CN114772746A - Method for removing soluble organic nitrogen in rainwater runoff - Google Patents
Method for removing soluble organic nitrogen in rainwater runoff Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/001—Runoff or storm water
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Abstract
The invention provides a method for removing soluble organic nitrogen in rainwater runoff, which mainly aims at removing the difficultly biodegradable soluble organic nitrogen, belongs to the technical field of pollutant removal, and can solve the technical problems that the existing bioretention system is complex in structure and an efficient method for removing the difficultly biodegradable soluble organic nitrogen is lacked. The technical scheme mainly comprises the following steps: after the steps of simplifying the structure of the biological retention system, screening a biological carbon modification method and screening the optimal addition amount of the modified biological carbon are sequentially carried out, the modified biological carbon is added into the simplified biological retention system according to the optimal addition amount to remove the nonbiodegradable soluble organic nitrogen, and the stability of the removal effect is verified. The method can be applied to the aspect of removing the difficultly biodegradable soluble organic nitrogen in the rainwater runoff.
Description
Technical Field
The invention belongs to the technical field of pollutant removal, and particularly relates to a method for removing soluble organic nitrogen in rainwater runoff.
Background
In recent years, as urbanization progresses more and more, the total area of the impervious surface increases sharply, rainwater infiltration decreases, and the surface runoff increases. Meanwhile, urban flood disasters frequently occur under the condition that extreme weather is continuously increased. Meanwhile, rainfall runoff containing a plurality of pollutants enters a receiving water body and causes water quality deterioration, so that higher ecological risks are caused, and sponge city construction is carried out at the right moment. For coastal areas, many rainwater runoffs may directly enter coastal water areas, influence the environmental quality of ocean water, and cause the mass propagation of marine algae to cause natural disasters such as green tide and the like. And when natural conditions such as temperature and acid rain change, the removal effect of sponge city construction measures on rainwater runoff pollutants can be influenced. Therefore, it is imperative to remove pollutants in rainwater runoff efficiently.
The rainwater runoff carries a large amount of nitrogen substances which are considered as the largest contributors of river total nitrogen, and the content of soluble organic nitrogen in the nitrogen contained in the rainwater runoff almost accounts for 52-75% of the total dissolved nitrogen, 41% of the soluble organic nitrogen is organic nitrogen which is difficult to biodegrade, and the nitrogen is difficult to be converted by microorganisms and leaves the water body. The organic nitrogen which is difficult to biodegrade in the rainwater runoff mainly refers to nitrogen compounds with benzene ring structures, such as lignin, tannin, pyrrole, indole and the like. Currently, most researches focus on the conversion removal of biodegradable organic nitrogen such as protein and the like to solve the environmental hazard caused by excessive nitrogen input into water bodies, and neglect the removal of refractory soluble organic nitrogen. Therefore, research to enhance the removal technology of nonbiodegradable soluble organic nitrogen is required.
The bioretention system is an effective measure for removing pollutants such as nitrogen, phosphorus, heavy metals and the like in the rainwater runoff through filtration, adsorption, ion exchange, plant absorption and microbial transformation. However, in order to improve the removal effect of common pollutants, the structural design of the existing bioretention system is more and more complex, and therefore, how to improve the removal effect of the refractory biodegradable soluble organic nitrogen on the premise of simplifying the structure of the bioretention system is a technical problem to be overcome by the invention.
Disclosure of Invention
The invention provides a method for removing soluble organic nitrogen in rainwater runoff aiming at the technical problems that the existing bioretention system is complex in structure and lacks an efficient method for removing refractory organic nitrogen.
In order to achieve the purpose, the invention adopts the technical scheme that:
the method for removing the soluble organic nitrogen in the rainwater runoff sequentially comprises the steps of simplifying the structure of a biological retention system, screening a biological carbon modification method and screening the optimal addition amount of modified biological carbon, then adding the modified biological carbon into the simplified biological retention system according to the optimal addition amount to remove the soluble organic nitrogen, and verifying the stability of the removal effect, wherein the soluble organic nitrogen is the organic nitrogen which is difficult to biodegrade and soluble.
In one embodiment, a method for removing soluble organic nitrogen from storm water runoff, comprising the steps of:
simplifying the structure of a biological retention system to obtain a simplified biological retention system, wherein the simplified biological retention system sequentially comprises a covering layer, a composite filler layer and a drainage layer from top to bottom;
comparing the removal effects of the biochar on the hardly biodegradable soluble organic nitrogen obtained by different modification methods, and screening a biochar modification method with the best removal effect;
performing biochar modification by using a modification method with the best removal effect to obtain modified biochar, comparing the removal effects of different addition amounts of the modified biochar on the difficultly biodegradable soluble organic nitrogen, obtaining the optimum addition amount of the modified biochar, adding the optimum addition amount of the modified biochar into the composite filler layer, and removing the difficultly biodegradable soluble organic nitrogen in the rainwater runoff;
after the organic nitrogen which is difficult to biodegrade and dissolve is removed, the change condition of the removal effect of the simplified bioretention system on the organic nitrogen which is difficult to biodegrade and dissolve under different environmental conditions is researched, and the stability of the system is evaluated.
In an embodiment, the biological retention system after simplifying includes biological retention post, lays a plurality of structural layers in biological retention post and sets up in the water inlet and the delivery port of biological retention post top and bottom, wherein, the structural layer includes overburden, composite packing layer and the drainage blanket that top-down arranged in proper order, and still lays the geotextile between the structural layer of difference.
In one embodiment, the covering layer is composed of coarse sand with the particle size of 0.5-1.0mm, the composite packing layer is a mixture of quartz sand and modified biochar, and the drainage layer is composed of gravel with the particle size of 8-10 mm;
the thickness of the covering layer is 5-15cm, the thickness of the composite filler layer is 25-35cm, and the thickness of the drainage layer is 5-15 cm.
In one embodiment, the addition amount of the modified biochar accounts for 0.5-1.0% of the total amount of the composite filler layer.
In one embodiment, the bioretention column is cylindrical, square or rectangular in shape.
In one embodiment, the method for modifying biochar with the best screening and removing effect specifically comprises the following steps: and respectively adding the quinone modified biochar, the acid modified biochar and the oxidation modified biochar into the composite filler layer, comparing the removal effects of the quinone modified biochar, the acid modified biochar and the oxidation modified biochar on the organic nitrogen which is difficult to biodegrade, and finally selecting the quinone modification as a modifying method of the biochar.
In one embodiment, the quinone modified biochar is prepared by the following method:
the algae biomass is added after air drying, crushing, grinding and sieving treatment in sequenceInto a crucible and at 4 ℃ min-1Heating at 400 deg.C, maintaining for 2-2.5h, naturally cooling, and sieving to obtain charcoal;
putting 20g of biochar into an erlenmeyer flask, adding 2-4mol/L of quinone compound, stirring for 4-12h at 28-35 ℃ in a shading mode by using a magnetic stirrer, and drying at 60-70 ℃ to obtain the quinone modified biochar.
In one embodiment, the algal biomass is selected from the genera enteromorpha or ulva of the family ulva of the green algae phylum, and the quinone compound is selected from the benzoquinone compounds or anthraquinone compounds.
In one embodiment, the green algae, Ulva, Enteromorpha of Ulvaceae is Enteromorpha, Ulva is Ulva, the benzoquinone compound is hydroquinone, and the anthraquinone compound is anthraquinone-2, 6-disulfonate or 9, 10-anthraquinone.
Compared with the prior art, the invention has the advantages and positive effects that:
1. according to the method for removing the soluble organic nitrogen in the rainwater runoff, on the basis of simplifying the conventional bioretention system, different biochar modification methods and the optimal addition amount of modified biochar are screened, and then the modified biochar is added into the simplified bioretention system according to the optimal addition amount to remove the difficultly biodegradable soluble organic nitrogen, so that the high-efficiency removal of the difficultly biodegradable soluble organic nitrogen is finally realized;
2. the simplified biological retention system provided by the invention has the characteristics of simple structural design, low manufacturing cost, ideal removal effect and the like.
Drawings
FIG. 1 is a schematic diagram of a simplified bioretention system according to an embodiment of the present invention;
FIG. 2 is a schematic view of a simplified bioretention system according to the present invention as provided in example 1;
FIG. 3 is a bar graph of the indole removal provided in example 1 of the present invention;
FIG. 4 is a bar graph of the indole removal provided in example 2 of the present invention;
FIG. 5 is a graph showing the effect of pH change on the removal of a simplified bioretention system according to an embodiment of the present invention;
FIG. 6 is a graph illustrating the effect of temperature change on the removal of a simplified bioretention system according to an embodiment of the present invention;
FIG. 7 shows the effect of different modification methods and different amounts of modified biochar on the removal of nonbiodegradable soluble organic nitrogen.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a method for removing soluble organic nitrogen in rainwater runoff, which comprises the steps of simplifying a structure of a bioretention system, screening a biochar modification method and screening the optimal addition amount of modified biochar, then adding the modified biochar into the simplified bioretention system according to the optimal addition amount to remove the soluble organic nitrogen, and verifying the stability of a removal effect, wherein the soluble organic nitrogen is difficultly biodegraded and soluble organic nitrogen.
In one embodiment, the method for removing the soluble organic nitrogen in the rainwater runoff comprises the following steps:
s1, simplifying the structure of the biological retention system to obtain a simplified biological retention system, wherein the simplified biological retention system sequentially comprises a covering layer, a composite filler layer and a drainage layer from top to bottom;
s2, comparing the removal effects of the biochar obtained by different modification methods on the difficultly biodegradable soluble organic nitrogen, and screening the biochar modification method with the best removal effect;
the reason why the present invention does not directly add biochar to the simplified bioretention system in the above-described step S2 is that: at present, biochar has proved to be an excellent adsorbent, and experiments show that it can remove 100-200mg/g organic matters, which indicates that it is a promising adsorbent for detoxifying organic matters, but there are many factors that influence the adsorption effect of biochar, for example, raw materials, specific surface area, pore size distribution, surface functional groups, etc. of biochar all affect the adsorption of organic matters, and the molecular weight and weight, hydrophobicity, aromaticity, and polarity of organic matters also affect the adsorption effect. Therefore, modifying the biochar is a solution for improving the effect of removing the difficultly biodegradable soluble organic nitrogen, but how to screen out a modification method which is most suitable for removing the difficultly biodegradable soluble organic nitrogen from a plurality of complicated modification methods and optimize the optimum addition amount is one of the technical difficulties which need to be overcome by the invention through organically combining the biochar with a biological retention tank. To overcome this difficulty, the present invention is improved mainly from the following aspects:
the structure of the biological detention pond is simplified; ② screening different biochar modification methods; thirdly, screening the optimum addition amount of the modified biochar; adding the modified biochar with the optimal addition amount into the simplified biological retention pool, and cooperatively removing the difficultly biodegradable soluble organic nitrogen in the rainwater runoff.
S3, modifying the biochar by using a modification method with the best removal effect to obtain modified biochar, comparing the removal effects of the modified biochar with different addition amounts on the organic nitrogen difficult to biodegrade, obtaining the most appropriate addition amount of the modified biochar, adding the most appropriate addition amount of the modified biochar into the composite filler layer, and removing the organic nitrogen difficult to biodegrade and soluble in rainwater runoff;
s4, after the organic nitrogen difficult to biodegrade and dissolve is removed, the change situation of the removal effect of the simplified biological retention system on the organic nitrogen difficult to biodegrade and dissolve under different environmental conditions is researched, and the stability of the system is evaluated.
In a specific embodiment, the biological detention system after simplifying includes biological detention post, lays a plurality of structural layers in the biological detention post and sets up in the water inlet and the delivery port of biological detention post top and bottom, wherein, the structural layer includes overburden, compound packing layer and the drainage blanket that top-down arranged in proper order, and still lays the geotextile between the structural layer of difference to prevent that the filler between each structural layer from mixing.
In the above embodiment, each structural layer functions as follows: the covering layer has the functions of attenuating the peak flow and the total flow of the rainwater runoff and promoting the permeation of the rainwater runoff and also has the filtering function; the composite medium layer has the functions of adsorbing and fixing pollutants, and the functional groups on the modified biochar can be complexed with the pollutants, precipitated, an electron donor acceptor and the like; the gravel in the drainage layer has a drainage function.
In a specific embodiment, the covering layer is composed of coarse sand with the particle size of 0.5-1.0mm, the composite packing layer is a mixture of quartz sand and modified biochar, and the drainage layer is composed of gravel with the particle size of 8-10 mm;
the thickness of the covering layer is 5-15cm, the thickness of the composite filler layer is 25-35cm, and the thickness of the drainage layer is 5-15 cm.
In a specific embodiment, the addition amount of the modified biochar accounts for 0.5-1.0% of the total amount of the composite filler layer, and specifically, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% or any value of the above-defined range selected according to actual needs falls within the protection scope of the present invention.
In a specific embodiment, the bioretention column shape includes, but is not limited to, a cylindrical, square or rectangular parallelepiped shape.
In one embodiment, the method for modifying biochar with the best screening and removing effect specifically comprises the following steps: and respectively adding the quinone modified biochar, the acid modified biochar and the oxidation modified biochar into the composite filler layer, comparing the removal effects of the quinone modified biochar, the acid modified biochar and the oxidation modified biochar on the organic nitrogen difficult to biodegrade, and finally selecting the quinone modification as a modification method of the biochar.
In one embodiment, the quinone modified biochar is prepared by the following method:
(1) the algae biomass is sequentially dried, crushed, ground and screened, added into a crucible and thenAt 4 ℃ min-1Heating at 400 deg.C, maintaining for 2-2.5h, naturally cooling, and sieving to obtain charcoal;
(2) putting 20g of biochar into an erlenmeyer flask, adding 2-4mol/L of quinone compound, stirring for 4-12h at 28-35 ℃ in a shading mode by using a magnetic stirrer, and drying at 60-70 ℃ to obtain the quinone modified biochar.
In a specific embodiment, the algal biomass is selected from the genera enteromorpha or ulva of the family ulva of the phylum chlorophyta, and the quinone compound is selected from the benzoquinone compounds or anthraquinone compounds.
In a specific embodiment, the green algae of genus enteromorpha of family ulva of phylum ulva is enteromorpha, the genus ulva is ulva, the benzoquinone compound is hydroquinone, and the anthraquinone compound is anthraquinone-2, 6-disulfonate or 9, 10-anthraquinone.
In order to more clearly and specifically describe the method for removing soluble organic nitrogen in rainwater runoff provided by the embodiment of the present invention, the following description will be made with reference to specific examples.
Example 1
The embodiment provides a method for removing soluble organic nitrogen in rainwater runoff, and the embodiment takes indole as a removal object, specifically:
(1) the structure layer of the biological retention system is basically arranged as follows: the bioretention system of this example is designed as a cylinder with a diameter of 15cm and a depth of 50cm, 45cm being used for the packing material (as shown in fig. 2), and the bioretention system comprises a covering layer, a composite packing layer and a drainage layer (information of each structural layer is shown in table 1) from top to bottom, and geotextile is added between each two layers to prevent the packing material from mixing. Five outlets are sequentially arranged at positions 5cm, 15cm, 25cm, 35cm and 45cm away from the surface of the covering layer, wherein the outlet at the bottom is used for water to flow out, and the other four outlets are used for collecting a water sample and a filler sample;
TABLE 1 Bioretention System layer information
(2) Grouping tests: removing nonbiodegradable soluble organic nitrogen in rainwater runoff according to the bioretention system provided in the step (1) (namely an experimental group), wherein the ratio of quartz sand to quinone modified biochar in the composite packing layer is 99.5:0.5 (namely 0.5% of quinone modified biochar is added), and meanwhile, two groups of control groups are additionally arranged in the embodiment and are respectively a biochar-free group and an unmodified biochar group, wherein all the composite packing layer in the biochar-free group is quartz sand;
(3) and (3) removing the difficultly biodegradable soluble organic nitrogen in the rainwater runoff according to the test groups shown in the step (2), wherein the concentration (calculated by N) of the indole fed into the bioretention system is 10mg/L, the water feeding time is 90min, the water feeding flow rate is controlled at 30mL/min, and after 60min of water feeding, water samples at different depths (5cm, 15cm, 25cm and 35cm) are collected to determine the indole content.
And (3) analyzing test results: the indole removal effect is shown in fig. 3, which shows that the indole removal rate by using the bioretention system of this example can reach 73.5% at most (i.e. experimental group), is 2.1 times higher than that of unmodified biochar and 4.7 times higher than that of unmodified biochar, and the indole is mainly removed at a position 5-15cm away from the surface of the covering layer.
Example 2
The embodiment provides a method for removing soluble organic nitrogen in rainwater runoff, and the embodiment takes indole as a removal object, specifically:
the bioretention system and experimental groups used in this example were the same as in example 1, except that the ratio of the quartz sand to the quinone-modified biochar in the composite filler layer in the experimental group was 99:1 (i.e., 1% quinone-modified biochar was added).
And (3) analysis of test results: the indole removal is shown in FIG. 4, which shows that the maximum indole removal rate achieved by the bioretention system of this example is 79.1% (i.e. experimental group), while the indole was also removed predominantly at a distance of 5-15cm from the blanket surface.
Example 3
The embodiment provides a biological retention system after the simplification and removes stability verification test of effect, specifically is:
after the rainstorm runoff simulation experiment of example 1-2 was completed, the two biochar retention systems to which 0.5% of quinone-modified biochar was added and 1% of quinone-modified biochar was added were changed to water inlet experiments at different temperatures (20 ℃, 30 ℃, 40 ℃) and different phs (4, 5, 6, and 7 when acid rain occurs), and the influence of the concentration of indole in water was analyzed to evaluate the indole removal effect of the simplified biochar retention systems under different environmental conditions.
And (3) analyzing test results: the results show that the influence on the concentration of indole in effluent is not significant when the pH value of the environmental factor is changed, which means that the adsorption is not substantially changed by the surface charges of the adsorbate and the adsorbent, i.e. the adsorption process is not substantially subjected to electrostatic attraction (FIG. 5); although the temperature change has a certain influence on the indole removal effect, the adsorption amount is slightly reduced only at a low temperature in winter, and the adsorption effect of the biochar on the indole is more remarkable at a higher temperature (fig. 6). The method for removing the organic nitrogen in the rainwater runoff can effectively remove the difficultly-biodegradable soluble organic nitrogen in the rainwater runoff, and the removing effect is not easily influenced by external environmental factors such as temperature, pH and the like.
Biochar modification method and optimum addition amount screening test
In order to improve the removal effect of the nonbiodegradable soluble organic nitrogen in the rainwater runoff, different biochar modification methods and the optimal addition amount of the modified biochar are subjected to screening tests, and the method specifically comprises the following steps:
(1) respectively carrying out acid modification, oxidation modification and quinone modification on the biochar, wherein the three modification methods comprise the following steps:
the acid modification method comprises the following steps: 20g of biochar (hereinafter referred to as "BC") was put into a conical flask, and 10% (v/v) H was added2SO4Stirring for 4h at 70 ℃ by using a magnetic stirrer, washing to neutral pH by using distilled water, and drying at 60 ℃ to obtain acid modified biochar (hereinafter referred to as SBC); the oxidation modification method comprises the following steps: 20g of BC was weighed out and added to 20% H2O2Stirring the solution at 25 ℃ for 4 hours, then repeatedly washing the solution with distilled water until the pH value is neutral, and drying the solution at 60 ℃ to obtain oxidized modified biochar (hereinafter referred to as HBC); the quinone modification method comprises the following steps: 20g of BC was placed in an Erlenmeyer flask and 2-4m was addedAnd (2) stirring the ol/L quinone compound (hydroquinone, anthraquinone-2, 6-disulfonate or 9, 10-anthraquinone) at 28-35 ℃ for 4-12h in a shading way by using a magnetic stirrer, and drying at 60-70 ℃ to obtain the quinone modified biochar (hereinafter referred to as DBC).
(2) Four biological detention systems are utilized, quartz sand and biological carbon with different proportions are added into composite packing layers of the respective detention systems, wherein the biological carbon is four unmodified and modified biological carbons of BC, SBC, HBC and DBC, the adding amounts are 0.1, 0.2, 0.5, 1.0, 1.5 and 2.0 percent respectively, the water inflow indole (counted by N) is 10mg/L of difficultly biodegradable soluble organic nitrogen (represented by indole), the water inflow time is 90min, and the water inflow flow rate is 30 mL/min. After 60min of water entry, the indole concentration in the effluent was determined.
And (3) analyzing test results: the removing effect of indole is shown in fig. 7, when the adding amount of the biochar and the modified biochar is increased from 0.1% to 2.0%, the removing rate of the unmodified biochar (namely BC group) on the indole is increased from 23.7% to 34.0%; when the addition amount of SBC and HBC is 2.0%, the removal rate is 31.0% and 57.5% at the highest respectively; and the removal rate of DBC to indole is increased along with the increase of the addition amount of the biochar and then is kept stable, the removal rate is obviously increased from 0.5 percent, the removal rate reaches 79.1 percent at the maximum when the removal rate is more than 1.0 percent, and the removal rate is not obviously increased when the biochar is continuously increased. Therefore, the factors of indole removal effect and cost are comprehensively considered, the quinone modified biochar is selected as the biochar with the optimal adsorption efficiency on the difficultly biodegradable soluble organic nitrogen, and 0.5-1.0% is taken as the optimal addition amount.
Finally, it should be added that the reason why the indole is selected as the nonbiodegradable soluble organic nitrogen in the examples of the present invention is that: indole is a common nonbiodegradable heterocyclic organic nitrogen in nature, is a typical nonbiodegradable soluble organic nitrogen, is difficult to be converted by microorganisms, is mainly derived from human and animal excreta and plant rhizosphere, has high-concentration indole in soil, and can enter along with rainfall runoff and harm water bodies.
Claims (10)
1. The method for removing the soluble organic nitrogen in the rainwater runoff is characterized by sequentially carrying out the steps of biological retention system structure simplification, biological carbon modification method screening and optimal addition amount screening of modified biological carbon, then adding the modified biological carbon into the simplified biological retention system according to the optimal addition amount to remove the soluble organic nitrogen, and carrying out removal effect stability verification, wherein the soluble organic nitrogen is the organic nitrogen which is difficult to biodegrade and soluble.
2. A method of removing dissolved organic nitrogen in stormwater runoff as claimed in claim 1, including the steps of:
simplifying the structure of a biological retention system to obtain a simplified biological retention system, wherein the simplified biological retention system sequentially comprises a covering layer, a composite filler layer and a drainage layer from top to bottom;
comparing the removal effects of the biochar on the hardly biodegradable soluble organic nitrogen obtained by different modification methods, and screening a biochar modification method with the best removal effect;
modifying the biochar by using a modification method with the best removal effect to obtain modified biochar, comparing the removal effects of the modified biochar with different addition amounts on the organic nitrogen difficult to biodegrade, and adding the most suitable addition amount of the modified biochar into the composite filler layer to remove the organic nitrogen difficult to biodegrade and soluble in rainwater runoff;
after the organic nitrogen difficult to biodegrade and dissolve is removed, the change condition of the removal effect of the simplified bioretention system on the organic nitrogen difficult to biodegrade and dissolve under different environmental conditions is researched, and the stability of the system is evaluated.
3. The method for removing soluble organic nitrogen in rainwater runoff according to claim 2, wherein the simplified bioretention system comprises a bioretention column, a plurality of structural layers laid in the bioretention column, and a water inlet and a water outlet which are arranged at the top and the bottom of the bioretention column, wherein the structural layers comprise a covering layer, a composite packing layer and a drainage layer which are sequentially arranged from top to bottom, and geotextiles are further laid among different structural layers.
4. The method for removing the soluble organic nitrogen in the rainwater runoff according to claim 2, wherein the covering layer is composed of coarse sand with the grain diameter of 0.5-1.0mm, the composite packing layer is a mixture of quartz sand and modified biochar, and the drainage layer is composed of gravel with the grain diameter of 8-10 mm;
the thickness of the covering layer is 5-15cm, the thickness of the composite filler layer is 25-35cm, and the thickness of the drainage layer is 5-15 cm.
5. The method for removing soluble organic nitrogen in rainwater runoff according to claim 4, wherein the addition amount of the modified biochar accounts for 0.5-1.0 percent of the total amount of the composite filler layer.
6. The method for removing soluble organic nitrogen in rainwater runoff according to claim 3, wherein the shape of the bioretention column is cylindrical, square or rectangular parallelepiped.
7. The method for removing soluble organic nitrogen in rainwater runoff according to claim 2, wherein the method for modifying the biochar with the best screening and removing effect comprises the following steps: and respectively adding the quinone modified biochar, the acid modified biochar and the oxidation modified biochar into the composite filler layer, comparing the removal effects of the quinone modified biochar, the acid modified biochar and the oxidation modified biochar on the organic nitrogen which is difficult to biodegrade, and finally selecting the quinone modification as a modifying method of the biochar.
8. The method for removing soluble organic nitrogen in rainwater runoff according to claim 7, wherein the quinone modified biochar is prepared by the following method:
the algae biomass is sequentially dried, crushed, ground and screened, and then added into a crucible at 4 ℃ for min-1Heating at 400 deg.C, maintaining for 2-2.5h, naturally cooling, and sieving to obtain charcoal;
putting 20g of biochar into an erlenmeyer flask, adding 2-4mol/L of quinone compound, stirring for 4-12h at 28-35 ℃ in a shading mode by using a magnetic stirrer, and drying at 60-70 ℃ to obtain the quinone modified biochar.
9. The method of claim 8, wherein the algal biomass is selected from the genus Enteromorpha or Ulva of the family Ulvaceae of the Chlorophyta, and the quinone compound is selected from the benzoquinone compound or the anthraquinone compound.
10. The method of claim 8, wherein the green algae of the genus Enteromorpha of the family Ulvaceae is Enteromorpha, the genus Ulva is Ulva, the benzoquinone compound is hydroquinone, and the anthraquinone compound is anthraquinone-2, 6-disulfonate or 9, 10-anthraquinone.
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