CN114749150A - Biochar loaded manganese oxide composite material and preparation method and application thereof - Google Patents
Biochar loaded manganese oxide composite material and preparation method and application thereof Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 211
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The invention discloses a biochar-loaded manganese oxide composite material as well as a preparation method and application thereof, wherein the biochar-loaded manganese oxide composite material comprises biochar formed by biomass pyrolysis and manganese oxide loaded on the biochar, and is prepared by the following method: step 1, preparing a manganese precursor solution: dissolving potassium permanganate in deionized water, and adjusting the pH value of the solution by using dilute sulfuric acid; step 2, dipping the biochar in the manganese precursor solution, heating in a water bath and stirring to obtain a sample; and 3, centrifuging the sample obtained in the step 2, taking a lower-layer solid sample, cleaning and drying to obtain the biochar loaded manganese oxide composite material. The biochar loaded manganese oxide composite material disclosed by the invention adopts common soil conditioner biochar as a base material, is cheap and easy to obtain, is environment-friendly, has multiple functions, high reaction or adsorption selectivity and good environmental compatibility, and has lower cost.
Description
Technical Field
The invention relates to the technical field of environmental remediation, in particular to a biochar-loaded manganese oxide composite material as well as a preparation method and application thereof.
Background
The sustainable development of agriculture is the foundation for guaranteeing the food safety in China. At present, the problem of severe soil pollution exists in agricultural land in China, and is one of the main bottlenecks restricting sustainable development of agriculture in China. According to the national soil pollution status survey bulletin issued in 2014: cadmium in heavy metals is more severely polluted. In addition, in recent years, due to the rapid development of the livestock farming industry and the large use of manure, antibiotics are present in relatively high concentrations in farmland soil in certain areas. The pollutants seriously damage the ecological function of farmland soil and influence the yield and quality of crops; on the other hand, these soil contaminants may be absorbed by plants and transferred at the nutrient level into the food chain and ultimately into the human body, endangering public health. Therefore, the problem of farmland soil pollution must be highly regarded and deeply studied to develop an efficient and low-cost farmland soil combined pollution control technology, so as to reduce the concentration or bioavailability of soil pollutants and eliminate the soil pollution and the harm to the ecological environment and human health.
At present, technologies for remediating contaminated farmland soil mainly comprise physical remediation, chemical remediation, biological remediation and other combined remediation technologies, and have a plurality of limitations, wherein the most important limitation factor is high cost and difficulty in removing a plurality of pollutants simultaneously. For example, phytoremediation and microbial remediation often have a relatively good remediation effect for a particular single or similar contaminant, while other contaminants that co-exist may have a deleterious effect on the plant or microbe being remediated and may affect its remediation function.
Research shows that the biochar can adsorb and remove various polar, nonpolar and ionic organic pollutants and inorganic pollutants such as heavy metals, metalloids, perchlorate and the like. And the biochar has the advantages of wide raw material preparation, no secondary pollution, low cost and the like, and is paid attention to by people. However, previous researches show that the application amount of the biochar directly used for soil pollutants is large in practice, and the passivation effect and the antibiotic removal effect of the single biochar and soil heavy metals are limited.
Disclosure of Invention
The invention aims to provide a biochar-loaded manganese oxide composite material aiming at the problem that the passivation effect and the antibiotic removal effect of single biochar and soil heavy metal are limited in the prior art.
The invention also provides a preparation method of the biochar loaded manganese oxide composite material.
The invention also provides an application of the biochar loaded manganese oxide composite material.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a biochar-supported manganese oxide composite material comprises biochar formed by biomass pyrolysis and manganese oxide supported on the biochar, and is prepared by the following method:
step 1, preparing a manganese precursor solution: dissolving potassium permanganate in deionized water, and adjusting the pH value of the solution by using dilute sulfuric acid;
and 3, centrifuging the sample obtained in the step 2, taking a lower-layer solid sample, cleaning and drying to obtain the biochar loaded manganese oxide composite material.
In the technical scheme, in the biochar-loaded manganese oxide composite material, the mass of a manganese element in a manganese oxide is 1-3% of the mass of the biochar-loaded manganese oxide composite material, and the biomass is corn straw, wheat straw or pine;
the area ratio of a Raman spectrum D band to a Raman spectrum G band of the biochar is 3.3-4.0;
the area ratio of the D band to the G band of the Raman spectrum of the biochar-loaded manganese oxide composite material is 3.2-3.9.
In the technical scheme, the biochar is prepared by the following method:
step S1, crushing and washing the corn straws, the wheat straws or the pine wood to remove solid impurities attached to the biomass, and drying to obtain an original material;
step S2, pyrolyzing the raw material obtained in the step S1 in a nitrogen atmosphere, and naturally cooling to room temperature to obtain biochar;
and step S3, performing ball milling treatment on the biochar obtained in the step S2, and then sieving the biochar for later use.
In the above technical scheme, in the step S1, the drying method includes naturally drying, and then drying, wherein when the time of the natural drying is 72-144 ℃, the drying temperature is 50-80 ℃, and the drying time is 12-36 hours;
in step S2, the pyrolysis process is: heating to 300-400 ℃ from 20-30 ℃ at a speed of 2-10 ℃/min, preserving heat for 2-5 hours, and then cooling along with the furnace;
in the step S3, the ball milling treatment is performed for 12-36 hours at 200-300 r/min, and the number of the sieved meshes is 100-200 meshes.
In the technical scheme, in the step 1, the molar concentration of potassium permanganate in the manganese precursor solution is 5-15 mM, 0.05-0.15M dilute sulfuric acid is used for adjusting the pH value of the solution to 2.5-3.5, and the dissolving operation is stirring at room temperature until the potassium permanganate is completely dissolved;
in the step 2, the mass ratio of the biochar to the potassium permanganate in the manganese precursor solution is (8-12): 1; the temperature of the water bath is 50-70 ℃, and the stirring time is 6-9 hours;
in the step 3, the rotation speed of centrifugation is 3000-4000 rpm/min, the centrifugation time is 5-8 minutes, deionized water is used for cleaning, the cleaning times are 4-6 times, the drying is carried out in a freeze dryer, the freeze-drying temperature is-30 to-60 ℃, and the time is 24-48 hours.
In the technical scheme, when the biochar is prepared from corn straws, in the biochar-loaded manganese oxide composite material, the mass of manganese is 1-2% of the mass of the biochar-loaded manganese oxide composite material, the valence states of manganese are +2 valence, +3 valence and +4 valence, and the surface loading amount of the manganese on the biochar is 2-3%;
when the biochar is prepared from wheat straws, in the biochar-loaded manganese oxide, the mass of manganese element is 1-2% of the mass of the biochar-loaded manganese oxide composite material, the valence states of manganese are +2, +3 and +4, and the loading capacity of the manganese element on the surface of the biochar is 5-6%;
when the biochar is prepared from pine, in the biochar-loaded manganese oxide, the mass of manganese element is 2-3% of the mass of the biochar-loaded manganese oxide composite material, the valence of manganese is +3 and +4, and the loading capacity of the manganese element on the surface of the biochar is 11-12%.
In another aspect of the invention, the application of the biochar-loaded manganese oxide composite material in removing antibiotics and/or heavy metal pollutants is provided.
In the technical scheme, the antibiotic is tetracycline, and the heavy metal pollutant is Cd2+。
In the technical scheme, the biochar-loaded manganese oxide composite material is added into the tetracycline solution with the concentration of 20mg/L according to the concentration of 0.25g/L, and the tetracycline removal rate is 28-35% after oscillation in a constant-temperature oscillation incubator at 25 ℃ for 72 hours;
to Cd with the concentration of 50mg/L2+Solution of 0.25g/L concentration to Cd2+Adding a biochar-loaded manganese oxide composite material into the solution, oscillating for 24 hours in a constant-temperature oscillation incubator at 25 ℃, and when the biochar is prepared by corn straws, Cd2+The adsorption capacity is 13-14 mg/g, and when the biochar is prepared from wheat straws, Cd is2+The adsorption amount is 10-11 mg/g,cd when the biochar is prepared from pine2+The adsorption capacity is 9-10 mg/g;
to Cd with the concentration of 50mg/L2+And 20mg/L tetracycline mixed solution, adding the biochar-loaded manganese oxide composite material into the tetracycline solution according to the concentration of 0.25g/L, wherein the tetracycline removal rate is 23-26% after 72 hours; after 24 hours, when the biochar is prepared by corn stover, Cd2+The adsorption capacity is 10-13 mg/g, and when the biochar is prepared from wheat straws, Cd is2+The adsorption capacity is 8-12 mg/g, and when the biochar is prepared from pine, Cd is2+The adsorption capacity is 8-10 mg/g.
In another aspect of the invention, a preparation method of a biochar loaded manganese oxide composite material is provided, which comprises the following steps:
a1, sequentially crushing and washing corn straws, wheat straws or pine trees to remove solid impurities attached to biomass, naturally drying for 24-48 hours, and drying for 12-36 hours at 70-80 ℃ to obtain an original material;
a2, pyrolyzing the raw material obtained in the step A1 in a nitrogen atmosphere, and naturally cooling to room temperature to obtain biochar, wherein the pyrolysis temperature is 300-400 ℃, the pyrolysis time is 2-5 hours, and the heating rate is 2-10 ℃/min;
step A3, performing ball milling treatment on the biochar obtained in the step A2 at a speed of 200-300 r/min for 12-36 h, and then sieving the biochar through a sieve of 100-200 meshes for later use;
step A4, preparing a manganese precursor solution: dissolving potassium permanganate in deionized water, stirring at room temperature until the potassium permanganate is completely dissolved, and adjusting the pH of the solution to 2.5-3.5 by using dilute sulfuric acid with the concentration of 0.05-0.5M to obtain a manganese precursor solution, wherein the molar concentration of potassium permanganate in the manganese precursor solution is 5-15 mM;
step A5, dipping the biochar in the manganese precursor solution, wherein the mass ratio of the biochar to potassium permanganate in the manganese precursor solution is (8-12): 1, heating in a water bath at 50-70 ℃ and stirring for 6-9 hours to obtain a primary sample;
and A6, centrifuging the sample obtained in the step A5 at 3000-4000 rpm/min for 5-8 minutes, taking a lower-layer solid sample, washing the solid sample with deionized water for 4-6 times, and drying the collected solid sample in a freeze dryer for 24-48 hours to obtain the biochar loaded manganese oxide composite material.
Compared with the prior art, the invention has the beneficial effects that:
1. the biochar loaded manganese oxide composite material provided by the invention adopts common soil conditioner biochar as a base material, is cheap and easily available, is environment-friendly, has multiple functions, high reaction or adsorption selectivity and good environmental compatibility, and has low cost.
2. The biochar loaded manganese oxide composite material disclosed by the invention can be used for removing typical antibiotic pollutants tetracycline and heavy metal cadmium under an environmental condition, the removing effect on the typical organic pollutant tetracycline and the adsorption effect on the typical heavy metal pollutant cadmium ion under the environmental condition are both remarkably improved, and the removing effect on the composite pollution of the tetracycline and the heavy metal cadmium ion is also remarkable.
3. The biochar loaded manganese oxide composite material disclosed by the invention is simple in preparation process, and the preparation process is easy to regulate and control, so that the requirements of actual production and application are hopefully met.
Drawings
FIG. 1 shows MnOxMaize straw biochar (sample 4), MnOx-Wheat straw biochar (sample 5), and MnOx-characterization of the X-ray photoelectron spectroscopy of pine charcoal (sample 6): (a) three kinds of MnOxFull scan spectrum of biochar, (b) MnOxMn 2p spectrogram of corn stalk biochar (c) MnOxMn 2p spectrogram of wheat straw biochar, (d) MnOx-Mn 2p spectrum of pine biochar.
FIG. 2 shows the different magnifications of (a) corn stalk biochar (sample 1), (b) wheat stalk biochar (sample 2), (c) pine biochar (sample 3), (d, g) MnOxBiochar from maize straw (sample 4), (e, h) MnOx-wheat straw biochar (sample 5) and (f, i) MnOxScanning electron microscope images of pine biochar (sample 6).
FIG. 3 shows corn stalk biochar (sample 1), wheat stalk biochar (sample 2), pine biochar (sample 3), and MnOxMaize straw biochar (sample 4), MnOx-wheat straw biochar (sample 5), and MnOx-X-ray diffraction pattern of pine charcoal (sample 6).
FIG. 4 shows MnO prepared from original biochar and manganese oxide loaded thereonx-raman spectra of biochar composites: (a) corn stalk biochar and MnOx-corn stover biochar, (b) wheat straw biochar and MnOx-wheat straw biochar, (c) pine biochar and MnOx-pine biochar.
FIG. 5 shows MnO prepared from blank, original biochar and manganese oxide loaded thereonxComparison of biochar composite for tetracycline removal performance: (a) corn stalk biochar and MnOx-corn stover biochar, (b) wheat stover biochar and MnOx-wheat straw biochar, (c) pine biochar and MnOx-pine biochar.
FIG. 6 shows MnO prepared from original biochar and manganese oxide loaded thereonx-biochar composite pair Cd2+Comparison of ion adsorption performance: (a) corn stalk biochar and MnOx-corn stover biochar, (b) wheat straw biochar and MnOx-wheat straw biochar, (c) pine biochar and MnOx-pine biochar.
FIG. 7 shows MnO prepared from original biochar and manganese oxide loaded thereonxComparison of the removal performance of the biochar composite material on tetracycline in a tetracycline-Cd combined pollution system: (a) corn stalk biochar and MnOx-corn stover biochar, (b) wheat straw biochar and MnOx-wheat straw biochar, (c) pine biochar and MnOx-pine biochar.
FIG. 8 shows MnO prepared from original biochar and manganese oxide loaded thereonxApplication of biochar composite material to Cd in tetracycline-Cd combined pollution system2+Ion adsorption performance comparison: (a) corn stalk biochar and MnOx-corn stalk biochar, (b) wheat stalk biocharAnd MnOx-wheat straw biochar, (c) pine biochar and MnOx-pine biochar.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A biochar-loaded manganese oxide composite material is prepared by the following method:
step A1, crushing and washing the corn straws, the wheat straws and the pine trees in sequence respectively to remove solid impurities attached to the biomass, naturally drying the biomass for 48 hours, and drying the biomass overnight at 60 ℃ to obtain an original material;
step A2, pyrolyzing the raw material obtained in the step 1 in a nitrogen atmosphere, and naturally cooling to room temperature to obtain biochar, wherein the pyrolysis temperature is 300 ℃, the pyrolysis time is 4 hours, and the heating rate is 5 ℃/min;
step A3, performing ball milling treatment on the biochar obtained in the step 2 for 24 hours at the speed of 300r/min, and then sieving the biochar with a 150-mesh sieve to obtain corn straw biochar (sample 1), wheat straw biochar (sample 2) and pine biochar (sample 3);
step A4, preparing a manganese precursor solution: dissolving 0.158g of potassium permanganate in 100mL of deionized water, stirring at room temperature until the potassium permanganate is completely dissolved, and adjusting the pH value of the solution to 3 by using dilute sulfuric acid with the concentration of 0.1M to obtain a manganese precursor solution;
step A5, respectively immersing 1.58g of biochar (sample 1, sample 2, sample 3) prepared according to step A3 in the manganese precursor solution obtained in the step A4, heating in a water bath at 60 ℃ and stirring for 8 hours to change the solution from purple to colorless and change the black biochar into brown solid precipitate, so as to obtain sample 4, sample 5, sample 6;
step A6, centrifuging the samples 4, 5 and 6 obtained in step A5 at 3000rpm/min for 5 minutes, removing the solid sample on the lower layer, washing the solid sample with deionized water for 5 times, and putting the collected solid sample at-4%Freezing in a refrigerator, and drying in a freeze dryer for 24 hr to obtain MnOx-corn stover biochar (sample 4), MnOxWheat straw biochar (sample 5), MnOxPine biochar (sample 6).
Example 2
Physical and chemical properties of the biochar (samples 1, 2 and 3) and the biochar-supported manganese oxide composite (samples 4, 5 and 6) obtained in example 1 were characterized. Firstly, the content of manganese in six samples is quantified by using an inductively coupled plasma atomic emission spectrometry, and the mass percent of the manganese in 6 materials is shown in table 1. The background manganese content in the three biochar materials (samples 1, 2, 3) was very low, below 0.02%. The manganese content in the biochar-loaded manganese oxide composite material (samples 4, 5 and 6) is 1.5 to 2.7 percent, which is much higher than that of the original biochar, and thus the successful loading of the manganese oxide is proved. After the biochar (sample 3) prepared by taking pine as a raw material is treated by the method in the embodiment 1, the prepared biochar loaded manganese oxide composite material (sample 6) has the highest load of manganese oxide, and the content of manganese element is 2.7%.
TABLE 1 manganese content of different materials
Further, the valence states of the elements on the surfaces of the three biochar-supported manganese oxide composite materials (samples 4, 5 and 6) obtained in example 1 are analyzed by using X-ray photoelectron spectroscopy (XPS), as shown in fig. 1, fig. 1a is a full-scanning graph of the three biochar-supported manganese oxide composite materials, and the results show that the three biochar-supported manganese oxide composite materials have similar energy spectral lines, and the main elements on the surfaces of the three materials are O, C and Mn, thereby further proving the successful loading of manganese oxide; wherein the surface loading (atomic percent) of Mn element is 2.67-11.9% (Table 2), the corresponding mass percent is 10.4-35.4%, and the Mn element content is higher than that of the whole material (Table 1), which indicates that the manganese oxide is mainly enriched on the surface of the composite material. FIGS. 1b, c, d respectively show MnOx-corn stover biochar, MnOx-wheatStraw biochar and MnOxMn 2p spectra of pine biochar, Mn 2p of the first two3/2The spectral peaks can be divided into three peaks at 640.8, 641.8 and 643.3eV, and Mn 2p1/2The spectral peaks can be separated into three peaks at 652.5 eV, 653.5 eV and 655.0eV, which belong to Mn (II), Mn (III) and Mn (IV), respectively, and prove that MnO isx-maize straw, MnOxThe valence states of Mn in the manganese oxide compound loaded by the two materials of the wheat straw comprise + 2-valence, + 3-valence and + 4-valence manganese; and analyzed in the same manner, MnOxThe valence state of the manganese element in the pine charcoal is mainly +3 valence and +4 valence.
TABLE 2 surface element content (atomic%) of different composites
The microscopic morphology of the 6 materials observed by scanning electron microscopy is shown in FIG. 2. The surfaces of all three original biochar were quite flat (fig. 2 a-c); manganese oxide nanoparticles are observed on the surface of the corresponding biochar-loaded manganese oxide composite material (figure 2 d-i). Wherein, MnO isxCubic particles with an edge length of about 100nm are observed on the surface of the wheat straw biochar, and MnOxThe distribution of manganese oxide in pine biochar (sample 6, FIG. 2f, i) was the most uniform and particles with a size of about 50nm were observed.
The X-ray diffraction (XRD) patterns of biochar (samples 1, 2, and 3) and the biochar manganese oxide-supported composite material (samples 4, 5, and 6) obtained after supporting manganese oxide are shown in fig. 3. The broad peak of the diffraction angle 2 theta of about 20 degrees in the graph shows that the main component of the biochar obtained by pyrolyzing the three different biomasses is amorphous carbon; the XRD spectrum of the biochar loaded with the manganese oxide does not show diffraction peaks of manganese dioxide or other manganese oxides, on one hand, the loading amount of the manganese oxide is relatively low, and on the other hand, the crystallinity of the manganese oxide is low.
The Raman (Raman) spectra of biochar (samples 1, 2, 3) and biochar-supported manganese oxide composites (samples 4, 5, 6) are shown in fig. 4. As can be seen in the figure, six kindsThe Raman spectra of the material are all 1350cm-1(D band) and 1580cm-1Two broad spectral peaks appear around (band G), which indicates that amorphous carbon and graphitic carbon exist in the biochar. Gaussian fitting is carried out on the Raman spectrograms of the six samples to obtain the peak areas of a D band and a G band, wherein the area ratio of the D band to the G band (I)D/IG) Inversely proportional to the degree of graphitization of the carbon material. As shown in Table 3, I of six materialsD/IGThe ratios are all higher, which indicates that the graphitization degree of the biochar material obtained by low-temperature pyrolysis is lower. Before and after the same biochar material is loaded with manganese oxide, the material ID/IGThe difference in value is small. In addition, the biochar loaded with the manganese oxide has a Raman spectrum in which a characteristic band of the manganese oxide is not observed (for example, delta-MnO)2At 500-650 cm in 510, 575-585 and 625--1Characteristic peaks exist within the range), and further confirm that the loading amount and crystallinity of manganese oxide are low, consistent with XRD results.
TABLE 3 Peak area ratio of D band and G band for different materials
Example 3
The performance of the biochar (samples 1, 2 and 3) obtained in example 1 and the biochar-supported manganese oxide composite material (samples 4, 5 and 6) obtained after the biochar-supported manganese oxide composite material is used for removing tetracycline in water is examined, and the experimental conditions are as follows: material addition amount: 0.25 g/L; initial concentration of tetracycline: 20 mg/L; pH 7.
A tetracycline stock solution having a concentration of 20g/L was prepared from methanol, and a tetracycline solution having a concentration of 20mg/L (pH 7, adjusted by a 0.1M NaOH solution and a HCl solution) was further prepared from the stock solution by dilution with deionized water. The 6 samples obtained in example 1 were added to the tetracycline solutions at a concentration of 0.25g/L, respectively, and a group of tetracycline solutions without any material added was used as a blank, and shaken (180rpm) in a 25 ℃ incubator at a constant temperature to examine the tetracycline removing ability. Samples were taken at various time points after the start of the experiment, filtered through a 0.22 μm aqueous polyethersulfone membrane needle filter, and the tetracycline concentration was measured at a wavelength of 355nm using an ultraviolet-visible spectrophotometer, the results are shown in FIG. 5.
In the blank group and the experimental group added with the biochar, tetracycline is not effectively removed, and the removal rate of tetracycline is obviously improved by the experimental group added with the biochar loaded manganese oxide composite material. Specifically, under the experimental conditions, the tetracycline removal rate after 72 hours of the blank group experiment is 6.4% + -0.1%, which proves that the tetracycline is slowly degraded under the condition of pH 7. When biochar exists in the system, the tetracycline removal effect is not remarkably improved compared with that of a blank control group, and the tetracycline removal rate is 5.8% +/-0.1% to 9.7 +/-0.2% after 72 hours, which indicates that 3 types of biochar materials can not remove the tetracycline under the experimental conditions. In the results of the three biochar-loaded manganese oxide composite material experimental groups, the removal rate of tetracycline is remarkably improved, and the removal rate of tetracycline is over 30% after 72 hours. Wherein MnO isxThe highest tetracycline removal rate of pine charcoal (sample 6) reached 33.6% +/-0.5%, consistent with the highest manganese oxide loading on the surface of pine charcoal, MnOxThe tetracycline removal rate of the corn stalk biochar is 32.4% +/-0.1%; MnO (MnO)xThe tetracycline removal rate of the wheat straw biochar is 28.2% +/-0.2%.
Example 4
The biochar (samples 1, 2 and 3) obtained in example 1 and the biochar manganese oxide-loaded composite material (samples 4, 5 and 6) obtained after the biochar manganese oxide is loaded are considered to adsorb Cd2+Ion performance, adsorption experiment conditions: material addition: 0.25 g/L; cd [ Cd ]2+Initial ion concentration: 50 mg/L; pH 7; background electrolyte concentration CaCl2：10mM。
With Cd (NO)3)2·4H2O preparing Cd with concentration of 1g/L2+Stock solution (with dilute HNO)3Adjusting pH to 6), further diluting with the stock solution to make concentration of 50mg/LCd (2)2+The solution (pH 7) was subjected to the experiment. Adding Cd into the solution at a concentration of 0.25g/L2+Adding three biochar (samples 1, 2 and 3) and three biochar-loaded manganese oxide composite materials (samples 4, 5 and 6) into the solution, oscillating the mixture in a constant-temperature oscillation incubator at 25 ℃ (180rpm), and inspecting the Cd content of the mixture2+Adsorption removal ability of (1). Sampling after carrying out adsorption experiments for different time (2, 6, 12 and 24 hours), filtering to remove solid materials, and measuring Cd in filtrate by using an inductively coupled plasma mass spectrometer2+And calculating the amount of adsorption. Measured Cd2+The change of the adsorption amount with adsorption time is shown in FIG. 6.
The cadmium adsorption quantity sequence of the three original biochar materials is as follows: corn stalk charcoal (7.3 plus or minus 0.04mg)>Pine wood charcoal (3.7 + -0.7 mg)>Wheat straw biochar (0.9 +/-0.7 mg). The cadmium adsorption capacity of the three materials loaded with the manganese oxide is obviously improved. MnOxThe highest adsorption capacity of the corn stalk biochar (sample 4) on cadmium reaches 13.3 +/-0.7 mg/g; the cadmium adsorption capacity of the loaded manganese oxide on the wheat straw biochar is improved to the maximum extent (more than 10 times): cd of wheat straw biochar (sample 2) 24 hours after experiment2+An adsorption amount of 0.9. + -. 0.7mg/g, and MnOxCd of wheat straw biochar (sample 5)2+An adsorption amount of 10.2. + -. 0.9mg/g (FIG. 6b), MnOxCd of pine charcoal (sample 6)2+The amount adsorbed was 9.7+ _0.2mg/g (FIG. 6 c).
Example 5
The performance of the biochar (samples 1, 2 and 3) obtained in example 1 and the biochar-loaded manganese oxide composite material (samples 4, 5 and 6) obtained after loading manganese oxide thereof in removing tetracycline-cadmium composite pollution in water is considered, and the experimental conditions are as follows: material addition: 0.25 g/L; cd [ Cd ]2+Initial ion concentration: 50 mg/L; initial concentration of tetracycline: 20 mg/L; pH 7; background electrolyte concentration CaCl2：10mM。
A20 mg/L tetracycline and 50mg/L Cd solution were prepared in the same manner as in example 3 and example 42+Mixed solution (pH 7). To a mixed solution of tetracycline and cadmium at a concentration of 0.25g/L were added 6 materials obtained in example 1, respectively, in groups ofAdding tetracycline-cadmium mixed solution of any material as blank control, shaking in a constant temperature shaking incubator at 25 deg.C (180rpm), and observing that it can remove tetracycline and Cd under the condition of composite contamination2+The ability of the cell to perform. The tetracycline removal effect is measured by sampling at different time points after the experiment is started, and the tetracycline concentration is measured at the 355nm wavelength by using an ultraviolet-visible spectrophotometer after the tetracycline removal effect is filtered by a 0.22 mu m water phase polyethersulfone membrane needle filter. Sampling after experiment is carried out for different time (2, 6, 12 and 24 hours), filtering to remove solid materials, and measuring Cd in filtrate by using an inductively coupled plasma mass spectrometer2+And calculating the amount of adsorption.
The tetracycline removal effect of 6 samples is shown in fig. 7, and the results after 72 hours are similar to those of example 3. In the blank group and the experimental group added with the original biochar, tetracycline is not effectively removed, and the removal rate of tetracycline is obviously improved by the biochar loaded with manganese oxide. Specifically, under the experimental conditions, the tetracycline removal rate after 72 hours of the blank group experiment is 6.1% + -0.1%, which proves that the tetracycline has Cd at pH 72+The self-degradation is slow under the condition of the concentration of 20 mg/L. When biochar exists in the system, the tetracycline removal effect is not obviously improved compared with that of a blank control group, and the tetracycline removal rates after 72 hours are respectively as follows: the composition comprises 6.1% +/-0.2% of corn straw biochar, 6.4% +/-0.1% of wheat straw biochar and 7.6% +/-0.1% of pine biochar, which indicates that under experimental conditions, the 3 biochar materials can not effectively remove tetracycline. The removal rate of tetracycline of the three biochar-loaded manganese oxide composite materials is remarkably improved, and the removal efficiency of tetracycline after 72 hours is respectively as follows: 23.1% +/-0.7% of corn straw biochar, 24.3% +/-0.3% of wheat straw biochar and 25.4% +/-0.4% of pine biochar, and the experimental time is prolonged to 168 hours, tetracycline is not effectively removed in a blank group and an experimental group added with the original biochar, and the removal rate of tetracycline is still remarkably improved by the biochar loaded with manganese oxide. Specifically, under the experimental conditions, the tetracycline removal rate after 168 hours of the blank group experiment is 8.9% + -0.1%, and when biochar exists in the system, the tetracycline removal effect is not higher than that of the blank control groupThe removal rate of tetracycline is remarkably improved from 8.1 +/-0.1% to 9.7 +/-0.1% after 168 hours, while the removal rate of tetracycline of the three biochar-loaded manganese oxide composite materials is remarkably improved, and the removal rate of tetracycline is 28 +/-0.2% after 168 hours. Compared with the condition of only tetracycline pollution in example 3, under the experimental condition, the results of the blank group and the experimental group added with the original biochar are not obviously different; the removal rate of tetracycline of the three biochar-loaded manganese oxide composite materials after 72 hours is reduced to a small extent and possibly combined with Cd2+Occupying sites of oxides of manganese. Meanwhile, experiments show that the degradation rate of tetracycline is slowed down after 72 hours, and the subsequent degradation can be related to self-hydrolysis.
Material pair Cd2+The change of the adsorption amount of (2) with adsorption time is shown in FIG. 8. The cadmium adsorption capacity of the three materials loaded with the manganese oxide is obviously improved. Specifically, the method comprises the following steps: after 24 hours, the adsorption capacity of the corn straw biochar is 5.5 +/-0.2 mg/g, the adsorption capacity of the wheat straw biochar is 3.9 +/-0.8 mg/g, and the adsorption capacity of the pine biochar is 3.7 +/-0.2 mg/g. In addition, the adsorption capacity of the composite material loaded with the manganese oxide after 24 hours is as follows: MnO (MnO)xThe highest adsorption quantity of the corn straw biochar to cadmium reaches 11.4 +/-1.3 mg/g; the cadmium adsorption capacity of the load manganese oxide to the wheat straw biochar is improved to the maximum extent, MnOxCd of wheat biochar2+The adsorption capacity is 10.1 +/-1.4; MnOxThe pine charcoal is also increased to 8.9 plus or minus 0.2 mg/g. Presence of Cd only as in example 42+Compared with the pollution condition, under the experimental condition, the Cd of the original biochar and the three biochar composite materials loaded with manganese oxide2+All with a small decrease in adsorption, probably related to competitive adsorption of tetracycline.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The biochar-supported manganese oxide composite material is characterized by comprising biochar formed by biomass pyrolysis and manganese oxide supported on the biochar, and is prepared by the following method:
step 1, preparing a manganese precursor solution: dissolving potassium permanganate in deionized water, and adjusting the pH value of the solution by using dilute sulfuric acid;
step 2, dipping the biochar in the manganese precursor solution, heating in a water bath and stirring to obtain a sample;
and 3, centrifuging the sample obtained in the step 2, taking a lower-layer solid sample, cleaning and drying to obtain the biochar loaded manganese oxide composite material.
2. The biochar-supported manganese oxide composite material according to claim 1, wherein in the biochar-supported manganese oxide composite material, the mass of a manganese element in a manganese oxide is 1-3% of the biochar-supported manganese oxide composite material, and the biomass is corn stalks, wheat stalks or pine wood;
the area ratio of a Raman spectrum D band to a Raman spectrum G band of the biochar is 3.3-4.0;
the area ratio of a D band to a G band of a Raman spectrum of the biochar-loaded manganese oxide composite material is 3.2-3.9.
3. The biochar-supported manganese oxide composite of claim 2, wherein the biochar is prepared by:
step S1, crushing and washing the corn straws, the wheat straws or the pine wood to remove solid impurities attached to the biomass, and drying to obtain an original material;
step S2, pyrolyzing the raw material obtained in the step S1 in a nitrogen atmosphere, and naturally cooling to room temperature to obtain biochar;
and step S3, performing ball milling treatment on the biochar obtained in the step S2, and then sieving the biochar for later use.
4. The biochar-supported manganese oxide composite material as claimed in claim 3, wherein in the step S1, the drying method comprises natural air drying and drying, wherein when the natural air drying time is 72-144 ℃, the drying temperature is 50-80 ℃, and the drying time is 12-36 hours;
in step S2, the pyrolysis process is: heating to 300-400 ℃ from 20-30 ℃ at a speed of 2-10 ℃/min, preserving heat for 2-5 hours, and then cooling along with the furnace;
in the step S3, the ball milling treatment is performed for 12-36 hours at 200-300 r/min, and the number of the sieved meshes is 100-200 meshes.
5. The biochar-loaded manganese oxide composite material according to claim 1, wherein in the step 1, the molar concentration of potassium permanganate in the manganese precursor solution is 5-15 mM, the pH of the solution is adjusted to 2.5-3.5 by using 0.05-0.15M dilute sulfuric acid, and the dissolving operation is stirring at room temperature until complete dissolving;
in the step 2, the mass ratio of the biochar to the potassium permanganate in the manganese precursor solution is (8-12): 1; the temperature of the water bath is 50-70 ℃, and the stirring time is 6-9 hours;
in the step 3, the rotation speed of centrifugation is 3000-4000 rpm/min, the centrifugation time is 5-8 minutes, deionized water is used for cleaning, the cleaning times are 4-6 times, the drying is carried out in a freeze dryer, the freeze-drying temperature is-30 to-60 ℃, and the time is 24-48 hours.
6. The biochar-supported manganese oxide composite material according to claim 2, wherein when the biochar is prepared from corn stalks, in the biochar-supported manganese oxide composite material, the mass of manganese is 1-2% of the biochar-supported manganese oxide composite material, the valence of manganese is +2, +3 and +4, and the surface loading of manganese on the biochar is 2-3%;
when the biochar is prepared from wheat straws, in the biochar-loaded manganese oxide, the mass of manganese elements is 1-2% of the mass of the biochar-loaded manganese oxide composite material, the valence states of manganese are +2, +3 and +4, and the surface loading capacity of the manganese elements on the biochar is 5-6%;
when the biochar is prepared from pine, in the biochar-loaded manganese oxide, the mass of manganese element is 2-3% of the mass of the biochar-loaded manganese oxide composite material, the valence of manganese is +3 and +4, and the loading capacity of the manganese element on the surface of the biochar is 11-12%.
7. Use of the biochar-loaded manganese oxide composite material of any one of claims 1-6 to remove antibiotics and/or heavy metal contaminants.
8. The use of claim 7, wherein the antibiotic is tetracycline and the heavy metal contaminant is Cd2+。
9. The application of claim 8, wherein the biochar-loaded manganese oxide composite material is added into the tetracycline solution with the concentration of 20mg/L according to the concentration of 0.25g/L, and the tetracycline removal rate is 28-35% after the mixture is shaken in a constant-temperature shaking incubator at 25 ℃ for 72 hours;
to Cd with the concentration of 50mg/L2+Solution of 0.25g/L concentration to Cd2+Adding a biochar-loaded manganese oxide composite material into the solution, oscillating the solution in a constant-temperature oscillation incubator at 25 ℃ for 24 hours, and when the biochar is prepared from corn straws, Cd2+The adsorption capacity is 13-14 mg/g, and when the biochar is prepared from wheat straws, Cd is2+The adsorption capacity is 10-11 mg/g, and when the biochar is prepared from pine, Cd is2+The adsorption capacity is 9-10 mg/g;
to Cd with the concentration of 50mg/L2+And a mixed solution of tetracycline with the concentration of 20mg/L, adding the biochar-loaded manganese oxide composite material into the tetracycline solution according to the concentration of 0.25g/L, wherein the removal rate of the tetracycline is 23-26% after 72 hours; after 24 hours, when the biochar is prepared by corn stover, Cd2+The adsorption capacity is 10-13 mg/g, and when the biochar is prepared from wheat straws, Cd2+The adsorption capacity is 8-12 mg/g, and Cd is obtained when the biochar is prepared by pine2+The adsorption capacity is 8-10 mg/g.
10. The preparation method of the biochar-loaded manganese oxide composite material is characterized by comprising the following steps of:
a1, crushing and washing corn straws, wheat straws or pine trees in sequence to remove solid impurities attached to biomass, naturally drying for 24-48 hours, and drying for 12-36 hours at 70-80 ℃ to obtain an original material;
a2, pyrolyzing the raw material obtained in the step A1 in a nitrogen atmosphere, and naturally cooling to room temperature to obtain biochar, wherein the pyrolysis temperature is 300-400 ℃, the pyrolysis time is 2-5 hours, and the heating rate is 2-10 ℃/min;
step A3, performing ball milling treatment on the biochar obtained in the step A2 at a speed of 200-300 r/min for 12-36 h, and then sieving the biochar through a sieve of 100-200 meshes for later use;
step A4, preparing a manganese precursor solution: dissolving potassium permanganate in deionized water, stirring at room temperature until the potassium permanganate is completely dissolved, and adjusting the pH of the solution to 2.5-3.5 by using dilute sulfuric acid with the concentration of 0.05-0.5M to obtain a manganese precursor solution, wherein the molar concentration of potassium permanganate in the manganese precursor solution is 5-15 mM;
step A5, dipping the biochar in the manganese precursor solution, wherein the mass ratio of the biochar to potassium permanganate in the manganese precursor solution is (8-12): 1, heating in a water bath at 50-70 ℃ and stirring for 6-9 hours to obtain a primary sample;
and A6, centrifuging the sample obtained in the step A5 at 3000-4000 rpm/min for 5-8 minutes, taking a lower-layer solid sample, washing the solid sample with deionized water for 4-6 times, and drying the collected solid sample in a freeze dryer for 24-48 hours to obtain the biochar loaded manganese oxide composite material.
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| CN115785957A (en) * | 2022-12-19 | 2023-03-14 | 中国地质科学院水文地质环境地质研究所 | Preparation method and application of nano manganese dioxide modified biochar passivator |
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