CN112705161A - Magnetic biochar and preparation method and application thereof - Google Patents
Magnetic biochar and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses magnetic biochar and a preparation method and application thereof. The preparation method of the magnetic biochar comprises the following steps: the agricultural and forestry waste is magnetized, and the particle size fraction of the adsorbent is reduced by a high-temperature pyrolysis and ball milling process to obtain the magnetic biochar. The magnetic charcoal has the advantages of simple preparation process, low energy consumption and high added value of products, and can effectively adsorb and remove antibiotics in wastewater.
Description
Technical Field
The invention belongs to the field of biochar materials, and particularly relates to magnetic biochar and a preparation method and application thereof.
Background
With the rapid development of industrial and agricultural in China, the total amount and the types of agricultural and forestry wastes are in an increasing trend, and the proper treatment of the agricultural and forestry wastes becomes a bottleneck problem which restricts the sustainable development of related industries. In recent years, agricultural and forestry waste is cracked at medium temperature (less than or equal to 700 ℃) in an anoxic or anaerobic environment, so that a new way is provided for efficient disposal of the waste agricultural and forestry waste, and meanwhile, the derived biochar is an environment restoration material with excellent performance. However, most biochar is powdery and difficult to separate and recover from an environmental medium, and the adsorbed pollutants are analyzed along with the evolution of space and time, so that the risk of secondary pollution exists. Therefore, how to overcome the bottleneck problem of the application of the biochar in removing pollutants in the water body is very important.
In recent years, transition metal salt is introduced in the preparation process of the biochar to prepare the magnetic biochar, so that the defects of the biochar in environmental remediation are effectively overcome, and the efficiency of the biochar is further improved. The mainstream preparation techniques of the magnetic biochar include impregnation-pyrolysis, hydrothermal method, coprecipitation method, etc., however, the removal capability of the magnetic biochar to the pollutants obtained by either preparation method is limited. The literature analysis shows that the magnetic biochar prepared at the present stage is mostly expressed in a micron-scale or even millimeter-scale, which may be a key reason for the limited efficacy of the magnetic biochar.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of magnetic biochar, and the biochar prepared by the method can better adsorb and remove pollutants in water.
The invention also provides the magnetic biochar prepared by the method.
The invention also provides an application of the magnetic biochar.
The preparation method of the magnetic biochar according to the embodiment of the first aspect of the invention comprises the following steps:
s1, removing impurities in the agricultural and forestry waste through acid treatment of the agricultural and forestry waste, and washing the agricultural and forestry waste to be neutral;
s2, adding the agricultural and forestry waste obtained in the step S1 into a solution containing an iron element to obtain a mixture;
s3, drying and calcining the mixture obtained in the step S2, and performing ball milling reinforcement to obtain the magnetic biochar.
According to some embodiments of the invention, the forestry waste of step S1 includes one or more of: rice hull, peanut shell, wheat straw, wood dust and corncob.
According to some embodiments of the invention, the pretreatment process of the forestry waste in step S1 includes one or more of the following: washing, drying in the air, crushing, removing impurities, stirring, mixing, centrifugal separation and the like.
According to some embodiments of the invention, the acid treatment in step S1 comprises one or more of: nitric acid, hydrochloric acid, sulfuric acid.
According to some embodiments of the invention, the raw material for preparing the solution containing iron element in step S2 includes one or more of the following: ferrous sulfate, ferrous chloride, ferric sulfate and ferric nitrate.
According to some embodiments of the invention, the particle size of the agricultural and forestry residues in the step S2 is 60-100 mesh, and the water content is less than 10%.
According to some embodiments of the invention, the iron content of the solution containing iron element in the step S2 is 5-20%; preferably, the iron content in the solution containing the iron element is 10-15%.
According to some embodiments of the invention, the mass-to-volume ratio of the forestry residues to the solution in the solution containing iron element in step S2 is 1: (5-20) g/mL; preferably, the mass volume ratio of the agricultural and forestry waste to the solution containing the iron element is 1: 10 g/mL.
According to some embodiments of the invention, the mixture in the step S2 is prepared by stirring and mixing the forestry and agricultural residues and the solution containing the iron element for 6-12 hours.
According to some embodiments of the present invention, the mixture in step S2 is obtained by solid-liquid separation.
According to some embodiments of the present invention, the drying temperature of the mixture in the step S3 is 80 to 90 ℃, and the drying time is 8 to 12 hours.
According to some embodiments of the invention, the water content of the mixture in the step S3 is 3% to 10%.
According to some embodiments of the invention, the mixture is dried in step S3, filled into a crucible, and then calcined in a muffle furnace.
According to some embodiments of the invention, the temperature raising program of the muffle furnace in the step S3 is 20 ℃/min, and the calcining temperature is 400-700 ℃; the calcination temperature is preferably 500-600 ℃.
According to some embodiments of the invention, after the muffle furnace reaches the set calcination temperature in the step S3, the calcination time of the mixture is 1-4 h; the calcination time is preferably 1-2 h.
According to some embodiments of the present invention, the calcining of step S3 creates an oxygen-deficient atmosphere by nitrogen gas, and the biochar impregnated in the solution containing the iron element is heated and solidified.
According to some embodiments of the present invention, the ball milling strengthening in step S3 specifically comprises the following steps: and mixing the magnetic biochar with ball milling beads, and carrying out ball milling.
According to some embodiments of the invention, the mass ratio of the magnetic biochar to the ball milling beads in the step S3 is 1: 50-200 parts of; the mass ratio of the magnetic biochar to the ball milling beads is preferably 1: 100 to 150.
According to some embodiments of the present invention, the ball milling in the step S3 is performed by using a planetary ball mill.
According to some embodiments of the invention, the rotation speed of the ball milling in the step S3 is 300-500 r/min; the rotating speed of the ball milling is preferably 300-400 r/min.
According to some embodiments of the invention, the time of ball milling in the step S3 is 1-24 h; the ball milling time is preferably 8-12 h.
According to the magnetic biochar of the second aspect of the invention, the magnetic biochar is prepared by the method.
The application of the magnetic biochar according to the third aspect embodiment of the invention is the application of the magnetic biochar in repairing antibiotic-polluted wastewater.
According to some embodiments of the invention, the application is the application of magnetic biochar in remediation of heavy metal contaminated wastewater.
According to some embodiments of the present invention, there is also provided a method for treating antibiotic-containing wastewater, the method including adding the magnetic biochar prepared as described above to the antibiotic-containing wastewater.
According to some embodiments of the invention, the concentration of the antibiotic in the antibiotic wastewater is 1-50 mg/L, and the addition amount is 0.5-4 g/L; preferably, the concentration of the antibiotics in the antibiotic wastewater is 5-30 mg/L, and the adding amount of the magnetic biochar is 1-1.5 g/L.
According to some embodiments of the invention, the antibiotic comprises one or more of triazoles, tetracyclines, sulfonamides, quinolones.
According to some embodiments of the invention, the antibiotic is fluconazole.
According to some embodiments of the present invention, there is also provided a method for treating heavy metal contaminated wastewater, the method comprising adding the magnetic biochar prepared as described above to the heavy metal-containing wastewater; the adding amount of the magnetic biochar is 0.5-4 g/L.
The magnetic biochar prepared according to the embodiment of the invention has at least the following beneficial effects: the agricultural and forestry waste is magnetized, the particle size fraction of the adsorbent is reduced through high-temperature pyrolysis and a ball milling process, and the prepared magnetic biochar is subjected to high-temperature pyrolysis and then reduced through the ball milling process to obtain the strengthened magnetic biochar; the scheme of the invention has the advantages of simple preparation process, low energy consumption and high added value of products, and the adoption of ball milling can obviously improve the adsorption performance of the magnetic biochar and effectively adsorb and remove antibiotics in wastewater.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an SEM image of magnetic biochar and ball-milled magnetic biochar according to an embodiment of the invention;
FIG. 2 is an XRD pattern of magnetic biochar and ball-milled magnetic biochar according to an embodiment of the present invention;
FIG. 3 is a VSM diagram of magnetic biochar and ball-milled magnetic biochar according to an embodiment of the invention;
FIG. 4 is a kinetic diagram of the adsorption removal of fluconazole by magnetic biochar and ball-milled magnetic biochar in the embodiment of the invention;
FIG. 5 is a temperature contour diagram of adsorption removal of fluconazole by magnetic biochar and ball-milled magnetic biochar in an embodiment of the present invention;
FIG. 6 is a diagram comparing the ability of magnetic biochar prepared from different types of agricultural and forestry waste and the ability of ball-milling magnetic biochar to adsorb and remove fluconazole according to an embodiment of the present invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
Examples
A method for preparing magnetic biochar by using agricultural and forestry waste comprises the following specific steps:
(1) washing the waste rice hulls with tap water, naturally airing, air drying, crushing, screening to 60-100 meshes, and storing in a dryer for later use;
(2) adding 10g of rice hulls obtained in the step (1) into a 500mL beaker of 50% nitric acid 30mL at 20-30 ℃, then carrying out immersion treatment for 6h, removing impurities in the rice hulls, and then washing with water to be neutral;
(3) centrifugally separating the treated rice hulls, respectively measuring 100mL of water, adding 6g of ferrous sulfate heptahydrate, stirring for 12 hours, and centrifugally separating to obtain a mixture;
(4) drying the centrifuged mixture at 80 ℃ for 12h by a drying oven;
(5) heating the dried mixture at the heating rate of 20 ℃/min to 600 ℃ in the nitrogen atmosphere for carbonization for 1.5 hours, cooling, taking out the magnetic biochar, grinding and sieving by a 100-mesh sieve to obtain the magnetic biochar without ball milling;
(6) weighing 1g of magnetic biochar, and mixing the magnetic biochar with ball grinding beads in a mass ratio of 1: ball milling is carried out for 12 hours at the rotating speed of 100 rpm/min and 400rpm/min, and the magnetic biochar after ball milling is obtained.
Comparative example
The component sources and the preparation method of the magnetic biochar are the same as the embodiment, and the difference is that the ball milling strengthening operation is not carried out, and the specific steps are as follows:
(1) washing waste rice hulls (which are completely the same as the embodiment) with tap water, naturally airing, drying, crushing, screening to 60-100 meshes, and storing in a dryer for later use;
(2) adding 10g of rice hulls obtained in the step (1) into a 500mL beaker of 50% nitric acid 30mL at 20-30 ℃, then carrying out immersion treatment for 6h, removing impurities in the rice hulls, and then washing with water to be neutral;
(3) centrifugally separating the treated rice hulls, respectively measuring 100mL of water, adding 6g of ferrous sulfate heptahydrate, stirring for 12 hours, and centrifugally separating to obtain a mixture;
(4) drying the centrifuged mixture at 80 ℃ for 12h by a drying oven;
(5) and (3) heating the dried mixture at the heating rate of 20 ℃/min in the nitrogen atmosphere, carbonizing at 600 ℃ for 1.5h, cooling, taking out the magnetic biochar, grinding and sieving by a 100-mesh sieve to obtain the magnetic biochar without ball milling.
First, physical characterization
And (4) performing characterization on the magnetic biochar without ball milling and the magnetic biochar with ball milling by using SEM, XRD, VSM and the like. SEM results of the magnetic biochar without ball milling prepared by the comparative example under different magnifications are shown as A and B in figure 1; SEM results of the ball-milled magnetic biochar prepared in the example under different magnifications are shown in C and D in figure 1, and it can be seen from the figure that the magnetic biochar without ball milling has abundant pore structures, a large number of spherical iron compound particles are distributed on the surface, the pore structures of the ball-milled magnetic biochar collapse, and the pore structures disappear. FIG. 2 is an XRD pattern of magnetic biochar and ball-milled magnetic biochar from which it can be seen that for untreated magnetic biochar there is a broad diffraction peak at 20-30 degrees 2 θ, these peaks are generally considered to be attributable to silica and amorphous iron oxide; the weak diffraction peak appearing at 44.3 ° matches the (110) interface corresponding to zero-valent iron (PDF No. 85-1410); the matched absorption peaks of (220), (100) and (440) appeared, which are consistent with those of ferroferric oxide (PDF NO. 74-0748). After ball milling, diffraction peaks of the magnetic biochar at 20-30 degrees still exist, but diffraction peaks belonging to the crystal face of ferroferric oxide (100) and the crystal face of zero-valent iron (110) are obviously enhanced. Through comparison analysis, the phase composition of the magnetic biochar before and after ball milling is not changed, and the magnetic biochar consists of silicon dioxide, ferroferric oxide and zero-valent iron; it is worth noting that ferroferric oxide and zero-valent iron in the magnetic biochar without being ball-milled are probably mainly in amorphous states, and the magnetic biochar ferroferric oxide and zero-valent iron after ball milling are better in crystal form, which indicates that the ball milling process is beneficial to the crystal form reconstruction of the ferroferric oxide and the zero-valent iron, so that the diffraction peak is obviously enhanced. Fig. 3 is a VSM diagram of magnetic biochar and ball-milled magnetic biochar, and it can be seen from the plot that the saturation magnetic susceptibility curve results of the magnetic biochar before and after ball milling indicate that the saturation magnetic susceptibility of the magnetic biochar after ball milling is 55.15emu/g, which is 2.38 times that of the magnetic biochar without ball milling, which may be caused by the improvement of crystallinity of iron and iron oxide particles thereof in the magnetic biochar due to ball milling, so that the magnetic domains of the crystal structure are arranged in order.
Second, dynamic fitting
The dynamics of removing fluconazole by magnetic charcoal adsorption comprises the following specific steps:
(1) adding 100mL of fluconazole solution with the initial concentration of 20mg/L into a conical flask;
(2) respectively adding a certain amount of magnetic biochar (the adding amount is 1g/L) into the conical flask, and placing the conical flasks in a full-temperature shaking incubator (200r/min, 30 +/-0.5 ℃) for shaking;
(3) samples were taken at pre-designed time intervals using a sacrificial test method and after passage through a 0.22 μm membrane, the fluconazole concentration was determined by HPLC. Wherein, the calculation formula of the removal rate of the conazole is shown in formula 1):
note: 1) in the formula, C0-initial mass concentration of fluconazole, mg/L; ceThe mass concentration of fluconazole at reaction equilibrium, mg/L.
The equilibrium adsorption amount calculation formula is shown in formula 2):
note: 2) in the formula, qe-the amount of adsorbent per unit mass in adsorption equilibrium, mg/g; c0And Ce-the initial mass concentration of fluconazole in solution and the mass concentration at adsorption equilibrium, mg/L; v-volume of solution, L; w is the dosage of the magnetic biochar, g.
In addition, the obtained data were fitted with a quasi-first order kinetic equation, a quasi-second order kinetic equation, and an Elovich equation, respectively. The adsorption kinetics equations are respectively:
quasi first order kinetic equation:
quasi-second order kinetic equation:
elovich equation:
qt＝α+βlnt 5)。
in the formula: q. q.seThe adsorption capacity in unit mass of the adsorbent in adsorption equilibrium is mg/L; q. q.stThe adsorption capacity in t time is mg/L; k is a radical of1、k2For the adsorption rate constants of the respective kinetic equations, α is the initial adsorption rate and β represents the desorption coefficient.
The results of kinetic fitting of fluconazole adsorbed by different magnetic biochar are shown in fig. 4. As can be seen from fig. 4 and table 1, different magnetic biochar have certain adsorption capacity to fluconazole, and reach equilibrium after 6h of reaction, wherein the equilibrium adsorption amount (Q) of ball-milling biochar to fluconazolee) 13.4mg/g, which is about 3 times that before ball milling. Further, as can be seen from the results of pseudo first-order kinetics, second-order kinetics and Elovich equation fitting, the fitting correlation of the untreated material to the fluconazole is greater than 0.92, while the pseudo first-order kinetics fitting condition of the ball-milled biochar is poor, and the Elovich equation fitting is optimal (up to 99%), which indicates that the adsorption mode of the material before and after ball milling is changed, and that the material may be mainly chemisorbed after ball milling. Two important parameters of the adsorption balance and the adsorption rate constant are integrated, which shows that the performance of the ball-milled magnetic biochar for adsorbing fluconazole is far superior to that of the magnetic biochar without ball milling.
TABLE 1 results of kinetics fitting of non-ball milled magnetic biochar and ball milled magnetic biochar adsorption
Three, isothermal curve fitting
An isotherm experiment for removing fluconazole by magnetic charcoal adsorption comprises the following steps: the adding amount of the magnetic biochar and the ball-milling magnetic material-saving carbon is respectively 1.5g/L, the concentration gradient of the fluconazole solution is 5, 10, 15, 20, 25 and 30mg/L in sequence, the mixture is placed in a full-temperature oscillator (250r/min, 20 +/-0.5 ℃, 30 +/-0.5 ℃, 40 +/-0.5 ℃) for oscillation for 6 hours, after sampling, the sample is filtered by a 0.22 membrane, and the concentration of the fluconazole is measured after the sample is diluted by a certain multiple. At the same time, the experimental data were fitted with Langmuir and Freundlich isothermal adsorption equations. The isothermal adsorption equations are respectively:
langmuir isothermal adsorption equation:
freundlich isothermal adsorption equation:
in the above formula, qeThe adsorption capacity in unit mass of the adsorbent in adsorption equilibrium is mg/g; q. q.smMg/g as maximum adsorption; ceConcentration of fluconazole at equilibrium, mg/L; kL、KFAnd n are both constants.
TABLE 2 results of isothermal curve fitting of non-ball milled magnetic biochar and ball milled magnetic biochar adsorption
The isothermal adsorption curve (T ═ 20, 30, 40 ℃) data of the two materials are fitted through the Langmuir equation and the Freundlich equation, as shown in fig. 5 and table 2, it can be seen from the graph that the adsorption amount of the fluconazole of different materials is continuously increased and gradually approaches to the saturation state along with the continuous increase of the equilibrium concentration of the fluconazole in the mixed system, and the adsorption equilibrium is reached. For the magnetic biochar without ball milling, the correlation coefficient of the Freundlich model is smaller than that of the Langmuir model, which shows that the process of adsorbing fluconazole by the magnetic biochar is mainly single-layer physical adsorption, and the maximum adsorption quantity is gradually increased along with the temperature rise. In contrast, the adsorption of fluconazole to the surface of ball-milled magnetic biochar was more consistent with the Freundlich model representing non-uniform surface adsorption, probably because the ball milling altered the particle size and surface structure of the magnetic biochar. In addition, 1/n is generally considered to be related to the strength of adsorption, and when it is between 0.1 and 0.5, it means that the adsorption is strong. For the ball-milled magnetic biochar, the 1/n value is reduced along with the increase of the temperature, but the value is kept between 0.3 and 0.4, which indicates that the ball-milled magnetic biochar has stronger adsorption effect on fluconazole.
Influence of biochar prepared from different biomass raw materials on adsorption removal of fluconazole
The adsorption result of the biochar prepared under the same conditions on fluconazole is shown in fig. 6, and it can be seen from the figure that different biomasses really have influence on the magnetic biochar to adsorb fluconazole, wherein the rice hull magnetic biomass adsorption performance is optimal, and the straw magnetic biochar adsorption capacity is lowest. However, no matter what kind of biomass magnetic biochar, the adsorption performance is obviously improved after ball milling, and the improvement range is 3-11 times of that before ball milling. The results prove that the ball milling synergistic effect is generally applicable to different magnetic biochar.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (10)
1. A preparation method of magnetic biochar is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, removing impurities in the agricultural and forestry waste through acid treatment of the agricultural and forestry waste, and washing the agricultural and forestry waste to be neutral;
s2, adding the agricultural and forestry waste obtained in the step S1 into a solution containing an iron element to obtain a mixture;
s3, drying and calcining the mixture obtained in the step S2, and performing ball milling reinforcement to obtain the magnetic biochar.
2. The method for preparing magnetic biochar as claimed in claim 1, wherein: the ball milling strengthening in the step S3 specifically comprises the following steps: and mixing the magnetic biochar with ball milling beads, and carrying out ball milling.
3. The method for preparing magnetic biochar as claimed in claim 1, wherein: the mass ratio of the magnetic biochar to the ball grinding beads in the step S3 is 1: 50 to 200.
4. The method for preparing magnetic biochar as claimed in claim 1, wherein: the agricultural and forestry waste comprises one or more of the following: rice hull, peanut shell, wheat straw, wood dust and corncob.
5. The magnetic biochar of claim 1, wherein: the preparation raw material of the solution containing the iron element comprises one or more of the following components: ferrous sulfate, ferrous chloride, ferric sulfate and ferric nitrate.
6. A magnetic biochar prepared by the method of any one of claims 1 to 5.
7. Use of magnetic biochar as claimed in claim 6, wherein: the application is the application of the magnetic biochar in repairing antibiotic polluted wastewater.
8. Use of magnetic biochar as claimed in claim 6, wherein: the application is the application of the magnetic biochar in repairing heavy metal polluted wastewater.
9. A method for treating wastewater containing antibiotics is characterized in that: the method comprises the following steps: adding the magnetic biochar of claim 6 to the antibiotic-containing wastewater; the concentration of antibiotics in the antibiotic-containing wastewater is 1-50 mg/L, and the adding amount of the magnetic biochar is 0.5-4 g/L.
10. A method for treating wastewater containing heavy metals is characterized by comprising the following steps: the method comprises the following steps: adding the magnetic biochar of claim 6 into the heavy metal-containing wastewater; the adding amount of the magnetic biochar is 0.5-4 g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113546952A (en) * | 2021-06-02 | 2021-10-26 | 华南师范大学 | Magnetic biochar soil remediation agent for soil heavy metal pollution and preparation method and application thereof |
| CN113563908A (en) * | 2021-07-02 | 2021-10-29 | 师大(清远)环境修复科技有限公司 | Magnetic biochar and preparation method and application thereof |
| CN114345299A (en) * | 2022-03-21 | 2022-04-15 | 农业农村部环境保护科研监测所 | Iron-carbon composite material for synchronously adsorbing cadmium and terramycin in water and preparation method thereof |
| CN114477683A (en) * | 2022-01-25 | 2022-05-13 | 安徽工程大学 | Pigment sludge treatment method |
| CN116393090A (en) * | 2023-03-08 | 2023-07-07 | 桂林理工大学南宁分校 | Magnetic macadamia nut shell biochar adsorption material and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113546952A (en) * | 2021-06-02 | 2021-10-26 | 华南师范大学 | Magnetic biochar soil remediation agent for soil heavy metal pollution and preparation method and application thereof |
| CN113546952B (en) * | 2021-06-02 | 2022-07-01 | 华南师范大学 | Magnetic biochar soil remediation agent for soil heavy metal pollution and application thereof |
| CN113563908A (en) * | 2021-07-02 | 2021-10-29 | 师大(清远)环境修复科技有限公司 | Magnetic biochar and preparation method and application thereof |
| CN114477683A (en) * | 2022-01-25 | 2022-05-13 | 安徽工程大学 | Pigment sludge treatment method |
| CN114477683B (en) * | 2022-01-25 | 2023-08-18 | 安徽工程大学 | Pigment sludge treatment method |
| CN114345299A (en) * | 2022-03-21 | 2022-04-15 | 农业农村部环境保护科研监测所 | Iron-carbon composite material for synchronously adsorbing cadmium and terramycin in water and preparation method thereof |
| CN114345299B (en) * | 2022-03-21 | 2022-05-24 | 农业农村部环境保护科研监测所 | Iron-carbon composite material for synchronously adsorbing cadmium and terramycin in water and preparation method thereof |
| CN116393090A (en) * | 2023-03-08 | 2023-07-07 | 桂林理工大学南宁分校 | Magnetic macadamia nut shell biochar adsorption material and preparation method and application thereof |
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