CN111617739A - Al-Mn modified biomass charcoal and preparation method and application thereof - Google Patents
Al-Mn modified biomass charcoal and preparation method and application thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- 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
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention relates to the technical field of carbon materials, and particularly relates to Al-Mn modified biomass charcoal, a preparation method thereof and application thereof in heavy metal wastewater adsorption. The method takes waste biomass as a raw material, firstly utilizes potassium carbonate to modify biomass charcoal, then carries Al-Mn oxide on the biomass charcoal through modification of aluminum and manganese oxides, and prepares the Al-Mn modified biomass charcoalHas porous structure and more oxygen-containing functional groups (-OH, Al)2O3AlOOH, MnO and MnO2Etc.) which exhibit good removal performance for heavy metal anion contaminants through reduction reaction, complexation reaction, as well as physical adsorption, electrostatic attraction, etc.
Description
Technical Field
The invention relates to the technical field of carbon materials, and particularly relates to Al-Mn modified biomass charcoal and a preparation method and application thereof.
Background
Wastewater discharged from industries such as leather, electroplating and metallurgy often contains heavy metal elements such as chromium, nickel and cadmium, and seriously threatens the global environmental safety. Ion exchange, chemical precipitation and membrane separation are common wastewater treatment methods at present, but these methods usually have the disadvantages of high cost or complex process. Compared with the method, the adsorption method is simpler and more convenient, and the consumed cost is lower.
Biomass charcoal is often used as an adsorbent due to its large specific surface area and porous structure, but its ability to remove pollutants from wastewater is still low. The metal oxide can also be used as an adsorbent for treating heavy metal pollutants in wastewater, but the metal oxide has low mechanical strength, a pore structure is not developed enough, and the metal oxide is not easy to fix in the using process.
Therefore, the modified biomass carbon has great significance in ensuring low price and large adsorption capacity and having a function of fixing metal oxides.
Disclosure of Invention
The invention provides Al-Mn modified biomass charcoal and a preparation method and application thereof, aiming at the technical problems that the adsorption capacity of common biomass charcoal is small and metal oxide is not easy to fix in the using process, waste biomass is used as a raw material, potassium carbonate is firstly used for modifying the biomass charcoal, then aluminum and manganese oxides are used for modifying, Al-Mn oxide is loaded on the biomass charcoal, and the prepared Al-Mn modified biomass charcoal has a porous structure and more oxygen-containing functional groups (-OH, Al)2O3AlOOH, MnO and MnO2Etc.) which exhibit good removal performance for heavy metal anion contaminants through reduction reaction, complexation reaction, as well as physical adsorption, electrostatic attraction, etc.
In a first aspect, the invention provides a preparation method of Al-Mn modified biomass charcoal, which comprises the following steps:
(1) preparation of potassium carbonate modified biomass charcoal: mixing the pretreated biomass raw material with K2CO3After being uniformly mixed, the mixture is pyrolyzed in a protective gas atmosphere;
(2) preparing Al-Mn modified biomass charcoal: soaking the potassium carbonate modified biomass charcoal in an Al-Mn solution, then pyrolyzing the solution under the atmosphere of protective gas, and grinding and drying the product after the product is cooled to room temperature to obtain the Al-Mn modified biomass charcoal.
Further, the step (1) is to mix the pretreated biomass raw material with K2CO3According to the weight ratio of 1: 2, uniformly mixing, and pyrolyzing in a nitrogen atmosphere at the pyrolysis temperature of 600-800 ℃, the heating rate of 5 ℃/min and the heat preservation time of 1-2 h.
Further, in the step (1), the pretreatment includes washing, drying and pulverizing of the biomass raw material.
Further, in the step (1), the biomass raw material includes at least one of leaves and straws.
Further, the mixture of the potassium carbonate modified biomass charcoal and the Al-Mn solution is dried and then pyrolyzed in the nitrogen atmosphere at the pyrolysis temperature of 600-800 ℃, the temperature rise rate of 5 ℃/min and the pyrolysis time of 1-2 h in the step (2).
Further, in the step (2), the Al-Mn solution is prepared by mixing 0.6953g of AlCl3·6H2O and 0.0759g of KMnO4Dissolved in 4mL of distilled water and stirred uniformly.
Further, in the step (2), 0.25g to 1.5g of biomass charcoal is impregnated in every 4mL of the Al-Mn solution.
In a second aspect, the invention provides a biomass charcoal prepared by the above preparation method.
In a third aspect, the invention provides application of the biomass charcoal prepared by the preparation method in heavy metal wastewater adsorption.
Further, the heavy metal wastewater is wastewater containing Cr (VI).
The beneficial effect of the invention is that,
the Al-Mn modified biomass charcoal provided by the invention has a larger total specific surface area (1173.360 m)2Per g) and total pore volume (0.541 cm)3The percentage of the micropore surface area and the micropore volume respectively reach 93.97 percent and 83.92 percent, a higher micropore occupation ratio can provide a larger specific surface area and effectively intercept heavy metal ions, and a small amount of mesopores can promote the transmission of the heavy metal ions, thereby being beneficial to the removal of Cr (VI); multi-stage porous junctionThe doping of aluminum oxide and manganese oxide with different valence states enables the material to have more adsorption sites, and the theoretical saturated adsorption capacity of the Al-Mn modified biomass carbon after 8 hours of adsorption can reach 158.73mg/g under the condition of 25 ℃ and the addition amount of 0.67g/L and the pH value of wastewater of 3.
The preparation method of the Al-Mn modified biomass charcoal provided by the invention has the advantages of wide raw material source, simplicity in operation and easiness in process control.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of BC, KBC, and AMKBC-1;
FIG. 2 is a graph of the surface topography and elemental composition of BC, KBC, and AMKBC-1;
FIG. 3 is an element distribution diagram of AMKBC-1;
FIG. 4 is an X-ray photoelectron spectrum of AMKBC-1;
FIG. 5 is a chart of a Langmuir model and Freundlich model fit of AMKBC-1 adsorbing Cr (VI).
In the figure, BC represents the biomass charcoal obtained in comparative example 1, KBC represents the potassium carbonate-modified biomass charcoal obtained in comparative example 2, and AMKBC-1 represents the Al-Mn-modified biomass charcoal obtained in example 1.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An Al-Mn modified biomass charcoal (hereinafter abbreviated as AMKBC-1) is prepared by taking phoenix tree leaves as biomass raw materials, cleaning, drying and crushing the phoenix tree leaves into phoenix tree leaf powder, and the preparation method comprises the following steps:
(1) preparation of potassium carbonate modified biomass charcoal: mixing pretreated folium Firmianae powder with K2CO3According to the following steps of 1: 2, putting the mixture into a tubular furnace after uniformly mixing, introducing nitrogen into the tubular furnace, carrying out pyrolysis in the nitrogen atmosphere, raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, and carrying out pyrolysis for 2 hours;
(2) preparing Al-Mn modified biomass charcoal: 0.6953g of AlCl were initially added to 4mL of distilled water3·6H2O and 0.0759g of KMnO4And uniformly mixing to obtain an Al-Mn solution, soaking 1g of potassium carbonate modified biomass carbon in the Al-Mn solution, drying the mixture, putting the dried mixture into a tubular furnace, introducing nitrogen into the tubular furnace, carrying out pyrolysis in the nitrogen atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, carrying out pyrolysis for 1h, cooling the product to room temperature, grinding and drying to obtain AMKBC-1.
Examples 2 to 4
As shown in table 1 below, examples 2 to 4 are different from example 1 in the amount of the potassium carbonate-modified biomass char used in the preparation of the Al — Mn modified biomass char in step (2). The Al-Mn modified biomass charcoals respectively prepared in the following embodiments 2-4 are AMKBC-2, AMKBC-3 and AMKBC-4.
TABLE 1 quality of potassium carbonate modified Biomass charcoal impregnated with Al-Mn solution per 4mL
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Quality of potassium carbonate modified biomass charcoal | 1g | 0.25g | 0.5g | 1.5g |
Comparative example 1
A Biomass Charcoal (BC) is prepared by taking phoenix tree leaves as biomass raw materials, cleaning, drying and crushing the phoenix tree leaves into phoenix tree leaf powder, and the preparation method comprises the following steps:
and (3) putting the pretreated phoenix tree leaf powder into a tubular furnace, introducing nitrogen into the tubular furnace, pyrolyzing the phoenix tree leaf powder in the nitrogen atmosphere, heating to 800 ℃ at the heating rate of 5 ℃/min, pyrolyzing the phoenix tree leaf powder for 2 hours, cooling the product to room temperature, grinding and drying the product to obtain the BC.
Comparative example 2
A potassium carbonate modified biomass charcoal (hereinafter abbreviated as KBC) is prepared by taking phoenix tree leaves as a biomass raw material, cleaning, drying and crushing the phoenix tree leaves into phoenix tree leaf powder, and the preparation method comprises the following steps:
mixing pretreated folium Firmianae powder with K2CO3According to the following steps of 1: 2, putting the mixture into a tubular furnace after uniformly mixing, introducing nitrogen into the tubular furnace, carrying out pyrolysis in the nitrogen atmosphere, heating to 800 ℃ at the heating rate of 5 ℃/min, carrying out pyrolysis for 2h, cooling the product to room temperature, grinding and drying to obtain the KBC.
Test example 1
As shown in FIG. 1, AMKBC-1, BC, and KBC were characterized for crystal structure by X-ray diffractometry. BC and KBC appear at about 23 deg. and 43 deg. 2 thetaThe diffraction peaks of the crystal faces of graphite (002) and graphite (100) indicate that the material is graphitized to a certain degree. Compared with BC and KBC, the composite material AMKBC-1 has a metal oxide peak, the 18.71 DEG and 28.42 DEG characteristic peaks are AlOOH peaks, and the 40.49 DEG characteristic peak is presumed to be MnO2Peak of (JCPDS: 30-0820). It can be seen that the manganese and aluminum modified biomass charcoal is adopted, so that the types of functional groups on the surface of the biomass charcoal are obviously enriched.
Test example 2
And (3) performing surface morphology and element composition characterization on AMKBC-1, BC and KBC by using a scanning electron microscope and an X-ray energy spectrometer.
As shown in the left column of fig. 2, BC is a block structure with relatively small pore content; KBC has a developed pore structure, indicating K2CO3The modification can improve the porosity of the biomass charcoal; the AMKBC-1 is still in a porous structure, compared with the KBC, a plurality of spherical particles are added on the surface of the AMKBC-1 and can be metal oxides on the load, which shows that the KBC not only can provide a larger specific surface area, but also can be used as a carrier of a nano material to disperse and stabilize the nano particles, the problem that the metal oxides are not easy to fix and agglomerate in the using process is solved, and the combination of the two can further improve the adsorption capacity of the composite material.
As shown in the right column of fig. 2, BC and KBC are mainly composed of two elements of C and O; AMKBC-1 mainly comprises C, O, Al and Mn elements, which shows that Al and Mn have been successfully modified on the modified biomass charcoal, and the modified biomass charcoal is helpful for enhancing the removal performance of the material on chromium ions.
The elemental distribution diagram of fig. 3 also illustrates that Al and Mn have been successfully modified on the modified biomass charcoal, and further demonstrates that the preparation method of the present invention can uniformly modify Al and Mn elements on the biomass charcoal.
Test example 3
And characterizing the element valence state of AMKBC-1 by an X-ray photoelectron spectrometer. As shown in FIG. 4, characteristic peaks of C1s, O1s, Al2p and Mn2p appear in the spectrum of AMKBC-1, which indicates that the preparation method successfully modifies aluminum and manganese on the modified biomass charcoal; in the high C1s spectrum, the peak at 283.7eV originates fromC-N functional group, the peak at 285.1eV indicates the presence of C ═ C bonds in the material; a high-resolution spectrum of O1s can be divided into three peaks: the peak at 531.6eV is due to lattice oxygen at the surface of the material (C-O, C ═ O), the peak at 532.6eV is due to organic oxygen (-OH or C-O-C), and the peak at 530.5eV is due to inorganic oxygen (M-O and M-OH, M representing the metal); the spectrum of Al2p shows that the aluminum element in the composite material is derived from Al2O3(ii) a Peaks in the Mn2p3/2 spectrum at 641.0eV and 642.1eV correspond to divalent manganese in MnO and MnO respectively2Tetravalent manganese in (iv).
Example 5Cr (VI) adsorption measurement experiment
50mL of Cr (VI) aqueous solutions with concentrations of 0, 0.004, 0.01, 0.02, 0.04, 0.08, 0.12, 0.16 and 0.20mg/L are prepared respectively, the absorbance is measured according to a dibenzoyl dihydrazide spectrophotometry method specified in GB/T7467-1987, and Cr (VI) standard curves of the concentration (C) and the absorbance (A) are drawn according to the data obtained by the experiment, and regression equations thereof are obtained.
0.01g of each of AMKBC-1, AMKBC-2, AMKBC-3, AMKBC-4, BC and KBC is taken, added into 30mL of Cr (VI) aqueous solution with the concentration of 100mg/L respectively, then put into a constant-temperature (25 ℃) water bath oscillator, oscillated for 5h at 180rpm, and then the content of Cr (VI) in the solution after adsorption is measured according to a dibenzoyl dihydrazide spectrophotometry specified in GB/T7467-1987. The test results are shown in table 2 below.
TABLE 2 adsorption amounts of Cr (VI) for examples 1-4 and comparative examples 1-2
As can be seen from Table 2, the passage K2CO3The modified biomass charcoal has a porous structure, and the specific surface area of the material is larger than that of BC, so that more active sites are provided for the adsorption of Cr (VI), and the adsorption effect of KBC and AMKBC on Cr (VI) is obviously better than that of BC. Meanwhile, the adsorption capacity of AMKBC-1 and AMKBC-4 to Cr (VI) is higher than that of KBCObviously increased, which indicates that the proper Al and Mn composite amount is helpful for improving the adsorption performance of the material, particularly when the solid-to-liquid ratio (g/mL) of the potassium carbonate modified biomass charcoal to the Al-Mn solution is 1: AMKBC-1 obtained in case 4 has the best effect on removing Cr (VI), and the adsorption amount is 56.87mg/g and is about 1.4 times of that of KBC under the condition of the embodiment.
Example 6 measurement experiment of saturated adsorption amount of AMKBC-1
Respectively preparing Cr (VI) solutions with the concentrations of 50, 75, 100, 125, 150, 175 and 200mg/L, adjusting the pH value of the solutions to 3, adding AMKBC-1 into the aqueous solution according to the adding amount of 0.67g/L, oscillating for 8 hours in a constant-temperature water bath oscillator under the conditions of 25 ℃ and 180r/min, filtering and sampling, measuring the absorbance according to a dibenzoyl dihydrazide spectrophotometry method specified in GB/T7467 + 1987, obtaining the concentration of the Cr (VI) solution after adsorption according to a standard curve drawn in example 5, establishing an isothermal adsorption model, and calculating the saturated adsorption amount of the AMBKC-1. The results of the model fitting and the isothermal adsorption model parameters for AMKBC-1 adsorbing Cr (VI) are shown in FIG. 5 and Table 3 below.
TABLE 3 isothermal adsorption model parameters for AMKBC-1 adsorption of Cr (VI)
Correlation coefficient R of Langmuir equation obtained by fitting20.9960, which is higher than 0.9288 of Freundlich equation, and the theoretical adsorption capacity 158.73mg/g calculated by Langmuir equation is closer to the experimental value 152.86mg/g, which shows that the Langmuir model can better describe the adsorption process of AMKBC-1 to Cr (VI), and also shows that the adsorption process is mainly monolayer adsorption.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the Al-Mn modified biomass charcoal is characterized by comprising the following steps:
(1) preparation of potassium carbonate modified biomass charcoal: mixing the pretreated biomass raw material with K2CO3After being uniformly mixed, the mixture is pyrolyzed in a protective gas atmosphere;
(2) preparing Al-Mn modified biomass charcoal: soaking the potassium carbonate modified biomass charcoal in an Al-Mn solution, then pyrolyzing the solution under the atmosphere of protective gas, and grinding and drying the product after the product is cooled to room temperature to obtain the Al-Mn modified biomass charcoal.
2. The method according to claim 1, wherein the step (1) is to mix the pretreated biomass material with K2CO3According to the weight ratio of 1: 2, uniformly mixing, and pyrolyzing in a nitrogen atmosphere at the pyrolysis temperature of 600-800 ℃, the heating rate of 5 ℃/min and the heat preservation time of 1-2 h.
3. The method according to claim 1, wherein the pretreatment in the step (1) includes washing, drying and pulverization of the biomass raw material.
4. The method of claim 1, wherein in step (1), the biomass material comprises at least one of leaves and stalks.
5. The preparation method of claim 1, wherein the step (2) is that after the mixture of the potassium carbonate modified biomass charcoal and the Al-Mn solution is dried, the mixture is pyrolyzed in a nitrogen atmosphere, wherein the pyrolysis temperature is 600 ℃ to 800 ℃, the heating rate is 5 ℃/min, and the pyrolysis time is 1h to 2 h.
6. As claimed in claimThe preparation method of (1), wherein in the step (2), the Al-Mn solution is prepared by mixing 0.6953g of AlCl3·6H2O and 0.0759g of KMnO4Dissolved in 4mL of distilled water and stirred uniformly.
7. The method according to claim 1, wherein in the step (2), 0.25g to 1.5g of the biochar is impregnated per 4mL of the Al — Mn solution.
8. Biomass charcoal prepared by the preparation method of any one of claims 1 to 7.
9. Use of the biomass charcoal according to claim 8 in adsorption of heavy metal wastewater.
10. The use according to claim 9, wherein the heavy metal-containing wastewater is cr (vi) -containing wastewater.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112275253A (en) * | 2020-09-18 | 2021-01-29 | 武汉科技大学 | Preparation method and application of modified biochar for adsorbing fluoride and cadmium ions in wastewater |
| CN113198431A (en) * | 2021-06-12 | 2021-08-03 | 清华大学深圳国际研究生院 | Preparation and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar |
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