacloprid (THI) and Acetamiprid (ACE) are respectively measured by utilizing high performance liquid chromatography-mass spectrometry, and the mineralization rates of the imidacloprid, thiamethoxam, clothianidin and Acetamiprid (ACE) are measured by utilizing a TOC/TN synchronous analyzer (Multi N/3100), and the mineralization capacity of the binary system to mineralize the neonicotinoid pesticide (the complete removal performance through mineralization rate reaction) is explored.
As can be seen from FIG. 13, the ball-milling hydrothermal synthesis MoS 2 sludge biochar BMSBC prepared by the method can efficiently activate peroxymonosulfate, and the removal rates of imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid with the concentration of 10mg/L at 60 min can reach 95.1%, 99.6%, 99.8%, 98.8% and 98.9% respectively.
Meanwhile, as shown in fig. 14, the ball-milling hydrothermal synthesis MoS 2 sludge biochar BMSBC activated peroxymonosulfate system prepared by the invention can mineralize neonicotinoid compounds with high efficiency, and the mineralization rates of imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid with the concentration of 10 mg/L can reach 71.9%, 81.9%, 84.6%, 88.1% and 77.0% respectively at 60 min.
In contrast to conventional adsorption and biodegradation techniques, adsorption techniques, while effective in removing contaminants from a body of water or gas, generally only transfer contaminants from one phase to another (e.g., from an aqueous phase to a solid phase) rather than thoroughly decomposing them, and thus the adsorbed contaminants still require further treatment or disposal; biodegradation technology, while capable of decomposing organic contaminants into smaller molecules or fully mineralizing into water and carbon dioxide, generally has a slow degradation rate and is greatly affected by environmental conditions (e.g., temperature, pH, nutrients, etc.) and contaminant properties; from the above test results, the invention has higher mineralization efficiency, and can thoroughly mineralize most pollutants into nontoxic water and carbon dioxide; therefore, the removal of the neonicotinoid compound in the invention is mainly based on complete degradation, and the high-efficiency removal of the neonicotinoid compound in water is achieved.
Application example 10
In this application example, the hydrothermal synthesis of MoS 2 sludge biochar is adopted, and the preparation method of the hydrothermal synthesis of MoS 2 sludge biochar is different from that of example 1 only in that: hydrothermally synthesizing MoS 2 sludge biochar at different hydrothermally synthesizing temperatures (160 ℃, 180 ℃ and 200 ℃); other steps and conditions were the same as in example 1.
The dosage of the MoS 2 sludge biochar is 5mg, the PMS concentration is 1 mmol/L, the imidacloprid concentration is 10 mg/L, the volume is 50mL, the imidacloprid is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at set time (0-60 min), and the imidacloprid residual concentration is measured by utilizing high performance liquid chromatography-mass spectrometry. The influence of different synthesis temperatures on the capability of hydrothermally synthesizing MoS 2 sludge biochar activated PMS to remove imidacloprid is explored.
As is clear from FIG. 15, the effect of removing imidacloprid is best when the synthesis temperature is 180 ℃. Reaction 60 min, the removal of imidacloprid was 74.4%. The reason is that at lower temperatures, the electron transfer capability of the synthesized MoS 2 may be reduced due to defects in its stacked structure, which may affect the activity in the catalytic process. At higher temperatures, the carbonization degree of the hydrothermally synthesized biochar is increased. During synthesis, cleavage of certain bonds may lead to release of volatile compounds, which may significantly reduce the number of oxygen-containing functional groups. The result shows that the catalytic performance of the MoS 2 sludge biochar in the hydrothermal synthesis can be improved at the optimized synthesis temperature.
Application example 11
In this application example, the hydrothermal synthesis of MoS 2 sludge biochar is adopted, and the preparation method of the hydrothermal synthesis of MoS 2 sludge biochar is different from that of example 1 only in that: under the mass ratio of different raw material elements (mass ratio of Mo element to C element=1:0.5, 1:1 and 1:2), preparing the MoS 2 sludge biochar by hydrothermal synthesis; other steps and conditions were the same as in example 1. Wherein Mo: c=1:1 corresponds to 2.3 g sodium molybdate: SBC of 1 g.
The dosage of the MoS 2 sludge biochar is 5 mg, the PMS concentration is 1 mmol/L, the imidacloprid concentration is 10 mg/L, the volume is 50mL, the imidacloprid is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at set time (0-60 min), and the imidacloprid residual concentration is measured by utilizing high performance liquid chromatography-mass spectrometry. The influence on the capability of removing imidacloprid of activated PMS of sludge biochar of the hydrothermal synthesis MoS 2 under different raw material ratios is explored.
As can be seen from fig. 16, when the raw material ratio was Mo: c=1:1 (2.3 g sodium molybdate and 1 g SBC), the imidacloprid removal effect was the best. Reaction 60 min, the removal of imidacloprid was 74.4%. The reason is that at lower SBC ratios (Mo: c=2:1, removal 56.3%), SBC provides insufficient loading sites for MoS 2, resulting in uneven distribution of MoS 2 on the SBC surface, affecting its stack thickness and thus reducing its electron transport capacity. When the SBC ratio is high (Mo: c=1:2, removal 69.9%), the formation of SBC surface functional groups during hydrothermal processes may be detrimental. In addition, it may result in a lower content of MoS 2 per weight of SBC surface loading, thereby reducing its catalytic activity. The result shows that the catalytic performance of the MoS 2 sludge biochar in the hydrothermal synthesis can be improved under the optimized raw material proportion.
Application example 12
In the application example, the MoS 2 sludge biochar is synthesized by adopting ball-milling hydrothermal method, and the preparation method of the MoS 2 sludge biochar by adopting the ball-milling hydrothermal method is different from that of the embodiment 1 only in that: the MoS 2 sludge biochar is prepared by ball milling hydrothermal synthesis under different ball milling rotating speeds (300 r, 500 r and 700 r), different ball material ratios (10:1, 20:1 and 50:1) and ball material times (1 h, 2 h and 4 h). Other steps and conditions were the same as in example 1.
The dosage of MoS 2 sludge biochar is 5mg, the PMS concentration is 1 mmol/L, the imidacloprid concentration is 10 mg/L, the volume is 50mL, the imidacloprid is stirred on a magnetic stirrer with the rotating speed of 500 rpm, sampling is carried out at set time (0-60 min), and the imidacloprid residual concentration is measured by utilizing high performance liquid chromatography-mass spectrometry. The influence on the capability of removing imidacloprid of the activated PMS of the sludge biochar of the hydrothermal synthesis MoS 2 under different ball milling parameters is explored.
As can be seen from fig. 17 to 19, the removal effect of imidacloprid is best when the ball milling speed is 500 r, the ball-to-material ratio is 20:1 and the ball milling time is 2 hours. Reaction 60min, the removal rate of imidacloprid is 95.1%. The reason is that optimizing ball milling parameters can increase the specific surface area and pore volume of the biochar, enhance the defect structure, introduce oxygen-containing functional groups and improve the stability of the material. Excessive grinding, however, can cause compaction and caking, resulting in a smooth and hard surface that is detrimental to the adhesion of contaminants and oxidants. Meanwhile, the agglomeration effect is obvious due to excessive ball milling, the loaded MoS 2 is unevenly distributed on the surface of the biochar, and the internal pores collapse. The result shows that the catalytic performance of the MoS 2 sludge biochar in the hydrothermal synthesis can be improved under the optimized ball milling condition.
In summary, the invention provides a method for removing neonicotinoid compounds in water by utilizing ball-milling hydrothermal synthesis MoS 2 sludge biochar and efficiently activating peroxymonosulfate, which can realize the recycling of main byproduct sewage sludge of urban sewage treatment plants and also can efficiently degrade and remove neonicotinoid compounds (imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid) in water, and has the following advantages:
(1) The ball-milling hydrothermal synthesis MoS 2 sludge biochar BMSBC prepared by the method can efficiently activate peroxymonosulfate, and the removal rate of imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid with the concentration of 10 mg/L at 60 min can reach 95.1%, 99.6%, 99.8%, 98.8% and 98.9% respectively.
(2) Compared with other technologies (adsorption, microbial degradation and the like), the ball-milling hydrothermal synthesis MoS 2 sludge biochar BMSBC activation peroxymonosulfate system prepared by the invention can efficiently mineralize neonicotinoid compounds, and the mineralization rates of imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid with the concentration of 10 mg/L can reach 71.9%, 81.9%, 84.6%, 88.1% and 77.0% respectively at the time of 60 min. The method realizes thorough removal of the neonicotinoid compound, and simultaneously has higher stable physical property and chemical property, and can realize efficient separation and recycling of the removed neonicotinoid compound from the aqueous solution.
Compared with the prior art, the invention provides a preparation method of the MoS 2 sludge biochar by ball milling hydrothermal synthesis, which can be applied to efficiently activating peroxymonosulfate, and specifically comprises the steps of placing the Sludge Biochar (SBC) prepared by pyrolysis into a reaction kettle containing sodium molybdate (NaMoO 4·2H2 O), thioacetamide (CH 3CSNH2) and polyethylene glycol (PEG 10000) solution, synthesizing the MoS 2 sludge biochar (MSBC) by hydrothermal carbonization, and then performing ball milling to obtain the MoS 2 sludge biochar (BMSBC) by ball milling hydrothermal synthesis. The biochar prepared by the method has excellent physical and chemical properties, can realize the efficient degradation of the neonicotinoid compound in water, can respectively achieve the maximum removal capacities of 95.1%, 99.6%, 99.8%, 98.8% and 98.9% on imidacloprid, thiamethoxam, clothianidin, thiacloprid and acetamiprid in water after 60 minutes of reaction, and has stronger recycling performance.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The preparation method of MoS 2 sludge biochar is characterized by comprising the following steps of:
(1) Washing and drying the residual sludge, and then carrying out pyrolysis, acid leaching, washing, drying, grinding and sieving to obtain sludge biochar;
(2) Uniformly mixing the sludge biochar with a molybdenum source, a sulfur source, a dispersing agent and a solvent, and obtaining the hydro-thermal synthesis MoS 2 sludge biochar through hydro-thermal synthesis reaction; and/or, further comprising:
(3) Performing ball milling on the sludge biochar obtained by the hydro-thermal synthesis of the MoS 2 to obtain the sludge biochar obtained by the ball milling hydro-thermal synthesis of the MoS 2.
2. The method for preparing MoS 2 sludge biochar according to claim 1, wherein in step (1), the temperature of the drying is 60-120 ℃; grinding and sieving with a 50-200 mesh sieve.
3. The method for preparing MoS 2 sludge biochar according to claim 1, wherein in step (1), pyrolysis is performed by heating up under a protective atmosphere, wherein the flow rate of the protective atmosphere is 0.2-0.6L/min, the heating up rate is 5-20 ℃/min, and the heating up is up to 400-800 ℃ for continuous pyrolysis of 60-120 min.
4. The method for preparing MoS 2 sludge biochar according to claim 1, wherein in the step (2), the molybdenum source is sodium molybdate and the sulfur source is thioacetamide.
5. The method for preparing MoS 2 sludge biochar according to claim 1, wherein in the step (2), the mass ratio of the molybdenum source, the sulfur source and the sludge biochar is (1.15-4.6): (4.6-13.8): (1-3).
6. The method for preparing MoS 2 sludge biochar according to claim 1, wherein in step (2), the ratio of sludge biochar to solvent is (1-3) g: (40-80) mL; the solvent adopts ultrapure water; the dispersing agent adopts polyethylene glycol solution with the concentration of 0.1-0.5 mol/L; the mass ratio of the dispersant to the sludge biochar is (0.1-0.4): 1.
7. The method for producing MoS 2 sludge biochar according to claim 1, wherein in the step (2), the hydrothermal synthesis reaction is a reaction of 720 min to 1440 min at 160 to 220 ℃; and after the hydrothermal synthesis reaction is finished, drying, grinding and sieving the solid obtained by filtering to obtain the MoS 2 sludge biochar for the hydrothermal synthesis.
8. The method for preparing MoS 2 sludge biochar according to claim 1, wherein in step (3), the ball milling rotation speed is 300-700-rpm, the ball milling time is 60-300-min, and the ball-to-material ratio is (10-100): 1.
9. The MoS 2 sludge biochar produced by the method of any one of claims 1-8, wherein the MoS 2 sludge biochar comprises a hydro-thermal synthesis of MoS 2 sludge biochar and/or a ball-milling hydro-thermal synthesis of MoS 2 sludge biochar.
10. Use of MoS 2 sludge biochar according to claim 9 for the removal of neonicotinoids from water by activating peroxymonosulfate.
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