CN111644149B - Preparation method of composite modified functional pig manure charcoal - Google Patents
Preparation method of composite modified functional pig manure charcoal Download PDFInfo
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Abstract
A composite modified functional pig manure carbon is characterized in that pig manure carbon modified by magnetic fly ash, chitosan, a dilute acid solution and deionized water are subjected to amination treatment, washing, filtering and drying. The invention also discloses a preparation method of the composite modified functional pig manure carbon. The waste pig manure and fly ash are fully utilized, and the composite modified functional pig manure carbon is obtained through high-temperature carbonization and amination treatment, can be used for adsorbing nitrogen and phosphorus in biogas slurry, is recycled in farmlands, and realizes efficient recycling and harmless treatment of the biogas slurry.
Description
Technical Field
The invention relates to activated carbon, in particular to modified pig manure carbon, which is applied to adsorption and recycling of nitrogen and phosphorus in biogas slurry and belongs to the field of comprehensive utilization of wastes and water treatment.
Background
The wastes of pig manure, cow manure, chicken manure and the like in the breeding industry are not harmlessly treated and utilized and are discharged randomly or directly discarded, so that a large amount of mineral nutrient elements such as nitrogen, phosphorus and potassium are lost, serious pollution hazards are caused to the water body environment, the soil environment and the atmospheric environment, and the health of human beings and animals is endangered.
Currently, many studies are being conducted to make these excreta into bioactive carbon as an environmental functional material, such as for decolorization, adsorption of heavy metals or other pollutants.
For related documents, reference may be made to the chinese patent application publication No. 201410248431.X, which discloses a method for preparing powdered activated carbon from cow dung (application publication No. CN 104003386A), and the method for preparing powdered activated carbon from cow dung is prepared from cow dung as a raw material by activating a composite activating agent formed by mixing phosphoric acid and a phosphoric acid series for 24 hours and then carbonizing at a high temperature.
Reference may also be made to the chinese patent application publication No. 201710399933.6, which discloses a method for producing pig manure biochar (application publication No. CN 107161975A), wherein pig manure raw material is uniformly mixed with calcium hydroxide to obtain pig manure mixture; drying the pig manure mixture; preparing a dried pig manure mixture into a stick and slicing; and carbonizing the pig manure mixture after the rod is sliced to prepare the pig manure biochar.
See also Chinese invention patent application with application number CN201811599838.1, which discloses a preparation method and application of alkali fused fly ash modified pig manure biochar (application publication number CN 109382073A), the application mixes fly ash and sodium hydroxide and then bakes the mixture to obtain alkali fused fly ash; and adding the alkali fusion fly ash into the pig manure to finally obtain the alkali fusion fly ash modified pig manure biochar.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a composite modified functional pig manure charcoal aiming at the technical status quo.
The second technical problem to be solved by the invention is to provide a composite modified functional pig manure carbon with strong nitrogen and phosphorus adsorption capacity aiming at the technical current situation.
The third technical problem to be solved by the invention is to provide a preparation method of the composite modified functional pig manure carbon with strong nitrogen and phosphorus adsorption capacity in biogas slurry aiming at the technical current situation.
The technical solution adopted by the present invention to solve the first and second technical problems is: the composite modified functional pig manure carbon is characterized in that magnetic fly ash modified pig manure carbon, chitosan, a dilute acid solution and deionized water are subjected to amination treatment, washing, filtering and drying, the mass ratio of the magnetic fly ash modified pig manure carbon to the chitosan is 2: 0.5-2: 1.0, and the dilute acid solution is HNO with the mass percentage concentration of 10-20% 3 Or H 2 SO 4 The ratio of the dilute acid solution to the deionized water is 1: 1.5-1: 2, and the solid-liquid volume ratio is 1: 3-1: 5.
The pig manure carbon modified by the optimized magnetic fly ash is prepared by the following method: the magnetic fly ash modified pig manure carbon is prepared from magnetic fly ash, dry pig manure powder and metal salt serving as raw materials and deionized water serving as a medium by oscillating, primary washing, filtering, primary drying, high-temperature carbonization, secondary washing and secondary drying, wherein the adding mass ratio of the magnetic fly ash to the dry pig manure powder is 1: 3-1: 5, and the metal salt is ZnCl 2 Or FeCl 3 The metal salt accounts for 3-5% of the total mass of the raw materials.
Further, Fe in the composite modified functional pig manure powder 3 O 4 The mixing amount is 5-15 wt%; the content of amino groups doped in the amination treatment is 5-10 wt%.
The technical scheme adopted by the invention for solving the third technical problem is as follows: a preparation method of compound modified functional pig manure powder is characterized by comprising the following steps:
dehydrating pig manure, wherein the water content of the dehydrated pig manure is 80-85%, and sequentially carrying out acid washing, drying and crushing to obtain dry pig manure powder; washing, drying and crushing the fly ash, and obtaining magnetic fly ash after magnetic field separation;
secondly, mixing the magnetic fly ash and the dry pig manure powder, adding deionized water and metal salt, oscillating for 4-8 hours at 35-50 ℃ and 200-350 r/min, then washing, filtering, and drying the product in vacuum for 12-24 hours at 90-110 ℃; calcining and carbonizing, washing the carbonized product, and drying in vacuum at 90-110 ℃ for 12-24 h to obtain magnetic fly ash modified pig manure carbon;
thirdly, adding chitosan, a dilute acid solution and deionized water into the magnetic fly ash modified pig manure carbon, firstly carrying out ultrasonic treatment for 2-6 h, then carrying out amination treatment, washing and filtering the product, and then carrying out vacuum drying for 12-24 h at the temperature of 90-110 ℃ to obtain the composite modified functional pig manure carbon.
Preferably, the acid washing, drying and crushing conditions of the pig manure in the step (I) are as follows: 1-2 mol/L H is adopted 3 PO 4 Or HNO 3 Dipping, stirring for 3-5 h, drying in an oven at 85-120 ℃ for 12-24 h, and then crushing to obtain particles<0.1mm。
Preferably, the magnetic field condition of the fly ash in the step (i) is as follows: separating magnetic metal in fly ash by high gradient magnetic separation equipment, introducing fly ash from the top of the equipment, introducing pure water into the side edge of the equipment, and allowing the magnetic field gradient to reach 10 4 ～10 8 T/m, the medium filling rate is 4-14%, the adding mass ratio of the fly ash to the pure water is 1: 1.5-1: 2.5, and the magnetic separation time is 30-90 minutes.
Preferably, the calcination carbonization conditions in the step (II) are as follows: the product is placed in a tube furnace, N 2 Raising the temperature to 550-750 ℃ at a constant speed of 5-10 ℃/min in an atmosphere with a speed of 300-600 mL/min, then continuously keeping the temperature for 3-5 h, and cooling to room temperature after the heat preservation time is over.
Preferably, the amination conditions in step (c) are as follows: and (3) completing amination treatment in a microwave digestion instrument under the power of 600-800W.
Preferably, the washing conditions in step (c) are as follows: washing with absolute ethyl alcohol and tap water alternately until the pH value of the solution is neutral.
Compared with the prior art, the invention has the advantages that: the pig manure is prepared into biochar which has a developed pore structure, rich oxygen-containing functional groups and a stable aromatized structure. As an environment functional material, the fertilizer can also improve soil fertility, improve nutrient element circulation, improve nutrient utilization rate and increase crop yield. More importantly, the raw materials are low in cost and easy to regenerate.
Fly ash is mainly from coal-fired power plants. The discharge amount of the fly ash in China is increased year by year, but the comprehensive utilization rate is only 30-40%. As a porous material, the fly ash has the advantages of large porosity, large specific surface area and the like. In addition, the physical and chemical properties of the fly ash and the biochar can play a role in soil improvement and restoration. Fe in fly ash 3 O 4 Can improve the activity of soil enzymes, and the biochar provides a place for the growth and reproduction of microorganisms by the unique pore structure of the biochar.
The waste pig manure and fly ash are fully utilized, and the composite modified functional pig manure carbon is obtained through high-temperature carbonization and amination treatment, can be used for adsorbing nitrogen and phosphorus in biogas slurry, is recycled in farmlands, realizes efficient recycling and harmless treatment of the biogas slurry, and enables the economic cost and the environmental benefit to reach the optimal level. The treatment of pig manure in livestock and poultry farms can be coupled with biogas slurry treatment to serve as farmland carbon-based fertilizer, pollution control and resource utilization are realized, and the application prospect is wide.
Drawings
FIG. 1 is an electron microscope picture of the composite modified functional pig manure carbon obtained in example 1.
FIG. 2 is an electron microscope picture of the composite modified functional pig manure carbon obtained in example 2.
FIG. 3 is an electron microscope picture of the composite modified functional pig manure carbon obtained in example 3.
FIG. 4 is an electron microscope picture of ordinary pig manure charcoal.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
Preparing materials:
1) raw material treatment: dehydrating raw material pig manure to the water content of about 80 percent, and adopting 1mol/L HNO 3 Dipping and stirringDrying for 3h in an oven at 90 deg.C for 20 hr, and pulverizing to particle size<0.1mm, and obtaining the dry pig manure powder. Washing fly ash with water for 2 times, drying in an oven at 90 ℃ for 20 hours, crushing and sieving.
2) Magnetic separation of fly ash: high-gradient magnetic separation equipment is adopted to separate Fe in fly ash 3 O 4 Feeding the fly ash treated in the step 1) from the top of the equipment, introducing pure water into the side edge of the equipment, wherein the adding mass ratio of the fly ash to the pure water is 1:2. magnetic field gradient of up to 10 4 T/m, the medium filling rate reaches 6%, and the magnetic fly ash is obtained after 30 minutes of magnetic field separation.
3) Modification and high-temperature carbonization: magnetic fly ash (mainly Fe) obtained in the step 2) 3 O 4 ) Mixing with dry pig manure powder, wherein the adding mass ratio of the magnetic fly ash to the dry pig manure powder is 1:3, adding deionized water and ZnCl with the mass fraction of 40 percent 2 Adding 3% of the active carbon into the solution, oscillating the solution in a constant temperature oscillator for 4 hours at 35 ℃ and 200r/min, washing the solution to be neutral by using tap water, and filtering the solution. And (3) placing the product at 90 ℃ and drying for 20h in vacuum. Placing the dried product in a tube furnace in N 2 Raising the temperature to 550 ℃ at a constant speed of 5 ℃/min under the atmosphere of 300mL/min, and then continuing to keep the temperature constant for 3 h. And after the heat preservation time is finished, cooling to room temperature, alternately washing the product subjected to carbonization treatment to be neutral by using absolute ethyl alcohol and tap water, and drying for 20 hours in vacuum at the temperature of 90 ℃ to obtain the magnetic fly ash modified pig manure carbon.
The metal salt zinc chloride is an activating agent of the pig manure carbon and has the catalytic dehydration function at high temperature; can play a role of a skeleton during carbonization, and can prepare the pig manure carbon with developed micropores. The pore-forming of the zinc chloride on the raw material is generally carried out at temperatures of 400 ℃ and higher. Along with the increase of the activation temperature, the reaction rate is increased continuously, the activation is more violent, a large number of micropores can be generated, the specific surface area of the prepared pig manure carbon is larger, and the types of oxygen-containing functional groups on the surface are more. In addition, the pig manure carbon after high-temperature calcination and carbonization is also beneficial to the loading of the magnetic fly ash and the adsorption. The dilute acid treatment is used for purification on one hand and is used for pretreatment for loading amino to remove organic impurities on the other hand.
4) Amination treatment: adding chitosan and HNO with the concentration of 10 percent into the magnetic fly ash modified pig manure carbon prepared in the step 3) 3 The mass ratio of the solution to the deionized water to the modified pig manure carbon to the chitosan is 2:1, the mass ratio of the dilute acid solution to the deionized water is 1:1.5, the solid-liquid volume ratio is 1: 3. the ultrasonic treatment is carried out for 2h, and then the amination treatment is completed in a microwave digestion instrument under the power of 600W. And alternately washing the product by absolute ethyl alcohol and tap water until the pH value of the solution is neutral, filtering, and drying in vacuum at 90 ℃ for 20 hours to obtain the compound modified functional pig manure carbon 1.
Example 2
Preparing materials:
1) raw material treatment: dehydrating raw material pig manure to the water content of about 82 percent, and adopting 1mol/L HNO 3 Soaking, stirring for 4 hr, oven drying at 100 deg.C for 16 hr, and pulverizing to particle size<0.1mm, and obtaining the dry pig manure powder. Washing fly ash with water for 3 times, drying in oven at 100 deg.C for 16 hr, pulverizing, and sieving.
2) Magnetic separation of fly ash: high-gradient magnetic separation equipment is adopted to separate Fe in fly ash 3 O 4 Feeding the fly ash treated in the step 1) from the top of the equipment, introducing pure water into the side edge of the equipment, wherein the adding mass ratio of the fly ash to the pure water is 1:2. magnetic field gradient of up to 10 6 T/m, the medium filling rate reaches 10%, and the magnetic fly ash is obtained after magnetic field separation for 60 minutes.
3) Modification and high-temperature carbonization: magnetic fly ash (mainly Fe) obtained in the step 2) 3 O 4 ) Mixing with dry pig manure powder, wherein the adding mass ratio of the magnetic fly ash to the dry pig manure powder is 1: 4, adding deionized water and ZnCl with the mass fraction of 40 percent 2 The mass percent of the additive is 4 percent, the mixture is oscillated in a constant temperature oscillator for 6 hours at 40 ℃ and 300r/min, and then the mixture is washed to be neutral by tap water and filtered. The product is dried in vacuum for 16h at 100 ℃. Placing the dried product in a tube furnace in N 2 Raising the temperature to 600 ℃ at a constant speed of 5 ℃/min in an atmosphere with the speed of 400mL/min, and then continuing to keep the temperature for 4 h. After the heat preservation time is over, cooling to room temperature, and adding absolute ethyl alcohol into the carbonized productAnd alternately washing the mixture to be neutral by tap water, and drying the mixture for 16 hours in vacuum at the temperature of 100 ℃ to obtain the magnetic fly ash modified pig manure carbon.
4) Amination treatment: adding chitosan and HNO with the concentration of 15 percent into the magnetic fly ash modified pig manure carbon prepared in the step 3) 3 The mass ratio of the solution to the deionized water added with the modified pig manure carbon to the chitosan is 2:1, the mass ratio of the dilute acid solution to the deionized water is 1:1.5, the solid-liquid volume ratio is 1: 3. the ultrasonic treatment is carried out for 4h, and then the amination treatment is completed in a microwave digestion instrument under the power of 700W. And alternately washing the product by adopting absolute ethyl alcohol and tap water until the pH value of the solution is neutral, filtering, and drying for 16 hours in vacuum at the temperature of 100 ℃ to prepare the compound modified functional pig manure carbon 2.
Example 3
Preparing materials:
1) raw material treatment: dehydrating the raw material pig manure until the water content is about 85 percent, and adopting 2mol/L HNO 3 Soaking, stirring for 4 hr, oven drying at 100 deg.C for 15 hr, and pulverizing to obtain particle size<0.1mm, and obtaining the dry pig manure powder. Washing fly ash with water for 4 times, drying in an oven at 120 deg.C for 12 hr, pulverizing, and sieving.
2) Magnetic separation of fly ash: high-gradient magnetic separation equipment is adopted to separate Fe in fly ash 3 O 4 Feeding the fly ash treated in the step 1) from the top of the equipment, introducing pure water into the side edge of the equipment, wherein the adding mass ratio of the fly ash to the pure water is 1:2. magnetic field gradient of up to 10 8 T/m, the medium filling rate reaches 14%, and the magnetic fly ash is obtained after magnetic field separation for 90 minutes.
3) Modification and high-temperature carbonization: magnetic fly ash (mainly Fe) obtained in the step 2) 3 O 4 ) Mixing with dry pig manure powder, wherein the adding mass ratio of the magnetic fly ash to the dry pig manure powder is 1: 4, adding deionized water and ZnCl with the mass fraction of 40 percent 2 The mass percent of the additive is 5 percent, the mixture is oscillated in a constant temperature oscillator for 8 hours at 50 ℃ and 350r/min, and then the mixture is washed to be neutral by tap water and filtered. The product is dried in vacuum at 120 ℃ for 12 h. Placing the dried product in a tube furnace in N 2 At a rate of 10 ℃/min under an atmosphere of 600mL/minRaising the temperature to 750 ℃ at a constant speed, and then continuing to keep the temperature constant for 5 hours. And after the heat preservation time is finished, cooling to room temperature, alternately washing the product subjected to carbonization treatment to be neutral by using absolute ethyl alcohol and tap water, and drying for 12 hours in vacuum at the temperature of 120 ℃ to obtain the magnetic fly ash modified pig manure carbon.
4) Amination treatment: adding chitosan and HNO with the concentration of 20 percent into the magnetic fly ash modified pig manure carbon prepared in the step 3) 3 The mass ratio of the solution to the deionized water added with the modified pig manure carbon to the chitosan is 2:1, the mass ratio of the dilute acid solution to the deionized water is 1:1.5, the solid-liquid volume ratio is 1: 3. the ultrasonic treatment is carried out for 6h, and then the amination treatment is completed in a microwave digestion instrument under the power of 800W. And alternately washing the product by absolute ethyl alcohol and tap water until the pH value of the solution is neutral, filtering, and drying in vacuum at 120 ℃ for 12 hours to obtain the compound modified functional pig manure carbon 3.
The application of the prepared composite modified functional pig manure carbon in biogas slurry nitrogen and phosphorus recovery is realized, and the specific implementation method is as follows:
the adsorption of nitrogen and phosphorus elements in the biogas slurry is realized by two reactors, wherein the first reactor is a fast filter tank for removing fine suspended substances in the biogas slurry, the filtering speed is 6m/h, a quartz sand filter material is adopted, and the thickness of a sand layer is about 70 cm. The second reactor is an adsorption tower which is divided into three layers, biogas slurry enters from the bottom and exits from the top, the inflow velocity is 30cm/s, and the biogas slurry sequentially passes through a middle grating, three pig manure carbon layers and a middle grating from bottom to top. Wherein the volume ratio from the bottom up of three-layer pig manure charcoal layer is 3 in proper order: 2:1, the hydraulic retention time is 48 h. And when the adsorption balance is achieved, the separated relatively clean biogas slurry is used as farmland irrigation or farm washing water, and the composite modified functional pig manure carbon in the adsorption tower is dried or dried to obtain the slow-release carbon-based fertilizer and returned to the field.
FIG. 4 is a photomicrograph of ordinary pig manure carbon (obtained by direct carbonization without magnetic fly ash modification and amination treatment). Referring to FIGS. 1, 2 and 3, the pig manure carbon in FIGS. 1, 2 and 3 has rough surface and porous structure, metal oxide is embedded into the pores, and the specific surface area of the material reaches 115cm when the material is subjected to pore measurement 3 /g、121cm 3 /g、111m 2 The volume of the medium and large pores is 0.212cm 3 /g、0.232cm 3 /g、0.203cm 3 Each g belongs to a mesoporous structure, and the contained iron oxide is mainly Fe of magnetic fly ash 3 O 4 The contents are respectively 8.4 wt%, 8.1 wt% and 7.7 wt%, and the contents of amino groups doped by amination are respectively 5.6 wt%, 5.8 wt% and 5.3 wt%.
The nitrogen and phosphorus adsorption performance of the composite modified functional pig manure carbon is analyzed, data in table 1 show that amino grafting and fly ash modification greatly improve the adsorption capacity of the pig manure carbon, the composite modified functional pig manure carbon has efficient adsorption on ammonia nitrogen, total nitrogen and total phosphorus of biogas slurry, the maximum adsorption capacity of the ammonia nitrogen is respectively 2.13 times, 1.91 times and 2.24 times higher than that of the common pig manure carbon, the maximum adsorption capacity of the total nitrogen is respectively 1.78 times, 1.94 times and 1.68 times higher than that of the common pig manure carbon, the maximum adsorption capacity of the total phosphorus is respectively 2.62 times, 2.12 times and 2.37 times higher than that of the common pig manure carbon, the treated nitrogen and phosphorus pollution of the biogas slurry is efficiently recycled to the functional pig manure carbon, the water quality of the biogas slurry is obviously improved, the requirement of farmland irrigation water quality is basically met, and the method can be used for irrigation or cleaning of livestock and poultry farms.
Table 1 comparison of common pig manure carbon and composite modified functional pig manure carbon in each embodiment on biogas slurry nitrogen and phosphorus adsorption performance
When the slow-release carbon-based fertilizer is applied, the content of nitrogen and phosphorus is measured, the optimal application amount is determined according to the physicochemical properties of soil, the application proportion is 3%, the influence of the application of the carbon-based fertilizer on the soil and crops is analyzed by adopting a basin picking experiment, and the data in table 2 show that after the slow-release carbon-based fertilizer is applied, the physicochemical properties of the soil are improved, the volume weight of the soil is respectively reduced by 13.7%, 11.1% and 8.5%, the fertilizer is more suitable for planting the crops, the original pH of the soil is acidic soil, the pH value is obviously increased after the carbon-based fertilizer is applied, and the soil acidification is effectively relieved. The carbon-based fertilizer is applied to improve the organic matter content of the soil by 23.3 percent, 18.8 percent and 26.9 percent, and effectively improve the fertility of the soil. The application of the carbon-based fertilizer improves the yield of the tomatoes, and the range of the tomato yield reaches over 50 percent, so that the carbon-based fertilizer obtained by the composite modification of the functional pig manure after saturation adsorption improves the soil structure and improves the fertility and also increases the plant yield, and has good practical application value.
Table 2 shows the effect of the modified functional pig manure charcoal on soil improvement and yield increase
The composite modified functional pig manure carbon is used for adsorbing nitrogen and phosphorus elements in biogas slurry, is used as a slow-release carbon-based fertilizer to be returned to the field after being adsorbed and saturated, and has the advantages of high and stable performance, economy, environmental protection, high recovered energy and easy application; the clean biogas slurry after adsorption and separation can be used as farmland irrigation or farm washing water, and is suitable for biogas slurry treatment engineering application or existing engineering improvement; the raw materials are from waste pig manure and fly ash, belong to the preparation technology of 'treating waste with waste' and sustainable development, effectively solve the problem of high added value utilization of the pig manure and the fly ash, and have good economic and environmental benefits.
Claims (6)
1. A preparation method of composite modified functional pig manure carbon is characterized by comprising the steps of carrying out amination treatment, washing, filtering and drying on pig manure carbon modified by magnetic fly ash, chitosan, a dilute acid solution and deionized water, wherein the adding mass ratio of the magnetic fly ash modified pig manure carbon to the chitosan is 2: 0.5-2: 1.0, and the dilute acid solution adopts HNO with the mass percentage concentration of 10-20% 3 Or H 2 SO 4 The ratio of the dilute acid solution to the deionized water is 1: 1.5-1: 2, and the solid-liquid volume ratio is 1: 3-1: 5;
the magnetic fly ash modified pig manure carbon is prepared from magnetic fly ash, dry pig manure powder and metal salt serving as raw materials and deionized water serving as a medium by oscillating, primary washing, filtering, primary drying, high-temperature carbonization at 550-750 ℃, secondary washing and secondary drying, wherein the adding mass ratio of the magnetic fly ash to the dry pig manure powder is 1: 3-1: 5, and the metal salt is ZnCl 2 Or FeCl 3 Metal salts ofThe adding mass proportion accounts for 3-5% of the total mass of the raw materials;
the method comprises the following steps:
step (ii) of
The amination conditions described in (1) are as follows: and (3) completing amination treatment in a microwave digestion instrument under the power of 600-800W.
2. The method according to claim 1, wherein the modified functional carbon is Fe-rich in pig manure 3 O 4 The mixing amount is 5-15 wt%; the content of amino groups doped in the amination treatment is 5-10 wt%.
3. The method according to claim 1, characterized by the steps of
The pickling, drying and crushing conditions of the pig manure are as follows: 1-2 mol/L H is adopted 3 PO 4 Or HNO 3 Dipping, stirring for 3-5 h, drying in an oven at 85-120 ℃ for 12-24 h, and crushing to obtain particle size<0.1 mm。
4. The method of claim 1, wherein the steps are carried out in the same manner as described above
The magnetic field condition of the fly ash is as follows: separating magnetic metal in fly ash by high gradient magnetic separation equipment, introducing fly ash from the top of the equipment, introducing pure water into the side edge of the equipment, and allowing the magnetic field gradient to reach 10 4 ~10 8 T/m, the medium filling rate is 4-14%, the addition mass ratio of the fly ash to pure water is 1: 1.5-1: 2.5, and the magnetic separation time is 30-90 minutes.
5. The method according to claim 1, characterized by the steps of
The calcining and carbonizing conditions are as follows: the product is placed in a tube furnace, N 2 Raising the temperature to 550-750 ℃ at a constant speed of 5-10 ℃/min in an atmosphere with a speed of 300-600 mL/min, then continuously keeping the temperature for 3-5 h, and cooling to room temperature after the heat preservation time is over.
6. The method according to claim 1, characterized by the steps of
The washing conditions described in (1) are as follows: washing with anhydrous alcohol and tap water alternately until the pH value of the solution is neutral.
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