CN110898804A - Biochar composite material and preparation method and application thereof - Google Patents
Biochar composite material 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- 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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- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a biochar composite material which comprises biochar and nano MnO uniformly doped in the biochar2Biochar and nano MnO2The mass ratio of (50-300) to (1); the specific surface area of the biochar composite material is 30-100m2(ii) in terms of/g. The raw materials of the biochar composite material provided by the invention are easy to obtain and low in price;the preparation process and the operation are simple, the preparation is rapid, the production period is short, special chemical equipment is not needed, and the mass production is easy; the product of the invention is nontoxic, environment-friendly, high in activity and high in removal efficiency of antibiotics in water.
Description
Technical Field
The invention belongs to the field of carbon materials, and particularly relates to a biochar composite material as well as a preparation method and application thereof.
Background
Antibiotics are commonly used to combat diseases and protect humans and animals against microbial infections. China is in the world's leading position in terms of antibiotic production capacity, with annual yields of about 21 million tons, 85% of which are used in animal, agricultural and medical applications. The widespread use of antibiotics has led to the frequent detection of residues in surface and ground water throughout the country. Antibiotics remain in the soil and sediments, adversely affecting ecosystem function. It may also have adverse effects on human health through endocrine disruption, and may induce resistance gene formation at relatively low concentrations with long-term exposure. Therefore, the antibiotic-containing wastewater must be treated prior to discharge into the water environment. The adsorption method is the most rapid, efficient, economical and environment-friendly method in antibiotic wastewater treatment and is widely applied. The key point of improving the application of the technology in dye wastewater treatment is to find an efficient adsorbent.
Biochar is an adsorption material with great prospect in pollutant treatment technology, and has the advantages of porous structure, complex surface, rich raw materials and economic benefit. However, there is still a large room for further improvement in the adsorption capacity of the original biochar. Another nanomaterial that has been widely reported to be effective adsorbents at present is manganese oxide, nanoscale MnOxThe particles have a higher specific surface area due to their superior polycrystalline structure and thus a stronger adsorption performance. However, MnO of nanometer sizexThe particles tend to agglomerate, which limits their practical application as adsorbents.
Disclosure of Invention
In order to solve the technical problems, the invention adopts a method with easily available raw materials, low price and simple preparation to prepare the biochar composite material for adsorbing and treating the antibiotic wastewater.
The biochar composite material provided by the invention comprises biochar and nano MnO uniformly doped in the biochar2。
Wherein the biochar and the nano MnO2The mass ratio of (50-300) to (1).
Wherein, the nano MnO2The particle size of (A) is 5-100 nm.
Wherein the specific surface area of the biochar composite material is 30-100m2/g。
The invention also provides a preparation method of the biochar composite material, which comprises the following steps:
(1) preparing a biochar material by adopting a pyrolysis method: pyrolyzing the mixture containing the biomass at the temperature of 673-;
the mixture also contains organic acid and manganese salt;
(2) adding the biochar material into an anaerobic manganese chloride solution, and uniformly stirring in an anaerobic environment to form biochar-Mn2+Mixing;
(3) mixing the biochar-Mn2+And dropwise adding the mixture into a solution containing potassium permanganate and strong base, stirring for reaction, aging at room temperature after the reaction is finished, filtering, washing, drying and grinding to obtain the biochar composite material.
Wherein, the biomass in the step (1) can be selected from at least one of straws, chaffs, straws and the like.
Wherein, the organic acid in the step (1) may be at least one selected from formic acid, acetic acid, benzoic acid, and the like. Further, the mass ratio of the organic acid to the biomass is (0.5-3): 100.
Wherein, the manganese salt in the step (1) can be at least one selected from manganese chloride, manganese sulfate and manganese nitrate. Further, the mass ratio of the manganese salt to the biomass is (0.5-3): 100.
Wherein, the pyrolysis process in the step (1) is carried out in an inert atmosphere, and the inert atmosphere is argon, nitrogen or helium, preferably nitrogen. For example, the flow rate of nitrogen is 300 to 500 mL/min.
Wherein, the pyrolysis temperature 673-873K in the step (1) is obtained by temperature programming, and the temperature rise rate is 276-288K/min.
Wherein the biomass material in the step (1) has an average particle size of 50 to 300 μm.
Wherein the concentration of the manganese chloride solution in the step (2) is 1.5-4.5 mmol/L.
Wherein the mass-volume ratio of the biochar material to the manganese chloride solution in the step (2) is (1-3) to (10-40) g/mL.
Wherein, the oxygen-free environment in the step (2) can be obtained by introducing nitrogen into the system.
Wherein, the stirring time in the step (2) can be 1-2 h.
Wherein, in the solution containing potassium permanganate and strong base in the step (3), the concentration of the potassium permanganate is 1-5mmol/L, and the concentration of the strong base is 5-10 mmol/L. Further, the volume of the solution containing potassium permanganate and strong base is the same as or different from the volume of the manganese chloride solution.
Wherein, the strong base in the step (3) can be sodium hydroxide or potassium hydroxide.
Wherein, the rotation speed of the stirring reaction in the step (3) is 200-300 r/min, and the time is 10-30 min.
Wherein the aging time in the step (3) is 12-36 h.
Wherein, the washing in the step (3) is washing alternately by adopting water and ethanol. Further, the number of washing is at least one, such as two or three.
Wherein, the drying temperature in the step (3) is 333-363K.
Illustratively, the preparation method comprises the following steps:
(1) loading the mixture containing rice husk powder, organic acid and manganese salt into quartz tank, placing into quartz tube furnace, sealing two ends of quartz tube, and charging N into the quartz tube furnace chamber from one end2Keeping inert atmosphere in the pyrolysis process, and collecting volatile products generated in the biomass pyrolysis process from the other end; adopts the temperature programming to raise the temperature to 673-873K at the speed of 276-288K/min,preserving heat for 1-3 h under the pressure of 1-10.0 MPa, then cooling to room temperature, grinding and sieving to obtain a biochar material;
the mass ratio of the rice husk powder to the organic acid to the manganese salt is 100 (0.5-3) to 0.5-3;
(2) adding 1-5mmol/L manganese chloride solution in N2Purifying for 10-30 min to remove dissolved oxygen, adding 1-3 g of the biochar material obtained in the step (1) into the 10-40 mL of manganese chloride solution, and adding into N2Stirring for 1-2 h to form biochar-Mn2+Mixing;
(3) adding the biochar-Mn dropwise into 10-40 mL of solution containing potassium permanganate and sodium hydroxide2+And (3) continuously stirring the mixture for reaction for 10-30 min, aging at room temperature for 12-36 h, drying at 333-363K, grinding and sieving to obtain the biochar composite material.
Wherein the room temperature refers to a temperature between 288 and 313K, and is 298K as an example.
The invention also provides the biochar composite material prepared by the method.
The invention also provides application of the biochar composite material in treating antibiotic wastewater. The antibiotic may be at least one selected from tetracycline hydrochloride (TC), Doxycycline (DC), and the like.
Preferably, the antibiotic wastewater treatment method comprises the following steps: adding the biochar composite material into the antibiotic wastewater solution with the concentration of 5-100 mg/L, adjusting the pH value of the system to 2.0-10.0, sealing, setting the reaction temperature to 298-318K, and carrying out constant-temperature oscillation treatment.
The invention has the beneficial effects that:
1. the raw materials of the biochar composite material provided by the invention are easy to obtain and low in price; the prepared biochar is fixedly loaded with manganese elements, and then the biochar and the solution system are loaded with the manganese elements to obtain the biochar composite material with high manganese content.
2. The preparation process and operation of the novel biochar are simple, the preparation is rapid, the production period is short, special chemical equipment is not needed, and the novel biochar is easy to produce in large scale;
3. the product of the invention is non-toxic and environment-friendly;
4. the biochar composite material disclosed by the invention is high in activity and high in removal efficiency of antibiotics in a water body.
Drawings
Fig. 1 is a scanning electron microscope image of the biochar composite prepared in example 1.
Fig. 2 is a transmission electron microscope image of the biochar composite prepared in example 1.
Fig. 3 shows the removal efficiency in example 2: (a) tetracycline hydrochloride (TC), (b) Doxycycline (DC).
FIG. 4 is the effect of pH on the adsorption effect in example 2.
FIG. 5 is the isotherm of the adsorption of tetracycline hydrochloride (TC) and Doxycycline (DC) by the biochar composite in example 2: (a) langmuir model for adsorption of TC, (b) Freundlich model for adsorption of TC, (c) Langmuir model for adsorption of DC, (d) Freundlich model for adsorption of DC.
FIG. 6 is the kinetics of adsorption of tetracycline hydrochloride (TC) and Doxycycline (DC) by the biochar composite in example 2: (a) the TC adsorption varied with time; (b) the amount of DC adsorption varied with time; (c) fitting results of a TC adsorption quasi-first-order kinetic model; (d) fitting results of a DC adsorption quasi-first-order kinetic model; (e) fitting results of a quasi-second-order kinetic model of TC adsorption; (f) and fitting results of a quasi-second-order kinetic model of DC adsorption.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The biochar composite material comprises biochar and nano MnO uniformly doped in the biochar2Biochar and nano MnO2Has a mass ratio of 100:1 and a specific surface area of 65 m2(ii) in terms of/g. The topography is shown in fig. 1 and fig. 2.
The preparation steps of the material are as follows:
(1) firstly, preparing a biochar material by adopting a pyrolysis method: a mixture containing rice husk powder, formic acid and manganese chloride (the mass ratio of the rice husk powder to the formic acid to the manganese chloride is 100: 1.5: 1.5) is put into a quartz groove and then put into a quartz tube furnace. Sealing two ends of the quartz tube, connecting the flexible tube, and filling N into the tube furnace chamber from one end2(400 mL/min), keeping inert atmosphere during pyrolysis, and collecting volatile products generated in the biomass pyrolysis process from the other end. The temperature is raised to 773K at 283K/min by adopting a temperature program, the temperature is kept for 2h at the peak temperature under the pressure of 6 MPa, and then the biochar material is obtained by cooling to the room temperature, grinding and sieving.
(2) Adding 4 mmol/L manganese chloride solution in N2Purifying for 20 min to remove dissolved oxygen, adding 1 g of biochar obtained in step (1) into the 30 mL of manganese chloride solution, and adding into N2Stirring for 1 h under the environment of (1) to form biochar-Mn2+And (3) mixing. To 20 mL of a solution containing potassium permanganate (4 mmol/L) and sodium hydroxide (8 mmol/L), biochar-Mn was added dropwise2+The mixture was stirred simultaneously with a magnetic stirrer at a rotational speed of 250 r/min. Continuously stirring for reaction for 20 min, aging at room temperature (298 +/-1K) for 24 h, drying at 353K, grinding, sieving to obtain biochar composite material, and recording as BC/MnO2。
Example 2
The biochar composite BC/MnO of example 1 was used2A method for treating antibiotic wastewater, wherein typical antibiotics take tetracycline hydrochloride (TC) and Doxycycline (DC) as examples, and the action principle is as follows:
the novel biochar composite obtained in step (2) of example 1, due to the incorporation of MnO2Compared with the original biochar, the composite material has the advantages that manganese elements appear on the surface, the carbon content is reduced, the oxygen content is increased, the total pore volume of the material is increased, the specific surface area and the pore structure are improved, and the adsorption performance of the composite material to antibiotics in an aqueous solution is greatly improved.
To investigate the removal efficiency for TC and DC. Two typical antibiotic solutions (tetracycline hydrochloride and doxycycline) were prepared at an initial concentration of 5 mg/L, respectively, and the pH was adjusted to 6.0. Putting 25 mL into a 100 mL conical flask, respectively adding 10, 20, 40, 80, 100 and 150 mg of the biochar composite material obtained in the example 1, sealing by a preservative film, setting the reaction temperature to 298K, putting the biochar composite material into a constant-temperature oscillator at the rotating speed of 170 r/min, oscillating for 24 hours, and sampling for determination. As can be seen from FIG. 3, with BC/MnO2The increase of the dosage gradually reduces the relative adsorption capacity to tetracycline hydrochloride and doxycycline, which is mainly due to excessive BC/MnO2The amount provides redundant adsorption sites, reducing the adsorbent utilization. The removal rate of tetracycline hydrochloride and doxycycline increases with the increase of the dosage of the adsorbent, mainly because the adsorption sites increase with the increase of the dosage of the adsorbent. BC/MnO can be seen in the figure2The removal capacity of tetracycline hydrochloride is slightly higher than that of doxycycline. Therefore, the novel biochar composite material can effectively remove tetracycline hydrochloride and doxycycline, and the removal rate is over 90 percent.
To investigate the effect of pH on the treatment effect. Two typical antibiotic solutions (tetracycline hydrochloride and doxycycline) with the initial concentration of 5 mg/L are respectively prepared, and the different pH values are set to be 2.0-10.0. And putting 25 mL of the composite material into a 100 mL conical flask, respectively adding 0.1 g of the biochar composite material obtained in the example 1, sealing the opening of the preservative film, setting the reaction temperature to 298K, putting the product into a constant-temperature oscillator with the rotation speed of 170 r/min, oscillating for 24 hours, and then sampling for determination. As can be seen from fig. 4, at a low pH, TC and DC exist mainly in a cationic form, and the surface of the biochar composite is positively charged, and thus, electrostatic repulsion may occur therebetween. Also, at high pH, antibiotics in anionic form are repelled by the negatively charged biochar surface, inhibiting adsorption of TC and DC. However, the removal rate did not change much over the pH range tested, indicating that electrostatic interaction is not the primary mechanism for adsorption of TC and DC by biochar composites, and other forces may form between the antibiotic and the carboxyl and hydroxyl groups on the surface of the new biochar composites. Therefore, the pH value has less influence on the adsorption of TC and DC by the novel biochar composite material.
To study the effect of contaminant concentration and reaction temperature on the treatment effect. Respectively preparing tetracycline hydrochloride and doxycycline hydrochloride solutions with initial concentrations of 5-100 mg/L, respectively taking 25 mL of the solutions, putting the solutions into a 100 mL conical flask, adjusting the pH value to 6.0, and respectively adding 0.1 g of the biochar composite material obtained in the example 1. Sealing the preservative film, setting the reaction temperature to be 298K, 308K and 318K respectively, placing the preservative film into a constant-temperature oscillator with the rotating speed of 170 r/min, oscillating for 24 hours, sampling and measuring, and analyzing the adsorption process by combining with an isotherm model. As can be seen from fig. 5, the experimental data show a lower correlation with the Langmuir model at the three temperatures studied. Adsorption data of the biological carbon composite material for adsorbing TC and DC at three temperatures are higher correlation coefficients with Freundlich, the Freundlich adsorption model assumes that an adsorption process occurs on a heterogeneous surface, and the adsorption capacity is related to equilibrium concentration, which indicates that the biological carbon composite material for adsorbing TC and DC conforms to the Freundlich adsorption model. As can be seen from FIG. 6, compared with the quasi-first order kinetic model, the data of the novel biochar composite adsorbing TC and DC are both similar to the quasi-second order kinetic model (II)R 2 = 0.999) fit better. The fitting result of the quasi-second order kinetic model shows that the process for controlling the adsorption of TC and DC of the biochar composite material is chemical adsorption. Therefore, the adsorption of the biochar composite material on TC and DC is chemical adsorption, and the biochar composite material shows stronger adsorption effect on TC and DC at several temperatures.
Comparative example 1
In contrast to example 1, the biomass preparation procedure was: (1) firstly, preparing a biochar material by adopting a pyrolysis method: putting the raw material of the rice husk powder into a quartz groove, and then putting the quartz groove into a quartz tube furnace. Sealing two ends of the quartz tube, connecting the flexible tube, and filling N into the tube furnace chamber from one end2(400 mL/min), maintaining inert atmosphere during pyrolysis, and collecting the biomass from the other endVolatile products from the pyrolysis of materials. Raising the temperature to 773K at 283K/min, keeping the peak temperature for 2h, cooling to room temperature, grinding, and sieving to obtain the biochar material.
Then, according to the step (2) of the example 1, a biomass composite material was prepared.
Procedure for testing antibiotic removal rate as in example 2: two typical antibiotic solutions (tetracycline hydrochloride and doxycycline) were prepared at an initial concentration of 5 mg/L, respectively, and the pH was adjusted to 6.0. And putting 25 mL of the composite material into a 100 mL conical flask, respectively adding 150 mg of the biochar composite material obtained in the example, sealing the opening of the plastic wrap, setting the reaction temperature to 298K, putting the plastic wrap into a constant-temperature oscillator with the rotation speed of 170 r/min, oscillating for 24 hours, and then sampling for measurement. The biochar composite material obtained in the example has a tetracycline hydrochloride removal rate of 83% and a doxycycline removal rate of 81%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A biochar composite material comprises biochar and nano MnO uniformly doped in the biochar2；
The biochar and the nano MnO2The mass ratio of (50-300) to (1).
2. The material as claimed in claim 1, wherein the biochar composite has a specific surface area of 30-100m2/g。
3. A method for preparing the biochar composite material as claimed in claim 1 or 2, which is characterized by comprising the following steps:
(1) preparing a biochar material by adopting a pyrolysis method: pyrolyzing the mixture containing the biomass at the temperature of 673-; the mixture also contains organic acid and manganese salt;
(2) adding the biochar material into an anaerobic manganese chloride solution, and uniformly stirring in an anaerobic environment to form biochar-Mn2+Mixing;
(3) mixing the biochar-Mn2+And dropwise adding the mixture into a solution containing potassium permanganate and strong base, stirring for reaction, aging at room temperature after the reaction is finished, filtering, drying and grinding to obtain the biochar composite material.
4. The method according to claim 3, wherein the biomass in the step (1) is at least one selected from straw, chaff and straw;
the pyrolysis process in the step (1) is carried out in an inert atmosphere, wherein the inert atmosphere is argon, nitrogen or helium;
in the step (1), the organic acid is selected from at least one of formic acid, acetic acid and benzoic acid, and the mass ratio of the organic acid to the biomass is (0.5-3): 100;
in the step (1), the manganese salt is selected from at least one of manganese chloride, manganese sulfate and manganese nitrate, and the mass ratio of the manganese salt to the biomass is (0.5-3): 100;
the pyrolysis temperature 673-873K in the step (1) is obtained by temperature programming, and the temperature rise rate is 276-288K/min;
the biomass material in the step (1) has an average particle size of 50 to 300 μm.
5. The production method according to claim 3, wherein the concentration of the manganese chloride solution in the step (2) is 1.5 to 4.5 mmol/L;
the mass-volume ratio of the biochar material to the manganese chloride solution in the step (2) is (1-3) to (10-40) g/mL;
the anaerobic environment in the step (2) is obtained by introducing nitrogen into the system;
the stirring time in the step (2) is 1-2 h.
6. The preparation method according to claim 3, wherein in the solution containing potassium permanganate and strong base in step (3), the concentration of potassium permanganate is 1-5mmol/L, and the concentration of strong base is 5-10 mmol/L;
in the step (3), the strong base is sodium hydroxide or potassium hydroxide;
the rotating speed of the stirring reaction in the step (3) is 200-300 r/min, and the time is 10-30 min;
the aging time in the step (3) is 12-36 h;
the drying temperature in the step (3) is 333-363K.
7. The production method according to any one of claims 3 to 6, characterized by comprising the steps of:
(1) loading the mixture containing rice husk powder, organic acid and manganese salt into quartz tank, placing into quartz tube furnace, sealing two ends of quartz tube, and charging N into the quartz tube furnace chamber from one end2Keeping inert atmosphere in the pyrolysis process, and collecting volatile products generated in the biomass pyrolysis process from the other end; heating to 673-873K at 276-288K/min by adopting programmed heating, preserving the heat for 1-3 h under the pressure of 1-10.0 MPa, cooling to room temperature, grinding and sieving to obtain a biochar material;
the mass ratio of the rice husk powder to the organic acid to the manganese salt is 100 (0.5-3) to 0.5-3;
(2) adding 1-5mmol/L manganese chloride solution in N2Purifying for 10-30 min to remove dissolved oxygen, adding 1-3 g of the biochar material obtained in the step (1) into the 10-40 mL of manganese chloride solution, and adding into N2Stirring for 1-2 h to form biochar-Mn2+Mixing;
(3) adding the biochar-Mn dropwise into 10-40 mL of solution containing potassium permanganate and sodium hydroxide2+And (3) continuously stirring the mixture for reaction for 10-30 min, aging at room temperature for 12-36 h, drying at 333-363K, grinding and sieving to obtain the biochar composite material.
8. Biochar composites prepared by the process of any one of claims 3 to 7.
9. Use of the biochar composite of claim 1 or 2 or 8 for treating antibiotic wastewater.
10. Use according to claim 9, characterized in that the treatment of antibiotic wastewater comprises the following steps: adding the biochar composite material into the antibiotic wastewater solution with the concentration of 5-100 mg/L, adjusting the pH value of the system to 2.0-10.0, sealing, setting the reaction temperature to 298-318K, and carrying out constant-temperature oscillation treatment.
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