CN102976490A - Method for in-situ bioremediation of pollution caused by chlorohydrocarbon of underwater - Google Patents
Method for in-situ bioremediation of pollution caused by chlorohydrocarbon of underwater Download PDFInfo
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Abstract
The invention discloses a method for in-situ bioremediation of pollution caused by chlorohydrocarbon of underwater, which specifically comprises a coupling process of anaerobic reductive dechlorination and aerobiotic oxydative degradation. An anaerobic reaction area and an aerobiotic reaction area are established in the front and back of a chlorohydrocarbon pollution area along the flowing direction of underwater in a zone of saturation. Poly-chlorohydrocarbon (trichloro or tetrachloro) in the anaerobic reaction area is quickly reduced and dechlorinated to low chlorohydrocarbon (monochloro or bichloro), the low chlorohydrocarbon is transferred to the aerobiotic reaction area and oxidized and degraded to products such as carbon dioxide. The anaerobic reaction area is realized by providing electron donor materials, a deoxidant and a reducer through the injection of an injection well, while the aerobiotic area is realized by aeration toward underground water.
Description
Technical field
The invention belongs to underground water recovery technique field, relate to a kind of biology in situ and repair the method that the underground water hydrochloric ether pollutes.
Background technology
Hydrochloric ether is widely used in the fields such as degreasing of aircraft engine, trolley part, electronic component and clothes.The eighties in last century, because the leakage of hydrochloric ether and the underground environmental pollution problem that improper discharging causes are paid attention to by people, the name of the hydrochloric ethers such as TCE begins frequently to come across in all kinds of reports with the identity of groundwater pollutant.Hydrochloric ether has strong carcinogenesis, and it has caused serious threat to health of people life and even existence.Hydrochloric ether belongs to heavy nonaqueous phase fluid (DNAPL), is slightly soluble in water, can pass aeration zone and zone of saturation after entering underground environment under action of gravitation, begins to assemble until arrive water-resisting layer, becomes a persistence and the very strong source of pollution of hazardness.The thorough reparation that hydrochloric ether pollutes has suitable difficulty.
Method for the reparation of hydrochloric ether polluted underground water mainly contains Pump-and-Treat method, chemical oxidization method, permeable reactive wall method and Natural Attenuation method etc. at present.The Pump-and-Treat method is the most representative underground water recovery technique, and the method, is recycled into below the earth's surface after then purifying with the earth's surface sewage disposal technology to the earth's surface by the water in the contaminated waterbearing stratum of extraction; The Pump-and-Treat method is subjected to the impact of hydrogeological conditions very large, and the operational cycle is long, expense is higher, has the possibility of repairing failure; Chemical oxidization method can be eliminated the pollution of hydrochloric ether, but is subjected to the organic impact that waits composition in the waterbearing stratum, and the oxygenant utilization ratio is low, and effective drug duration is short, and rehabilitation expense is expensive; The permeable reactive wall method adopts zero-valent metal as reductive agent hydrochloric ether to be carried out dechlorination, and its cost is low, have again a persistence, but its speed of reaction is very low, and can only repair the body of groundwater by the reaction wall; Biological process refers to the process that hydrochloric ether is degraded by microorganisms in underground environment; In the underground environment of aerobic, microorganism as electron donor(ED), to electron acceptor(EA) (for example oxygen), and is resolved into carbonic acid gas, water and chlorine with hydrochloric ether with transfer transport with hydrochloric ether; In underground environment, there is other electron donor(ED) (food source of microorganism), and the electron acceptor(EA)s such as oxygen in the underground environment are consumed totally, hydrochloric ether will become electron acceptor(EA) and finish the reduction process that hydrogen replaces chlorine, generates the environmental sound materials such as ethene and ethane; Compare with other restorative procedures, biological process has the advantages such as rehabilitation cost is low, non-secondary pollution, has good application prospect.
Biological restoration is repaired the hydrochloric ether pollution and is had certain problem, microorganism under anaerobic can make hydrochloric ether realize reduction dechlorination by the mode of direct metabolism or altogether metabolism, but along with chlorine atom in the polychlorohydrocarbon (such as trieline, zellon etc.) is replaced one by one by hydrogen atom, speed of reaction can descend gradually, accumulation can appear in the intermediate product (such as a vinylchlorid, Ethylene Dichloride etc.) of therefore low chlorine in environment, these materials have stronger toxicity, and the harm of environment is growing on and on.Under aerobic conditions, only have low hydrochloric ether to be used as the direct metabolism of electron donor(ED) by microorganism and resolve into water and carbonic acid gas, and polychlorohydrocarbon can only be by the altogether mechanism degraded of metabolism of microorganism; Not only speed is slow for metabolic mechanism altogether, and will consume ten times of electron donor(ED)s to improve quality of hydrochloric ether.Therefore, anaerobic reduction dechlorinating process and aerobic oxidation degradation method have limitation separately.
Summary of the invention
The method that the object of the present invention is to provide a kind of low cost, non-secondary pollution, reliably original position reparation underground water hydrochloric ether to pollute, namely adopt the coupling of anaerobic reduction dechlorination and two kinds of biological renovation methods of aerobic oxidative degradation, realize the thorough removing that hydrochloric ether pollutes in the underground water.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of biology in situ is repaired the method that the underground water hydrochloric ether pollutes, determine underground water Pollution Plume scope by site investigation assessment in early stage, along the Groundwater Flow direction, set up anaerobic reaction district and aerobic reactor zone before and after in Pollution Plume, the anaerobic reaction district is by laying the medicament Injection Well, injects oxygen scavenger in the zone of saturation, to electronics material and reductive agent, and polychlorohydrocarbon is become low hydrochloric ether by the fast restore dechlorination; Aerobic reactor zone makes to hang down to be degraded to water and carbonic acid gas after hydrochloric ether migrates to aerobic zone by laying aeration well and extraction well.
The described electron donor(ED) material that provides is in seaweed powder, sucrose, vegetables oil or the lower molecular weight lipid acid one or more.
Described oxygen scavenger is one or more in sodium bisulfite, Potassium hydrogen sulfite or the V-Brite B.
Described reductive agent is one or more in zeroth order iron powder, zeroth order zinc powder or the zeroth order aluminium powder, and particle diameter is 100nm-500 μ m.
The composition of described injection medicament is as follows by weight:
Oxygen scavenger: 1-30 part
Provide the electron donor(ED) material: 20-50 part
Reductive agent: 20-50 part
Be configured to the suspension liquid of water before medicament injects, by weight, chemical content is 1%-30%.
The medicament Injection Well spacing in anaerobic reaction district is 1-10m, and Injection Well extends to zone of saturation, under the promotion of compressed nitrogen medicament is injected into well and it is disperseed towards periphery, and injection pressure is 0.5-2MPa.
Described aeration well extends to the following zone of saturation of ground water table, and extraction well extends to the above aeration zone of ground water table, realizes that by aeration in underground water the low hydrochloric ether that migrates to aerobic zone is degraded to water and carbonic acid gas.
Sneak into ammonia in the described aeration and pass into together Water table.
Described aeration well spacing is 2-10m, and the extraction well spacing is 2-10m, and aeration rate is controlled at 10-5000mL/min by aeration pump, and extraction well links to each other with vacuum pump, sneaks into ammonia in the aeration well nitrogenous source is provided, and the aeration rate of ammonia is 1-10mL/min.
Be provided with monitor well in described anaerobic reaction district and the aerobic reactor zone, monitor well extends to below the ground water table, and monitoring project pollutant load, dissolved oxygen content, microbe colony distribute.
The invention has the beneficial effects as follows: the invention provides the method for a kind of low cost, non-secondary pollution, the pollution of reliably original position reparation underground water hydrochloric ether, compare with other method, realized the coupling of anaerobic reduction dechlorination and two kinds of technology of aerobic oxidative degradation; Formed the permeable reactive wall that forms with anaerobe and Zero-valent Iron at anaerobic zone medicament Injection Well and medicament diffusion zone thereof, made the polychlorohydrocarbon reduction dechlorination become low hydrochloric ether; Realized the thorough degraded of aerobic bacteria to low hydrochloric ether at aerobic zone by the aeration oxygen supply.The method realizes control and improvement that hydrochloric ether is polluted having overcome the problem that generates poisonous intermediate product in the traditional biological repairing method with the cost of less, has realized the degree of depth degraded of hydrochloric ether, has safeguarded the safety of underground water.
Description of drawings
Fig. 1 is anaerobic reduction dechlorination technology and the aerobic oxygenolysis technology coupling synoptic diagram of the method for biology in situ reparation underground water hydrochloric ether of the present invention pollution.
Embodiment
As shown in Figure 1, biology in situ of the present invention is repaired the method that the underground water hydrochloric ether pollutes, determine underground water Pollution Plume scope by site investigation assessment in early stage, along the Groundwater Flow direction, set up anaerobic reaction district and aerobic reactor zone before and after in Pollution Plume, the anaerobic reaction district is by laying the medicament Injection Well, injects oxygen scavenger in the zone of saturation, to electronics material and reductive agent, and polychlorohydrocarbon is become low hydrochloric ether by the fast restore dechlorination; Aerobic reactor zone makes to hang down to be degraded to water and carbonic acid gas after hydrochloric ether migrates to aerobic zone by laying aeration well and extraction well.
The described electron donor(ED) material that provides is in seaweed powder, sucrose, vegetables oil or the lower molecular weight lipid acid one or more.
Described oxygen scavenger is one or more in sodium bisulfite, Potassium hydrogen sulfite or the V-Brite B.
Described reductive agent is one or more in zeroth order iron powder, zeroth order zinc powder or the zeroth order aluminium powder, and particle diameter is 100nm-500 μ m.
The composition of described injection medicament is as follows by weight:
Oxygen scavenger: 1-30 part
Provide the electron donor(ED) material: 20-50 part
Reductive agent: 20-50 part
Be configured to the suspension liquid of water before medicament injects, by weight, chemical content is 1%-30%.
The medicament Injection Well spacing in anaerobic reaction district is 1-10m, and Injection Well extends to zone of saturation, under the promotion of compressed nitrogen medicament is injected into well and it is disperseed towards periphery, and injection pressure is 0.5-2MPa.
Described aeration well extends to the following zone of saturation of ground water table, and extraction well extends to the above aeration zone of ground water table, realizes that by aeration in underground water the low hydrochloric ether that migrates to aerobic zone is degraded to water and carbonic acid gas.
Sneak into ammonia in the described aeration and pass into together Water table.
Described aeration well spacing is 2-10m, and the extraction well spacing is 2-10m, and aeration rate is controlled at 10-5000mL/min by aeration pump, and extraction well links to each other with vacuum pump, sneaks into ammonia in the aeration well nitrogenous source is provided, and the aeration rate of ammonia is 1-10mL/min.
Be provided with monitor well in described anaerobic reaction district and the aerobic reactor zone, monitor well extends to below the ground water table, and monitoring project pollutant load, dissolved oxygen content, microbe colony distribute.
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail:
Determine underground water Pollution Plume scope by site investigation assessment in early stage, along the Groundwater Flow direction, anaerobic reaction district and aerobic reactor zone are set up in front and back in Pollution Plume.The anaerobic reaction district is by laying the medicament Injection Well, injects oxygen scavenger in the zone of saturation, realizes to electronics material and reductive agent.Aerobic reactor zone is realized by laying aeration well and extraction well.
Described anaerobic reaction district inject medicament comprise oxygen scavenger, to electronics material and reductive agent.Injecting the composition of medicament calculates by weight as follows:
Oxygen scavenger: 1-10 part
Give the electronics material: 20-50 part
Reductive agent: 20-50 part
Need before medicament injects it is configured to the aqueous solution or suspension liquid, chemical content is 1%-30%.The medicament Injection Well spacing in anaerobic reaction district is 1-10m, and Injection Well extends to zone of saturation, under the promotion of compressed nitrogen medicament is injected into well and it is disperseed towards periphery, and injection pressure is 0.5-2MPa.
Many mouthfuls of aeration wells and extraction well are set in the described aerobic reactor zone.Aeration well extends to the following zone of saturation of ground water table, and extraction well extends to the above aeration zone of ground water table.The aeration well spacing is 2-10m, and the extraction well spacing is 2-10m.Aeration rate is controlled at 10-5000mL/min by aeration pump, and extraction well links to each other with vacuum pump.According to the nutritional status of underground environment, sneak into the appropriate amounts of ammonia air lift in the aeration well for nitrogenous source, the aeration rate of ammonia is 1-10mL/min.
Be provided with monitor well in described anaerobic reaction district and the aerobic reactor zone, monitor well extends to below the ground water table, and monitoring project comprises pollutant load, dissolved oxygen content, microbe colony distribution etc.
The present invention is applicable to reparation and the contamination of the body of groundwater that polluted by hydrochloric ether and controls, as administering the heavy nonaqueous phase fluid contamination source that is made of chlorinated solvent such as trieline, chloroforms etc.Before recovery project begins, must determine Pollution Plume scope, the hydrogeological conditionss such as groundwater velocity.
Embodiment 1
Certain factory's migration old site underground water is subject to the pollution of seepage chlorinated solvent, and Pollution Plume length is 300m, and width is 60m, and Groundwater Flow speed is 5m/d, and ground water table is 6m.The content of various pollutents is listed in the table 1 in the Pollution Plume.
Table 1 pollutent situation table look-up
| Pollutent | Content (mg/L) | The security filtering value | Super screening value multiple |
| Chloroform | 105 | 0.27 | 388 |
| Trieline | 150 | 0.046 | 3259 |
| 1,2-dichloroethene | 65 | 0.41 | 158 |
| Methylene dichloride | 23 | 11 | 1 |
As shown in Figure 1, according to investigation in early stage of Polluted area, in Pollution Plume, delimit in take distance source of pollution 150m to the 200m scope and be anaerobism reparation district, take 200m to the 250m scope in delimitation as aerobic reparation district.Take 5m as spacing, broad ways is made a call to 24 mouthfuls of medicament Injection Wells and 12 mouthfuls of monitor wells in anaerobism reparation district, and well depth is 8-15m.Inject medicament and be solid content and be the mix suspending solution of 5% seaweed powder, iron powder, sodium bisulfite, do in the component that seaweed powder accounts for 35%, iron powder accounts for 60%, sodium bisulfite accounts for 5%.The medicament injection rate is the 1000L/ mouth, minute 20 batches of injections.Make a call to 24 mouthfuls of aeration wells, 24 mouthfuls of extraction wells and 12 mouthfuls of monitor wells at aerobic zone, aeration well and extraction well spacing are 5m, and the aeration well well depth is 15m, and the extraction well well depth is 5m.Start first vacuum pump, the aeration zone of top, groundwater pollution zone is pumped into negative pressure, then start aeration pump, carry out continuous aeration, aeration rate begins to bring up to gradually 3000mL/min from 10mL/min.After 3 months, the content of the various pollutents of underground water restoring area all is lower than the security filtering value through continuous aeration.
Embodiment 2
Certain base air depot maintenance factory long-time a large amount of trielines that use in the processing of component and retrofit process have detected the trieline pollution as grease-removing agent in the underground water near maintenance factory, concentration is up to 15.9mg/L.After in the Pollution Plume scope, delimiting anaerobism reparation district and aerobic reparation district, set up some medicament Injection Wells, monitor well, aeration well.
Inject the suspension liquid that water ratio is 80% sucrose, nano zero valence iron, sodium bisulfite that consists of of medicament, do that sucrose accounts for 40% in the component, nano zero valence iron accounts for 50%, and sodium bisulfite accounts for 10%.Aeration control about 50mL/min, after 6 months in the underground water trieline be down to below the 5 μ g/L, reached drinking water standard.
Embodiment 3
Certain factory's zellon storage tank generation incident of leakage is found zellon to have occurred in the underground water after finishing the earth's surface cleaning work, and concentration is 10mg/L.The approximately long 5m of Polluted area, wide 1.6m.Centered by pollution source area, set up the anaerobic reaction district.Because Polluted area is less, descend the oxygen in water can the self-assembling formation aerobic reactor zone peripherally.
Inject the mixed solution that water ratio is 70% vegetables oil, V-Brite B, nano zinc powder that consists of of medicament, vegetables oil accounts for 50% in the component, and V-Brite B accounts for 20%, and nano zinc powder accounts for 30%.After three months in the underground water content of zellon be down to below the 10 μ g/L.
In sum, content of the present invention is not limited in the above-described embodiment, and the knowledgeable people in the same area can propose other embodiment easily within technical director's thought of the present invention, but this embodiment comprises within the scope of the present invention.
Claims (10)
1. a biology in situ is repaired the method that the underground water hydrochloric ether pollutes, it is characterized in that, determine underground water Pollution Plume scope by site investigation assessment in early stage, along the Groundwater Flow direction, set up anaerobic reaction district and aerobic reactor zone before and after in Pollution Plume, the anaerobic reaction district is by laying the medicament Injection Well, injects oxygen scavenger in the zone of saturation, to electronics material and reductive agent, and polychlorohydrocarbon is become low hydrochloric ether by the fast restore dechlorination; Aerobic reactor zone makes to hang down to be degraded to water and carbonic acid gas after hydrochloric ether migrates to aerobic zone by laying aeration well and extraction well.
2. biology in situ according to claim 1 is repaired the method that the underground water hydrochloric ether pollutes, and it is characterized in that, the described electron donor(ED) material that provides is in seaweed powder, sucrose, vegetables oil or the lower molecular weight lipid acid one or more.
3. biology in situ according to claim 1 is repaired the method that the underground water hydrochloric ether pollutes, and it is characterized in that described oxygen scavenger is one or more in sodium bisulfite, Potassium hydrogen sulfite or the V-Brite B.
4. biology in situ according to claim 1 is repaired the method that the underground water hydrochloric ether pollutes, and it is characterized in that described reductive agent is one or more in zeroth order iron powder, zeroth order zinc powder or the zeroth order aluminium powder, and particle diameter is 100nm-500 μ m.
5. biology in situ according to claim 1 is repaired the method that the underground water hydrochloric ether pollutes, and it is characterized in that the composition of described injection medicament is as follows by weight:
Oxygen scavenger: 1-30 part
Provide the electron donor(ED) material: 20-50 part
Reductive agent: 20-50 part
Be configured to the suspension liquid of water before medicament injects, by weight, chemical content is 1%-30%.
6. biology in situ according to claim 1 is repaired the method that the underground water hydrochloric ether pollutes, it is characterized in that, the medicament Injection Well spacing in anaerobic reaction district is 1-10m, Injection Well extends to zone of saturation, under the promotion of compressed nitrogen medicament is injected into well and it is disperseed towards periphery, injection pressure is 0.5-2MPa.
7. biology in situ according to claim 1 is repaired the method that the underground water hydrochloric ether pollutes, it is characterized in that, described aeration well extends to the following zone of saturation of ground water table, extraction well extends to the above aeration zone of ground water table, realizes that by aeration in underground water the low hydrochloric ether that migrates to aerobic zone is degraded to water and carbonic acid gas.
8. biology in situ according to claim 7 is repaired the method that the underground water hydrochloric ether pollutes, and it is characterized in that, sneaks into ammonia in the described aeration and passes into together Water table.
9. biology in situ according to claim 8 is repaired the method that the underground water hydrochloric ether pollutes, it is characterized in that, described aeration well spacing is 2-10m, the extraction well spacing is 2-10m, aeration rate is controlled at 10-5000mL/min by aeration pump, extraction well links to each other with vacuum pump, sneaks into ammonia in the aeration well nitrogenous source is provided, and the aeration rate of ammonia is 1-10mL/min.
10. biology in situ according to claim 1 is repaired the method that the underground water hydrochloric ether pollutes, it is characterized in that, be provided with monitor well in described anaerobic reaction district and the aerobic reactor zone, monitor well extends to below the ground water table, and monitoring project pollutant load, dissolved oxygen content, microbe colony distribute.
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| CN105645487A (en) * | 2016-03-11 | 2016-06-08 | 清华大学 | Colloid sustained-release material for underground water in-situ remediation and preparation method of colloid sustained-release material for underground water in-situ remediation |
| CN107720853A (en) * | 2017-11-20 | 2018-02-23 | 中国环境科学研究院 | DNAPL pollution amelioration system and method in underground water based on pollution resistance control |
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| CN109179677A (en) * | 2018-10-24 | 2019-01-11 | 湖南新九方科技有限公司 | A kind of complex media PRB restorative procedure of chlorohydrocarbon polluted underground water |
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| CN109839492A (en) * | 2019-04-02 | 2019-06-04 | 中国地质科学院水文地质环境地质研究所 | A kind of aeration zone-underground water pollution association analogue experiment method |
| CN110794111A (en) * | 2019-12-18 | 2020-02-14 | 济南大学 | Method for analyzing migration and conversion rules of chlorinated hydrocarbon pollution in underground water |
| CN111069260A (en) * | 2020-01-13 | 2020-04-28 | 中新曜昂环境修复(江苏)有限公司 | In-situ treatment of non-aqueous contaminants in soil and groundwater |
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| CN114853180A (en) * | 2022-03-23 | 2022-08-05 | 陕西省微生物研究所 | Biological agent, degradation agent, system and application for deeply degrading polychlorinated phenol |
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