CN115888626A - Potassium-based magnetic biochar and preparation method and application thereof - Google Patents
Potassium-based magnetic biochar and preparation method and application thereof Download PDFInfo
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- CN115888626A CN115888626A CN202211490806.4A CN202211490806A CN115888626A CN 115888626 A CN115888626 A CN 115888626A CN 202211490806 A CN202211490806 A CN 202211490806A CN 115888626 A CN115888626 A CN 115888626A
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- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 89
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000011591 potassium Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 22
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 22
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 21
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 21
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000008247 solid mixture Substances 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract 5
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 44
- 229960000282 metronidazole Drugs 0.000 claims description 44
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 17
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- 239000000243 solution Substances 0.000 description 20
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 11
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 235000017060 Arachis glabrata Nutrition 0.000 description 3
- 241001553178 Arachis glabrata Species 0.000 description 3
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- 235000018262 Arachis monticola Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
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- 239000002028 Biomass Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
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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 1
- 241000609240 Ambelania acida Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses potassium-based magnetic biochar and a preparation method thereof. The preparation method of the potassium-based magnetic biochar comprises the following steps: 1) Adding agricultural and forestry wastes into the mixed solution of ferrous sulfate and potassium sulfate, dipping and centrifuging to obtain a solid mixture; 2) And calcining the solid mixture to obtain the potassium-based magnetic biochar. The potassium-based magnetic biochar is prepared from ferrous sulfate, potassium sulfate and agricultural and forestry wastes, so that potassium and iron can be effectively prevented from being separated out, and the risk of secondary pollution is reduced.
Description
Technical Field
The invention relates to the field of waste resource utilization, in particular to potassium-based magnetic biochar and a preparation method and application thereof.
Background
Magnetic Biochar (MBC) is generally a type of biochar synthesized from waste biomass and iron salts having magnetic propertiesThe responsive porous material has the advantages of wide raw material source, simple preparation, low cost and the like, and is widely applied to the field of environmental remediation. Research has proved that MBC can effectively activate hydrogen peroxide (H) 2 O 2 ) Oxidants such as Persulfate (PS) and Peroxymonosulfate (PMS) generate free radicals with strong oxidizing property to degrade organic pollutants in water. However, the MBC activating oxidant has the problem of low efficiency in the process of degrading organic matters. For example, yi et al found that MBC prepared from herb residue and peanut shells activates H 2 O 2 The removal rate of MNZ was less than 25%. Similarly, dong et al found that MBC activated persulfate to degrade polycyclic aromatics, but the activity was poor, with only 21% of polycyclic aromatics being removed. Therefore, how to further enhance the activation efficiency of MBC is a matter of great concern.
As a composite material, the component composition and the occurrence form difference of the components of MBC are key factors influencing the activation performance. The key components of MBC that are effective in activating the oxidant are mainly Fe (ii), persistent free radicals, and oxygen-containing groups (C = O and O-C = O), among others. Therefore, modulating the active ingredient content in MBC is a powerful breakthrough to improve MBC activation performance. Compared with other components, the MBC has stronger accessibility for increasing the activation efficiency by regulating the content of Fe (II) in the MBC. From the previous research reports, there are several ways to regulate the content of Fe (II) compounds in MBC: 1) Biomass that synthesizes MBC is preferred. For example, yi et al found, by semi-quantitative analysis, that the content of Fe (II) in MBC synthesized using bagasse with high cellulose content was about 3 times higher than that synthesized using herb residue as a raw material; 2) Regulating and controlling the pyrolysis temperature for synthesizing the MBC. For example, chen et al successfully increased the Fe (II) content in the magnetic biochar from 0.9% to 16.8% by changing the temperature during pyrolysis; 3) Doping other elements. For example, cai et al have found that doping with Cu during the preparation of MBC increases the Fe (II) content of MBC from 10% to 30%. Yu et al increased the Fe (II) content of MBC from 0.8mg/L to 2.8mg/L by doping with N. According to the research result, the content of Fe (II) in the MBC is regulated and controlled by doping other elements, so that the activation efficiency of the MBC is improved more conveniently. In spite of this, it is possible to provide,however, the doped elements have a problem of precipitation, which may cause secondary pollution. For example, xu et al have studied a novel peanut shell BC catalyst coupled amorphous Cu doped FeOOH cluster for activating PS to degrade TC with 9.6% Cu in the reaction process 2+ There is a leak. Therefore, it is important to dope with suitable elements during the synthesis of MBC to reduce the risk of secondary contamination.
Disclosure of Invention
In order to solve the problem of precipitation of doped elements of magnetic biochar in the prior art, one purpose of the invention is to provide a preparation method of potassium-based magnetic biochar, the other purpose of the invention is to provide potassium-based magnetic biochar, the third purpose of the invention is to provide application of the potassium-based magnetic biochar, and the fourth purpose of the invention is to provide a treatment method of wastewater containing metronidazole.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of potassium-based magnetic biochar, which comprises the following steps:
1) Adding agricultural and forestry wastes into a mixed solution of ferrous sulfate and potassium sulfate, dipping and centrifuging to obtain a solid mixture;
2) And calcining the solid mixture to obtain the potassium-based magnetic biochar.
Preferably, in the preparation method, the agricultural and forestry waste comprises one of peanut shells and wood chips; further preferably, the agricultural and forestry waste is wood chips; in some preferred embodiments of the invention, the particle size of the wood chips is 0.01-0.02cm and the moisture content of the wood chips is 15-20%.
Preferably, in the preparation method, in the step 1), the mass percent of the iron element in the mixed solution of the ferrous sulfate and the potassium sulfate is 10-20%; further preferably, the mass percent of the iron element in the mixed solution of the ferrous sulfate and the potassium sulfate is 12 to 18 percent; in some preferred embodiments of the present invention, the weight percentage of the iron element in the mixed solution of ferrous sulfate and potassium sulfate is 14%.
Preferably, in the preparation method, in the step 1), the mass percent of potassium element in the mixed solution of ferrous sulfate and potassium sulfate is 10-20%; further preferably, the mass percent of the potassium element in the mixed solution of the ferrous sulfate and the potassium sulfate is 12 to 18 percent; still more preferably, the mass percentage of the potassium element in the mixed solution of ferrous sulfate and potassium sulfate is 15%.
Preferably, in the preparation method, in the step 1), the mass volume ratio of the agricultural and forestry waste to the mixed solution of the ferrous sulfate and the potassium sulfate is 1g: (35-50) mL; further preferably, the mass volume ratio of the agricultural and forestry waste to the mixed solution of the ferrous sulfate and the potassium sulfate is 1g: (35-45) mL; still further preferably, the mass volume ratio of the agricultural and forestry waste to the mixed solution of ferrous sulfate and potassium sulfate is 1g: (38-42) mL.
Preferably, in the preparation method, in the step 1), the soaking time is 1.5-2.5h; further preferably, the time for soaking is 1.8-2.2h; still more preferably, the time of immersion is 2 hours.
Preferably, in the preparation method, the pH value of the mixed solution of the ferrous sulfate and the potassium sulfate is 6.0-7.0; further preferably, the pH value of the mixed solution of the ferrous sulfate and the potassium sulfate is 6.2-6.8; in some preferred embodiments of the present invention, the pH of the mixed solution of ferrous sulfate and potassium sulfate is 6.5.
Preferably, in the preparation method, in the step 2), the solid mixture is calcined at the temperature rising rate of 15-25 ℃/min to 550-650 ℃ under the protective atmosphere; more preferably, the temperature is raised to 550-650 ℃ at a temperature raising rate of 18-22 ℃/min.
Preferably, in the preparation method, in the step 2), the calcining temperature is 550-650 ℃; further preferably, the temperature of calcination is 580-620 ℃; still more preferably, the temperature of calcination is 600 ℃.
Preferably, in the preparation method, in the step 2), the calcining time is 1.5-2.5h; further preferably, the calcining time is 1.8-2.2h; still more preferably, the calcination time is 2.0h.
Preferably, in the preparation method, in the step 2), the potassium-based magnetic biochar is obtained by cooling to room temperature after calcination, grinding and sieving by a 100-mesh sieve.
The invention provides a potassium-based magnetic biochar in a second aspect, and the potassium-based magnetic biochar is prepared by the preparation method.
Preferably, the specific surface area of the potassium-based magnetic biochar is 260-400m 2 (ii)/g; further preferably, the specific surface area of the potassium-based magnetic biochar is 284-345m 2 /g。
Preferably, the potassium-based magnetic biochar has a micropore volume (Vm) of 60 to 85cm 3 (ii)/g; further preferably, the potassium-based magnetic biochar has a micropore volume of 65 to 80cm 3 /g。
Preferably, the potassium-based magnetic biochar has a pore volume (Vt) of 0.05-0.25cm 3 (ii)/g; further preferably, the pore volume of the potassium-based magnetic biochar is 0.1-0.2cm 3 /g。
Preferably, the potassium-based magnetic biochar has an average micropore diameter (D) of 2.0 to 2.5nm; further preferably, the potassium-based magnetic biochar has an average micropore diameter of 2.15 to 2.25nm.
Preferably, the mass percentage of the potassium element in the potassium-based magnetic biochar is 0.4-0.5%.
Preferably, the mass percentage of the iron element in the potassium-based magnetic biochar is 0.7-0.9%.
The third aspect of the invention provides application of the potassium-based magnetic biochar prepared by the preparation method in treatment of metronidazole-containing wastewater.
The fourth aspect of the invention provides a method for treating wastewater containing metronidazole, which comprises the step of putting the potassium-based magnetic biochar and persulfate prepared by the preparation method into the wastewater containing metronidazole.
Preferably, in the treatment method, the adding amount of the potassium-based magnetic biochar is 0.1-1g/L; further preferably, the adding amount of the potassium-based magnetic biochar is 0.5-1g/L.
Preferably, in the treatment method, the persulfate is added in an amount of 0.5-5mmoL/L; further preferably, the adding amount of the persulfate is 0.5-3mmoL/L; still more preferably, the persulfate is added in an amount of 1mmoL/L.
Preferably, in the treatment method, the concentration of metronidazole in the wastewater is 1-50mg/L; further preferably, the concentration of metronidazole in the wastewater is 10-30mg/L.
Preferably, in this treatment, the wastewater has a pH of 3 to 8.
The invention has the beneficial effects that:
1. the potassium-based magnetic biochar is prepared from ferrous sulfate, potassium sulfate and agricultural and forestry wastes, so that potassium and iron can be effectively prevented from being separated out, and the risk of secondary pollution is reduced.
2. The method for preparing the potassium-based magnetic biochar by using the agricultural and forestry wastes in one step is not only favorable for cost control but also favorable for environmental protection, has the advantages of simple preparation method, few process steps and low energy consumption, is easy to realize large-scale production, and simultaneously has no waste water or sludge in the preparation process, thereby avoiding secondary pollution or secondary wastes.
3. The magnetic biochar modified material prepared from the agricultural and forestry waste only needs to be added with a small amount of persulfate, so that the metronidazole removing effect is remarkable, the added value of the product is high, and the removing method is simple and efficient.
Drawings
Fig. 1 is an SEM image of potassium-based magnetic biochar prepared in example 1.
FIG. 2 is an SEM-mapping chart of the potassium-based magnetic biochar prepared in example 1.
Fig. 3 is an XRD pattern of the potassium-based magnetic biochar prepared in example 1.
FIG. 4 is an XPS plot of Fe (2 p) for the potassium-based magnetic biochar and magnetic biochar prepared in the examples.
FIG. 5 is a graph showing the results of degrading metronidazole with potassium-based magnetic biochar and magnetic biochar.
FIG. 6 is a graph showing the removal of metronidazole by potassium-based magnetic biochar at different dosages in example 4.
FIG. 7 is a graph of metronidazole removal with potassium-based magnetic biochar at different PS loadings for example 5.
FIG. 8 is a graph of metronidazole removal with potassium-based magnetic biochar at different initial pH's for example 6.
FIG. 9 is a graph showing the removal of metronidazole from sewage in the simulation of example 7.
Detailed Description
The present invention will be described in further detail with reference to examples. It will also be understood that the following examples are included merely for purposes of further illustrating the invention and are not to be construed as limiting the scope of the invention, as the invention extends to insubstantial modifications and adaptations of the invention following in the light of the principles set forth herein. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can make a selection within suitable ranges through the description herein, and are not intended to be limited to the specific data of the following examples.
Example 1
The embodiment provides a method for preparing potassium-based magnetic biochar, which comprises the following steps:
1) At room temperature, 4.9651g of ferrous sulfate heptahydrate and 3.1114g of potassium sulfate are added into 200mL of deionized water, so that the mass percent of iron element in the mixed solution of the ferrous sulfate and the potassium sulfate is 14%, the mass percent of potassium element is 15%, and the pH value is 6.5;
2) Adding 5g of sawdust particles which are washed and crushed to be 0.015cm in particle size and air-dried until the water content is 15-20% into 200mL of mixed solution of ferrous sulfate and potassium sulfate in the step 1), soaking for 2h at room temperature, centrifuging, and pouring out supernatant liquid to obtain a solid mixture with the water content of 15%;
3) Heating the solid mixture obtained in the step 2) to 600 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere, calcining for 2h, cooling to room temperature, grinding, and sieving with a 100-mesh sieve to obtain the potassium-based magnetic biochar (KMBC).
Example 2
This example provides a method for preparing Magnetic Biochar (MBC) that differs from example 1 in that the preparation process is not doped with K, and the remaining steps are identical to potassium-based magnetic biochar.
An SEM image of the potassium-based magnetic biochar prepared in example 1 is shown in fig. 1; the SEM-mapping chart of the potassium-based magnetic biochar prepared in example 1 is shown in FIG. 2. The XRD pattern of the biochar prepared in example 1 is shown in fig. 3.
As shown in FIG. 1, the potassium-based magnetic biochar has a rough surface, developed pores and a honeycomb shape; as can be seen from FIG. 2, fe and K are mainly distributed on the surface and pore walls of the potassium-based magnetic biochar.
As can be seen from FIG. 3, K is respectively shown in the potassium-based magnetic biochar 2 SO 4 And Fe 3 O 4 Characteristic peaks (alignment by software jade6.0 and XRD standard card).
Further analysis by XPS revealed (FIG. 4) that Fe element on the potassium-based magnetic biochar (KMBC) was mainly bound in the form of triiron tetroxide, and unmodified Magnetic Biochar (MBC) was mainly bound in the form of iron sesquioxide and triiron tetroxide;
the potassium-based magnetic biochar is successfully prepared from agricultural and forestry waste.
BET data of the magnetic biochar prepared in examples 1 and 2 are shown in table 1:
TABLE 1
| Kind of material | SA(m 2 /g) | V m (cm 3 /g) | V t (cm 3 /g) | D(nm) |
| MBC | 344.6 | 79.1 | 0.2 | 2.2 |
| KMBC | 284.9 | 65.4 | 0.1 | 2.1 |
Note: SA specific surface area, vm micropore volume, vt pore volume, D average micropore diameter
Example 3
Degradation experiment for removing metronidazole by potassium-based magnetic charcoal activated PS:
first, 1mM of PS is taken, after the PS is completely dissolved, 0.5g/L of potassium-based magnetic biochar prepared in example 1 and magnetic biochar prepared in example 2 are respectively added into a 250mL conical flask, 100mL of metronidazole solution with the initial concentration of 20mg/L are sequentially added, the mixture is oscillated in a constant temperature oscillator at the temperature of 25 ℃ and in the dark at 250r/min, 2 parallel samples are arranged in each group, when the preset sampling time point is reached, the reaction solution is magnetically separated, the supernatant is taken to pass through a 0.22 mu m filter membrane, and then the concentration of metronidazole in the solution is measured by using a high performance liquid chromatography.
The results are shown in fig. 5, when PS is introduced into the potassium-based magnetic biochar system, the removal rate of metronidazole is 98.4%, which is about 13.1 times that of the magnetic biochar/PS system; in addition, from the fitted reaction rate constant, the degradation rate of the potassium-based magnetic biochar/PS system is 0.025min -1 Is 65.7 times of the magnetic biochar/PS system. Therefore, the potassium-based magnetic biochar can efficiently activate PS to generate a large number of active species so as to efficiently remove metronidazole, and the introduction of K is also proved to powerfully enhance the activation efficiency of the magnetic biochar.
Example 4
Degradation experiment of removing metronidazole by catalyzing PS with potassium-based magnetic biochar under different adding amounts of potassium-based magnetic biochar:
1mM of PS is taken firstly, after the PS is completely dissolved, 0.1g/L, 0.5g/L and 1g/L of the potassium-based magnetic biochar prepared in the embodiment 1 are respectively added into a 250mL conical flask, 100mL of metronidazole solution with the initial concentration of 20mg/L is sequentially added, the mixture is oscillated in a constant temperature oscillator at 25 ℃ and under the condition of keeping out of the light at 250r/min, 2 parallel samples are arranged in each group, when the preset sampling time point is reached, the reaction solution is magnetically separated, the supernatant is taken and filtered through a 0.22 mu m filter membrane, and then the concentration of metronidazole in the solution is measured by using a high performance liquid chromatography.
As a result, as shown in FIG. 6, when the potassium-based magnetic charcoal dosage was increased from 0.1g/L to 0.5g/L, the metronidazole degradation rate was increased from 23.0% to 98.4%. The main reason is that the increase of the potassium-based magnetic biochar can provide more active sites, improve the activation efficiency of PS and promote more active free radicals to be generated in the system. When the adding amount of the potassium-based magnetic biochar is increased to 1.0g/L, the difference between the final degradation effect and 0.5g/L after the reaction is finished is not more than 2.1 percent. Therefore, the optimum adding amount of the potassium-based magnetic biochar is preferably 0.5g/L.
Example 5
Degradation experiment of removing metronidazole by catalyzing PS with potassium-based magnetic biochar under the condition of different PS adding amounts:
0.5mM, 1mM, 3mM and 5mM of PS are taken firstly, after the PS is completely dissolved, 0.5g/L of potassium-based magnetic biochar is taken and added into 250mL conical flasks respectively, 100mL of metronidazole solution with the initial concentration of 20mg/L is sequentially added, the mixture is oscillated in a constant temperature oscillator at 25 ℃ and under the condition of keeping out of the sun at 250r/min, 2 parallel samples are arranged in each group, when the preset sampling time point is reached, the reaction solution is magnetically separated, the supernatant is taken and passes through a 0.22 mu m filter membrane, and then the concentration of metronidazole in the solution is measured by using a high performance liquid chromatography.
The results are shown in FIG. 7, and the experimental results of metronidazole degradation by PS dosage to potassium-based magnetic biochar/PS system show that when the dosage of PS is increased from 0.5mM to 1mM, the metronidazole degradation rate is increased from 83.0% to 98.4%; however, when the dosage of PS is increased, the degradation rate of metronidazole is gradually reduced, which is mainly caused by excessive PS and SO 4 · - Cause a reaction therebetween to result in SO 4 · - And (4) consumption.
Example 6
Degradation experiment of removing metronidazole by using potassium-based magnetic biochar activated PS under different pH conditions:
taking 1mM PS, after completely dissolving, respectively adding 0.5g/L potassium-based magnetic biochar into 250mL conical bottles, sequentially adding 100mL metronidazole solution with the initial concentration of 20mg/L, adding NaOH solution to adjust the pH to be 3, 6.5, 8 and 10 respectively, oscillating in a constant-temperature oscillator at 25 ℃ and under the condition of keeping out of the sun, setting 2 parallel samples in each group, performing magnetic separation on the reaction solution when a preset sampling time point is reached, taking supernate, passing through a 0.22 mu m filter membrane, and determining the concentration of metronidazole in the solution by using a high performance liquid chromatography.
The results are shown in fig. 8, and the results of the solution initial pH on the potassium-based magnetic biochar/PS system for metronidazole removal show that the metronidazole removal rate decreases from 96.1% to 87.9% when the pH is lowered from 8 to 3. This is mainly due to excessive H + Will quench SO directly 4 · - And free radicals, thereby decreasing the removal efficiency of Metronidazole (MNZ). Further, when the pH was increased to 10, the removal rate of MNZ was reduced to 19.4%. This is mainly due to SO under alkaline conditions 4 .- Mainly with OH - And thus the consumption of free radicals.
Example 7
Simulating a degradation experiment for removing metronidazole from the sewage;
firstly taking 1mM PS, after completely dissolving, respectively adding 0.5g/L potassium-based magnetic biochar into 250mL conical bottles, sequentially adding 100mL of metronidazole solution with the initial concentration of 20mg/L and 0.05, 0.1, 0.5, 1 and 0g/L humic acid, oscillating in a constant-temperature oscillator at 25 ℃ and under the condition of keeping out of the sun at 250r/min, setting 2 parallel samples in each group, carrying out magnetic separation on reaction solution when a preset sampling time point is reached, taking supernate, passing through a 0.22 mu m filter membrane, and measuring the concentration of metronidazole in the solution by using a high performance liquid chromatography, wherein the result is shown in figure 9.
Example 8
Metal element precipitation experiment;
firstly taking 1mM PS, after completely dissolving, respectively adding 0.5g/L potassium-based magnetic biochar into 250mL conical flasks, sequentially adding 100mL metronidazole solution with the initial concentration of 20mg/L, oscillating in a constant-temperature oscillator at 25 ℃ and in a dark condition at 250r/min, setting 2 parallel samples in each group, carrying out magnetic separation on the reaction solution when a preset sampling time point is reached, taking supernate, passing through a 0.22 mu m filter membrane, and determining the total iron content by using an atomic absorption spectrophotometer. Iron ions and potassium ions are not detected in the solution, which shows that the KMBC/PS system can effectively prevent the precipitation of iron and potassium without secondary pollution.
The above tests show that: the potassium-based magnetic biochar activated PS prepared by the method has an excellent removal effect on metronidazole, which shows that a scheme for preparing the magnetic biochar by using agricultural and forestry waste and modifying the magnetic biochar by using potassium is feasible and has an outstanding effect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of potassium-based magnetic biochar is characterized by comprising the following steps:
1) Adding agricultural and forestry wastes into a mixed solution of ferrous sulfate and potassium sulfate, dipping and centrifuging to obtain a solid mixture;
2) And calcining the solid mixture to obtain the potassium-based magnetic biochar.
2. The preparation method according to claim 1, characterized in that in step 1), the weight percentage of the iron element in the mixed solution of ferrous sulfate and potassium sulfate is 10-20%, and the weight percentage of the potassium element is 10-20%.
3. The preparation method according to claim 2, wherein in the step 1), the mass-to-volume ratio of the agricultural and forestry waste to the mixed solution of the ferrous sulfate and the potassium sulfate is 1g: (35-50) mL.
4. The method of claim 1, wherein the impregnation time in step 1) is 1.5 to 2.5 hours.
5. The method according to claim 1, wherein the temperature of the calcination in step 2) is 550 to 650 ℃.
6. A potassium-based magnetic biochar, which is prepared by the preparation method of any one of claims 1 to 5.
7. The potassium-based magnetic biochar of claim 6, wherein the specific surface area of the potassium-based magnetic biochar is 260-400m 2 /g。
8. Use of the potassium-based magnetic biochar prepared by the preparation method of any one of claims 1 to 5 in treatment of metronidazole-containing wastewater.
9. A method for treating wastewater containing metronidazole, characterized by comprising the step of adding the potassium-based magnetic biochar prepared by the preparation method of any one of claims 1 to 5 and persulfate into the wastewater containing metronidazole.
10. The treatment method according to claim 9, wherein the potassium-based magnetic biochar is added in an amount of 0.1-1g/L; the adding amount of the persulfate is 0.5-5mmoL/L.
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