CN112010285A - Ball-milling biochar and application thereof as photocatalyst in degradation of enrofloxacin - Google Patents
Ball-milling biochar and application thereof as photocatalyst in degradation of enrofloxacin Download PDFInfo
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- CN112010285A CN112010285A CN201910458444.2A CN201910458444A CN112010285A CN 112010285 A CN112010285 A CN 112010285A CN 201910458444 A CN201910458444 A CN 201910458444A CN 112010285 A CN112010285 A CN 112010285A
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- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229960000740 enrofloxacin Drugs 0.000 title claims abstract description 69
- 238000000498 ball milling Methods 0.000 title claims abstract description 42
- 230000015556 catabolic process Effects 0.000 title claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 5
- 239000012498 ultrapure water Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 241000219000 Populus Species 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 27
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 8
- 229940088710 antibiotic agent Drugs 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 238000006552 photochemical reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
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- 239000012528 membrane Substances 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 241001465754 Metazoa Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
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- 230000001699 photocatalysis Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses ball-milling biochar and application thereof as a photocatalyst in degradation of enrofloxacin, wherein the preparation method of the ball-milling biochar comprises the following steps: the method comprises the steps of cleaning sawdust with ultrapure water, drying for 12-18 h at 60-80 ℃, cooling to room temperature of 20-25 ℃, crushing, sieving with a 50-100 mesh sieve to obtain a sieved material, pyrolyzing the sieved material at N ℃ for 2-4 h, cooling to obtain original biochar, ball-milling the original biochar in a ball-milling tank for 12-24 h at room temperature of 20-25 ℃, and collecting a product to obtain the ball-milled biochar. The removal rate of the ball-milled biochar on enrofloxacin, which is obtained by the preparation method, is up to 80.2 percent, and is greatly improved compared with the original biochar.
Description
Technical Field
The invention belongs to the technical field of enrofloxacin degradation, and particularly relates to ball-milled biochar and application thereof as a photocatalyst in enrofloxacin degradation.
Background
Enrofloxacin belongs to fluoroquinolone antibiotics, is specified as an antibiotic special for animals in China, and is widely applied to treatment of infectious diseases caused by bacteria in livestock breeding industry. But most of the antibiotics entering the animal body cannot be absorbed, and about 60-90% of the antibiotics are discharged outside and enter the environment. As a large amount of water bodies are polluted due to abuse of antibiotics, the polluted water bodies destroy the environment and seriously threaten human health, and how to remove the antibiotics becomes a subject of extensive research of researchers. The conventional methods for removing antibiotics comprise an adsorption method, a photocatalytic method, a chemical oxidation method, an electrocatalysis method and the like, however, the methods have some defects, such as the adsorption method cannot completely remove pollutants, the chemical oxidation method can introduce chemical reagents, and the electrocatalysis method has high cost. The photocatalytic method can effectively utilize solar energy, and is simple, convenient and efficient, so that the method is widely concerned.
The biochar has wide sources of preparation materials, simple and efficient preparation method and excellent material adsorption performance, is widely applied to the fields of agriculture and environmental remediation, and is a material with wide application prospect. In order to improve the adsorption performance of the biochar on pollutants, the biochar is often subjected to modification treatment. The commonly used modification methods comprise steam activation, acid-base modification or coating and the like, but the methods usually consume large energy, are complex to operate and have the problems of secondary pollution, so that the research of the economic and environment-friendly modification methods is necessary. Common semiconductor photocatalysts such as titanium dioxide only respond to ultraviolet light, and therefore, it is necessary to research visible light photocatalysts capable of responding to visible light.
Disclosure of Invention
The invention aims to solve the problems of difficult treatment of waste biomass and poor adsorption performance of a photocatalyst in the process of removing organic pollutants such as antibiotics and the like in water, and provides a preparation method of ball-milled biochar.
The invention also aims to provide the ball-milled biochar obtained by the preparation method.
The invention also aims to provide a method for degrading enrofloxacin by using the ball-milling biochar.
The invention also aims to provide application of the ball-milling biochar as a photocatalyst in degradation of enrofloxacin.
The purpose of the invention is realized by the following technical scheme.
A preparation method of ball-milled biochar comprises the following steps:
1) cleaning sawdust with ultrapure water, drying at 60-80 ℃ for 12-18 h, cooling to room temperature of 20-25 ℃, crushing, sieving with a 50-100 mesh sieve to obtain a sieved material, pyrolyzing the sieved material at N ℃ for 2-4 hours, and cooling to obtain original biochar, wherein N is 300-700;
in the step 1), the process of pyrolyzing the sieved material at N ℃ for 2-4 hours is as follows: and heating the sieved material from the room temperature of 20-25 ℃ to N ℃, and pyrolyzing the sieved material at the N ℃ for 2-4 hours, wherein the heating rate of heating from the room temperature of 20-25 ℃ to the N ℃ is 10 ℃/min.
In the step 1), the wood chips are poplar wood chips.
2) Ball-milling original biochar in a ball-milling tank for 12-24 hours at the room temperature of 20-25 ℃, and collecting products to obtain the ball-milled biochar.
In the step 2), the mass ratio of the original biochar to the grinding balls in the ball-milling tank is 1 (50-150).
In the step 2), the rotating speed of the ball milling tank is 100-300 rpm.
In the step 2), the rotation direction of the ball milling tank is changed at intervals of 4-6 h in the ball milling process.
In the step 2), the diameter of the grinding ball is 3-15 mm, preferably the grinding ball is a mixture of grinding balls with the diameters of 3mm, 5mm and 15mm, wherein the mass ratio of the grinding balls with the diameters of 3mm, 5mm and 15mm is 3:5: 2. The ball-milling biochar obtained by the preparation method.
The method for degrading enrofloxacin by ball-milling biochar comprises the following steps: adding ball-milling biochar into the enrofloxacin solution, adjusting the pH value to 3-11 to obtain a solution to be degraded, stirring the solution to be degraded for 1.5-2 h under a dark condition, and reacting for 2-3 h under visible light illumination.
In the technical scheme, the wavelength of the visible light illumination is 400-780 nm
In the technical scheme, the concentration of the enrofloxacin in the enrofloxacin solution is 20 mg/L.
In the technical scheme, the mass of ball-milling biochar added into each liter of enrofloxacin solution is 0.10-0.30 g.
The ball-milling biochar is used as a photocatalyst to be applied to degradation of enrofloxacin.
In the technical scheme, the removal rate of the enrofloxacin can reach 80.2 percent at most.
The invention has the following beneficial effects:
1. the preparation method of the invention prepares the agricultural wastes into functional materials by a simple and low-consumption method, and realizes the reutilization of the agricultural wastes.
2. After the biological carbon is ball-milled, the structure is changed into a spherical shape from the original tubular shape, the grain diameter is obviously reduced, and the grain size is in a nanometer level.
3. Compared with the original biochar (wood chips), the ball-milling biochar has more oxygen-containing functional groups, smaller particle size and more abundant defect structures, and is favorable for improving the adsorption performance of the biochar and generating active oxygen radicals.
4. The removal rate of the ball-milled biochar on enrofloxacin, which is obtained by the preparation method, is up to 80.2 percent, and is greatly improved compared with the original biochar.
Drawings
FIG. 1(a) is an SEM of raw biochar obtained in example 1 of the present invention;
FIG. 1(b) is an SEM of raw biochar obtained in example 2 of the present invention;
FIG. 1(c) is an SEM of the raw biochar obtained in example 3 of the present invention;
FIG. 1(d) is an SEM of the ball-milled biochar obtained in example 4 of the present invention;
FIG. 1(e) is an SEM of the ball-milled biochar obtained in example 5 of the present invention;
FIG. 1(f) is an SEM of the ball-milled biochar obtained in example 6 of the present invention;
FIG. 1(g) is a TEM of the raw biochar obtained in example 1 of the present invention;
FIG. 1(h) is a TEM of a ball-milled biochar obtained in example 4 of the present invention;
FIG. 2 is FTIR plots of the raw biochar obtained in examples 1-3 and the ball-milled biochar obtained in examples 4-6;
FIG. 3(a) is a C1s XPS spectrum of biochar obtained in examples 1 and 4 of the present invention;
FIG. 3(b) is a C1s XPS spectrum of biochar obtained in examples 2 and 5 of the present invention;
FIG. 3(C) is a C1s XPS spectrum of biochar obtained in examples 3 and 6 of the present invention;
FIG. 3(d) is an O1s XPS spectrum of biochar obtained in examples 1 and 4 of the present invention;
FIG. 3(e) is an O1s XPS spectrum of biochar obtained in examples 2 and 5 of the present invention;
FIG. 3(f) is an O1s XPS spectrum of biochar obtained in examples 3 and 6 of the present invention;
FIG. 4(a) is a graph showing the removal of enrofloxacin (C/C) by the methods of examples 7, 10, 21 and 24 according to the present invention0)；
FIG. 4(b) is a diagram showing the removal of enrofloxacin by the methods of examples 8, 11, 22 and 25;
FIG. 4(c) is a graph showing the removal of enrofloxacin by the methods of examples 9, 12, 23 and 26;
FIG. 5 shows the removal of enrofloxacin by the methods of examples 10, 13 to 16, 24 and 27 to 30;
FIG. 6 shows the removal of enrofloxacin by the methods of examples 10, 17 to 20, 24 and 31 to 34.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
The purity of the drug products referred to in the following examples is as follows:
the apparatus referred to in the following examples is as follows:
examples 1 to 3 (comparative)
A method for preparing raw biochar comprises the following steps:
cleaning poplar chips with ultrapure water, drying for 12h at 60 ℃, cooling to room temperature of 20-25 ℃, crushing, sieving with a 100-mesh sieve to obtain a sieved material, placing the sieved material in a muffle furnace, heating to N ℃ from the room temperature of 20-25 ℃, pyrolyzing for 3 hours at the temperature of N ℃, and cooling to the room temperature of 20-25 ℃ to obtain the original biochar, wherein the heating rate of heating to N ℃ from the room temperature of 20-25 ℃ is 10 ℃/min. The N values are shown in Table 1.
TABLE 1
| Examples | N (unit:. degree. C.) | Name of raw biochar obtained in example |
| Example 1 | 300 | BC300 |
| Example 2 | 500 | BC500 |
| Example 3 | 700 | BC700 |
Examples 4 to 6
A preparation method of ball-milled biochar comprises the following steps:
1) cleaning poplar chips with ultrapure water, drying for 12h at 60 ℃, cooling to room temperature of 20-25 ℃, crushing, sieving with a 100-mesh sieve to obtain a sieved material, placing the sieved material in a muffle furnace, heating to N ℃ from the room temperature of 20-25 ℃, pyrolyzing for 3 hours at the temperature of N ℃, and cooling to the room temperature of 20-25 ℃ to obtain the original biochar, wherein the heating rate of heating to N ℃ from the room temperature of 20-25 ℃ is 10 ℃/min.
2) Placing original biochar in a 500mL agate ball-milling tank at room temperature of 20-25 ℃, sealing the agate ball-milling tank in a high-energy ball mill, carrying out ball milling on the original biochar in the agate ball-milling tank for 24 hours, and collecting a product to obtain ball-milled biochar, wherein the mass ratio of the original biochar to grinding balls in the ball-milling tank is 1:100, and the rotating speed of the agate ball-milling tank is 200 rpm; during the ball milling process, the rotating direction of the ball milling tank is changed every 6 h. The grinding balls in the agate ball-milling tank are a mixture of grinding balls with the diameters of 3mm, 5mm and 15mm, wherein the mass ratio of the grinding balls with the diameters of 3mm, 5mm and 15mm is 3:5: 2. The N values are shown in Table 2.
TABLE 2
| Examples | N (unit:. degree. C.) | Name of ball-milled biochar obtained in example |
| Example 4 | 300 | BM300 |
| Example 5 | 500 | BM500 |
| Example 6 | 700 | BM700 |
FIG. 1 is an SEM image and a TEM image of the original biochar and the ball-milled biochar in examples 1-6, and it can be seen that the particle size of the ball-milled biochar is obviously reduced from the original micron-scale to the nanometer-scale, the form is also changed from irregular block to regular sphere, and the reduction of the particle size is beneficial to the adsorption of the biochar on enrofloxacin.
Fig. 2 is FTIR graphs of the original biochar and the ball-milled biochar in examples 1-6, the types of functional groups of the original biochar decrease with the increase of pyrolysis temperature, and the types of functional groups of the ball-milled biochar increase, which indicates that new oxygen-containing functional groups can be introduced by ball milling, which is beneficial to removing the generation of persistent radicals and active oxygen radicals in the reaction.
Fig. 3 is an XPS graph of the raw biochar and the ball-milled biochar in examples 1 to 6, in which the content of O — C ═ O and the content of O/C increased after ball milling, indicating that the content of oxygen-containing functional groups increased after ball milling, which is consistent with the FTIR results.
Examples 7 to 20
The method for degrading enrofloxacin by using the material to be tested, wherein the material to be tested is any one of the original biochar obtained in examples 1-3 and the ball-milled biochar obtained in examples 4-6, and the method comprises the following steps: adding a material to be detected into 50mL of enrofloxacin solution, adjusting the pH value to Q to obtain a solution to be degraded, putting the solution to be degraded into a photochemical reactor, stirring for 1.5h under a dark condition to achieve adsorption balance, and reacting for 2.5h under visible light illumination (a 500W xenon lamp), wherein the enrofloxacin solution is an enrofloxacin aqueous solution, and the concentration of enrofloxacin in the enrofloxacin solution is 20 mg/L. The mass of the ball-milling biochar put into each liter of enrofloxacin solution is C g. The materials to be tested, C and Q values are shown in Table 3. Taking 3mL of the degradation solution to be used as a sample every 0.5h in the reaction process of the photochemical reaction instrument, and measuring the concentration at 271nm by using an ultraviolet-visible spectrophotometer after the sample passes through a 0.45 mu m filter membrane.
TABLE 3
| Examples | Material to be measured | C(g/L) | Q | Numbering |
| Example 7 | Example 1 | 0.20 | 5 | BC300 (dark 1.5h + light 2.5h) |
| Example 8 | Example 2 | 0.20 | 5 | BC500 (dark 1.5h + light 2.5h) |
| Example 9 | Example 3 | 0.20 | 5 | BC700 (dark 1.5h + light)2.5h) |
| Example 10 | Example 4 | 0.20 | 5 | BM300 (dark 1.5h + light 2.5h) |
| Example 11 | Example 5 | 0.20 | 5 | BM500 (dark 1.5h + light 2.5h) |
| Example 12 | Example 6 | 0.20 | 5 | BM700 (dark 1.5h + light 2.5h) |
| Example 13 | Example 4 | 0.10 | 5 | BM300 (dark 1.5h + light 2.5h) |
| Example 14 | Example 4 | 0.15 | 5 | BM300 (dark 1.5h + light 2.5h) |
| Example 15 | Example 4 | 0.25 | 5 | BM300 (dark 1.5h + light 2.5h) |
| Example 16 | Example 4 | 0.30 | 5 | BM300 (dark 1.5h + light 2.5h) |
| Example 17 | Example 4 | 0.20 | 3 | BM300 (dark 1.5h + light 2.5h) |
| Example 18 | Example 4 | 0.20 | 7 | BM300 (dark 1.5h + light 2.5h) |
| Example 19 | Example 4 | 0.20 | 9 | BM300 (dark 1.5h + light 2.5h) |
| Example 20 | Example 4 | 0.20 | 11 | BM300 (dark 1.5h + light 2.5h) |
Examples 21 to 34
The method for degrading enrofloxacin by using the material to be tested, wherein the material to be tested is any one of the original biochar obtained in examples 1-3 and the ball-milled biochar obtained in examples 4-6, and the method comprises the following steps: adding a material to be detected into 50mL of enrofloxacin solution, adjusting the pH value to Q to obtain a solution to be degraded, putting the solution to be degraded into a photochemical reactor, and stirring for 4h under a dark condition, wherein the enrofloxacin solution is enrofloxacin aqueous solution, and the concentration of enrofloxacin in the enrofloxacin solution is 20 mg/L. The mass of the ball-milling biochar put into each liter of enrofloxacin solution is C g. The materials to be tested, C and Q values are shown in Table 4. Taking 3mL of the degradation solution to be used as a sample every 0.5h in the reaction process of the photochemical reaction instrument, and measuring the concentration at 271nm by using an ultraviolet-visible spectrophotometer after the sample passes through a 0.45 mu m filter membrane.
TABLE 4
| Examples | Material to be measured | C(g/L) | Q | Numbering |
| Example 21 | Example 1 | 0.20 | 5 | BC300 (dark 4h) |
| Example 22 | Example 2 | 0.20 | 5 | BC500 (dark 4h) |
| Example 23 | Example 3 | 0.20 | 5 | BC700 (dark 4h) |
| Example 24 | Example 4 | 0.20 | 5 | BM300 (dark 4h) |
| Example 25 | Example 5 | 0.20 | 5 | BM500 (dark 4h) |
| Example 26 | Example 6 | 0.20 | 5 | BM700 (dark 4h) |
| Example 27 | Example 4 | 0.10 | 5 | BM300 (dark 4h) |
| Example 28 | Example 4 | 0.15 | 5 | BM300 (dark 4h) |
| Example 29 | Example 4 | 0.25 | 5 | BM300 (dark 4h) |
| Example 30 | Example 4 | 0.30 | 5 | BM300 (dark 4h) |
| Example 31 | Example 4 | 0.20 | 3 | BM300 (dark 4h) |
| Example 32 | Example 4 | 0.20 | 7 | BM300 (dark 4h) |
| Example 33 | Example 4 | 0.20 | 9 | BM300 (dark 4h) |
| Practice ofExample 34 | Example 4 | 0.20 | 11 | BM300 (dark 4h) |
FIG. 4 shows the removal of enrofloxacin from the materials to be tested obtained in examples 1 to 6, along the ordinate C/C0Wherein C represents the residual concentration of enrofloxacin in the sample, C0Represents the initial concentration of enrofloxacin in the enrofloxacin aqueous solution (C)020mg/L), if the removal rate is R, C/C01-R. The removal rates of the original biochar BC300, BC500 and BC700 to enrofloxacin under illumination are respectively 29.2%, 21.9% and 13.9%, and the removal rates of the ball-milled biochar BM300, BM500 and BM700 to enrofloxacin under illumination are respectively 80.2%, 73.1% and 33.3%, so that the light removal effect of the ball-milled biochar to enrofloxacin can be obviously improved, and the removal effect of the BM300 to enrofloxacin is the best.
In fig. 4, the blank (dark 4h) and the blank (dark 1.5h + light 2.5h) have the following meanings:
blank (dark 4 h): measuring 50mL of enrofloxacin solution, adjusting the pH value to 5 to obtain a first blank liquid, putting the first blank liquid into a photochemical reaction instrument, and stirring for 4 hours under a dark condition, wherein the enrofloxacin solution is an enrofloxacin aqueous solution, and the concentration of enrofloxacin in the enrofloxacin solution is 20 mg/L. First blank liquid in the photochemical reaction instrument reaction process, every 0.5h take 3mL first blank liquid as sample, sample through 0.45 μm filter membrane, ultraviolet-visible spectrophotometer at 271nm position to determine the concentration.
Blank (dark 1.5h + light 2.5 h): measuring 50mL of enrofloxacin solution, adjusting the pH value to 5 to obtain a second blank liquid, putting the second blank liquid into a photochemical reaction instrument, stirring for 1.5h under a dark condition to achieve adsorption balance, and reacting for 2.5h under visible light illumination (500W xenon lamp), wherein the enrofloxacin solution is an enrofloxacin aqueous solution, and the concentration of enrofloxacin in the enrofloxacin solution is 20 mg/L. And 3mL of second blank liquid is taken as a sample every 0.5h in the reaction process of the photochemical reaction instrument, and the concentration of the sample is measured at 271nm by using an ultraviolet-visible spectrophotometer after the sample passes through a 0.45-micrometer filter membrane.
FIG. 5 shows the removal of enrofloxacin by the methods of examples 10, 13 to 16, 24 and 27 to 30, and the removal ability of enrofloxacin was evaluated by the difference between the removal rate of enrofloxacin under light conditions and the removal rate under dark conditions. It can be seen that the difference increases and then decreases with the increase of the BM300 dosage, and when the BM300 dosage is 0.20g/L, the removal rate of 20mg/L enrofloxacin is the highest, and is 80.2%.
FIG. 6 shows the removal of enrofloxacin by the methods of examples 10, 17 to 20, 24 and 31 to 34, and the removal ability of enrofloxacin was evaluated by the difference between the removal rate of enrofloxacin under light conditions and the removal rate under dark conditions. It can be seen that as the pH of the solution increases, the difference increases and then decreases, and there is an optimum pH. When the initial pH of the enrofloxacin solution is 5 and the adding amount of BM300 is 0.20g/L, the removal rate of 20mg/L enrofloxacin is the highest and is 80.2%.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The preparation method of the ball-milled biochar is characterized by comprising the following steps:
1) cleaning sawdust with ultrapure water, drying at 60-80 ℃ for 12-18 h, cooling to room temperature of 20-25 ℃, crushing, sieving with a 50-100 mesh sieve to obtain a sieved material, pyrolyzing the sieved material at N ℃ for 2-4 hours, and cooling to obtain original biochar, wherein N is 300-700;
2) ball-milling original biochar in a ball-milling tank for 12-24 hours at the room temperature of 20-25 ℃, and collecting products to obtain the ball-milled biochar.
2. The preparation method according to claim 1, wherein in the step 1), the process of pyrolyzing the sieved material at N ℃ for 2-4 hours is as follows: heating the sieved material from room temperature of 20-25 ℃ to N ℃, and pyrolyzing the sieved material at the N ℃ for 2-4 hours; the wood chips are poplar wood chips.
3. The preparation method of the biological carbon material is characterized in that in the step 2), the mass ratio of raw biological carbon to grinding balls in a ball milling tank is 1 (50-150);
the rotating speed of the ball milling tank is 100-300 rpm, and the rotating direction of the ball milling tank is changed at intervals of 4-6 h in the ball milling process.
4. The preparation method according to claim 3, wherein in the step 2), the grinding balls have a diameter of 3-15 mm, preferably a mixture of grinding balls with a diameter of 3mm, a diameter of 5mm and a diameter of 15mm, wherein the mass ratio of the grinding balls with a diameter of 3mm, a diameter of 5mm and a diameter of 15mm is 3:5: 2.
5. The ball-milled biochar obtained by the preparation method according to any one of claims 1 to 4.
6. The method for degrading enrofloxacin by ball-milling biochar as claimed in claim 5, which comprises the following steps: adding ball-milling biochar into the enrofloxacin solution, adjusting the pH value to 3-11 to obtain a solution to be degraded, stirring the solution to be degraded for 1.5-2 h under a dark condition, and reacting for 2-3 h under visible light illumination.
7. The method of claim 6, wherein the visible light illumination has a wavelength of 400-780 nm.
8. The method as claimed in claim 7, wherein the mass of the ball-milled biochar is 0.10-0.30g per liter of enrofloxacin solution.
9. The use of the ball-milled biochar of claim 5 as a photocatalyst in the degradation of enrofloxacin.
10. The use of claim 9, wherein the enrofloxacin removal rate is up to 80.2%.
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