CN113477218A - Potassium dihydrogen phosphate modified biochar and preparation method and application thereof - Google Patents
Potassium dihydrogen phosphate modified biochar and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides potassium dihydrogen phosphate modified biochar and a preparation method and application thereof, and belongs to the technical field of wastewater treatment. Pretreating raw materials, calcining to obtain biochar, preparing to obtain a potassium dihydrogen phosphate modified solution, adding the biochar into the potassium dihydrogen phosphate modified solution, stirring and filtering to obtain a product, and calcining the product to obtain the potassium dihydrogen phosphate modified biochar. The potassium dihydrogen phosphate modified biochar prepared by the invention has stronger adsorption capacity on lead, and provides a new material and a method for controlling lead pollution of water and comprehensively utilizing agricultural and forestry waste biomass.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, and particularly relates to potassium dihydrogen phosphate modified biochar and a preparation method and application thereof.
Background
Heavy metal pollution caused by wastewater generated by industrial departments such as mining, chemical engineering, petroleum refining and the like has become a serious environmental problem. Pb (II) is a highly toxic heavy metal pollutant widely existing in industrial wastewater, and the excessive discharge of Pb (II) can cause serious harm to the natural environment and human health. The biomass forms stable biochar after pyrolysis and carbonization, can greatly reduce carbon emission generated by biomass combustion and natural degradation, and achieves the purpose of resource utilization of waste production and nutrient waste. The carbonized biomass can be used as a high-efficiency pollution control material for sewage treatment, and can also be applied to soil to store carbon in the soil and improve and repair the soil. The backfilling process of forming the biomass charcoal after carbonization is also a carbon dioxide capture and carbon sink process, is a very effective carbon fixation and emission reduction new way, and has positive significance for the vision goal of' striving for realizing carbon neutralization in 2060 years in China. The market potential of the biomass energy industry is receiving increasing attention under the lead of the "carbon neutralization" goal and the rural joy strategy.
As a novel pollution control material, the biochar has the characteristics of carbon-rich regeneration, rich reserves, environmental friendliness, low price and the like, and has wide prospects in the field of wastewater treatment. The biomass such as straw, corncob and the like produced in the agricultural planting process in China has wide sources and low price, and the prepared biochar has the characteristics of large surface area, large porosity, stable structure and the like, but the plant-derived biochar has more complex physicochemical properties and is difficult to have more outstanding chemical functional properties, the adsorption capacity of the plant-derived biochar on Pb (II) is low, and the plant-derived biochar only comes from lignin in plants, and a large amount of cellulose and hemicellulose are gradually decomposed in the pyrolysis process, so the yield of the plant-derived biochar is low, and the application in the environment is limited to a certain extent. Based on the above, the invention provides potassium dihydrogen phosphate modified biochar, and a preparation method and application thereof, so as to improve the removal capacity of heavy metals in wastewater.
Disclosure of Invention
The invention provides potassium dihydrogen phosphate modified biochar, and a preparation method and application thereof, so as to improve the removal capacity of heavy metals in wastewater.
The invention aims to provide a preparation method of monopotassium phosphate modified biochar, which comprises the following steps:
step 1, raw material pretreatment: soaking the raw materials in deionized water, removing impurities on the surface of the raw materials, drying the raw materials to constant weight, crushing and sieving the dried raw materials to obtain pretreated raw materials;
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.4-0.8mol/L, performing ultrasonic treatment for 20-30min to uniformly disperse the monopotassium phosphate, adding the biochar in the step 2, stirring at room temperature for 2-3 hours, and filtering to obtain a product for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried product in an anaerobic tube furnace, raising the temperature from room temperature to 450-550 ℃ at the rate of 10-20 ℃/min, preserving the temperature for 50-90min, and cooling to room temperature to obtain the potassium dihydrogen phosphate modified biochar.
Preferably, the average particle size of the monopotassium phosphate modified biochar is 438-3221.7nm, and the pH value is 6.50-7.34.
Preferably, the drying temperature in the step 3 is 105-115 ℃, and the drying time is 8-9 h.
Preferably, the raw materials in the step 1 are crushed and sieved by a sieve with the diameter of 1-2 mm; and (3) crushing the dried product in the step (3) and sieving the crushed product by a sieve of 1-2mm before placing the crushed product in an anaerobic tube furnace.
Preferably, the raw material in the step 1 is one of wheat ears, wheat straws, corn straws and cow dung mixture.
Preferably, when the raw material is a mixture of corn stalks and cow dung, the pretreatment of the raw material in the step 1 is specifically as follows: soaking corn straws in deionized water to remove impurities on the surface of the corn straws, drying the corn straws to constant weight, crushing the corn straws, sieving the crushed corn straws with a 2mm sieve, drying cow dung to constant weight, grinding the cow dung with the 2mm sieve, and uniformly mixing the corn straws and the cow dung to obtain a pretreatment raw material; wherein the addition amount of the corn straws is 20 percent of the cow dung.
Preferably, the temperature rise rate in the anaerobic tubular furnace in the step 3 is 15 ℃/min.
The second purpose of the invention is to prepare the potassium dihydrogen phosphate modified biochar according to the method.
The third purpose of the invention is to provide the application of the potassium dihydrogen phosphate modified biochar in wastewater treatment.
Compared with the prior art, the invention has the following beneficial effects:
the invention respectively takes wheat ears, wheat straws, corn straws and corn straw-cow dung as raw materials to prepare biochar, and potassium dihydrogen phosphate is used for modification treatment; the biological carbon prepared by taking wheat as a raw material is mainly used for removing Pb (II) due to chemical precipitation, and the amount of phosphorus-containing mineral substances is increased after potassium dihydrogen phosphate is loaded, so that the precipitation effect with lead is enhanced. The biochar prepared by using the corn as the raw material has loose pores, and a great amount of phosphate minerals in the cow dung are prepared into the biochar which has a good lead removing effect. The removal of Pb (II) by the biochar is mainly the complexing action of functional groups of a surface adsorbent, and the number of the functional groups is increased after the potassium dihydrogen phosphate is modified. The potassium dihydrogen phosphate modified charcoal has strong adsorption capacity on lead, and the invention provides a new material and a method for controlling water lead pollution and comprehensively utilizing agriculture and forestry waste biomass.
Drawings
FIG. 1 is a graph showing the average particle size of each biochar;
FIG. 2 is a graph showing the pH of each biochar;
FIG. 3 is a comparison graph of lead adsorption by adding cow dung to corn raw material;
FIG. 4 is a graph comparing the lead adsorption amounts of different biochar.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly and clearly understood, the technical solutions in the embodiments of the present invention are described below in conjunction with the accompanying drawings and the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
In the examples, the average particle size of biochar and potassium dihydrogen phosphate modified biochar was measured by a laser particle sizer; determination of pH according to mass of solids (g): weighing 1.00g of biochar or potassium dihydrogen phosphate modified biochar according to the liquid volume (mL) of 1:20, adding 20mL of deionized water, stirring for 1h, standing for 10min, and measuring the pH value of the supernatant.
Example 1
Step 1, soaking corn straws in deionized water, removing surface impurities, drying to constant weight, and crushing wheat ears through a 2mm sieve to obtain a pretreated raw material;
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.73mol/L, performing ultrasonic treatment for 20min to uniformly disperse the monopotassium phosphate, adding the biochar in the step 2, stirring for 2 hours at room temperature, performing suction filtration, drying for 8 hours at 105 ℃ to obtain a product, and crushing the product through a 2mm sieve for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an anaerobic tube furnace, raising the temperature from room temperature to 500 ℃ at the heating rate of 15 ℃/min, preserving the temperature for 50min, and cooling to room temperature to obtain the monopotassium phosphate modified biochar, which is marked as CO-K.
Example 2
Step 1, soaking corn straws in deionized water, removing surface impurities, drying to constant weight, crushing wheat ears through a 2mm sieve, and then uniformly mixing the corn straws and cow dung to obtain a pretreatment raw material; wherein the addition amount of the corn straws is 20 percent of the cow dung.
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.73mol/L, performing ultrasonic treatment for 20min to uniformly disperse the monopotassium phosphate, adding the biochar in the step 2, stirring for 2 hours at room temperature, performing suction filtration, drying for 8 hours at 105 ℃ to obtain a product, and crushing the product through a 2mm sieve for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an anaerobic tubular furnace, raising the temperature from room temperature to 500 ℃ at the heating rate of 15 ℃/min, preserving the temperature for 50min, and cooling to room temperature to obtain the potassium dihydrogen phosphate modified biochar, which is marked as COC-K.
Example 3
Step 1, soaking the wheat ears in deionized water to remove surface impurities, drying to constant weight, and crushing the wheat ears through a 2mm sieve to obtain a pretreated raw material;
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.73mol/L, performing ultrasonic treatment for 20min to uniformly disperse the monopotassium phosphate, adding the biochar in the step 2, stirring for 2 hours at room temperature, performing suction filtration, drying for 8 hours at 105 ℃ to obtain a product, and crushing the product through a 2mm sieve for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an oxygen-insulated tube furnace, raising the temperature from room temperature to 500 ℃ at the heating rate of 15 ℃/min, preserving the temperature for 50min, and cooling to room temperature to obtain the monopotassium phosphate modified biochar, which is marked as EOW-K.
Example 4
Step 1, soaking wheat straws in deionized water to remove surface impurities, drying to constant weight, and then crushing the wheat straws through a 2mm sieve to obtain a pretreated raw material;
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.73mol/L, performing ultrasonic treatment for 20min to uniformly disperse the monopotassium phosphate, adding the biochar in the step 2, stirring for 2 hours at room temperature, performing suction filtration, drying for 8 hours at 105 ℃ to obtain a product, and crushing the product through a 2mm sieve for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an anaerobic tube furnace, raising the temperature from room temperature to 500 ℃ at the heating rate of 15 ℃/min, preserving the temperature for 50min, and cooling to room temperature to obtain the monopotassium phosphate modified biochar, which is recorded as WS-K.
Example 5
Step 1, soaking wheat straws in deionized water to remove surface impurities, drying to constant weight, and then crushing the wheat straws through a 1mm sieve to obtain a pretreated raw material;
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.4mol/L, performing ultrasonic treatment for 30min to uniformly disperse the solution, adding the biochar in the step 2, stirring for 3 hours at room temperature, performing suction filtration, drying at 115 ℃ for 9 hours to obtain a product, and crushing the product through a 1mm sieve for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an anaerobic tube furnace, raising the temperature from room temperature to 450 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 90min, and cooling to room temperature to obtain the monopotassium phosphate modified biochar, which is recorded as WS-K.
Example 6
Step 1, soaking corn straws in deionized water to remove surface impurities, drying to constant weight, and then crushing wheat ears and sieving by a 1.43mm sieve to obtain a pretreated raw material;
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.8mol/L, performing ultrasonic treatment for 30min to uniformly disperse the monopotassium phosphate, adding the biochar in the step 2, stirring at room temperature for 2.5 hours, performing suction filtration, drying at 110 ℃ for 9 hours to obtain a product, and crushing the product through a 1.43mm sieve for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an anaerobic tube furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 70min, and cooling to room temperature to obtain the monopotassium phosphate modified biochar, which is marked as CO-K.
Example 7
Step 1, soaking the wheat ears in deionized water to remove surface impurities, drying to constant weight, and crushing the wheat ears through a 2mm sieve to obtain a pretreated raw material;
Step 3, preparing the monopotassium phosphate modified biochar: adding monopotassium phosphate into deionized water to prepare a solution with the concentration of 0.6mol/L, performing ultrasonic treatment for 20min to uniformly disperse the monopotassium phosphate, adding the biochar in the step 2, stirring at room temperature for 2.5 hours, performing suction filtration, drying at 105 ℃ for 8 hours to obtain a product, and crushing the product through a 2mm sieve for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an oxygen-insulated tube furnace, increasing the temperature from room temperature to 480 ℃ at the heating rate of 15 ℃/min, preserving the temperature for 85min, and cooling to room temperature to obtain the monopotassium phosphate modified biochar, which is marked as EOW-K.
Comparative example 1
The biochar prepared by using the corn straws as the raw material is marked as CO, and the specific preparation method is the same as the steps 1-2 in the example 1.
Comparative example 2
The biochar prepared by taking corn straws and cow dung as raw materials is marked as COC, and the specific preparation method is the same as the steps 1-2 in the example 2.
Comparative example 3
The biochar prepared by using the wheat ears as the raw materials is marked as EOW, and the specific preparation method is the same as the steps 1-2 in the embodiment 3.
Comparative example 4
The biochar prepared from wheat straw as a raw material is denoted as WS, and the specific preparation method is the same as the step 1-2 in the example 4.
The average particle size and pH of each biochar were illustrated by examples 1 to 4 and comparative examples 1 to 4, as shown in FIGS. 1 and 2.
The adsorption and fixation of the biochar on the heavy metal in the water body mainly comes from the complexing action of functional groups on the surface of the biochar, and the exchange between the biochar and heavy metal ions acts on the physical adsorption action, wherein the influence of the physical adsorption on the overall adsorption effect is lower. The specific surface area and pore structure of biochar are major factors affecting its physical adsorption and are susceptible to modification conditions. In examples 1 to 4, the particle size of the potassium dihydrogen phosphate-modified biochar was increased and the specific surface area was relatively decreased. As can be seen from FIG. 1, the average particle sizes of CO, COC, EOW and WS are 2958.3nm, 384.9nm, 1900nm and 826.3nm respectively, after the modification by monopotassium phosphate, the average particle sizes of CO-K, COC-K, EOW-K are 263.4nm, 1182.6nm and 451nm respectively larger than the average particle sizes of CO, COC and EOW, and only the average particle size of WS-K is 388.3nm smaller than the average particle size of WS.
FIG. 2 shows the pH values of biochar, and as can be seen from FIG. 2, the pH values of CO-K, COC-K, EOW-K, WS-K are 6.50, 7.16, 7.34 and 7.1 respectively. The pH of the raw biochar is alkaline, probably due to the evolution of alkaline salts from the raw material during thermal cracking, wherein the pH of COC is 1.36 higher than that of CO, probably because cow dung contains a large amount of mineral elements which may start to separate from the organic matrix after carbonization, thus raising the pH of the biochar. After the potassium dihydrogen phosphate modified biochar, the pH was decreased to various degrees, but was kept between 6 and 8, indicating that the content of acidic functional groups of the potassium dihydrogen phosphate modified biochar was increased.
The use of potassium dihydrogen phosphate-modified biochar in wastewater treatment is illustrated below by examples 1 to 4 and comparative examples 1 to 4.
The amount of lead adsorbed was calculated according to the following method
Wastewater simulation: weighing lead nitrate, adding water to dilute and prepare 1000mg/L lead standard stock solution, adding nitric acid to maintain the stability of the stock solution, and simulating wastewater by using the stock solution.
With 0.1mol/L HNO3Adjusting the pH value of the wastewater to 3 with NaOH, respectively weighing 0.05g of different biochar, adding 600mg/L of lead nitrate solution, oscillating at 25 ℃ for 24h at an oscillation rate of 180r/min, filtering, measuring the lead concentration, and obtaining the lead concentration according to the initial lead concentration and the residual lead concentration through a formula Q ═ (C)0-Ce)/C0X 100% lead adsorption rate was calculated by the formula q ═ C0-Ce) The lead adsorption amount was calculated by multiplying V/(m × 1000), wherein Q represents the adsorption rate, and C0Denotes the initial concentration of the solution in mg/L, CeRepresents the adsorption equilibrium concentration of the solution, and the unit is mg/L, and q represents the adsorption quantity of the adsorbent per unit mass; v represents the volume of the reaction solution in mL, and m represents the mass of the adsorbent in g.
Table 1 shows the adsorption amount and adsorption rate of lead by different biochar. The biochar taking the corn as the raw material is easier to adsorb heavy metal lead than the biochar taking the wheat as the raw material, probably because the two have different structures. The specific surface area of the wheat raw material biochar is lower, the pore structure is incomplete, part of pores are burned, mineral substance ash content is more, the pore diameter is larger, in addition, the wheat raw material biochar has higher carbonate, inorganic mineral components such as phosphate and silicon dioxide and higher cation exchange capacity, the corn raw material biochar has a loose structure, more active sites can be exposed, the chemical adsorption is more favorably carried out, more small pores are distributed in the large pores of the corn raw material biochar, the specific surface area of the corn raw material biochar is favorably increased, in addition, the organic carbon and functional groups in the corn raw material biochar have higher content, and the heavy metal ion and oxygen-containing functional group complexing effect also increases the adsorption capacity to heavy metals. Probably, the adsorption effect of the complexing lead is more obvious, so that the adsorption effect of the biochar prepared by taking the corn as the raw material is better than that of the biochar prepared by taking the wheat as the raw material.
TABLE 1 adsorption amount and adsorption rate of lead by different biochar
FIG. 3 is a comparison graph of lead adsorption amounts of cow dung added in corn raw materials, and results show that the COC adsorption amount is slightly lower than CO (lower by 30.1mg/g), but the COC-K adsorption amount is far higher than that of CO-K, and the COC-K adsorption amount is increased by 177.1mg/g and is increased by 59.1% compared with that of CO-K, so that the cow dung is added in corn straws to prepare biochar, and the biochar is modified by potassium dihydrogen phosphate to remarkably increase the lead adsorption amount.
FIG. 4 is a graph comparing the lead adsorption amounts of different biochar. The adsorption effect on lead in water before modification of each biochar is poor, and the adsorption amounts of CO, COC, EOW and WS are respectively 112.4mg/g, 82.3mg/g, 50.9mg/g and 44.8 mg/g. Compared with the adsorption amounts of CO, COC, EOW and WS, the adsorption amounts of CO-K, COC-K, EOW-K, WS-K are respectively increased by 187.4mg/g, 394.6mg/g, 28.8mg/g and 1.7mg/g, the adsorption amounts are respectively increased by 166.8%, 478.0%, 56.6% and 3.8%, the adsorption effects of the monopotassium phosphate modified biochar are greatly improved, wherein the adsorption effect of COC-K on lead is the best, and the adsorption rate reaches 79.5%.
The potassium dihydrogen phosphate is used for modifying the biochar made of different raw materials, and the modifying effect of the biochar made of corn is better than that of the biochar made of wheat, and the reasons for the modifying effect are as follows: the corn stalk biochar has high organic carbon and functional group content, loose pore structure and large specific surface area, and mainly removes Pb (II) in a solution through surface adsorption and the complexing action of the functional group, so that the corn stalk biochar can be well combined with potassium dihydrogen phosphate. The potassium dihydrogen phosphate has stronger adsorption capacity to lead after being modified, and the invention provides a new material and a method for controlling the lead pollution of water and comprehensively utilizing agricultural and forestry waste biomass.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The preparation method of the monopotassium phosphate modified biochar is characterized by comprising the following steps:
step 1, raw material pretreatment: soaking the raw materials in deionized water, removing impurities on the surface of the raw materials, drying the raw materials to constant weight, crushing and sieving the dried raw materials to obtain pretreated raw materials;
step 2, preparing biochar: and (3) placing the pretreated raw materials in an anaerobic tube furnace, heating the raw materials to 450-550 ℃ from room temperature at the heating rate of 10-20 ℃/min, preserving the heat for 50-90min, and cooling the raw materials to room temperature to obtain the biochar.
Step 3, preparing the monopotassium phosphate modified biochar: adding potassium dihydrogen phosphate into deionized water to prepare a solution with the concentration of 0.4-0.8mol/L, performing ultrasonic treatment for 20-30min to uniformly disperse the solution, adding the biochar in the step 2, stirring at room temperature for 2-3 hours, filtering to obtain a product, and crushing and sieving the product for later use; wherein the mass ratio of the potassium dihydrogen phosphate to the biochar is 1: 1;
and (3) placing the dried and sieved product in an anaerobic tube furnace, raising the temperature from room temperature to 450-550 ℃ at the heating rate of 10-20 ℃/min, preserving the temperature for 50-90min, and cooling to room temperature to obtain the potassium dihydrogen phosphate modified biochar.
2. The method for preparing monopotassium phosphate modified biochar as claimed in claim 1, wherein the monopotassium phosphate modified biochar has an average particle size of 438-3221.7nm and a pH value of 6.50-7.34.
3. The method as claimed in claim 1, wherein the drying temperature in step 3 is 105-115 ℃, and the drying time is 8-9 h.
4. The method for preparing monopotassium phosphate modified biochar according to claim 1, wherein the raw materials in step 1 are crushed and sieved by a 1-2mm sieve; and (3) crushing the dried product in the step (3) and sieving the crushed product by a sieve of 1-2mm before placing the crushed product in an anaerobic tube furnace.
5. The method for preparing monopotassium phosphate modified biochar according to claim 4, wherein the raw material in the step 1 is one of wheat ears, wheat straws, corn straw and cow dung mixture.
6. The method for preparing monopotassium phosphate modified biochar as claimed in claim 5, wherein when the raw material is a mixture of corn stalks and cow dung, the pretreatment of the raw material in the step 1 specifically comprises the following steps: soaking corn straws in deionized water to remove impurities on the surface of the corn straws, drying the corn straws to constant weight, crushing the corn straws, sieving the crushed corn straws with a 2mm sieve, drying cow dung to constant weight, grinding the cow dung with the 2mm sieve, and uniformly mixing the corn straws and the cow dung to obtain a pretreatment raw material; wherein the addition amount of the corn straws is 20 percent of the cow dung.
7. The method for preparing monopotassium phosphate modified biochar as claimed in claim 1, wherein the temperature rise rate in the anaerobic tubular furnace in the step 3 is 15 ℃/min.
8. A monopotassium phosphate modified biochar prepared by the method of any one of claims 1 to 7.
9. Use of the monopotassium phosphate-modified biochar of claim 8 in wastewater treatment.
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| CN115646449A (en) * | 2022-12-26 | 2023-01-31 | 农业农村部环境保护科研监测所 | Preparation method of biochar dephosphorizing material and application of biochar dephosphorizing material in adsorption of water body Pb (II) |
| CN116462181A (en) * | 2023-05-08 | 2023-07-21 | 山东建筑大学 | Potassium dihydrogen phosphate modified biochar material, preparation method and application thereof |
| CN117228703A (en) * | 2023-08-21 | 2023-12-15 | 宜都兴发化工有限公司 | Method for reducing impurity fluorine in phosphogypsum |
| CN117339566A (en) * | 2023-09-08 | 2024-01-05 | 东北大学 | Potassium dihydrogen phosphate modified co-pyrolysis biochar-chitosan, preparation method and application |
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| CN114477452A (en) * | 2022-03-08 | 2022-05-13 | 浙江工业大学 | Method for removing tetracycline antibiotics in landfill leachate |
| CN115646449A (en) * | 2022-12-26 | 2023-01-31 | 农业农村部环境保护科研监测所 | Preparation method of biochar dephosphorizing material and application of biochar dephosphorizing material in adsorption of water body Pb (II) |
| CN116462181A (en) * | 2023-05-08 | 2023-07-21 | 山东建筑大学 | Potassium dihydrogen phosphate modified biochar material, preparation method and application thereof |
| CN117228703A (en) * | 2023-08-21 | 2023-12-15 | 宜都兴发化工有限公司 | Method for reducing impurity fluorine in phosphogypsum |
| CN117339566A (en) * | 2023-09-08 | 2024-01-05 | 东北大学 | Potassium dihydrogen phosphate modified co-pyrolysis biochar-chitosan, preparation method and application |
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Application publication date: 20211008 |