CN108046404B - In-situ chemical oxidation remediation method for organic-polluted underground water - Google Patents
In-situ chemical oxidation remediation method for organic-polluted underground water Download PDFInfo
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- CN108046404B CN108046404B CN201711386753.0A CN201711386753A CN108046404B CN 108046404 B CN108046404 B CN 108046404B CN 201711386753 A CN201711386753 A CN 201711386753A CN 108046404 B CN108046404 B CN 108046404B
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
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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
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Environmental & Geological Engineering (AREA)
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- Organic Chemistry (AREA)
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- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The invention discloses an in-situ chemical oxidation remediation method for organic polluted groundwater, which comprises the following steps: injecting the solution A into organic matter polluted underground water, and maintaining for 6-18 hours; injecting the solution B, and curing for 2-6 hours; finally injecting the solution C and curing for 12-24 hours; circulating the above steps until the detection of the underground water pollutants reaches the standard; the solution A is a mixed solution of ferrate, an alkaline solution and a stabilizer; the solution B is a complexing agent aqueous solution; the solution C is hydrogen peroxide diluted by water. The invention adopts ferrate to pre-oxidize and wrap the non-soluble reducing substance of the sediment part, reduces the content of pollutants and reducing substances in the underground water, and simultaneously, ferrate provides iron ions for hydrogen peroxide to form catalytic oxidation reaction, thereby achieving the effect of efficiently removing organic pollutants. The chemical method is applied to in-situ chemical oxidation of underground water, and can obtain better oxidation effect.
Description
Technical Field
The invention relates to a remediation method of polluted underground water, in particular to an in-situ chemical oxidation treatment method of organic polluted underground water, belonging to the technical field of underground water remediation.
Background
With the rapid development of the economic society, the optimization of the industrial structure, the transformation of the urban functional areas and the adjustment of the urban layout, a large number of chemical enterprises are transferred and moved out of the central area of the urban city, and a large number of polluted industrial sites are left, wherein a plurality of sites have the problem of organic pollution. Common organic pollutants include benzene series (BTEX), chlorinated hydrocarbons, phenols, nitroaromatics, and the like. Because these organic pollutants have moderate solubility, they can migrate and diffuse with the groundwater flow, thus causing long-term harm and negative effects to regional soil and groundwater ecosystems, and because of the moderate volatility and strong toxicity of the organic solvents, they can be exposed to the human body through the atmospheric migration path, thus causing harm to the health of residents on the site and around.
Chemical oxidation is a common wastewater treatment technique that is also commonly used for remediation of contaminated groundwater. Chemical oxidizing agents are added into underground water to chemically oxidize target organic pollutants, and chemical structures of organic matters are damaged, so that toxicity of polluted underground water is reduced, and the effect of reducing environmental risks is achieved. The underground water chemical oxidation technology has the characteristics of strong applicability, high efficiency and simple operation, and has the key point of selection and use of an oxidation reagent.
Common chemical oxidizing agents for groundwater include hydrogen peroxide, persulfates, permanganates, and the like. The hydrogen peroxide can generate hydroxyl free radicals through the catalysis of added ferrous sulfate, and has stronger oxidizing capacity; persulfate can generate slow and continuous oxidation effect and is beneficial to the diffusion of the oxidation medicament; the permanganate has the effect of selectively oxidizing pollutants such as polycyclic aromatic hydrocarbon and the like.
In recent years, a novel green oxidation material, namely a ferrate reagent, has higher potential, excellent oxidation selectivity and sterilization effect, and shows stronger application potential in the aspect of polluted water body remediation. But it presents great difficulties in its application due to its poor stability, especially in aqueous solution. In addition, the ferrate has higher unit price, which also limits the application of the ferrate in chemical oxidation remediation of polluted underground water.
Disclosure of Invention
Aiming at the problems of low medicament oxidation efficiency in the conventional in-situ chemical oxidation remediation of organic polluted underground water, the invention provides an in-situ chemical oxidation remediation method of organic polluted underground water.
An in-situ chemical oxidation remediation method for organic-polluted groundwater comprises the following steps:
injecting the solution A into organic matter polluted underground water, and maintaining for 6-18 hours; injecting the solution B, and curing for 2-6 hours; finally injecting the solution C and curing for 12-24 hours; circulating the above steps until the detection of the underground water pollutants reaches the standard;
the solution A is a mixed solution of ferrate, an alkaline solution and a stabilizer;
the solution B is a complexing agent aqueous solution;
the solution C is hydrogen peroxide diluted by water.
The circulation is that the solution A is injected into the organic matter polluted underground water and is maintained for 6-18 hours; injecting the solution B, and curing for 2-6 hours; and finally injecting the solution C and curing for 12-48 hours.
The invention provides a method for improving the stability of a ferrate solution in an injection stage by adopting ferrate as an oxidant and adopting methods of regulating pH, adding inorganic ions for improving stability and the like. By injecting in combination with hydrogen peroxide, the efficiency of oxidation is increased and the cost of oxidation is reduced. The ferrate is used for pre-oxidation and wrapping the non-soluble reducing substance of the sediment part, so that the content of pollutants and reducing substances in the underground water is reduced, and simultaneously, the ferrate provides iron ions for the hydrogen peroxide to form a catalytic oxidation reaction, thereby achieving the effect of efficiently removing the organic pollutants. The chemical method is applied to in-situ chemical oxidation of underground water, and can obtain better oxidation effect.
Preferably, the curing time after the solution A is added is 12-18 hours, the oxidation time after the solution B is added is 4-6 hours, and the curing time after the solution C is added is 24-48 hours.
Preferably, the total injection amount of the solution A is 2-6% of the volume of the aquifer in the restoration range, the total injection amount of the solution B is 1-2% of the volume of the aquifer in the restoration range, and the total injection amount of the solution C is 3-10% of the volume of the aquifer in the restoration range.
Determining the total injection amount, determining the number of injection rounds according to the number of the injection wells and the single injection amount of each well, wherein the maximum injection amount of each well is 2-3m3Left and right.
Preferably, the preparation concentration of the alkaline solution is 1-3 mmol/L, and the preparation concentration of ferrate in the solution A is 10-30 mmol/L; the molar weight of the stabilizer prepared is 1/10-1/50 of the molar weight of ferrate. The solution A is prepared by dissolving ferrate in alkaline solution and adding small amount of stabilizer.
Further preferably, the preparation concentration of the alkaline solution is 1.5-2.5 mmol/L, and the preparation concentration of ferrate in the solution A is 15-25 mmol/L; the molar weight of the stabilizer prepared is 1/10-1/20 of the molar weight of ferrate.
Further preferably, the ferrate is potassium ferrate or sodium ferrate; the alkaline solution is sodium hydroxide solution or potassium hydroxide solution; the stabilizer is at least one of potassium iodide, potassium iodate, sodium silicate and copper chloride.
Preferably, the complexing agent is sodium oxalate, potassium oxalate, sodium citrate or disodium EDTA; the concentration of the complexing agent aqueous solution is 3-10 mmol/L. The preparation method of the solution B is to dissolve the complexing agent in water. Further preferably, the concentration of the complexing agent aqueous solution is 3-5 mmol/L.
Preferably, the preparation method of the solution C comprises the steps of diluting hydrogen peroxide and water, wherein the preferable preparation concentration of the hydrogen peroxide is 7-15%; further preferably, the preparation concentration of the hydrogen peroxide is 7-10%.
Preferably, the solution A, the solution B and the solution C are injected through underground water injection wells or underground saturated water layers injected by a direct-push type medicament injection device. The thickness of the underground saturated water layer is 5-10 m.
Before injection, underground water in-situ injection wells arranged in a system grid or injection points arranged in the system grid are established in a region to be treated, and a mobile direct-push type medicament injection device is adopted for injection.
Preferably, the density of the underground water in-situ injection well or injection point is 30-100 m per unit2Arranging an injection well or an injection point; further preferably, the thickness is 30-40 m2An injection well or point is provided.
Preferably, the organic pollutant is one or more of benzene, 1, 2-dichloroethylene, 2-chlorotoluene, 4-chlorotoluene, chloroform, carbon tetrachloride, 1, 2-dichloroethane, trichloroethylene and 1,2, 4-trichlorobenzene.
Further preferred are mixtures of chloroform, carbon tetrachloride, 1, 2-dichloroethane, trichloroethylene, 1,2, 4-trichlorobenzene. A more preferred in situ remediation method comprising the steps of: before in-situ chemical oxidation injection, injection sites distributed in a system grid are established in the range of an area to be repaired, and each injection site is 30-40 m2An injection point is arranged in the device, a movable direct-push type medicament injection device is adopted for injection, a solution A containing 18-22 mmol/L potassium ferrate, 1.8-2.2 mmol/L sodium hydroxide, 1.8-1.2 mmol/L potassium iodide and 1.8-2.2 mmol/L copper chloride is prepared, and 1.4-1.6 m of the solution is injected into each point3After reacting for 17-18 h, injecting a B solution containing 4.5-5 mmol/L sodium oxalate into each well, and injecting the solution into each well for 0.4-0.6 m3Injecting 6-8% hydrogen peroxide solution 1.8-2.2 m into each well after reacting for 5-6 hours3Reacting for 46-48 h for 3-5 injection cycles.
A most preferred in situ remediation process comprising the steps of: before in-situ chemical oxidation injection, injection sites distributed in a system grid are established in the range of an area to be repaired, and each injection site is 30-40 m2Setting an injection point, injecting by using a movable direct-push type medicament injection device to prepare a solution A containing 20mmol/L potassium ferrate, 2mmol/L sodium hydroxide, 1mmol/L potassium iodide and 1mmol/L copper chloride solution, and injecting the solution 1.5m per point3After reacting for 18h, injecting solution B containing 5mmol/L sodium oxalate into each well, and injecting the solution 0.5m into each well3After 6 hours of reaction, 8% hydrogen peroxide solution was injected into each well for 2m3Reacted for 48h for 3 injections.
Aiming at the in-situ chemical oxidation of the organic polluted underground water, the ferrate and the hydrogen peroxide are applied in a combined way, so that the removal efficiency of the oxidant to the target pollutants is improved. Ferrate has higher electrode potential (+2.2V), and simultaneously, the reduced product iron hydroxide of ferrate can generate the effect of flocculation and precipitation, and the reaction of ferrate can greatly wrap and precipitate to remove reducing substances in underground water. In addition, the ferrate can be added to improve the content of iron ions in underground water, and can catalyze hydrogen peroxide to generate hydroxyl radicals so as to improve the oxidizing capability of the hydrogen peroxide. Thus, the combined administration of ferrate and hydrogen peroxide reduces the amount of ferrate and saves the cost of the oxidizing agent compared to ferrate alone. Compared with the single use of hydrogen peroxide, the method has higher oxidation efficiency. In addition, the stability of the ferrate solution is improved by adding the stabilizing agent, the reaction rate of the ferrate is controlled by adjusting the pH value of the solution, the effectiveness of iron ion catalysis in underground water is increased by utilizing the complexing agent, and the effect of chemical oxidation is further improved. The groundwater in-situ oxidation remediation technology is simple to operate, high in oxidation efficiency and free of secondary pollution, and is an effective organic pollution groundwater remediation technology.
Detailed Description
Further description will be given below with respect to another use form of the groundwater extraction oxidation and the groundwater in-situ chemical oxidation, according to the embodiment of the present invention.
Example 1:
the process of underground water in-situ chemical oxidation is simulated in a laboratory underground water remediation simulation tank, 20L of prepared benzene and 1, 2-dichloroethylene polluted underground water is added into the simulation tank filled with sandy soil, the concentration of the benzene in the underground water is about 26mg/L, the concentration of the 1, 2-dichloroethylene is about 5.6mg/L, and the pH value is about 6.5.
Preparing solution A comprising 20mmol/L sodium ferrate, 2mmol/L potassium hydroxide and 0.5mmol/L potassium iodate; preparing 4mmol/L potassium oxalate solution B; the solution C is 15% hydrogen peroxide.
1L of solution A is injected through an injection well arranged in a simulation tank, 0.5L of solution B is injected after 6-hour curing, and 2L of solution C is injected after 3-hour curing. After 24 hours of maintenance, the content of benzene and 1, 2-dichloroethylene is measured by sampling, the removal rate of benzene can reach 82.7 percent, and the removal rate of 1, 2-dichloroethylene can reach 99.4 percent.
Example 2:
the area of the ground water pollution area of a pesticide factory is about 4000m2The thickness of the aquifer is about 10m, and the porosity of the saturated aquifer soil is 46 percent. Average of benzene, 2-chlorotoluene, 4-chlorotoluene and chloroform in the regionConcentration values were 2081. mu.g/L, 1732. mu.g/L, 3366. mu.g/L and 105. mu.g/L, respectively. Before in-situ chemical oxidation injection, 40 underground water in-situ injection wells arranged in a system grid are established in an area range. Preparing solution A containing 10mmol/L potassium ferrate, 1mmol/L sodium hydroxide and 1mmol/L potassium iodide, and injecting the solution 2m per well3. After reacting for 8h, injecting the solution B containing 3mmol/L sodium citrate into each well, and injecting the solution into each well for 1m3After 4 hours of reaction, 7% hydrogen peroxide solution was injected into each well for 8m3And reacting for 12h, and sampling after 10 rounds of total injection to determine the concentration of the organic pollutants. The test results showed that the average concentration values of benzene, 2-chlorotoluene, 4-chlorotoluene and chloroform in the region were decreased by 77.65%, 89.13%, 95.39% and 91.48%, respectively.
Example 3:
the area of the underground water pollution area of a certain pesticide factory is about 3500m2The thickness of the aquifer is about 6m, and the porosity of the saturated aquifer soil is 42%. The average concentration values of chloroform, carbon tetrachloride, 1, 2-dichloroethane, trichloroethylene and 1,2, 4-trichlorobenzene in the region were 4210. mu.g/L, 8094. mu.g/L, 2279. mu.g/L, 329. mu.g/L and 1536. mu.g/L, respectively. Before in-situ chemical oxidation injection, 100 injection sites distributed in a system grid are established in an area range, and a movable direct-pushing medicament injection device is adopted for injection. A solution containing 20mmol/L potassium ferrate, 2mmol/L sodium hydroxide, 1mmol/L potassium iodide and 1mmol/L copper chloride was prepared, and 1.5m of the solution was injected into each spot3. After reacting for 18h, injecting solution B containing 5mmol/L sodium oxalate into each well, and injecting the solution 0.5m into each well3After 6 hours of reaction, 8% hydrogen peroxide solution was injected into each well for 2m3Reacting for 48h, and sampling after 3 times of total injection to determine the concentration of the organic pollutants. The results of the tests showed that the average concentration values of benzene, 2-chlorotoluene, 4-chlorotoluene and chloroform in the region decreased by 85.21%, 94.36%, 93.13%, 97.71% and 87.54%, respectively.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (3)
1. An in-situ chemical oxidation remediation method for organic-polluted groundwater is characterized by comprising the following steps:
injecting the solution A into organic matter polluted underground water, and maintaining for 6-18 hours, wherein the total injection amount of the solution A is 2-6% of the volume of the aquifer in the restoration range; injecting the solution B again, and maintaining for 2-6 hours, wherein the total injection amount of the solution B is 1-2% of the volume of the aquifer in the restoration range; finally injecting the solution C for curing for 12-48 hours, wherein the total injection amount of the solution C is 3-10% of the volume of the aquifer in the repair range; circulating the above steps until the detection of the underground water pollutants reaches the standard;
the solution A is a mixed solution of ferrate, an alkaline solution and a stabilizer; the preparation concentration of the alkaline solution is 1-3 mmol/L, and the preparation concentration of ferrate in the solution A is 10-30 mmol/L; the molar weight of the stabilizer prepared is 1/10-1/50 of the molar weight of ferrate;
the solution B is a complexing agent aqueous solution; the concentration of the complexing agent aqueous solution is 3-10 mmol/L;
the solution C is hydrogen peroxide diluted by water; the mass percentage of the diluted hydrogen peroxide is 7-15%;
the solution A, the solution B and the solution C are injected into an underground saturated water layer through an underground water injection well or a direct-push type medicament injection device;
before injection, underground water in-situ injection wells arranged in a system grid or injection points arranged in the system grid are established in a region to be treated, and a mobile direct-push type medicament injection device is adopted for injection;
the setting density of underground water in-situ injection wells or injection points is 30-100 m per well2An injection well or point is provided.
2. The in situ chemical oxidative remediation method of claim 1 wherein the ferrate is potassium ferrate or sodium ferrate; the alkaline solution is sodium hydroxide solution or potassium hydroxide solution; the stabilizer is at least one of potassium iodide, potassium iodate, sodium silicate and copper chloride.
3. The in-situ chemical oxidation remediation method of claim 1, wherein the complexing agent is sodium oxalate, potassium oxalate, sodium citrate, or disodium EDTA.
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| CN110451628A (en) * | 2019-07-30 | 2019-11-15 | 济南大学 | A kind of restorative procedure of trichloro ethylene polluted underground water |
| CN111721903B (en) * | 2020-05-26 | 2021-06-11 | 北京市环境保护科学研究院 | Method for determining in-situ oxidation repair radius of underground water |
| CN111661911B (en) * | 2020-06-01 | 2022-02-22 | 五邑大学 | Method for removing organic pollutants in water |
| CN111760899B (en) * | 2020-06-22 | 2021-08-24 | 南京农业大学 | Feeding improvement method for repairing toxic organic contaminated soil through oxidant compounding oxidation |
| CN111922061B (en) * | 2020-07-16 | 2022-07-08 | 中铁科学研究院有限公司成都分公司 | Soil remediation agent and preparation method and application thereof |
| CN112551799B (en) * | 2020-10-10 | 2022-05-17 | 西华师范大学 | Underground water pollution treatment strengthening treatment device and treatment method |
| CN112756388B (en) * | 2020-12-16 | 2023-02-03 | 湖南恒凯环保科技投资有限公司 | Method for repairing underground water by polymer flooding enhanced in-situ chemical oxidation |
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