CN112537839A - Method for remedying heavy metal pollution of underground water in river network area by using calcium peroxide-pyrite - Google Patents
Method for remedying heavy metal pollution of underground water in river network area by using calcium peroxide-pyrite Download PDFInfo
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- CN112537839A CN112537839A CN202011285058.7A CN202011285058A CN112537839A CN 112537839 A CN112537839 A CN 112537839A CN 202011285058 A CN202011285058 A CN 202011285058A CN 112537839 A CN112537839 A CN 112537839A
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- pyrite
- acetochlor
- calcium peroxide
- underground water
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention belongs to the technical field of water treatment, and discloses a method for remedying organic pollution of underground water in a river network area by using calcium peroxide-pyrite. According to the invention, calcium peroxide and pyrite are added into a water sample to be treated; carrying out degradation reaction; the dosage of the calcium peroxide is 20-30 times of that of the acetochlor, and the dosage of the pyrite is 600 times of that of the acetochlor with the concentration of 400-. According to the invention, calcium peroxide and pyrite are added into underground water polluted by acetochlor by controlling a certain reaction condition, and the removal rate of acetochlor in the underground water can reach 100% under the condition that the initial pH is acidic. The method organically combines the calcium peroxide and the pyrite, has the advantages of economy, environmental protection, high removal efficiency, simple process flow, convenient operation and the like, and can be applied to the in-situ remediation of underground water pollution, in particular to the in-situ remediation of the underground water organic pollution in a pyrite enrichment area.
Description
Technical Field
The invention belongs to the technical field of water treatment, relates to a method for remedying organic matter pollution of underground water, and particularly relates to a method for remedying organic matter pollution in underground water by using calcium peroxide and pyrite in a synergistic manner.
Background
With the widespread use of herbicides and the continuous and intensive research on their performance, the food safety problems brought by them are receiving more and more attention. Wherein Acetochlor (Acetochlor, molecular formula C)14H20ClNO2) Is a representative chloramide herbicide, and is widely applied to preemergence control of crops due to the advantages of high herbicidal activity, safety to the crops, low price, stable property and the like. But acetochlor has carcinogenicity (which is marked as B-2 carcinogen by the United states environmental protection agency), is used in a large amount, has a long degradation period in a natural environment, and can enter water bodies to pollute underground water along with the actions of surface runoff, leaching and the like after the acetochlor remained in soil. Poses a threat to the ecological environment, human beings, animals and plants.
Conventional treatment processes for groundwater pollution currently include ex-situ remediation techniques and in-situ remediation techniques. The ex-situ repair technique has the advantages of high processing efficiency and short period, but the required later maintenance cost is high, and the risk of tailing and rebounding exists. The in-situ repair technology needs less cost and has less interference and influence on the environment. Comprises a permeable reactive barrier repairing technology, an in-situ biological repairing technology and an in-situ chemical repairing technology. Wherein the in-situ chemical repair technology is concerned by the advantages of quick effect, simple operation and the like. The Fenton method is one of the more conventional methods for degrading acetochlor, but the traditional oxidant hydrogen peroxide is easy to waste due to too high oxygen release rate, and the exothermic heat of Fenton reaction can further accelerate the decomposition of hydrogen peroxide. The hydrogen peroxide has short service life, uneven distribution in underground water and insufficient contact time with pollutants, and the treatment effect is difficult to achieve. And the chemical reagent cost is high, the cost is high for general repair work, and secondary pollution is possibly brought.
Therefore, an economical, efficient and secondary pollution-free chemical reagent needs to be found.
Disclosure of Invention
The invention aims to provide a chemical reagent and a method for effectively and quickly removing acetochlor pollution. The method aims to solve the problem that the reaction effect is poor due to the fact that hydrogen peroxide is decomposed too fast in the traditional Fenton, and the conventional ferrous ions are replaced by pyrite existing in the natural environment, so that the reaction rate is improved, and the repair cost is saved.
Calcium peroxide (CaO)2) White or light yellow crystal powder, has obvious thermodynamic stability, is not easy to decompose, is an excellent oxygen donor, and is also a hydrogen peroxide slow-release agent. Substitute hydrogen peroxide and ferrous ion and constitute kind fenton reagent in the fenton reaction, can solve hydrogen peroxide and decompose too fast in traditional fenton reaction, the not good problem of reaction effect.
Pyrite (FeS)2) Is the most abundant sulfide mineral in the terrestrial environment. Due to natural processes and human activities, pyrite is oxidized by exposure to aerobic conditions, producing high concentrations of dissolved ferrous iron (Fe)2+) Hydrogen ion (H)+) Sulfate ion (SO)4 2-) And other ionic acid liquids. Pyrite can be oxidized by oxygen (O)2) And hydrogen peroxide (H)2O2) Fenton's reaction takes place to generate hydroxyl radical (. OH), which can also effectively oxidize and degrade pollutants. And the acid environment after oxidation is favorable for the Fenton reaction. Therefore, on the basis of repeated test analysis, the method adopts a calcium peroxide-pyrite system to restore acetochlor pollution in underground water.
The present invention has been completed based on the above-mentioned studies.
The invention provides a method for repairing basement organic pollution in a river network area, which comprises the following steps:
collecting a groundwater sample to be treated containing acetochlor pollutants;
pretreating the collected groundwater sample to be treated to remove suspended objects;
adding calcium peroxide and pyrite into a groundwater sample to be treated;
uniformly stirring in a proper container for more than 30 minutes to carry out degradation reaction and remove acetochlor in the groundwater sample to be treated;
the dosage of the calcium peroxide is 20-30 times of the concentration of the acetochlor in the underground water, for example, the dosage of the calcium peroxide is 20 times, 24 times, 28 times and the like of the concentration of the acetochlor in the underground water by mass ratio. Preferably, the dosage of the calcium peroxide is 25 times of the concentration of the acetochlor in the underground water.
The dosage of the pyrite is 600 times of 400-fold of the concentration of the acetochlor in the groundwater. For example, the dosage of the pyrite is 420 times, 450 times, 480 times, 520 times, 560 times, etc. of the concentration of the acetochlor in the groundwater by mass ratio. Preferably, the dosage of the pyrite is 500 times of the concentration of the acetochlor in the groundwater.
Preferably, the pH value of the water sample to be treated is adjusted to 3-4 before adding or oxidizing calcium and pyrite. The pH can be adjusted using conventional acid-base reagents or equipment, for example, using hydrochloric acid and sodium hydroxide.
Preferably, the average particle size of the pyrite is less than 100 meshes.
Preferably, the concentration of the acetochlor in the water sample to be treated is not higher than 10mg/L, such as 2mg/L, 5mg/L or 8mg/L, and the like.
Preferably, the temperature of the degradation reaction is 20-30 ℃.
Preferably, the time of the degradation reaction is not less than 120 minutes. In a preferred embodiment of the present invention, degradation times of 1 minute, 5 minutes, 10 minutes, 30 minutes, 60 minutes, etc. are used.
Preferably, the degradation reaction is carried out in a constant temperature oscillator at a rotation speed of 100-300 rpm. For example, the temperature of the constant temperature oscillator is normal temperature, and the rotating speed is 190 r/min.
The invention also provides a composition containing calcium peroxide and pyrite in a molar ratio of calcium peroxide to pyrite: 1 part of pyrite: 1.5-1: 30. the composition can be put into a water sample to be treated and used for removing acetochlor in the water sample.
Specifically, the invention relates to a method for synergistically repairing organic matter pollution in underground water by using calcium peroxide-pyrite. Firstly, hydrochloric acid and sodium hydroxide are used for adjusting the pH value of acetochlor wastewater, then calcium peroxide and pyrite are added into the wastewater, and then the wastewater is placed in a constant temperature oscillator for degradation reaction. The removal rate of acetochlor in the underground water after treatment can reach 100 percent.
Experiments show that calcium peroxide mainly plays a role in providing oxygen and serving as a slow release agent of hydrogen peroxide, and the generated oxygen and the generated hydrogen peroxide can accelerate the oxidation of pyrite and generate hydroxyl radicals so as to degrade acetochlor. The main function of pyrite is to provide an acidic reaction environment and divalent iron in the oxidation process, and to provide an acidic environment for fenton action in addition to degrading acetochlor.
In the calcium peroxide/pyrite system, calcium peroxide dissolves in water-generated hydrogen peroxide and dissolved Fe2+The reaction produces OH through the Fenton mechanism. The specific process is that calcium peroxide is dissolved in water to generate H2O2，H2O2Oxidation of pyrite to produce Fe3 +Then Fe3+Oxidation of pyrite to produce Fe2+，Fe2+And H2O2The reaction produces OH. Thus, calcium peroxide dissolves in water to produce H2O2In the reaction with pyrite, Fe2+With Fe3+The circulation of (2) controls the generation of OH which can effectively remove organic pollutants in the sewage.
According to the invention, calcium peroxide and pyrite are added into underground water polluted by acetochlor by controlling a certain reaction condition, and the removal rate of acetochlor in the underground water can reach 100% under the condition that the initial pH is acidic. The invention selects the organic combination of calcium peroxide and pyrite, and compared with the method for removing acetochlor by adding ferrous iron as other oxidants, the H generated by dissolving the calcium peroxide in water2O2In the reaction with pyrite, Fe2+With Fe3+The method controls the generation of OH, has the advantages of high removal efficiency, simple process flow, convenient operation and the like, and can be applied to the in-situ remediation of organic polluted groundwater in river network areasAnd (5) repeating or pumping water.
The invention has the beneficial effects that:
the method has the advantages of simple process flow, convenient operation and high removal efficiency, effectively utilizes the synergistic effect of the calcium peroxide and the pyrite, has the advantages of economy, environmental protection, high removal efficiency, simple process flow, convenient operation and the like, and can be applied to the in-situ remediation of groundwater pollution, particularly the in-situ remediation of organic pollution of groundwater in a pyrite enrichment area.
Drawings
FIG. 1 is a graph comparing the removal of acetochlor from pyrite, calcium peroxide and pyrite plus calcium peroxide.
Wherein 250mL of groundwater containing acetochlor was prepared as the water sample to be detected, as shown in example 1.
500mg/L of pyrite was charged, the initial pH was adjusted to 3, and the reaction was carried out for 2h at 25 ℃ in a thermostated shaker at 190 r/min. With increasing reaction time, acetochlor was not removed.
25mg/L of calcium peroxide was added, the initial pH was adjusted to 3, and the reaction was carried out at 25 ℃ for 2 hours in a constant temperature shaker at 190 r/min. With the increase of the reaction time, the removal rate of the acetochlor reaches 0.3 percent from 10min, and then the removal rate does not increase any more, and the process is slightly repeated.
25mg/L of calcium peroxide and 500mg/L of pyrite were charged, the initial pH was adjusted to 3, and the reaction was carried out at 25 ℃ for 2 hours in a constant temperature oscillator of 190 r/min. The removal rate of acetochlor rapidly reached 64% within 10min, followed by a gradual rise to 88% within 30min, 98% within 60min and nearly 100% within 2 h.
Therefore, the calcium peroxide and the pyrite are used simultaneously, so that the mutual interference is avoided, and the acetochlor can be quickly removed.
Detailed Description
In order to better illustrate the present invention, the present invention is further illustrated by examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparing 250mL of underground water containing 10mg/L of acetochlor, adding 25mg/L of calcium peroxide and 500mg/L of pyrite into the underground water, adjusting the initial pH value to 3, and reacting for 2 hours in a constant-temperature oscillator at 25 ℃ at 190r/min, wherein the removal rate of the acetochlor in the underground water reaches 100%.
Examples 2 to 4
The prepared groundwater and the added calcium oxide and pyrite have the same amount, and the removal rate of acetochlor is as follows in different reaction time:
| examples | Reaction time (minutes) | Acetochlor removal rate (%) |
| Example 2 | 10 | 64 |
| Example 3 | 30 | 88 |
| Example 4 | 60 | 98 |
Example 5
500mg/L of pyrite was charged, the initial pH was adjusted to 3, and the reaction was carried out for 2h at 25 ℃ in a thermostated shaker at 190 r/min. With increasing reaction time, acetochlor was not removed.
Example 6
25mg/L of calcium peroxide was added, the initial pH was adjusted to 3, and the reaction was carried out at 25 ℃ for 2 hours in a constant temperature shaker at 190 r/min. With the increase of the reaction time, the removal rate of the acetochlor reaches 0.3 percent from 10min, and then the removal rate does not increase any more, and the process is slightly repeated.
Comparing examples 5 and 6 with example 1, it can be seen that the acetochlor removal rate is low when calcium peroxide alone or pyrite is used, however, the calcium peroxide and pyrite are used together, which not only does not interfere with each other, but also can rapidly remove acetochlor.
As those skilled in the art will appreciate, the present invention may be embodied in many other specific forms without departing from the spirit or scope thereof. Although embodiments of the present invention have been described, it is to be understood that the present invention should not be limited to those embodiments but various changes and modifications can be made by one skilled in the art within the spirit and scope of the present invention as hereinafter claimed.
Claims (10)
1. A method for remedying underground water organic pollution by adding an oxidant to over pyrite is characterized by comprising the following steps:
collecting a groundwater sample to be treated containing acetochlor pollutants;
pretreating the collected groundwater sample to be treated to remove impurities;
adding calcium peroxide and pyrite into a groundwater sample to be treated;
uniformly stirring the mixture in a proper container for more than 30 minutes to perform degradation reaction and remove acetochlor in the groundwater sample to be treated.
2. The method as claimed in claim 1, wherein the calcium peroxide is added in an amount of 20-30 times the concentration of acetochlor in the groundwater, and the pyrite is added in an amount of 400-600 times the concentration of acetochlor in the groundwater.
3. The method according to claim 1, characterized in that the pH value of the water sample to be treated is adjusted to 3-4 before adding calcium peroxide or pyrite.
4. The method as claimed in claim 1, wherein the concentration of acetochlor in the water sample to be treated is not higher than 10 mg/L.
5. The method of claim 1, wherein the degradation reaction temperature is 20-30 ℃.
6. The method of claim 1, wherein the degradation reaction time is not less than 120 minutes.
7. The method as claimed in claim 1, wherein the degradation reaction is carried out in a constant temperature oscillator at a speed of 100-300 rpm.
8. The method according to claim 1, characterized in that the pyrite average particle size is less than 100 mesh.
9. A composition comprising calcium peroxide and pyrite in a molar ratio of calcium peroxide to calcium pyrite: 1 part of pyrite: 1.5-1: 30.
10. use of a composition according to claim 9, wherein said composition is placed in a water sample to be treated for the removal of acetochlor therefrom.
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Cited By (1)
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| CN115231680A (en) * | 2022-06-28 | 2022-10-25 | 同济大学 | Preparation method and application of biochar loaded nano zero-valent iron material |
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