CN110845076A - Combined remediation method for atrazine-polluted water body - Google Patents
Combined remediation method for atrazine-polluted water body Download PDFInfo
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- CN110845076A CN110845076A CN201911104709.5A CN201911104709A CN110845076A CN 110845076 A CN110845076 A CN 110845076A CN 201911104709 A CN201911104709 A CN 201911104709A CN 110845076 A CN110845076 A CN 110845076A
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- atrazine
- persulfate
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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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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
A combined remediation method for atrazine polluted water relates to a remediation method for polluted water, and is characterized in that nutrients for promoting microbial growth are added into the polluted water, and ventilation is performed to degrade atrazine parent and partial intermediate metabolites. Then persulfate microcapsules are added to generate compound free radical groups (OH, SO) through chemical oxidation reaction4 ‑And O2 ‑Etc.) degrading atrazine metabolites (triazine ring-containing substances) which the microorganisms cannot degrade. The molar ratio of the nutrient C to N to P for stimulating the growth of the microorganisms is 100:10:1, a phosphorus source and a nitrogen source are added, the carbon source is atrazine and metabolites thereof, and the estimation is carried out according to the actual pollutant concentration. The invention combines the microorganism stimulation method and the chemical oxidation method in sequence, avoids the incomplete degradation of the pollutants, reduces the unnecessary consumption of the oxidant, improves the degradation effect of the pollutants, and produces more suitable productsThe compound free radical group which is suitable for degrading target pollutants is suitable for repairing the water body polluted by the atrazine and the metabolites thereof.
Description
Technical Field
The invention relates to a polluted water body remediation method, in particular to a combined remediation method for an atrazine polluted water body.
Background
In recent years, the problem of organic pollution of water in China is receiving more and more attention. Due to the use of a large amount of herbicide, the phenomenon that Organochlorine Pesticides (OCPs) in farmland soil and surface water (underground water) exceed standards generally exists. Wherein the triazine herbicide taking Atrazine (Atrazine) as a main component is continuously used for many years. The atrazine has stable structure, strong water solubility, difficult degradation, slow process of mineralization by microorganisms and longer half-life period in natural environment. The parent body of atrazine in the environment is easily degraded by microorganisms, but the main degradation products of atrazine, such as Deethylatrazine (DEA), Deisopropylatrazine (DIA), Hydroxyatrazine (HA) and the like, are difficult to be utilized by microorganisms to degrade, wherein the toxicity of DEA and DIA is similar to that of atrazine, and the DEA and DIA have higher polarity and stability and can be reserved in the water environment for a long time. Conventional methods such as addition of exogenous microorganisms, phytoremediation, etc. have poor results.
The biological stimulation is to promote the propagation and growth of microorganisms by adding nutrient substances or ventilating and the like, increase the activity of indigenous microorganisms and further enhance the degradation of atrazine. The biostimulation has the advantages of low cost and good effect, has certain degradation capability on atrazine matrix, but is difficult to be completely mineralized by microorganisms due to the existence of triazine ring in atrazine structure, so that the combined treatment needs to be carried out by combining other repair means.
The chemical remediation technology has the advantages of strong universality on organic pollutants, good remediation effect, short time and the like, and particularly has the advantages of complex organic polluted waterAnd (3) a body. Persulfate (S)2O8 2−) Is a common oxidant in the chemical remediation of organic polluted water, and after being activated by a certain mode (heat, alkali, transition metal and the like), a persulfate system can generate sulfate free radicals (SO) with oxidability4 −·，E0= 2.6V) and hydroxyl radical (. OH, E)0= 2.8V), atrazine and its metabolites can theoretically be completely degraded. The persulfate has good water solubility, can be fully contacted with organic pollutants such as atrazine and the like in water, and can be degraded into micromolecular organic matters and even be completely mineralized. While the unactivated persulfate can exist in the water environment for a long time, forming a harmful protective layer for preventing new input pollutants.
Atrazine and its metabolites are chemically stable and are hydrolyzed only by heating in acidic or alkaline medium. Because the structure of the microbial composite material contains a triazine ring, the microbial composite material is difficult to degrade by microorganisms in nature. And about 50% of atrazine and metabolites are combined with heavy metals such as copper, cadmium, zinc and the like and humic acid and the like to form a compound, the form can hardly be naturally degraded by microorganisms, and thus, part of atrazine is promoted to remain in soil for a long time and is continuously released into a water environment. Structurally, atrazine is a cyanuric acid derivative, and a degradation product of atrazine is accumulated in the environment due to the large-scale use of atrazine. The s-triazine ring structure of cyanuric acid is stable and cannot be decomposed by conventional methods. The persulfate can locally generate a strong oxidation environment to generate sulfate radicals, hydroxyl radicals, singlet oxygen and the like to induce the decomposition of the broken bonds of the cyanuric acid ring, thereby achieving the purpose of complete mineralization.
The persulfate can react with organic pollutants and organic matters and inorganic matters in the water body, and can be directly injected into the water body to react at a high speed. This also results in a large difference between the theoretical oxidant demand and the actual oxidant consumption. Not only reduces the repairing effect and causes the waste of the medicament, but also brings secondary pollution. Therefore, it is necessary to adopt a certain method (such as microcapsule technology) to slow down the reaction rate of the persulfate and the pollutant and to increase the contact probability of the free radical and the pollutant.
Disclosure of Invention
The invention aims to provide a combined remediation method for atrazine-polluted water, which adopts a remediation method combining microbial stimulation and chemical oxidation, reduces the using amount of an oxidant, improves the removal efficiency of pollutants, reduces secondary pollution caused by sulfate generated by reaction, provides a method combining microbial stimulation and persulfate microcapsule oxidation, and remediates water polluted by atrazine and metabolites thereof.
The purpose of the invention is realized by the following technical scheme:
a combined remediation method for atrazine-polluted water comprises the steps of taking potassium persulfate, ammonium persulfate or sodium persulfate as core materials, taking paraffin and stearic acid as wall materials, doping inert materials of silicon dioxide, diatomite or bentonite, preparing lipophilic microcapsules by using an oil phase separation method, and adding persulfate microcapsules to degrade residual organic pollutants after microorganisms stimulate and degrade part of atrazine matrix; adding nutrient substances for promoting the growth of microorganisms into a polluted water body, ventilating, and degrading atrazine parent and partial intermediate metabolites; then persulfate microcapsules are added to generate compound free radical groups (OH, SO) through chemical oxidation reaction4 -And O2 -Etc.) degrading atrazine metabolites (triazine ring-containing substances) which cannot be degraded by microorganisms; the nutrient for stimulating the growth of the microorganism, a phosphorus source and a nitrogen source are added, the carbon source is atrazine and metabolites thereof, and the estimation is carried out according to the actual pollutant concentration; the preparation method of the microcapsule repaired by the method comprises the following steps:
(1) dissolving stearic acid or paraffin in anhydrous alcohol, stirring, heating to 65 deg.C to dissolve completely, and adding inert substance such as silicon dioxide, diatomaceous earth or bentonite;
(2) then adding ammonium persulfate, potassium persulfate or sodium persulfate according to the proportion, stopping stirring, and performing ultrasonic treatment to uniformly disperse the ammonium persulfate, the potassium persulfate or the sodium persulfate in the wall material solution;
(3) stopping ultrasound, reducing the temperature while stirring to reduce the solubility of the wall material, condensing and separating out the wall material by taking persulfate as a core, and cooling to form the microcapsule.
The microbial stimulant is used for the combined remediation method for the atrazine-polluted water body, the molar ratio of C to N to P is 100:10:1, and the phosphorus source is sodium phosphate (Na)3PO4·12H2O) or calcium phosphate (Ca)3(PO4)2) The nitrogen source is ammonium sulfate ((NH)4)2SO4) Or ammonium Nitrate (NH)4NO3) (ii) a The carbon source is atrazine and metabolites thereof, and is estimated according to the actual pollutant concentration.
According to the combined restoration method for the atrazine-polluted water body, the microcapsule core material is composed of persulfate, and the wall material is composed of paraffin and stearic acid; the core material is as follows: the proportion of wall materials is 2: 5; inert substances such as silicon dioxide, diatomite or bentonite are added into the microcapsules, and the mass of the inert substances is 1/10-1/5 of the microcapsules.
The combined remediation method for the atrazine-polluted water body comprises the following steps of: atrazine, deethylatrazine, deisopropylatrazine, hydroxyaatrazine, deithyldeisopropylatrazine and cyanuric acid.
The combined remediation method for the atrazine-polluted water body is applied as follows: firstly, promoting the degradation of atrazine parent and partial intermediate products by adopting a microbial stimulation method, and then degrading a compound containing a triazine ring structure which cannot be degraded by microorganisms by utilizing persulfate microcapsules to restore the water body.
The invention has the advantages and effects that:
the invention combines the microorganism stimulation method and the chemical oxidation method in sequence, avoids the incomplete degradation of the pollutants, reduces the unnecessary consumption of the oxidant, improves the degradation effect of the pollutants, generates the compound free radical group which is more suitable for the degradation of the target pollutants, and is suitable for the repair of the water body polluted by the atrazine and the metabolites thereof.
1. The preparation method provided by the invention has the advantages of simple process, safe operation and management, cheap and easily-obtained chemical raw materials and the like.
2. The invention adopts a repairing method combining microbial stimulation and chemical oxidation, reduces the dosage of the oxidant, improves the removal efficiency of pollutants, and reduces the secondary pollution caused by sulfate generated by reaction.
3. The method for microencapsulating the persulfate can reduce the reaction rate of the persulfate and the organic pollutants and form a protective layer in a water body.
4. The invention is suitable for water bodies polluted by long-term atrazine and metabolites thereof, can be repaired in situ, and has small influence on the environment.
Drawings
Fig. 1 is a schematic diagram of the principle of the present invention.
Detailed Description
The following provides a specific embodiment of the method for removing atrazine and its metabolites from a water body by the microbial stimulation and chemical oxidation method, but the invention is not limited thereto.
The invention takes potassium persulfate, ammonium persulfate or sodium persulfate as core materials, takes paraffin, stearic acid and the like as wall materials, and is doped with inert materials such as silicon dioxide, diatomite or bentonite and the like, and the lipophilic microcapsule is prepared by an oil phase separation method. After the microorganism stimulates and degrades part of atrazine parent, persulfate microcapsules are added to degrade the residual organic pollutants.
The target pollutants comprise atrazine and metabolites thereof, namely deethylatrazine, deisopropylatrazine, hydroxyatrazine, deethyldeisopropylatrazine, cyanuric acid and the like. The repairing method is a microorganism stimulation and chemical oxidation combined method, and the method comprises the steps of adding nutrient substances for promoting the growth of microorganisms into the polluted water body, ventilating and degrading atrazine parent bodies and partial intermediate metabolites. Then persulfate microcapsules are added to generate compound free radical groups (OH, SO) through chemical oxidation reaction4 -And O2 -Etc.) degrading microorganismsAtrazine metabolites (triazine ring containing substances) which cannot be degraded. The nutrient for stimulating the growth of the microorganism, the phosphorus source and the nitrogen source are added, the carbon source is atrazine and metabolites thereof, and the estimation is carried out according to the actual pollutant concentration. The persulfate microcapsules are stable in a clean water environment, in water containing pollutants, lipophilic substances in microcapsule wall materials can be contacted with light non-aqueous phase organic pollutants on the water surface and heavy non-aqueous phase organic pollutants at the water bottom, persulfate in core materials is slowly released into the water environment, and free radicals with strong oxidizing property are generated to degrade the pollutants under the action of an activating agent.
The mol ratio of the nutrient substance C to the nutrient substance N to the nutrient substance P is 100:10:1, and the phosphorus source is sodium phosphate (Na)3PO4·12H2O) or calcium phosphate (Ca)3(PO4)2) The nitrogen source is ammonium sulfate ((NH)4)2SO4) Or ammonium Nitrate (NH)4NO3). The carbon source is atrazine and metabolites thereof, and is estimated according to the actual pollutant concentration. The potassium persulfate, the ammonium persulfate or the sodium persulfate are white solid powder and are industrially pure; paraffin, stearic acid, etc. as solids; silica, diatomaceous earth or bentonite, etc. as solids; the mass ratio of the core material to the wall material in the microcapsule is 1/5, and the mass of the inert material is 1/10-1/5 of the microcapsule. The application method of microbial stimulation specifically comprises the following steps: the nutrient substances are uniformly scattered in the water body and aerated, and the nutrient substances can be fully and uniformly mixed in the water body through mechanical stirring. The application method of the persulfate microcapsule comprises the following steps: the microcapsules are uniformly scattered in the water body, and the persulfate microcapsules can be fully mixed in the water body through mechanical stirring. The nutrient substances have the function of promoting the growth of indigenous microorganisms, thereby degrading atrazine precursors and part of organic pollutants capable of being utilized by the microorganisms. The persulfate has the main function of generating sulfate free radicals and hydroxyl free radicals with strong oxidizing property after being activated, and oxidizing organic pollutants in a water body into carbon dioxide and water to achieve the purpose of removing the pollutants. The persulfate microcapsules can exist in water for a long time, and persulfate in the microcapsules can be slowly released toThe purpose of degrading organic pollutants is achieved in the environment. The persulfate microcapsules can be slowly dissolved in water to repair underground water.
Example 1
The formula of the microbial stimulation nutrient salt comprises the following components:
the persulfate microcapsule formula comprises the following components: ammonium persulfate 20 g, stearic acid 50 g, core material: the ratio of wall materials is 2: 5.
Dissolving 50 g stearic acid or paraffin in anhydrous ethanol, stirring, heating to 65 deg.C to dissolve, and adding 10 g silicon dioxide, diatomite or bentonite; then adding 20 g of ammonium persulfate, stopping stirring, and performing ultrasonic treatment to uniformly disperse the ammonium persulfate in the wall material solution; stopping ultrasound, reducing the temperature while stirring to reduce the solubility of the wall material, condensing and precipitating by taking ammonium persulfate as a core, and cooling to form the ammonium persulfate microcapsule.
Taking 1L of actual atrazine-polluted water (the atrazine concentration is 100 mug/L), adding 10 g of ammonium persulfate microcapsules, reacting for 7 days, wherein the atrazine concentration and metabolites thereof are completely degraded, and only a small amount of cyanuric acid (about 50 mug/L) which is difficult to degrade exists.
Example 2
The persulfate microcapsule formula comprises the following components: 20 g of potassium persulfate, 50 g of stearic acid, and a core material: the ratio of wall materials is 2: 5.
Dissolving 50 g stearic acid or paraffin in anhydrous ethanol, stirring, heating to 65 deg.C to dissolve, and adding 10 g silicon dioxide, diatomite or bentonite; then 20 g of potassium persulfate is added, the stirring is stopped, and the potassium persulfate is uniformly dispersed in the wall material solution by ultrasonic waves; stopping ultrasound, reducing the temperature while stirring to reduce the solubility of the wall material, condensing and precipitating potassium persulfate serving as a core, and cooling to form the potassium persulfate microcapsule.
1L of actual atrazine-polluted water (the concentration of atrazine is 100 mug/L) is taken, 10 g of potassium persulfate microcapsules are added, and the atrazine concentration and metabolites thereof are completely degraded after 7 days of reaction. The better degradation may be due to the fact that potassium persulfate has a lower solubility than ammonium persulfate and the oxidant is released more slowly and therefore more easily and sufficiently contacts the contaminants.
Example 3
The persulfate microcapsule formula comprises the following components: 20 g of sodium persulfate and 50 g of stearic acid, and a core material: the ratio of wall materials is 2: 5.
Dissolving 50 g stearic acid or paraffin in anhydrous ethanol, stirring, heating to 65 deg.C to dissolve, and adding 10 g silicon dioxide, diatomite or bentonite; then 20 g of sodium persulfate is added, the stirring is stopped, and the sodium persulfate is uniformly dispersed in the wall material solution by ultrasonic waves; stopping ultrasound, reducing the temperature while stirring to reduce the solubility of the wall material, condensing and precipitating potassium sodium persulfate serving as a core, and cooling to form the sodium persulfate microcapsule.
Taking 1L of artificially prepared atrazine-polluted water 30 mg/L, adding 10 g of sodium persulfate microcapsules, and completely degrading the atrazine after 7 days of reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (5)
1. A combined remediation method for atrazine-polluted water is characterized by comprising the steps of taking potassium persulfate, ammonium persulfate or sodium persulfate as core materials, taking paraffin and stearic acid as wall materials, doping inert materials of silicon dioxide, diatomite or bentonite, preparing lipophilic microcapsules by using an oil phase separation method, and adding persulfate microcapsules to degrade residual organic pollutants after microorganisms stimulate and degrade part of atrazine matrix; adding nutrient substances for promoting the growth of microorganisms into a polluted water body, ventilating, and degrading atrazine parent and partial intermediate metabolites; then persulfate microcapsules are added to generate compound free radical groups (OH, SO) through chemical oxidation reaction4 -And O2 -Etc.) degrading atrazine metabolites (triazine ring-containing substances) which cannot be degraded by microorganisms; nutrient substance stimulating microbial growth, phosphorusAdding a source and a nitrogen source, wherein the carbon source is atrazine and metabolites thereof, and estimating according to the actual pollutant concentration; the preparation method of the repair microcapsule comprises the following steps:
(1) dissolving stearic acid or paraffin in anhydrous alcohol, stirring, heating to 65 deg.C to dissolve completely, and adding inert substance such as silicon dioxide, diatomaceous earth or bentonite;
(2) then adding ammonium persulfate, potassium persulfate or sodium persulfate according to the proportion, stopping stirring, and performing ultrasonic treatment to uniformly disperse the ammonium persulfate, the potassium persulfate or the sodium persulfate in the wall material solution;
(3) stopping ultrasound, reducing the temperature while stirring to reduce the solubility of the wall material, condensing and separating out the wall material by taking persulfate as a core, and cooling to form the microcapsule.
2. The combined remediation method for atrazine-contaminated water as claimed in claim 1, wherein the microbial stimulant comprises a molar ratio of C: N: P of 100:10:1, and the phosphorus source is sodium phosphate (Na)3PO4·12H2O) or calcium phosphate (Ca)3(PO4)2) The nitrogen source is ammonium sulfate ((NH)4)2SO4) Or ammonium Nitrate (NH)4NO3) (ii) a The carbon source is atrazine and metabolites thereof, and is estimated according to the actual pollutant concentration.
3. The combined remediation method for the atrazine-polluted water body as claimed in claim 1, wherein the microcapsule core material is composed of persulfate, and the wall material is composed of paraffin and stearic acid; the core material is as follows: the proportion of wall materials is 2: 5; inert substances such as silicon dioxide, diatomite or bentonite are added into the microcapsules, and the mass of the inert substances is 1/10-1/5 of the microcapsules.
4. The combined remediation method for atrazine-contaminated water according to claim 1, wherein the atrazine and its metabolites: atrazine, deethylatrazine, deisopropylatrazine, hydroxyaatrazine, deithyldeisopropylatrazine and cyanuric acid.
5. The combined remediation method for atrazine-contaminated water according to claim 1, characterized in that the application of said method is: firstly, promoting the degradation of atrazine parent and partial intermediate products by adopting a microbial stimulation method, and then degrading a compound containing a triazine ring structure which cannot be degraded by microorganisms by utilizing persulfate microcapsules to restore the water body.
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| CN112778227A (en) * | 2021-01-05 | 2021-05-11 | 南昌航空大学 | Method for detoxifying atrazine triazine herbicide under alkaline condition |
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