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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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 239000000126 substance Substances 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000005067 remediation Methods 0.000 title claims description 18
- 239000000243 solution Substances 0.000 claims abstract description 70
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003673 groundwater Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000002347 injection Methods 0.000 claims description 56
- 239000007924 injection Substances 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000003814 drug Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical group [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 5
- 229940039790 sodium oxalate Drugs 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000003403 water pollutant Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000005538 encapsulation Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 9
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Processing Of Solid Wastes (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
本发明公开了一种有机物污染地下水的原位化学氧化修复方法，包括如下步骤：将A溶液注射至有机物污染地下水中，养护6～18小时；再注射B溶液，养护2～6小时；最后注射C溶液养护12～24小时；如此循环至地下水污染物检测达标；所述A溶液为高铁酸盐、碱性溶液和稳定剂的混合液；所述B溶液为络合剂水溶液；所述C溶液为水稀释后的双氧水。本发明采用高铁酸盐进行预氧化和包裹沉淀部分非可溶的还原物质，降低地下水中污染物和还原性物质的含量，同时高铁酸盐为过氧化氢提供铁离子，形成催化氧化反应，达到有机污染物高效去除的效果。将该化学方法应用于地下水的原位化学氧化，可取得较好的氧化效果。The invention discloses an in-situ chemical oxidation restoration method for organic-contaminated groundwater, comprising the following steps: injecting solution A into the organic-contaminated groundwater, and curing for 6-18 hours; injecting solution B, curing for 2-6 hours; and finally injecting The C solution is maintained for 12 to 24 hours; it is circulated in this way until the detection of groundwater pollutants reaches the standard; the A solution is a mixed solution of ferrate, an alkaline solution and a stabilizer; the B solution is an aqueous complexing agent; the C solution It is hydrogen peroxide diluted with water. In the invention, ferrate is used for pre-oxidation and encapsulation of precipitation part of insoluble reducing substances, so as to reduce the content of pollutants and reducing substances in groundwater. Effective removal of organic pollutants. The chemical method is applied to the in-situ chemical oxidation of groundwater, and a good oxidation effect can be obtained.
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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| CN109675922A (en) * | 2018-12-27 | 2019-04-26 | 武汉瑞景环境修复工程有限公司 | The method of in-situ oxidation, gas phase extracting combined system and rehabilitating soil |
| CN109942072B (en) * | 2019-04-23 | 2022-04-22 | 天津华勘环保科技有限公司 | Method for degrading chlorohydrocarbon by activating persulfate through natural polyphenol |
| 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 | Improved method of feeding and remediating toxic organic polluted soil by compounding oxidant |
| 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 | A kind of groundwater pollution control 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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