CN114653737A - In-situ chemical reduction and enhanced biological combined remediation method for hexavalent chromium contaminated soil and underground water - Google Patents
In-situ chemical reduction and enhanced biological combined remediation method for hexavalent chromium contaminated soil and underground water Download PDFInfo
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- CN114653737A CN114653737A CN202210343024.1A CN202210343024A CN114653737A CN 114653737 A CN114653737 A CN 114653737A CN 202210343024 A CN202210343024 A CN 202210343024A CN 114653737 A CN114653737 A CN 114653737A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 34
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 238000005067 remediation Methods 0.000 title claims description 17
- 239000003124 biologic agent Substances 0.000 claims abstract description 4
- 230000008439 repair process Effects 0.000 claims description 22
- 235000015097 nutrients Nutrition 0.000 claims description 20
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- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- 241000894006 Bacteria Species 0.000 claims description 10
- 239000003673 groundwater Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
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- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 241001148470 aerobic bacillus Species 0.000 claims 1
- 239000008177 pharmaceutical agent Substances 0.000 claims 1
- 239000013043 chemical agent Substances 0.000 abstract description 5
- 235000016709 nutrition Nutrition 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 5
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- 238000003723 Smelting Methods 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
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- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000035764 nutrition Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 239000002680 soil gas Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
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Abstract
The invention provides an in-situ chemical reduction and enhanced biological combined restoration method for hexavalent chromium polluted soil and underground water, which comprises the steps of arranging a restoration well, injecting a chemical reducing agent solution into the restoration well, pretreating high-concentration hexavalent chromium in the soil and the underground water through chemical reduction, greatly reducing the concentration of the hexavalent chromium in the soil and the underground water, then injecting an aerobic biological agent and a nutritional aid into the restoration well to carry out in-situ enhanced biological restoration, realizing the stable standard reaching of the hexavalent chromium in the soil and the underground water, and simultaneously solving the problems of secondary pollution such as chemical agent residue, large increase of site salt content and the like in the traditional chemical reduction restoration method.
Description
Technical Field
The invention relates to a soil and underground water pollution treatment technology, in particular to an in-situ chemical reduction and reinforced biological combined remediation method for hexavalent chromium polluted soil and underground water.
Background
Chromium is mainly derived from fur and tanning pollution, electroplating pollution, chromium salt, textile printing and dyeing pollution, chromium ore smelting pollution and the like. Chromium exists in soil mainly in a trivalent form and a hexavalent form, wherein trivalent chromium is mainly attached to soil components in a hydroxide form and is difficult to migrate and low in toxicity, and hexavalent chromium exists mainly in an anion form and is high in mobility and high in biotoxicity. The conventional hexavalent chromium soil and groundwater treatment mainly adopts a chemical reduction agent to reduce hexavalent chromium into trivalent chromium. The traditional chemical reduction method has the advantages that the chemical reduction agent is easy to oxidize and short in timeliness, trivalent chromium formed by chemical reduction is deposited on the surface of a soil aggregate, hexavalent chromium inside the aggregate cannot be fully treated, the cohesive soil is difficult to reach the standard, and underground water rebounding exceeding standards is caused along with slow release of the hexavalent chromium inside the soil aggregate. In order to enable soil and underground water to reach the standard by a traditional chemical reduction method, chemical reduction agents are often excessive, so that the problems of secondary pollution such as chemical agent residue and large site salinity rise are caused.
Patent document (CN 102652956B) discloses an in-situ leaching treatment method for chromium-contaminated soil, which is a leaching combined extraction treatment process, and the content of chromium in the treated soil is still greater than 67mg/kg, which cannot meet the target requirements of site remediation in the prior art.
Patent document (202010563301.0) discloses a repairing agent for repairing hexavalent chromium-contaminated soil and a method for repairing hexavalent chromium-contaminated soil by using the same, which comprises the steps of preparing the repairing agent, digging soil, rolling and crushing the soil by using a soil repairing machine, applying medicines and stirring, and the like.
Patent document (202111214328. X) discloses a method for repairing hexavalent chromium-contaminated soil, which comprises the steps of soaking chromium-contaminated soil to be repaired in alkali liquor, and then adding reducing sugar to perform a reduction reaction to reduce hexavalent chromium in the soil to trivalent chromium. The treatment method needs to excavate soil for ectopic treatment, and has high energy consumption.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an in-situ chemical reduction and enhanced biological combined restoration method for hexavalent chromium polluted soil and underground water. The principle of bioremediation of hexavalent chromium is to reduce hexavalent chromium to trivalent chromium by means of a biological reductase produced by microorganisms. The microorganisms continuously play a role for a long time, so that the soil and underground water can stably reach the standard, and the problems of secondary pollution such as chemical agent residue, large increase of site salinity and the like in the traditional chemical reduction repair method are solved.
The purpose of the invention is realized by the following technical scheme:
an in-situ chemical reduction and reinforced biological combined restoration method for hexavalent chromium polluted soil and underground water comprises the following steps:
1) respectively laying a repair well group in the aeration zone and the saturation zone;
2) arranging a groundwater monitoring well group in the saturated zone;
3) injecting a chemical reduction agent into the repair well under pressure to carry out chemical repair;
4) and injecting nutrient substances and aerobic biological bacteria into the repairing well for bioremediation.
The bioremediation of step 4) comprises:
4a) respectively injecting nutrient substances into the aeration zone and the saturation zone repair well under pressure;
4b) aerobic biological bacteria for biologically reducing hexavalent chromium are injected into the aeration zone and the saturated zone repairing well;
4c) nutrient substances are injected into the repair wells of each aeration zone and each saturation zone in an intermittent small dosage manner, so that the concentration of the nutrient substances reaches more than 2 mg/L;
4d) and continuously or intermittently injecting aerobic gas compressed gas into the saturated zone repairing well to ensure that the content of dissolved oxygen in the underground water monitoring well is more than 2mg/L until the hexavalent chromium in the aeration zone soil, the saturated zone soil and the underground water reaches the standard.
The chemical reducing agent includes, but is not limited to, sodium sulfide, ferrous sulfate, or calcium polysulfide.
The nutrients include, but are not limited to, glucose, molasses, or ammonium salts.
The restoration well is a multifunctional injection well and is used for injecting chemical reduction agents, nutrient substances, aerobic biological agents and aerobic gas compressed gas.
The aerobic biological bacteria are screened and domesticated in advance, and hexavalent chromium is converted into trivalent chromium in a co-metabolism mode under an aerobic condition.
Before the step 4), the pH value of the soil and the underground water is adjusted to be between 5.5 and 9.5 by injecting a medicament into the repair well if necessary.
The aerobic gas is oxygen or air.
Compared with the existing soil bioremediation technology, the invention has the advantages that:
1) the technical scheme realizes the combined application of chemical reduction and microbial remediation, firstly utilizes the chemical reduction agent to remove high-concentration hexavalent chromium, and then utilizes the microbes to continuously remediate residual low-concentration hexavalent chromium, so that the hexavalent chromium in soil and underground water stably reaches the standard, and simultaneously solves the problems of secondary pollution such as chemical agent residue, large increase of site salt and the like in the traditional chemical reduction remediation method.
2) The technology can realize the in-situ combined remediation of the polluted soil and the underground water, realize the co-treatment of the water and the soil, and avoid the defects of ex-situ remediation technologies such as earthwork excavation, transportation, storage treatment and the like. The technology is suitable for hexavalent chromium polluted sites with different pollution degrees, and has a wide application range.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic view of the arrangement of the apparatus for repairing a metal object by the method of the present invention.
Detailed Description
The method and effect of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
The invention provides an in-situ chemical reduction and reinforced biological combined remediation method for hexavalent chromium contaminated soil and underground water, which comprises the following steps:
1) respectively laying a repair well group in an aeration zone and a saturation zone;
2) arranging a groundwater monitoring well group in the saturated zone;
3) injecting a chemical reduction agent into the restoration well under pressure, so as to greatly reduce the concentration of hexavalent chromium in the soil and the underground water; wherein the chemical reducing agent comprises sodium sulfide, ferrous sulfate, calcium polysulfide, etc.;
4) respectively injecting nutrient substances into the aeration zone and the saturation zone repair well under pressure; the nutrient substances comprise glucose, molasses, ammonium salt and the like;
5) aerobic biological bacteria for biologically reducing hexavalent chromium are injected into the aeration zone and the saturated zone repairing well;
6) nutrient substances are injected into the repair wells of each aeration zone and each saturation zone in an intermittent small dosage manner, so that the concentration of the nutrient substances reaches more than 2 mg/L;
7) oxygen gas (such as air or oxygen) compressed gas is continuously or intermittently injected into the saturated zone repairing well, so that the content of dissolved oxygen in the underground water monitoring well is more than 2mg/L until the hexavalent chromium in the aeration zone soil, the saturated zone soil and the underground water reaches the standard.
FIG. 1 shows a schematic layout of a device using the method described above, wherein 1-the zone of saturation repairs the well; 2-repairing the well in the gas-covered zone; 3-a monitoring well; 4-a compressed gas tank; 5-a bacteria liquid/nutrition auxiliary storage tank; 6-chemical agent storage tank.
Specific examples of the use of the above method are provided below:
example 1
In a certain hexavalent chromium polluted land, soil and underground water are both seriously polluted, the water level of the underground water is buried by about 5m, and the restoration depth is 20 m.
(1) Respectively laying repair well groups in the aeration zone and the saturation zone, wherein the repair well spacing of the aeration zone is 3m, and the repair well spacing of the saturation zone is 6 m;
(2) underground water monitoring wells are arranged in the middle of the saturated zone restoration wells, and the arrangement density of the underground water monitoring wells is 800m per second2Arranging a port;
(3) pressurizing and injecting 2% sodium sulfide solution into each repair well in batches by using a water pump until the concentration of hexavalent chromium in soil is reduced to below 30mg/kg and the concentration of hexavalent chromium in underground water is reduced to below 10 mg/L;
(4) after 500L of glucose (5 g/L) and ammonium sulfate (0.5 g/L) mixed nutrient solution is injected into each restoration well under pressure by a water pump, compressed air is continuously injected for 10 minutes, and nutrient substances are quickly diffused into soil around the restoration wells;
(5) injecting 20L of hexavalent chromium aerobic biological reducing bacteria liquid into each restoration well by adopting a water pump in a pressurizing manner, continuously injecting compressed air for 10 minutes, and quickly diffusing the aerobic biological bacteria liquid into soil around the restoration well;
(6) after continuously injecting the mixed nutrient solution of glucose (5 g/L) and ammonium sulfate (0.5 g/L) at a flow rate of 2L/min for 30 minutes, each remediation well continuously injects compressed oxygen for 10 minutes, and then intermittently injects the mixed nutrient solution again under pressure for 12 hours. Circulating in this way, the concentrations of glucose and ammonium sulfate in the underground water monitoring well are respectively maintained to be more than 50mg/L and 5 mg/L;
(7) compressed air is injected into the saturated zone repairing wells in turn, so that the concentration of dissolved oxygen in the underground water is maintained to be more than 2mg/L, and the oxygen content in the soil gas reaches more than 5 percent until hexavalent chromium in the soil and the underground water reaches the standard.
Example 2
The concentration of hexavalent chromium in soil of a certain polluted site reaches the standard, but the concentration of hexavalent chromium in underground water exceeds the standard, the maximum concentration is about 20mg/L, and the restoration depth is 15 m.
(1) Laying underground water repairing well groups, wherein the distance between repairing wells is 5 m;
(2) arranging underground water monitoring wells in the middle of the repair well, wherein the arrangement density of the monitoring wells is one per 1000 square meters;
(3) injecting 1% ferrous sulfate solution into each restoration well by a water pump in an intermittent injection mode until the concentration of hexavalent chromium in the underground water monitoring well is reduced to below 2 mg/L;
(4) injecting 200L of mixed solution of molasses (2 g/L) and ammonium sulfate (0.2 g/L) into each remediation well by a water pump under pressure, continuously injecting compressed air for 10 minutes, and rapidly diffusing sucrose into soil around the remediation wells;
(5) injecting 10L of hexavalent chromium aerobic biological reducing bacteria liquid into each restoration well by adopting a water pump in a pressurizing manner, continuously injecting compressed air for 10 minutes, and quickly diffusing the aerobic biological agent into soil around the restoration well;
(6) after continuously injecting the mixed solution of molasses (2 g/L) and ammonium sulfate (0.2 g/L) at a flow rate of 1L/min for 30 minutes, compressed air was continuously injected for 10 minutes, and then the mixed solution was intermittently injected under pressure for 12 hours. Circulating in this way, the concentration of molasses and ammonium sulfate in the underground water monitoring well is respectively maintained to be more than 20mg/L and 2 mg/L;
(7) and aerating each repair well by using an air compressor in turn to maintain the concentration of dissolved oxygen in the underground water monitoring well to be more than 2mg/L until the hexavalent chromium in the underground water reaches the standard.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the scope of the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. An in-situ chemical reduction and reinforced biological combined remediation method for hexavalent chromium contaminated soil and underground water is characterized by comprising the following steps:
1) respectively laying a repair well group in the aeration zone and the saturation zone;
2) arranging a groundwater monitoring well group in the saturated zone;
3) injecting a chemical reduction agent into the repair well under pressure to carry out chemical repair;
4) injecting nutrient substances and aerobic biological bacteria into the remediation well for bioremediation.
2. The method for the in situ chemical reduction and enhanced bioremediation of hexavalent chromium contaminated soil and groundwater according to claim 1, wherein said bioremediation of step 4) comprises:
4a) respectively injecting nutrient substances into the aeration zone and the saturation zone repair well under pressure;
4b) aerobic biological bacteria for biologically reducing hexavalent chromium are injected into the aeration zone and the saturated zone repairing well;
4c) nutrient substances are injected into the repair wells of each aeration zone and each saturation zone in an intermittent small dosage manner, so that the concentration of the nutrient substances reaches more than 2 mg/L;
4d) and continuously or intermittently injecting aerobic gas compressed gas into the saturated zone repairing well to ensure that the content of dissolved oxygen in the underground water monitoring well is more than 2mg/L until the hexavalent chromium in the aeration zone soil, the saturated zone soil and the underground water reaches the standard.
3. The method of claim 1 for the in situ chemical reduction and enhanced bioremediation of hexavalent chromium contaminated soil and groundwater, wherein said chemical reducing agent includes but is not limited to sodium sulfide, ferrous sulfate, or calcium polysulfide.
4. The method for the in situ chemical reduction and enhanced bioremediation of hexavalent chromium contaminated soil and groundwater of claim 1, wherein said nutrients include, but are not limited to, glucose, molasses, or ammonium salts.
5. The method for the in situ chemical reduction and enhanced bioremediation of hexavalent chromium contaminated soil and groundwater according to claim 1, wherein said remediation well is a multi-functional injection well for injecting chemical reduction agents, nutrients, aerobic biological agents, and aerobic gas compressed gas.
6. The method of claim 1 wherein said aerobic bacteria are selected, acclimated and co-metabolized aerobically to convert hexavalent chromium to trivalent chromium.
7. The method for the in situ chemical reduction and enhanced biological combined remediation of hexavalent chromium contaminated soil and groundwater of claim 1, wherein prior to step 4), the pH of the soil and groundwater is adjusted to a pH range of 5.5 to 9.5 by injecting a pharmaceutical agent through the remediation well if necessary.
8. The method of claim 2 wherein said aerobic gas is oxygen or air.
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| CN116986738A (en) * | 2023-09-26 | 2023-11-03 | 包头市生态环境局综合保障中心(包头市生态环境监控监测中心) | Chromium-polluted underground water in-situ chemical and biological combined restoration method |
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| CN115815311A (en) * | 2023-02-08 | 2023-03-21 | 北京中地泓科环境科技有限公司 | Control and repair system and method for polluted underground water |
| CN116986738A (en) * | 2023-09-26 | 2023-11-03 | 包头市生态环境局综合保障中心(包头市生态环境监控监测中心) | Chromium-polluted underground water in-situ chemical and biological combined restoration method |
| CN116986738B (en) * | 2023-09-26 | 2023-12-26 | 包头市生态环境局综合保障中心(包头市生态环境监控监测中心) | Chromium-polluted underground water in-situ chemical and biological combined restoration method |
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