CN113198419A - Substrate in-situ covering nitrogen resistance control removal material and preparation method and application thereof - Google Patents
Substrate in-situ covering nitrogen resistance control removal material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113198419A CN113198419A CN202110429501.1A CN202110429501A CN113198419A CN 113198419 A CN113198419 A CN 113198419A CN 202110429501 A CN202110429501 A CN 202110429501A CN 113198419 A CN113198419 A CN 113198419A
- Authority
- CN
- China
- Prior art keywords
- substrate
- nitrogen
- calcium bentonite
- particles
- black carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a substrate in-situ covering nitrogen resistance control removal material and a preparation method and application thereof, the material is in the form of porous black carbon particles, the particle size of the material is larger than 0.5mm, the components comprise biochar, calcium bentonite and sodium carbonate, the mass ratio of the biochar to the calcium bentonite is 1: 2-1: 6, and sodium bicarbonate is used as a pore-forming agent and is added in an amount of 5% of the total mass of the biochar and the calcium bentonite. The preparation method is characterized in that charcoal powder prepared by using poplar chips as biomass raw materials and calcium bentonite are activated at high temperature to prepare black charcoal particles. The application is that the black carbon particles are laid on the eutrophic substrate to achieve the purposes of controlling nitrogen of the substrate and reducing the risk of secondary pollution. The invention realizes the purpose of removing the nitrogen resistance of the substrate and overcomes the problems of overlarge laying thickness of the covering agent, easy disturbance and easy ingestion by benthonic animals.
Description
Technical Field
The invention relates to a substrate in-situ covering nitrogen resistance control removal material and a preparation method and application thereof, belonging to the technical field of water environment pollution treatment.
Background
The substrate is used as the largest global ecosystem and is the source and sink of the migration and transformation of a plurality of pollutants (nutrient elements, heavy metals and persistent organic pollution). Urban rivers have been accumulated in various pollutants due to discharge of industrial wastewater, domestic sewage, and the like all the year round. With the proposal of action plan for preventing and treating water pollution, the exogenous pollution control strength is enhanced, the water environment quality is improved, and simultaneously, the substrate has the risk of secondary pollution caused by the release of accumulated pollution. The nitrogen released by the substrate can be a leading factor for causing water eutrophication under certain conditions. Therefore, endogenous pollution control is especially necessary.
The substrate in-situ covering technology can effectively control the release of endogenous pollutants, and compared with ex-situ repairing technologies such as dredging, the construction is convenient because the substrate does not need to be transferred, and the influence on environmental conditions is small. However, the application of the substrate covering technology still has the following problems: (1) the covering material has poor pollution control effect, and the thickness of a laying layer needs to be increased for effectively controlling the release of pollutants, so that the water level is raised, and the water volume is reduced; (2) the covering material has small mass and is easy to float by disturbance of water flow, benthonic animals and the like, so that the covering effect is influenced; (3) the covering material has small volume and is easy to be ingested by benthic organisms, thereby generating adverse ecological effect.
The existing patent, namely an in-situ remediation method for sediment nitrogen nutritive salt pollution (patent application number: 201210502673.8), proposes that clinoptilolite, palygorskite and diatomite are used for preparing a nitrogen immobilization material and mixed with a slow-release oxygen material and loaded into an in-situ remediation pile, so that ammonia nitrogen in a substrate can be effectively adsorbed, but the thickness of a covering layer is as high as 20-30 cm, and the method is not suitable for shallow rivers and lakes. The carbon material is used as an active covering material, and compared with physical masking covering materials such as gravel, fly ash and the like, the carbon material has better physical and chemical adsorption performance on pollutants, and can effectively reduce the thickness of a covering layer. However, the carbon material formed by pyrolysis is light and easy to float, and is not suitable for use as a covering material. In the existing patent of an in-situ covering and repairing method of water body heavy metal polluted sediment (patent application number: 201710012038.4), a plurality of materials are covered in multiple layers to repair the heavy metal polluted sediment, wherein the lowermost layer is a mixed packing layer of activated carbon and sand grains. The method of covering with sand particles can reduce floating, but reduce the effect of blocking pollutants. In order to ensure effective pollutant blocking, the thickness of a paving layer needs to be increased or the paving layer needs to be combined with other paving materials, so that the cost and the construction difficulty are increased.
Disclosure of Invention
In order to solve the technical problems, the invention provides a substrate in-situ covering nitrogen resistance control removal material and a preparation method and application thereof, and the specific technical scheme is as follows:
a substrate in-situ covering nitrogen resistance control removal material is in the form of porous black carbon particles, the particle size is larger than 0.5mm, the components comprise biochar, calcium bentonite and sodium carbonate, a large number of pore structures are arranged between the biochar and the calcium bentonite, and the surface of the biochar forms a microporous structure due to high-temperature pyrolysis; the mass ratio of the biochar to the calcium bentonite is 1: 2-1: 6.
Further, the sodium carbonate accounts for 4-6% of the total mass of the biochar and the calcium bentonite.
The preparation method of the substrate in-situ covering nitrogen resistance control removal material comprises the following steps:
the method comprises the following steps: sieving poplar chips, drying, and then putting into an atmosphere furnace for high-temperature pyrolysis to obtain charcoal powder;
step two: uniformly mixing calcium bentonite, sodium bicarbonate and charcoal powder, adding a proper amount of water, stirring to form particles, drying the particles, and performing high-temperature activation to prepare the black carbon particles.
Further, the first step specifically comprises: sieving poplar chips with a sieve of 10-30 meshes, putting the poplar chips into an oven of 80 ℃ for drying until the water content is lower than 5 wt%, putting the poplar chips into an atmosphere furnace after drying, introducing nitrogen with the flow rate of 0.3-0.5L/min, heating to 500-700 ℃ at the heating rate of 5 ℃/min, and standing for 120min for high-temperature pyrolysis to obtain the charcoal powder.
Further, the second step is specifically as follows: mixing charcoal powder, calcium bentonite and sodium bicarbonate according to a mass ratio of 20: 40-120: 3-7, adding 20mL of deionized water, uniformly stirring to obtain particles, drying in an oven at 80 ℃, drying until the water content is lower than 5%, placing the dried particles in an atmosphere furnace, introducing nitrogen at the flow rate of 0.3-0.5L/min, heating to 200 ℃ at the heating rate of 2-5 ℃/min, standing for 30min, volatilizing sodium bicarbonate to generate carbon dioxide to form a porous structure, heating to 580 ℃ at the heating rate of 5-10 ℃/min, standing for 30min, and activating the black carbon particles at high temperature.
The application of the substrate in-situ covering nitrogen-controlled removal material comprises the following steps:
the black carbon particles prepared by the method are used as a substrate covering agent, and are flatly paved on a polluted substrate through a barge, wherein the paving thickness is 3-5 cm;
if the aquatic vegetation recovery needs to be carried out on the polluted substrate in the later period, the black carbon particles and the polluted substrate are mixed in equal volume proportion, and the black carbon particles are flatly paved on the polluted substrate through a barge.
The invention has the beneficial effects that:
the wood chip biochar pyrolyzed at medium temperature and low speed has higher graphitization degree than the biochar prepared at low temperature, retains partial surface active groups, and has good fixing and removing effects on nitrogen. The addition of the calcium bentonite overcomes the defects that the charcoal powder is difficult to settle and is easy to be ingested by benthic organisms, and meanwhile, the bentonite also has good adsorption capacity on nitrogen, so that the nitrogen fixing capacity of the prepared black charcoal particles cannot be reduced due to mixed doping.
The method utilizes wood dust as a biomass raw material, adds calcium bentonite and a small amount of sodium bicarbonate, prepares the black carbon particle covering agent under the conditions of medium-low temperature pyrolysis and activation, effectively controls the release of substrate nitrogen, particularly ammonia nitrogen, and promotes the conversion of the nitrogen and the utilization of the nitrogen by microorganisms. Overcoming the floating phenomenon of the covering agent caused by hydraulic disturbance and the like. The materials are environment-friendly, the preparation method is simple, the maximum utilization of resources is achieved, the problem of water environment pollution is effectively solved, and good economic benefit and environmental benefit are achieved.
The invention realizes the purpose of removing the nitrogen resistance of the substrate and overcomes the problems of overlarge laying thickness of the covering agent, easy disturbance and easy ingestion by benthonic animals.
Drawings
FIG. 1 is a photograph of a real object of example 4 of the present invention;
FIG. 2 is an SEM photograph of example 4 of the present invention;
FIG. 3 is a contour diagram and a three-dimensional curved surface diagram of the optimized preparation conditions of the materials in example 10;
FIG. 4 is a graph showing isothermal adsorption of example 4 material on ammonia nitrogen;
FIG. 5 is a graph showing the change of nitrogen element with time in example 11.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings.
Example 1:
according to the invention, charcoal powder prepared by using poplar chips as a biomass raw material and calcium-based bentonite are activated at high temperature to prepare black carbon particles, and the black carbon particles are laid on a eutrophic substrate, so that the purposes of controlling nitrogen in the substrate and reducing the risk of secondary pollution are achieved.
The preparation process of the black carbon particles in the embodiment is as follows:
s1: sieving poplar chips with a 20-mesh sieve, drying in an oven at 80 ℃ for 12h, drying, putting in an atmosphere furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 600 ℃ at the heating rate of 5 ℃/min, standing for 120min, and performing high-temperature pyrolysis to obtain the charcoal powder.
S2: 5g of charcoal powder, 20 g of calcium bentonite and 1.25g of sodium bicarbonate are uniformly mixed, 20mL of deionized water is added, the mixture is uniformly stirred into granules, and then the granules are placed into an oven with the temperature of 80 ℃ for drying for 12 hours. And (3) putting the dried particles into an atmosphere furnace, introducing nitrogen with the flow rate of 0.5L/min, heating to 200 ℃ at the heating rate of 2 ℃/min, and staying for 30min, so as to volatilize the sodium bicarbonate to generate carbon dioxide to form a porous structure. Then heating to 580 ℃ at the heating rate of 5 ℃/min and staying for 30min, and activating the black carbon particles at high temperature.
Example 2: the preparation method is the same as example 1, wherein 5g of charcoal powder, 10 g of calcium bentonite and 0.75 g of sodium bicarbonate are mixed uniformly.
Example 3: the preparation method is the same as example 1, wherein 5g of charcoal powder, 30 g of calcium bentonite and 1.75g of sodium bicarbonate are mixed uniformly.
Example 4: the preparation method is the same as example 1, wherein the pyrolysis temperature of the charcoal is 500 ℃, 5g of charcoal powder, 10 g of calcium bentonite and 0.75 g of sodium bicarbonate are mixed uniformly.
Example 5: the preparation method is the same as example 1, wherein the pyrolysis temperature of the biochar is 500 ℃, 5g of charcoal powder, 20 g of calcium bentonite and 1.25g of sodium bicarbonate are mixed uniformly.
Example 6: the preparation method is the same as example 1, wherein the pyrolysis temperature of the biochar is 500 ℃, 5g of charcoal powder, 30 g of calcium bentonite and 1.75g of sodium bicarbonate are mixed uniformly.
Example 7: the preparation method is the same as example 1, wherein the pyrolysis temperature of the biochar is 700 ℃, 5g of charcoal powder, 10 g of calcium bentonite and 0.75 g of sodium bicarbonate are mixed uniformly.
Example 8: the preparation method is the same as example 1, wherein the pyrolysis temperature of the biochar is 700 ℃, 5g of charcoal powder, 20 g of calcium bentonite and 1.25g of sodium bicarbonate are uniformly mixed.
Example 9: the preparation method is the same as example 1, wherein the pyrolysis temperature of the biochar is 700 ℃, 5g of charcoal powder, 30 g of calcium bentonite and 1.75g of sodium bicarbonate are mixed uniformly.
Example 10: the black carbon particles obtained in examples 1 to 9 were subjected to a nitrogen removal response surface curve design experiment, design expert10 software was used to design an experiment at 3-factor 3 level, and the optimal preparation conditions of the black carbon material were determined by using the response surface curve method with the removal rates of ammonia nitrogen and nitrate nitrogen as response values. Factors are the pyrolysis temperature (500 ℃, 600 ℃, 700 ℃), the material ratio of the biochar to the calcium bentonite (1: 2, 1:4, 1: 6) and the addition amount (10 g/L, 20 g/L,30 g/L). The experiment adopts a 150 mL conical flask as a reactor, and deionized water is prepared to contain ammonia Nitrogen (NH)4 +-N) and nitro Nitrogen (NO)3 --N), substrate, pure water =1:10 (mass ratio), and the slurry-water mixture is put into a gas bath constant temperature oscillation box and oscillated for 30min at 150 rpm and 25 ℃ to prepare substrate leaching liquor. Placing a proper amount of substrate leaching liquor and a nitrogen-containing solution into a 150 mL conical flask, adding a certain amount of black carbon particles, oscillating at constant temperature in a gas bath at 150 rpm and 25 ℃, reacting for 12h, sampling, filtering the solution through a 0.45-micrometer microporous filter membrane, and measuring NH4 +-N and NO3 -And (4) calculating the nitrogen removal efficiency of the black carbon particles according to the N concentration.
As shown in figure 1, the prepared 97 wt% of black carbon particles have particle sizes of more than 0.5mm and good sedimentation performance. As shown in figure 2, a large number of pore structures are formed between the biochar and the calcium bentonite, and the surface of the biochar forms a microporous structure due to high-temperature pyrolysis, so that the formation of the structures is beneficial to the effective combination of the black carbon particles and the nitrogen. From table 1, it can be found that the increase of the pyrolysis temperature leads the pore structure of the prepared black carbon particles to be mainly microporous and the specific surface area to be increased. The pore volume of the black carbon particles prepared at 500 ℃ is dominated by mesopores and macropores. Referring to table 1, the pore structure of the prepared black carbon particles at each temperature is given.
TABLE 1 pore Structure of Black carbon particles
The surface charge number and the acidity and alkalinity are used as two major indexes of the surface property of the material to influence the adsorption property of the material, and the Zeta potential and the pH value are selected to characterize the surface property of the black carbon particles, as shown in Table 2. The electronegativity of the surface of the black carbon particles increases with increasing pH, consistent with the tendency of Zeta potential (lower potential). If under acidic conditions, H in solution+And NH4 +The effect of adsorbing ammonia nitrogen is poor due to competition of adsorption sites. The pH value of the particles gradually increases with the increase of the pyrolysis temperature, indicating materialThe ratio of the basic functional groups contained in the material is increased, so that H can be reduced+The occurrence of the adsorption competition phenomenon of (1). Referring to table 2, surface properties of the black carbon particles prepared at each temperature are given.
TABLE 2 surface Properties of the Black carbon particles
| Sample (I) | Example 5500 deg.C | Example 1600 deg.C | Example 8700 deg.C |
| Zeta potential (mV) | -22.95 | -26.95 | -27.30 |
| pH | 10.25 | 10.35 | 10.53 |
The model fitting with ammonia nitrogen removal rate as a response variable accords with a quadratic polynomial model, and the fitting result of the model with nitrate nitrogen as the response variable is not obvious. Therefore, ammonia nitrogen removal was chosen as an indicator of optimization. As shown in figure 3, the optimal conditions for preparing the black carbon particles by taking the ammonia nitrogen removal rate as the response amount are that the pyrolysis temperature is 500 ℃, the material ratio of the biochar to the calcium bentonite is 1:2, and the adding amount is 30 g/L. The reason is that the more the black carbon particles are added, the more active points are acted with nitrogen, and the more obvious the ammonia nitrogen removal effect is. The calcium bentonite added in the invention has the function of forming larger particles with the biochar and increasing the settling property of the biochar. Meanwhile, the calcium bentonite also has the adsorption capacity to nitrogen. The valence bonds of the oxygen-containing functional groups on the surface of the biochar pyrolyzed at 500 ℃ are not completely broken due to high temperature, and a part of surface active groups have dominant surface adsorption. FIG. 5 shows Langmuir isothermal adsorption curve and Freundlich isothermal adsorption curve of the material of example 4 on ammonia nitrogen, the adsorption process on ammonia nitrogen is more in accordance with Freundlich equation, and the surface adsorption is mainly dominated by multilayer heterogeneous adsorption. The space pore structure of the black carbon particles, the abundance of the surface functional groups and the like not only influence the adsorption of nitrogen, but also influence the attachment of microorganisms in the actual environment and the bioavailability of adsorbed pollutants.
Example 11:
in order to research the nitrogen resistance control removal effect of the preferred black carbon particle covered substrate, the black carbon particles with the particle size of more than 2 mm are divided into coarse particles, and the black carbon particles with the particle size of 0.5-2 mm are divided into fine particles. The experimental device is an organic glass cylindrical reactor with the inner diameter of 10 cm and the height of 35 cm. The experimental groups are set to 1# (12 cm substrate +18 cm overlying water), 2# (12 cm substrate +3cm coarse particles +15 cm overlying water), 3# (12 cm substrate +3cm fine particles +15 cm overlying water), 4# (10 cm substrate + 5cm volume ratio 1:1 coarse particle to substrate mixture +15 cm overlying water), and 5# (10 cm substrate + 5cm volume ratio 1:1 fine particle to substrate mixture +15 cm overlying water). Periodically taking 40 mL of overlying water with the height of 20 cm of the reactor, and detecting NH4 +-N, nitrite Nitrogen (NO)2 --N），NO3 -Variation of N and of Total Nitrogen (TN). NH of each group4 +-N，NO2 --N，NO3 -The contents of-N and TN are shown in Table 3.
TABLE 3 non-parametric multiple comparisons of the Behrens-Fisher test (P < 0.05 significance)
FIG. 5 is a graph showing the change of nitrogen element with time in example 11. Fig. 5 shows that in the experimental period 31 d, the concentrations of ammonia nitrogen and total nitrogen in the overlay water of the reactor paved with the black carbon particles are generally lower than those in the reactor not paved with the black carbon particles (Behrens-Fisher test, P < 0.05), which indicates that the black carbon particles have better capability of fixing ammonia nitrogen and reducing total nitrogen. Generally, ammonia nitrogen of the overburden water is converted into nitrite nitrogen and nitrate nitrogen through oxidation reaction along with the change of time, and a part of nitrogen is removed through adsorption and fixation of materials and utilization of microorganisms. It is seen from fig. 5 that the coarse and fine particle coverage is not significantly different from the nitrogen change of the overlying water, but overall the coarse particle coverage is slightly better than the fine particle coverage. The abundant pore structure of black carbon granules provides good inhabitation places for microorganisms, and is beneficial to the conversion and removal of nitrogen.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (6)
1. A substrate in-situ covering nitrogen resistance control removal material is characterized in that: the biological carbon is in a porous black carbon particle form, the particle size is larger than 0.5mm, the components comprise biological carbon, calcium bentonite and sodium carbonate, a large number of pore structures are arranged between the biological carbon and the calcium bentonite, and the surface of the biological carbon forms a microporous structure due to high-temperature pyrolysis; the mass ratio of the biochar to the calcium bentonite is 1: 2-1: 6.
2. The substrate in-situ covering nitrogen-controlled removal material as claimed in claim 1, wherein: the sodium carbonate accounts for 4-6% of the total mass of the biochar and the calcium bentonite.
3. The preparation method of the substrate in-situ covering nitrogen resistance control removal material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: sieving poplar chips, drying, and then putting into an atmosphere furnace for high-temperature pyrolysis to obtain charcoal powder;
step two: uniformly mixing calcium bentonite, sodium bicarbonate and charcoal powder, adding a proper amount of water, stirring to form particles, drying the particles, and performing high-temperature activation to prepare the black carbon particles.
4. The method for preparing the substrate in-situ covering nitrogen-controlled removal material according to claim 3, characterized in that: the first step is specifically as follows: sieving poplar chips with a sieve of 10-30 meshes, putting the poplar chips into an oven of 80 ℃ for drying until the water content is lower than 5 wt%, putting the poplar chips into an atmosphere furnace after drying, introducing nitrogen with the flow rate of 0.3-0.5L/min, heating to 500-700 ℃ at the heating rate of 5 ℃/min, and staying for 120min for high-temperature pyrolysis to obtain the charcoal powder.
5. The method for preparing the substrate in-situ covering nitrogen-controlled removal material according to claim 3, characterized in that: the second step is specifically as follows: mixing charcoal powder, calcium bentonite and sodium bicarbonate according to a mass ratio of 20: 40-120: 3-7, adding 20mL of deionized water, uniformly stirring to obtain particles, drying in an oven at 80 ℃, drying until the water content is lower than 5%, placing the dried particles in an atmosphere furnace, introducing nitrogen at the flow rate of 0.3-0.5L/min, heating to 200 ℃ at the heating rate of 2-5 ℃/min, standing for 30min, volatilizing sodium bicarbonate to generate carbon dioxide to form a porous structure, heating to 580 ℃ at the heating rate of 5-10 ℃/min, standing for 30min, and activating the black carbon particles at high temperature.
6. The application of the substrate in-situ covering nitrogen resistance control removal material is characterized in that: the method comprises the following steps:
the black carbon particles prepared by the method are used as a substrate covering agent, and are flatly paved on a polluted substrate through a barge, wherein the paving thickness is 3-5 cm;
if the aquatic vegetation recovery needs to be carried out on the polluted substrate in the later period, the black carbon particles and the polluted substrate are mixed in equal volume proportion, and the black carbon particles are flatly paved on the polluted substrate through a barge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110429501.1A CN113198419B (en) | 2021-04-21 | 2021-04-21 | Substrate in-situ covering nitrogen resistance control removal material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110429501.1A CN113198419B (en) | 2021-04-21 | 2021-04-21 | Substrate in-situ covering nitrogen resistance control removal material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113198419A true CN113198419A (en) | 2021-08-03 |
| CN113198419B CN113198419B (en) | 2022-06-21 |
Family
ID=77027677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110429501.1A Active CN113198419B (en) | 2021-04-21 | 2021-04-21 | Substrate in-situ covering nitrogen resistance control removal material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113198419B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314729A (en) * | 2021-11-17 | 2022-04-12 | 安吉国千环境科技有限公司 | Efficient denitrification composite material for water environment treatment |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075079A1 (en) * | 1999-06-05 | 2000-12-14 | Herbst Juergen | Method for dispersing insoluble mineral sediments and additives for carrying out this method |
| US7160483B1 (en) * | 2000-11-27 | 2007-01-09 | Eric Christian Hince | Solid-chemical composition for the non-exothermic chemical oxidation and aerobic bioremediation of environmental contaminants |
| US20160068417A1 (en) * | 2014-09-04 | 2016-03-10 | Clean Chemistry | Systems and method of water treatment utilizing reactive oxygen species and applications thereof |
| CN106673088A (en) * | 2017-01-11 | 2017-05-17 | 广东省农业科学院农业资源与环境研究所 | Modifier for wet magnesium desulphurization slag, wet magnesium desulphurization slag and preparation method of wet magnesium desulphurization slag |
| US20180327681A1 (en) * | 2015-10-08 | 2018-11-15 | The Carbon Basis Company Ltd. | Biochar products and method of manufacture thereof |
| CN111285574A (en) * | 2020-03-23 | 2020-06-16 | 湖南科技大学 | Preparation method and application of bottom sediment heavy metal pollution remediation agent |
| CN111729644A (en) * | 2020-07-31 | 2020-10-02 | 河海大学 | Biochar-bentonite porous composite ball and preparation method thereof |
-
2021
- 2021-04-21 CN CN202110429501.1A patent/CN113198419B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075079A1 (en) * | 1999-06-05 | 2000-12-14 | Herbst Juergen | Method for dispersing insoluble mineral sediments and additives for carrying out this method |
| US7160483B1 (en) * | 2000-11-27 | 2007-01-09 | Eric Christian Hince | Solid-chemical composition for the non-exothermic chemical oxidation and aerobic bioremediation of environmental contaminants |
| US20160068417A1 (en) * | 2014-09-04 | 2016-03-10 | Clean Chemistry | Systems and method of water treatment utilizing reactive oxygen species and applications thereof |
| US20180327681A1 (en) * | 2015-10-08 | 2018-11-15 | The Carbon Basis Company Ltd. | Biochar products and method of manufacture thereof |
| CN106673088A (en) * | 2017-01-11 | 2017-05-17 | 广东省农业科学院农业资源与环境研究所 | Modifier for wet magnesium desulphurization slag, wet magnesium desulphurization slag and preparation method of wet magnesium desulphurization slag |
| CN111285574A (en) * | 2020-03-23 | 2020-06-16 | 湖南科技大学 | Preparation method and application of bottom sediment heavy metal pollution remediation agent |
| CN111729644A (en) * | 2020-07-31 | 2020-10-02 | 河海大学 | Biochar-bentonite porous composite ball and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 卢少勇等: "镧改性、钠基和钙基膨润土净化污染河水中磷的效果", 《给水排水》 * |
| 宋婷婷等: "不同原料生物炭对铵态氮的吸附性能研究", 《农业环境科学学报》 * |
| 陈仕稳等: "改性膨润土颗粒对微污染水中有机物和氨氮的吸附", 《环境工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314729A (en) * | 2021-11-17 | 2022-04-12 | 安吉国千环境科技有限公司 | Efficient denitrification composite material for water environment treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113198419B (en) | 2022-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111135790B (en) | Dephosphorization composite adsorbent, preparation method thereof and application thereof in sewage treatment | |
| CN101475362B (en) | Biochemical ceramic as well as preparation method and application thereof | |
| CN111533395B (en) | Substrate improvement material for polluted river sediment and preparation method and application thereof | |
| CN111097374B (en) | Preparation method of oxygen-carrying and adsorption composite functional material and application of oxygen-carrying and adsorption composite functional material in water body remediation | |
| CN109225126A (en) | A kind of porous phosphorus removing filtrate and preparation method thereof based on diatomite and tripoli | |
| CN111410379B (en) | Efficient phosphorus removal method for domestic sewage | |
| Xiong et al. | Application of biochar in modification of fillers in bioretention cells: A review | |
| CN113416088A (en) | Modified anorthite ceramsite capable of adsorbing ammonia nitrogen and preparation method thereof | |
| CN111039658A (en) | Phosphorus removal ceramsite and preparation method thereof | |
| CN113198419B (en) | Substrate in-situ covering nitrogen resistance control removal material and preparation method and application thereof | |
| CN108975626B (en) | Landscape water treatment facilities with nitrogen phosphorus recovery effect | |
| CN112844309A (en) | Multi-effect biochar-based composite material and preparation method and application thereof | |
| CN202849197U (en) | Deep purification and combined denitrification system for polluted ground water | |
| CN115322008A (en) | Porous biological filler for purifying polluted seawater and preparation method and application thereof | |
| CN112678895B (en) | Water purifying agent and preparation method and application thereof | |
| KR100919777B1 (en) | Solid material for wastewater treatment and fabricating method the same | |
| Dai et al. | PERFORMANCE AND MECHANISM OF PHOSPHORUS REMOVAL BY CALCIUM-LOADED CLAY GRANULAR ADSORBENTS. | |
| CN112371085A (en) | Steel pickling sludge modified sludge activated carbon for rainwater treatment | |
| KR101901279B1 (en) | Adsorption carrier using industrial wastes and method of manufacturing thereof | |
| CN113248075A (en) | Preparation and use method of wetland filler | |
| JPH1057991A (en) | Treating material of dredged mud and its treatment | |
| KR100886737B1 (en) | Functional media and manufacture method for water purification using briquet ashes | |
| CN113694965B (en) | Flower-shaped composite photocatalytic material with stem and preparation method and application thereof | |
| KR20210085322A (en) | Media for Water Treatment Using Zeolite and Preparation Method thereof | |
| CN110575812A (en) | environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |