CN114602457B - Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon - Google Patents

Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon Download PDF

Info

Publication number
CN114602457B
CN114602457B CN202210220431.3A CN202210220431A CN114602457B CN 114602457 B CN114602457 B CN 114602457B CN 202210220431 A CN202210220431 A CN 202210220431A CN 114602457 B CN114602457 B CN 114602457B
Authority
CN
China
Prior art keywords
fungus chaff
magnetic
mbc
carbon
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210220431.3A
Other languages
Chinese (zh)
Other versions
CN114602457A (en
Inventor
郭艾英
秦保平
刘冬梅
蔡爱军
吉志新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei Normal University of Science and Technology
Original Assignee
Hebei Normal University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei Normal University of Science and Technology filed Critical Hebei Normal University of Science and Technology
Priority to CN202210220431.3A priority Critical patent/CN114602457B/en
Publication of CN114602457A publication Critical patent/CN114602457A/en
Application granted granted Critical
Publication of CN114602457B publication Critical patent/CN114602457B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B01J35/33—
    • B01J35/615—
    • B01J35/635—
    • B01J35/647—
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2101/38—Organic compounds containing nitrogen

Abstract

The invention discloses a preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff charcoal, belonging to the technical field of catalysts, and comprising the following steps: (1) preparation of magnetic fungus chaff charcoal: fully grinding and mixing potassium ferrate and fungus chaff powder in a mortar, calcining under the condition of inert gas, and naturally cooling to obtain magnetic fungus chaff carbon; (2) preparation of MgMnLDH-MBC: weighing a metal source, mixing the metal source, the magnetic fungus chaff carbon and the alkali solution, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, centrifuging after the reaction is completed, washing the precipitate with water for 3 times, drying, calcining, and naturally cooling to obtain MgMnLDH-MBC. Meanwhile, the application of the obtained magnetic manganese-magnesium bimetallic fungus chaff carbon in the catalytic degradation of antibiotics in wastewater is disclosed. The preparation method provided by the invention is simple and easy to operate, raw material sources are widely and easily available, the production cost is low, and a new idea is provided for a water purification technology.

Description

Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon.
Background
The ciprofloxacin (CIProfloxacin, CIP) is also called ciprofloxacin, is a third-generation quinolone antibacterial synthetic drug, has particularly outstanding antibacterial activity and bactericidal effect, and has wide application range and large dosage. The ciprofloxacin which is not metabolized finally enters the water body, and forms a potential threat to the living environment and the health of human beings. In recent years, the development of efficient, green, low cost catalytic systems to eliminate water borne pathogens has been one of the research hotspots. Although conventional water disinfection technologies such as chlorination, ozone and ultraviolet rays can effectively remove harmful substances in water and inhibit microbial growth, antibiotics in water environment are difficult to remove by the methods. Thus, the development of safer, more environmentally friendly water disinfection technologies to achieve low cost pathogen inactivation, and the removal of antibiotics remains the main direction of research.
The biochar is a carbon-rich material produced by heating biomass under the anoxic condition, has large specific surface area and more oxygen-containing functional groups, and simultaneously has low cost and easy acquisition of raw materials, and has potential development space in the aspects of energy sources, environment and the like. The fungus chaff is used as an edible fungus culture medium, has huge yield, but has lower utilization rate and is easy to cause environmental pollution. Most of the materials are piled or incinerated in the conventional open air mode except for few materials used as feeds and fertilizers, so that environmental pollution is easily caused. Few fungus chaff is made into biochar as an environmental adsorbent, but at present, research on preparing biochar by utilizing fungus chaff and exerting the adsorption performance of the biochar is relatively few.
Therefore, how to provide a method for preparing biochar for adsorbing and decomposing antibiotics by using fungus chaff is a problem to be solved by the person skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of magnetic magnesium-manganese bimetallic fungus chaff charcoal comprises the following steps:
(1) Preparing magnetic fungus chaff charcoal: fully grinding and mixing potassium ferrate and fungus chaff powder in a mortar for 5-8min, calcining under the condition of inert gas, and naturally cooling to obtain magnetic fungus chaff carbon;
(2) Preparation of MgMnLDH-MBC: weighing a metal source, mixing the metal source, the magnetic fungus chaff charcoal and the alkali solution, stirring for 2 hours at the room temperature at the rotating speed of 120r/min, centrifuging after the reaction is completed, washing the precipitate with water for 3 times, drying, calcining, and naturally cooling to obtain MgMnLDH-MBC.
The beneficial effects are that: the preparation method is simple, the raw materials are convenient to obtain, and the method is convenient to popularize and use.
Preferably, in the step (1), the mass ratio of the potassium permanganate to the fungus chaff powder is 2:5.
The beneficial effects are that: the invention can promote the development of the edible fungus industry by effectively utilizing the fungus chaff. Meanwhile, fe generated during the proportional calcination of the raw materials 3 O 4 Can be completely loaded on the fungus chaff carbon, and effectively reduces secondary pollution of residual potassium permanganate to water.
Preferably, the inert gas in the step (1) is argon, and the flow rate is 0.5L/min;
the calcination temperature is 550-750 ℃ and the calcination time is 3h;
the temperature rising rate before calcination is 10 ℃/min.
The beneficial effects are that: the invention uses argon gas to effectively avoid the risks of high purity gas explosion and the like, and can ensure the sufficient gas in the furnace chamber of the atmosphere furnace under the gas flow so as to fully calcine the material, and simultaneously, the calcination temperature and time can avoid insufficient calcination of the material or excessive calcination of the mushroom bran carbon into CO 2 And H 2 O, in addition, the proper temperature rising rate defined in the invention can avoid damage to instrument elements and generation of other impurities, and can obtain products with good performance.
Preferably, in the step (2), the addition ratio of the metal source, the magnetic fungus chaff charcoal and the alkali solution is 0.075-0.3g:0.025g:25mL.
The beneficial effects are that: the proportion of the raw materials just enables the metal source to be fully loaded on the magnetic fungus chaff charcoal, and excessive or insufficient materials can cause waste or incomplete loading.
Preferably, the metal source is MgCl 2 ·6H 2 O and MnCl 2 ·4H 2 Mixtures of O and said MgCl 2 ·6H 2 O and MnCl 2 ·4H 2 The molar ratio of O is (1-2): 1.
the beneficial effects are that: the ratio of Mg to Mn can influence the PMS activation effect of the composite nano material, and the addition ratio of the Mg to Mn is the optimal combination for exerting a functional synergistic effect in a MgMnLDH-MBC/PMS system.
Preferably, the alkali solution is NaOH and Na 2 CO 3 And the concentration of NaOH is 0.2mol/L, and the Na is 2 CO 3 The concentration was 0.1mol/L.
The beneficial effects are that: the invention uses NaOH and Na 2 CO 3 Adjusting the pH of the solution to 8-10 to facilitate the formation of Mg (OH) 2 And Mn (OH) 2 And precipitating, namely synthesizing the supported bimetallic catalyst by using a homogeneous coprecipitation method, and the operation is simple and easy to implement.
Preferably, in the step (2), the centrifugation speed is 3000-5000r/min, and the centrifugation time is 3-5min;
the drying temperature is 40-80 ℃ and the drying time is 12h.
The beneficial effects are that: the centrifugation rate and time are determined according to the components and the particle size of the sample, and the prepared solid material can be completely separated from the solution in the step (2), so that the method is simple, time-saving and labor-saving, and material loss is avoided; the drying temperature and time can ensure that the material is completely dried and the components are not destroyed, thus laying a foundation for the next operation.
Preferably, the calcination temperature in the step (2) is 300 ℃ and the calcination time is 3 hours;
the temperature rising rate before calcination is 5 ℃/min.
The beneficial effects are that: the setting of the calcination temperature and time in the invention can ensure that the preparation of the product is carried out on the premise of ensuring safety, the obtained magnesium-manganese double-layer metal oxide has larger surface area, good dispersion, exposes active sites and a large number of bases, is easy to combine with magnetic biochar, improves electronic conductivity and thermal stability, and improves the pollutant removal rate; the temperature rising rate is moderate, which is beneficial to keeping the shape of the material, avoiding generating impurities and reducing the service life of the furnace.
The application of the magnetic magnesium-manganese bimetal fungus chaff carbon obtained by the preparation method in the catalytic degradation of antibiotics in wastewater.
Preferably, the method comprises the following steps:
adding the magnetic magnesium-manganese bimetallic fungus chaff carbon and the peroxymonosulfate into the antibiotic wastewater, uniformly mixing and continuously stirring;
the mass ratio of the antibiotic to the magnetic magnesium-manganese bimetallic fungus chaff carbon to the peroxymonosulfate is 1:60:120;
the antibiotic comprises ciprofloxacin;
the stirring speed is 120rpm/min, and the stirring time is 1h.
The beneficial effects are that: the magnetic magnesium-manganese bimetallic fungus chaff carbon can activate Peroxymonosulfate (PMS) to degrade ciprofloxacin in water.
Compared with the prior art, the invention discloses a preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff charcoal, wherein the MgMnLDH-MBC bimetallic type biological charcoal catalyst is synthesized by taking the magnetic fungus chaff charcoal as a carrier and adopting a homogeneous coprecipitation method, and the phase, morphology and specific surface area of the obtained composite nano material are analyzed by adopting an XRD, a high-resolution transmission electron microscope, a field emission scanning electron microscope and the like. Meanwhile, the catalytic performance of the MgMnLDH-MBC composite nano material is evaluated by activating persulfate to degrade ciprofloxacin, and examining the influence of catalyst dosage, persulfate concentration, temperature, pH value and the like on the degradation efficiency and reaction rate of ciprofloxacin. The invention provides a new direction for edible fungus chaff treatment and a new thought for water purification technology.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a drawing showing XRD diffraction patterns of the bran carbons obtained in example 1 and comparative examples 1 to 3 of the present invention;
FIG. 2 is a drawing showing SEM images of the fungus chaff charcoal obtained in example 1 and comparative examples 1-3 of the present invention, wherein FIG. 2 (a) is BC, FIG. 2 (b) is MBC, FIG. 2 (c) is MgMnLDO-MBC, and FIG. 2 (c') is a partially enlarged picture of FIG. 2 (c);
FIG. 3 is a drawing showing TEM image (FIG. 3 (a)) and high-resolution transmission electron microscope image (FIG. 3 (b)) of MgMnLDO-MBC obtained in example 1 of the present invention;
FIG. 4 is a drawing showing N of the fungus chaff charcoal obtained in example 1 and comparative examples 1 to 3 of the present invention 2 Adsorption-desorption isotherms (fig. 4 (a) -4 (c)) and pore size distribution diagrams (fig. 4 (d) -4 (f)), wherein fig. 4 (a), 4 (d) are BC, fig. 4 (b), 4 (e) are MBC, and fig. 4 (c), 4 (f) are MgMnLDO-MBC;
FIG. 5 is a graph showing the degradation efficiency (FIG. 5 (a)) and kinetic analysis (FIG. 5 (b)) of MgMnLDO-MBC on ciprofloxacin prepared in examples 1 and 2-3 of the present invention;
FIG. 6 is a graph showing the degradation efficiency (FIG. 6 (a)) and kinetic analysis (FIG. 6 (b)) of MgMnLDO-MBC on ciprofloxacin prepared in examples 1 and 4-5 of the present invention;
FIG. 7 is a graph showing the degradation efficiency (FIG. 7 (a)) and kinetic analysis (FIG. 7 (b)) of different treatments of the present invention on ciprofloxacin;
FIG. 8 is a graph showing the effect of the reaction parameters of the present invention on ciprofloxacin degradation and reaction kinetics analysis; wherein, FIG. 8 (a) is the reaction parameter used as catalyst, FIG. 8 (b) is the reaction parameter used as PMS, FIG. 8 (c) is the reaction parameter used as initial pH value, and FIG. 8 (d) is the reaction parameter used as reaction temperature; the inset in fig. 8 (a) -8 (d) is an analysis of the kinetics of the reaction under the corresponding reaction conditions;
FIG. 9 is a graph showing the degradation efficiency of MgMnLDO-MBC to ciprofloxacin (FIG. 9 (a)) and the mineralization rate of MgMnLDO-MBC (FIG. 9 (b)) obtained in example 1 of the present invention in 5 cycles.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of magnetic magnesium-manganese bimetallic fungus chaff charcoal comprises the following steps:
(1) Grinding 2g of potassium ferrate and 5g of fungus chaff powder in a mortar for 5-8min until the mixture is fully ground and mixed, then placing the mixture in an atmosphere furnace, setting argon flow to be 0.5L/min, heating to a temperature of 10 ℃/min, heating to 550-750 ℃ for calcining for 3h, naturally cooling, and sealing, drying and storing the obtained magnetic fungus chaff charcoal (MBS);
(2) Weighing Mg: mn molar ratio is 2:1 MgCl 2 ·6H 2 O and MnCl 2 ·4H 2 The O reagent is used as a metal source and 0.15g of the metal source is mixed with 0.025g of magnetic fungus chaff charcoal and 25mL of alkali solution (NaOH concentration is 0.2mol/L; na) 2 CO 3 Concentration: 0.1 mol/L), then stirring at a stirring speed of 120r/min for 2h at room temperature, then centrifuging for 3-5min at a rotating speed of 3000-5000r, washing the precipitate with deionized water for 3 times, and then drying at 40-80 ℃. And then placing the mixture into a muffle furnace, calcining for 3 hours at 300 ℃, heating at a speed of 5 ℃/min, and naturally cooling. The material is MgMnLDH-MBC.
Example 2
The preparation method of the magnetic magnesium-manganese bimetallic fungus chaff carbon is different from the embodiment 1 in that:
metal source Mg in step (2): mn molar ratio is 1:1.
example 3
The preparation method of the magnetic magnesium-manganese bimetallic fungus chaff carbon is different from the embodiment 1 in that:
metal source Mg in step (2): mn molar ratio of 1.5:1.
example 4
The preparation method of the magnetic magnesium-manganese bimetallic fungus chaff carbon is different from the embodiment 1 in that:
the metal source addition in step (2) was 0.075g.
Example 5
The preparation method of the magnetic magnesium-manganese bimetallic fungus chaff carbon is different from the embodiment 1 in that:
the metal source addition amount in the step (2) was 0.3g.
Application example 1
The application of the magnetic magnesium-manganese bimetallic fungus chaff carbon in degrading antibiotics in wastewater comprises the following steps:
30mg of MgMnLDO-MBC magnetic nanocomposite is weighed and placed in a 100mL conical flask, 50mL of ciprofloxacin solution with the concentration of 10mg/L and 50mg of PMS are added, and the mixture is subjected to oscillation reaction for 1h at the rotation speed of a shaking table of 120rpm/min at 25 ℃. After degradation, the MgMnLDO-MBC material is recovered by a magnet adsorption method, washed three times by deionized water, and then dried at 60 ℃ for a cycle test.
Comparative example 1
The preparation method of the magnetic magnesium-manganese bimetallic fungus chaff carbon is different from the embodiment 1 in that:
in the step (1), 5g of fungus chaff is used, and the material obtained by calcining for 3 hours at 550 ℃ is fungus chaff charcoal (BC).
Comparative example 2
The preparation method of the magnetic magnesium-manganese bimetallic fungus chaff carbon is different from the embodiment 1 in that:
in step (1) 2g K 2 FeO 4 Mixing with 5g of fungus chaff powder, and calcining at 550 ℃ for 3 hours to obtain the magnetic fungus chaff charcoal (MBC).
The technical effects are as follows:
1. XRD result analysis
The XRD diffraction pattern of FIG. 1 shows BC,The MBC and MgMnLDH-MBC magnetic nanocomposite material is 10-70 percent ° Crystalline structure and phase composition in the (2 theta) range. The broad diffraction peak with 2θ around 26 ° indicates that BC has an amorphous carbon structure. At the same time find SiO after the fungus chaff is calcined 2 And CaCO (CaCO) 3 (104) Has strong peak average and a large amount of burnt gypsum (CaSO 4 ·0.5H 2 O) and dolomite [ CaMg (CO) 3 ) 2 ]Characteristic peaks. As can be seen from the MBC diffraction pattern, when K is added 2 FeO 4 Later, the intensity of the graphite peaks is reduced, possibly due to the low crystallinity of the graphite carbon or the higher intensity of the iron signal causing the characteristic peaks to be masked. The 2 theta values are at 30.2 °, 35.7 °, 43.4 °, 53.9 °, 57.4 ° and 63.2 ° (d=0.29, 0.25, 0.21, 0.17, 0.16 and 0.15 nm) with sharp diffraction peaks, and Fe 3 O 4 (220), (311), (400), (422), (511) and (440) crystal planes one-to-one (JCPCDS 75-1372). The XRD pattern of MgMnLDO-MBC has no MgMnLDH typical peak (2θ=11.5°, d) 003 =0.77 nm), which may be caused by structural collapse of MgMnLDH during calcination. The new peak at 2θ=18.2° (d=0.48 nm) corresponds to Mg 2 MnO 4 The (101) crystal face (JCPDS 72-1336) shows that the bimetallic component of the MgMnLDO-MBC material is Mg 2 MnO 4 。
2. SEM and TEM result analysis
The invention further researches the morphology, structure and characteristics of MgMnLDO-MBC magnetic nanocomposite, wherein, FIG. 2 is SEM image of BC (a), MBC (b) and MgMnLDO-MBC (c), and (c') is a partial enlarged image of FIG. 2 (c). As can be seen from fig. 2 (a), the fungus chaff charcoal is a sheet layer, has a rough surface and is porous, a large number of pores and scraps exist, and the structure increases the specific surface area of the material and provides a plurality of potential adsorption sites. As can be seen from FIG. 2 (b), the MBC nanocomposite has a plurality of micron-sized spheres of different particle sizes on top of the lamellar structure, indicating Fe 3 O 4 The nano particles are uniformly distributed on the surface of the biochar or embedded in the carbon layer, so that agglomeration is avoided. However, after MgMn double-layer metal oxide modification, the MBC lamellar structure surface becomes coarser, and as can be seen from FIG. 2c', the nano lamellar surface takes on a non-uniform flower-like and lamellar structure, which is caused by structural collapse of MgMnLDH-MBC during calcination(FIG. 2 (c)). FIG. 3 (a) is a TEM image of MgMnLDO-MBC and (b) is a High Resolution Transmission Electron Microscope (HRTEM) image of MgMnLDO-MBC material. FIG. 3 (a) TEM image further shows that MgMnLDH-MBC material has a plate-like structure, and the lattice spacing in FIG. 3 (b) is 0.25nm, and 0.48nm corresponds to Fe respectively 3 O 4 (311) crystal face and Mg 2 MnO 4 This is consistent with XRD results. Further proved that MgMnLDO-MBC is a magnetic material (Fe 3 O 4 ) And by Mg and Mn bimetal modification.
3. BET result analysis
FIGS. 4 (a) and 4 (d) are BC, FIGS. 4 (b) and 4 (e) are MBC and FIGS. 4 (c) and 4 (f) are N of MgMnLDO-MBC 2 Adsorption-desorption isotherms and BJH pore size distribution plots. As can be seen from FIGS. 4 (a) -4 (c), according to the International Union of Pure and Applied Chemistry (IUPAC) classification, N of three materials 2 Adsorption-desorption isotherms all belong to the IV curve of the H3-type hysteresis loop. As can be seen from the pore size distribution in FIG. 4 (e), the MBC composite material has a pore size peak value of about 2nm and is mainly composed of micropores. However, the pore size peak distribution of BC and MgMnLDO-MBC composites is 2-40nm (FIGS. 4 (d) and (f)), which is classified as mesoporous. BC. BET specific surface areas, pore volumes and average pore diameters of MBC and MgMnLDO-MBC are shown in Table 1. As is clear from Table 1, the specific surface area of MgMnLDO-MBC is 129.7m 2 /g, higher than BC (38.1 m 2 /g) and MBC (39.3 m 2 G) which is related to the collapse of the nanoplatelets into a heterogeneous flower-like or plate-like structure upon calcination after modification with Mg and Mn bimetal. The larger specific surface area indicates that MgMnLDO-MBC can provide more catalytic active sites. Compared with BC and MBC, mgMnLDO-MBC has larger pore volume and pore diameter, and is beneficial to the diffusion of antibiotics (such as ciprofloxacin) on the surface of the material.
TABLE 1
4. Analysis of biochar activated PMS degraded ciprofloxacin
The ratio of the concentration of the ciprofloxacin solution at the reaction time t to the initial concentration is taken as the degradation efficiency of the ciprofloxacin, the correlation dynamics analysis is calculated by an ln (C/C0) =kt formula, C0 represents the initial concentration of the ciprofloxacin, and C is the concentration of the ciprofloxacin at the reaction time t. k is the apparent rate constant.
(1) MgMnLDO-MBC degradation ciprofloxacin prepared by different Mg/Mn molar ratios
The research and examination of MgMnLDO-MBC prepared by different Mg/Mn molar ratios shows the degradation efficiency and kinetic analysis of ciprofloxacin, and the results are shown in FIG. 5.
As can be seen from FIG. 5 (a), mgMnLDO-MBC prepared by different Mg/Mn molar ratios has different efficiencies on ciprofloxacin, and the degradation efficiency of activated PMS on ciprofloxacin is highest when the molar ratio is 2. As is clear from FIG. 5 (b), when the Mg/Mn molar ratio is 2, the apparent rate constant after PMS activation is 0.12min -1 300 times of the single PMS, 10 times and 1.9 times of MgMnLDO-MBC activated PMS prepared at the molar ratio of 1 and 1.5 respectively.
(2) MgMnLDO-MBC degradation ciprofloxacin prepared by MgMnLDO and MBC in different mass ratios
The research examined the degradation efficiency of MgMnLDO-MBC prepared from MgMnLDO and MBC with different mass ratios on ciprofloxacin (FIG. 6 (a)) and kinetic analysis (FIG. 6 (b)). As can be seen from FIG. 6 (a), the mass ratio of MgMnLDO to MBC is different, and the efficiency of activating PMS to degrade ciprofloxacin is also different. When the mass ratio of MgMnLDO to MBC is 6:1, the degradation efficiency is highest, and the degradation efficiency of degrading ciprofloxacin is reduced when the degradation efficiency is higher or lower than the mass ratio. As can be seen from FIG. 6 (b), the apparent rate constants after activating PMS were 12 and 1.4 times that of MgMnLDO-MBC activated PMS prepared at mass ratios of 3:1 and 12:1, respectively, at mass ratios of 6:1. Thus, the materials used after this study were Mg: the MgMnLDO/MBC composite material prepared by the bimetallic and magnetic fungus chaff carbon mass ratio of 6:1 is tested with Mn molar ratio of 2.
(3) Activation of PMS by different biochar materials to degrade ciprofloxacin
The results and kinetic analysis of the degradation efficiency of different biochar materials and PMS on ciprofloxacin are shown in FIG. 7 (reaction conditions: [ PMS] 0 =1.2 g/L, [ catalyst ]] 0 =0.6 g/L, [ ciprofloxacin ]] 0 =10mg/L, t=25℃). As can be seen from FIG. 7 (a), the concentration of ciprofloxacin after 60min was found in the presence of PMS alone or in the presence of BC and MgMnLDO-MBC aloneThe ratio was close to 1, indicating that ciprofloxacin was hardly degraded. When MBC material alone was present, the concentration of ciprofloxacin was slightly reduced, indicating that small amounts of ciprofloxacin were degraded. When the material and PMS exist simultaneously, the concentration of ciprofloxacin is obviously reduced, particularly MgMnLDO-MBC material, after PMS is activated, the concentration ratio of ciprofloxacin is close to 0.1 after 60min, which indicates that over 90 percent of ciprofloxacin is degraded and the effect is best. As can be seen from FIG. 7 (b), the apparent rate constants after MgMnLDO-MBC activation of PMS were 6.4 and 2.4 times that of BC and MBC activation of PMS, respectively.
(5) Influence of different reaction conditions on degradation rate of ciprofloxacin
The effect of different catalyst amounts, PMS amounts, reaction temperatures and pH values on ciprofloxacin removal was examined using MgMnLDO-MBC as a material, and the results are shown in FIG. 8 (reaction conditions: [ PMS ]] 0 =1.2 g/L, [ catalyst ]] 0 =0.6 g/L, [ ciprofloxacin ]] 0 ＝10mg/L,T＝25℃)。
As can be seen from FIG. 8 (a), when the PMS concentration was 1.2g/L, the reaction temperature was 25℃and the pH of the solution was 6.6, mgMnLDO-MBC nanocomposite materials of different concentrations were added, and the degradation rate of ciprofloxacin was gradually increased as the reaction time was prolonged. When the concentration of MgMnLDO-MBC is 0.6g/L, the degradation rate of ciprofloxacin is 90.4 percent at maximum. As can be seen from the degradation kinetics of FIG. 8 (a), the pseudo first order kinetics model of the catalyst usage versus ciprofloxacin degradation compliance function, the apparent rate constants corresponding to material usage of 0.2, 0.4, 0.6 and 0.8g/L are respectively 0.02min -1 、0.05min -1 、0.12min -1 And 0.06min -1 The result shows that k tends to be increased and then decreased with increasing catalyst dosage, and the reaction rate constant is maximum when the concentration is 0.6 g/L.
As can be seen from FIG. 8 (b), when MgMnLDO-MBC concentration was 0.6g/L, the reaction temperature was 25℃and the pH of the solution was 6.6, the ciprofloxacin degradation efficiency tended to increase and then decrease with increasing PMS concentration. Wherein, the degradation efficiency of ciprofloxacin is highest at the PMS concentration of 1.4g/L, but the degradation efficiency is not greatly different from that at the PMS concentration of 1.2g/L. Continuing to increase PMS concentration to 1.8g/LPMS, ciprofloxacin degradation efficiency and rate constant decreased due to the following reasons:
(1) When the PMS addition amount is large, the active site on the surface of the MgMnLDO-MBC nanocomposite is saturated, free radical generation is limited, and the degradation efficiency of ciprofloxacin is reduced.
(2) Some of the unactivated PMS in solution will be associated with SO 4 - And OH, resulting in the formation of less active SO 5 - And HSO 4 - (see equations (1-3)) thereby reducing the degradation rate of ciprofloxacin.
As can be seen from the inset of FIG. 8 (b), the PMS concentration was 1.2 and the constant k was 0.12min at 1.4g/L, respectively -1 And 0.13min -1 The difference is not large, SO in the reaction solution is increased in consideration of the increase of the PMS dosage 4 - Concentration, therefore, the subsequent test concentration was chosen to be 1.2g/L.
·OH+HSO 5 — →SO 5 - ·+H 2 O (1)
SO 4 - ·+HSO 5 — →SO 5 - ·+HSO 4 - (2)
SO 4 - ·+·OH→HSO 4 — +1/2O 2 (3)
As can be seen from FIG. 8 (c), mgMnLDO-MBC concentration is 0.6g/L, PMS concentration is 1.2g/L, reaction temperature is 25 ℃, and pH of the catalytic system affects ciprofloxacin degradation. More than 90% of ciprofloxacin is degraded at a pH of 4.0-6.0, but the degradation rate of ciprofloxacin is significantly reduced (less than 75%) at a pH of 8.0-10.0, indicating that acidic conditions favor degradation of ciprofloxacin.
As can be seen from FIG. 8 (d), when MgMnLDO-MBC concentration was 0.6g/L, PMS concentration was 1.2g/L, and pH of the solution was 6.6, the elevated temperature had an accelerating effect on the degradation rate of ciprofloxacin. The k values at 15 ℃, 25 ℃, 35 ℃ and 45 ℃ are respectively 0.027min -1 、0.12min -1 、0.13min -1 And 0.13min -1 The initial temperature is 25-45 ℃, the effect on the degradation efficiency of ciprofloxacin is small, but the degradation rate of ciprofloxacin is reduced when the temperature is lower than 25 ℃, and the reaction rate constant is reduced.
As a result, mgMnLDO-MBC can effectively degrade ciprofloxacin by activating PMS in a wide temperature range (25-45 ℃) and pH value range (4-6.6).
5. Stability and mineralization rate analysis of MgMnLDO-MBC (reaction conditions: [ PMS ]] 0 =1.2 g/L, [ catalyst ]] 0 =0.6 g/L, [ ciprofloxacin ]] 0 ＝10mg/L，T＝25℃)。
In the catalytic degradation experiment of ciprofloxacin, a MgMnLDO-MBC nanocomposite cycle test was performed, and the result is shown in FIG. 9 (a).
In the first cycle, the MgMnLDO-MBC catalytic degradation rate is 90.5%, and after 5 cycles, the ciprofloxacin degradation rate can still reach 50%, which indicates the relative stability of the material. The resulting decrease in catalytic efficiency of the material is associated with the loss of some material during the recovery purge and the spillage of Mg and Mn ions during the catalysis. To better illustrate the MgMnLDO-MBC catalytic performance, the Total Organic Carbon (TOC) removal efficiency of the composite nanomaterial on ciprofloxacin was studied, and the result is shown in FIG. 9 (b). As can be seen from FIG. 9 (b), mgMnLDO-MBC has a mineralization rate of 39.8% in 60min, indicating that MgMnLDO-MBC has sufficient stability in degrading ciprofloxacin.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. The preparation method of the magnetic magnesium-manganese bimetallic fungus chaff charcoal is characterized by comprising the following steps of:
(1) Preparing magnetic fungus chaff charcoal: grinding potassium ferrate and fungus chaff powder in a mortar for 5-8min, calcining under the condition of inert gas, and naturally cooling to obtain magnetic fungus chaff carbon;
(2) Preparation of MgMnLDH-MBC: weighing a metal source, mixing with magnetic fungus chaff charcoal and alkali solution, stirring for 2 hours at a rotating speed of 120r/min at room temperature, centrifuging after the reaction is completed, washing the precipitate with water for 3 times, drying, calcining, and naturally cooling to obtain MgMnLDH-MBC;
wherein, the addition ratio of the metal source, the magnetic fungus chaff charcoal and the alkali solution in the step (2) is 0.075-0.3g:0.025g:25mL of the metal source is MgCl 2 ·6H 2 O and MnCl 2 ·4H 2 Mixtures of O and said MgCl 2 ·6H 2 O and MnCl 2 ·4H 2 The molar ratio of O is (1-2): 1, a step of;
the application of the magnetic manganese-magnesium bimetallic fungus chaff carbon in catalytic degradation of antibiotics in wastewater.
2. The method for preparing the magnetic magnesium-manganese bimetallic fungus chaff charcoal according to claim 1, wherein the mass ratio of potassium ferrate to fungus chaff powder in the step (1) is 2:5.
3. The method for preparing the magnetic magnesium manganese bimetallic mushroom bran carbon according to claim 1, wherein the inert gas in the step (1) is argon, and the flow is 0.5L/min; the calcination temperature is 550-750 ℃ and the calcination time is 3h;
the temperature rising rate before calcination is 10 ℃/min.
4. The method for preparing the magnetic magnesium manganese bimetallic mushroom bran carbon as claimed in claim 1, wherein the alkali solution comprises NaOH and Na 2 CO 3 And the concentration of NaOH is 0.21mol/L, and the Na is 2 CO 3 The concentration was 0.1mol/L.
5. The preparation method of the magnetic magnesium manganese bimetallic fungus chaff charcoal according to claim 1, which is characterized in that the centrifugation rate in the step (2) is 3000-5000r/min, and the centrifugation time is 3-5min;
the drying temperature is 40-80 ℃ and the drying time is 12h.
6. The method for preparing the magnetic magnesium manganese bimetallic fungus chaff carbon according to claim 1, which is characterized in that the calcining temperature in the step (2) is 300 ℃ and the calcining time is 3 hours;
the temperature rising rate before calcination is 5 ℃/min.
7. The method for preparing the magnetic magnesium-manganese bimetallic mushroom bran carbon as claimed in claim 1, wherein the application comprises the following steps: adding the magnetic magnesium-manganese bimetallic fungus chaff carbon and the peroxymonosulfate into the antibiotic wastewater, uniformly mixing and continuously stirring;
the mass ratio of the antibiotic to the magnetic magnesium-manganese bimetallic fungus chaff carbon to the peroxymonosulfate is 1:60:120;
the antibiotic comprises ciprofloxacin;
the stirring speed was 120rpm and the stirring time was 1h.
CN202210220431.3A 2022-03-08 2022-03-08 Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon Active CN114602457B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210220431.3A CN114602457B (en) 2022-03-08 2022-03-08 Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210220431.3A CN114602457B (en) 2022-03-08 2022-03-08 Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon

Publications (2)

Publication Number Publication Date
CN114602457A CN114602457A (en) 2022-06-10
CN114602457B true CN114602457B (en) 2024-02-09

Family

ID=81861034

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210220431.3A Active CN114602457B (en) 2022-03-08 2022-03-08 Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon

Country Status (1)

Country Link
CN (1) CN114602457B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109513424A (en) * 2018-12-17 2019-03-26 中南大学 A kind of carbon/hydrotalcite compound adsorbent and its preparation, application and regeneration method in heavy metal adsorption
CN110665512A (en) * 2019-09-27 2020-01-10 浙江大学 Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof
CN111359578A (en) * 2019-11-30 2020-07-03 华南理工大学 Layered magnesium-manganese composite material for copper ion adsorption and preparation method and application thereof
KR20210000079A (en) * 2019-06-24 2021-01-04 한국과학기술연구원 Composite comprising biochar based rice husk and layered double oxides and method for fabricating the same
CN113457624A (en) * 2021-06-18 2021-10-01 广西大学 Modified mushroom dreg biochar and preparation method thereof
CN113559858A (en) * 2021-08-09 2021-10-29 青岛农业大学 Preparation method and application of biochar-based composite material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109513424A (en) * 2018-12-17 2019-03-26 中南大学 A kind of carbon/hydrotalcite compound adsorbent and its preparation, application and regeneration method in heavy metal adsorption
KR20210000079A (en) * 2019-06-24 2021-01-04 한국과학기술연구원 Composite comprising biochar based rice husk and layered double oxides and method for fabricating the same
CN110665512A (en) * 2019-09-27 2020-01-10 浙江大学 Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof
CN111359578A (en) * 2019-11-30 2020-07-03 华南理工大学 Layered magnesium-manganese composite material for copper ion adsorption and preparation method and application thereof
CN113457624A (en) * 2021-06-18 2021-10-01 广西大学 Modified mushroom dreg biochar and preparation method thereof
CN113559858A (en) * 2021-08-09 2021-10-29 青岛农业大学 Preparation method and application of biochar-based composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Multifunctional magnetic MgMn-oxide composite for efficient purification of Cd2+ and paracetamol pollution: Synergetic effect and stability;Meiqing Chen等;《Journal of Hazardous Materials》;第388卷;122078 *

Also Published As

Publication number Publication date
CN114602457A (en) 2022-06-10

Similar Documents

Publication Publication Date Title
Cui et al. Synthesis of a novel magnetic Caragana korshinskii biochar/Mg–Al layered double hydroxide composite and its strong adsorption of phosphate in aqueous solutions
CN108483444B (en) Preparation method of alpha-FeOOH nanorod-loaded porous biochar composite material
Zhang et al. Citrate modified ferrihydrite microstructures: facile synthesis, strong adsorption and excellent Fenton-like catalytic properties
KR20120021993A (en) Method for preparing mesoporous carbon comprising iron oxide nanoparticles
CN114425340B (en) Preparation of biochar modified cobalt-iron bimetallic composite catalyst and application of biochar modified cobalt-iron bimetallic composite catalyst in catalytic degradation of tetracycline
Zha et al. Cadmium removal in waste water by nanostructured TiO 2 particles
CN107837816B (en) Fe2O3/g-C3N4Composite system, preparation method and application
Gao et al. High-performance magnetic carbon materials in dye removal from aqueous solutions
CN109110742B (en) Mesoporous carbon prepared by manganese compound and preparation method thereof
CN113860911A (en) High-entropy ferrite porous ceramic material and preparation method and application thereof
JP4955952B2 (en) Production method of activated carbon
CN108097210A (en) A kind of preparation method of nano-metal-oxide and porous active carbon composite material
Cai et al. Template-free synthesis of hierarchical γ-Al 2 O 3 nanostructures and their adsorption affinity toward phenol and CO 2
Yang et al. High-temperature CO2 adsorption by one-step fabricated Nd-doped Li4SiO4 pellets
CN115845791B (en) Preparation method and application of Ca/La-based perovskite adsorption material
CN111547720A (en) Method for removing water antibiotics by using heterogeneous atom doped porous biomass carbon material
Chen et al. rGO-stabilized MnO/N-doped carbon nanofibers for efficient removal of Pb (II) ion and catalytic degradation of methylene blue
Cendrowski et al. Graphene nanoflakes functionalized with cobalt/cobalt oxides formation during cobalt organic framework carbonization
Zheng et al. Hierarchical mesoporous carbon nanosheets for efficient organic pollutants removal
JP5551144B2 (en) Activated carbon and its manufacturing method
TWI589351B (en) Carbon adsorbent, the manufacturing method thereof, and the using method thereof
CN114602457B (en) Preparation method and application of magnetic magnesium-manganese bimetallic fungus chaff carbon
Ding et al. Biomass porous carbon as the active site to enhance photodegradation of oxytetracycline on mesoporous gC 3 N 4
Zhang et al. Hierarchical flower-like Bi 2 WO 6 hollow microspheres: facile synthesis and excellent catalytic performance
Wang et al. Shape evolution of Cu-doped Mn3O4 spinel microcrystals: influence of copper content

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant