CN105753178B - A kind of method of enhancement microbiological in-situ immobilization chlorohydrocarbon polluted underground water - Google Patents
A kind of method of enhancement microbiological in-situ immobilization chlorohydrocarbon polluted underground water Download PDFInfo
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- CN105753178B CN105753178B CN201610278463.3A CN201610278463A CN105753178B CN 105753178 B CN105753178 B CN 105753178B CN 201610278463 A CN201610278463 A CN 201610278463A CN 105753178 B CN105753178 B CN 105753178B
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- chlorohydrocarbon
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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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- Biodiversity & Conservation Biology (AREA)
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- Water Supply & Treatment (AREA)
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- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
It is to promote the removal of chlorohydrocarbon by physics chemical action and microbiological deterioration in the underground water for being polluted the injection of weak acid ferric ammonium by chlorohydrocarbon the present invention relates to a kind of method of enhancement microbiological in-situ immobilization chlorohydrocarbon polluted underground water.Salt of weak acid is reducing agent, can promote the moral Krebs cycle of microorganism, and iron ion is oxidant, generates pyrite with sulfuric acid reactant salt, ammonium is pH buffer, while providing nitrogen source for microorganism.Initially quickly dechlorination process is completed by physical and chemical process, reaction forms pyrite first, promote the removal of pollutant with suction-operated by precipitating, weak acid ferric ammonium can guarantee effective combination of two kinds of approach, can enhance microorganism to the degradation capability of chlorinated hydrocarbon contaminants.
Description
Technical field
The present invention relates to groundwater remediation fields in environmental protection, specifically, being a kind of enhancement microbiological in-situ immobilization
The method of chlorohydrocarbon polluted underground water.
Background technique
More and more underground water and soil are just by the pollution of chlorohydrocarbon, and the reparation of polluted soil and underground water is in recent years
To be concerned.Since different Site characteristics are different, the inherent characteristic of target organic pollutant and environmental condition limits place
Repairing effect.
Microorganism in situ recovery technique can effectively remove target organic pollutant, the process master of microbial degradation chlorohydrocarbon
If being realized by a series of slowly continuous electron transfer reaction.Electron donor, food source, electron acceptor and micro- life
The matrix of object growth can promote the Natural Attenuation of pollutant.Some researchers attempt different natural and chemical additions
Agent is added in contaminated underground water, such as kelp and Zero-valent Iron.
Chinese patent literature CN102976490A discloses a kind of method that biology in situ repairs the pollution of underground water chlorohydrocarbon,
Chinese patent literature CN1668535A disclose it is a kind of for in-situ immobilization by the soil of contaminated with halogenated hydrocarbons and/or the load of underground water
Body catalyst, it includes the adsorbent for being impregnated with Zero-valent Iron, and wherein the adsorbent can adsorb the halogenated hydrocarbons, patent documents above
It is by the way that Zero-valent Iron is added in contaminated underground water as reducing agent.But the inherent condition of some underground water limits
The promotion performance of above-mentioned material, causes the removal rate of pollutant to reduce.For example, when sulphates content is very high in underground water,
Sulfate is reduced to sulfide, and sulfide reduces the bioactivity of microorganism to the toxic effect of microorganism, is unfavorable for giving birth to
The progress of object dechlorination reaction, limits the decaying of pollutant.Therefore it is directed to the higher chlorohydrocarbon polluted underground water of sulphates content
Microbial treatment, in order to maintain the progress of microorganism dechlorination process, it is necessary to reduce the concentration of sulfide.In addition, biological dechlorination
Harmful by-products, such as cis-trans dichloroethylene and vinyl chloride are often generated in the process, cause secondary pollution.
To sum up, for the microbial treatment in situ of the higher chlorohydrocarbon polluted underground water of sulphates content, it is necessary to find
One kind, which can either reduce by-product yield again, can evade sulphates content limitation, the method for reducing sulphide in situ concentration.
Summary of the invention
Strengthen micro- life by microbial pathway and the degradation of non-microorganism approach simultaneously the purpose of the present invention is to provide a kind of
The method of object in-situ immobilization chlorohydrocarbon polluted underground water.
Non-microorganism path: non-microorganism path is carried out using reacting between sulfate and iron ion.Ferric iron
It is reduced to ferrous iron, electronics is provided at any time and is reacted with sulfide.Meanwhile sulfide and iron ion form pyrite, pyrite is
Soil mineral with good reducing power.This process has double dominant, firstly, pyrite is promoted by forming suspended matter
The removal of target organic pollutant reduces the production quantity of sulfide in addition, pyrite can also participate in reaction as reducing agent,
Sulfide is alleviated to the toxicity of dechlorination microorganism, and then enhances biological dechlorination.Pyrite possesses the reflecting point of limited quantity
Position is used for the absorption of organic pollutant.Because sulfate is constantly consumed during pyrite formation, sulfate and mesh
Mark pollutant is gradually weakened in the competition of reaction point.Pyrite can promote the precipitating of organic pollutant, reduce dechlorination
The accumulation of harmful side product in the process will not generate secondary pollution.Although this process can remove a large amount of pollutant,
Non-microorganism path is of short duration, it is also necessary to which microorganism dechlorination process at a slow speed removes remaining pollutant.
Microorganism path: weak acid ferric ammonium can stimulate the activity of microorganism (acetogen or methanogen etc.), realize
Microorganism dechlorination lasting for a long time.Dechlorination becomes serial reaction, is integrated with two kinds of ways of microorganism dechlorination and physical chemistry dechlorination
Diameter.Each component part of medicaments plays different effects: salt of weak acid is reducing agent, can promote the De Keleibu of microorganism
This circulation, iron ion is oxidant, generates pyrite with sulfuric acid reactant salt, and ammonium is pH buffer, neutralizes anaerobic dechlorination and generates
Acidic materials, while providing nitrogen source for microorganism.The generation of harmful by-products is avoided, weak acid ferric ammonium provides electronics friendship
Medium is changed, microbial metabolism is used for.In addition, (iron ion and salt of weak acid) can speed up reduction dechlorination under electron carrier existence condition
Process.
The first aspect of the present invention provides a kind of method of enhancement microbiological in-situ immobilization chlorohydrocarbon polluted underground water, is
In the underground water that the injection of weak acid ferric ammonium is polluted by chlorohydrocarbon, chlorine is promoted by physics chemical action and microbiological deterioration
For the removal of hydrocarbon.
Usage amount of the weak acid ferric ammonium in underground water is 10~1000mg/L.It is 100- it is preferable to use amount
500mg/L。
The weak acid ferric ammonium is selected from one of ferric citrate, iron ammonium oxalate or ferric ammonium ethylene diamine tetraacetate or two
Kind or more.When the weak acid ferric ammonium is two or more in ferric citrate, iron ammonium oxalate or ferric ammonium ethylene diamine tetraacetate
It is arbitrary proportion between each compound in mixture when mixture.
The injection realizes that the channel used is described for interim stick or permanent well by the method for high-pressure injection
High pressure is realized by liquid pump.
The content of sulfate is 10~500mg/L in the chlorohydrocarbon polluted underground water.The sulfate is sulfuric acid
Magnesium, sodium sulphate etc., the sulfate can inhibit microbial degradation chlorohydrocarbon.
The concentration of chlorohydrocarbon is 0.1~200ug/L in the chlorohydrocarbon polluted underground water.The chlorohydrocarbon is trichlorine
Ethylene or 1,2- dichloroethylene.
The second aspect of the present invention provides weak acid ferric ammonium in microorganism in situ and repairs answering in chlorohydrocarbon polluted underground water
With.
The weak acid ferric ammonium is selected from one of ferric citrate, iron ammonium oxalate or ferric ammonium ethylene diamine tetraacetate or two
Kind or more, optimization citric acid iron ammonium.
The invention has the advantages that:
The present invention chooses weak acid iron ammonium to solve the problems, such as microorganism dechlorination process under sulfate existence condition
Salt injects in the underground water polluted by chlorohydrocarbon as medicaments, and by its solution.The introducing of weak acid ferric ammonium can promote
Chlorohydrocarbon is degraded by microbial pathway and non-microorganism approach simultaneously, the dechlorination process of accelerating ground water.Salt of weak acid is reduction
Agent can promote the moral Krebs cycle of microorganism, and iron ion is oxidant, generate pyrite, ammonium with sulfuric acid reactant salt
For pH buffer, while nitrogen source is provided for microorganism.Initially quickly dechlorination process is completed by physical and chemical process, first
First reaction forms pyrite, promotes the removal of pollutant with suction-operated by precipitating, in addition, weak acid ferric ammonium can guarantee two
Effective combination of kind approach, can enhance microorganism to the degradation capability of chlorinated hydrocarbon contaminants.
Specific embodiment
It elaborates below with reference to embodiment to specific embodiment provided by the invention.
Embodiment 1
Experimental procedure: 5.0L simulated wastewater solution is prepared, wherein sodium sulfate concentration 100mg/L, trichloro ethylene and 1,2-
The concentration of dichloroethylene is to be uniformly mixed for 50ug/L, measures the concentration (for 50.8ug/L) and 1,2- of trichloro ethylene first
The concentration of dichloroethylene (for 49.5ug/L).Then 0.5g ironic citrate is added into simulated wastewater solution under stirring conditions
Ammonium, concentration 100mg/L.
As a result with phenomenon: after ferric citrate addition after, produced rapidly in solution pyrite precipitating, stand 5min after,
Pyrite precipitating is completed.The residue of trichloro ethylene is dense after taking supernatant liquor to be added using gas chromatograph for determination ferric citrate
Degree, the results showed that, the residual concentration of trichloro ethylene and 1,2-dichloroethene is respectively 24.5ug/L and 28.7ug/L.Therefore,
51.8% trichloro ethylene and 42.0% 1,2-dichloroethene are removed, and are primarily due to ferric citrate and sulfuric acid reactant salt
Pyrite is generated, a large amount of trichloro ethylene and 1,2-dichloroethene can be adsorbed in the formation and precipitation process of pyrite,
And then obtain higher removal rate.
Embodiment 2
Experimental procedure:
Experiment 1 prepares 5.0L simulated wastewater solution, wherein sodium sulfate concentration 100mg/L, trichloro ethylene and 1,2- bis-
The concentration of vinyl chloride is 50ug/L, and thermophilic organic methane producing strains (organophilum), bacterial concentration are added into solution
Control is in 1.0*109CFU/mL-2.0*109CFU/mL is uniformly mixed.Measure the concentration of trichloro ethylene first (for 49.5ug/L)
With the concentration of 1,2- dichloroethylene (for 49.9ug/L).Then 0.5g lemon is added into simulated wastewater solution under stirring conditions
Lemon acid iron ammonium and 0.5g iron ammonium oxalate measure the concentration of trichloro ethylene and 1,2-dichloroethene after concentration 100mg/L, 2h；
Every the concentration of a trichloro ethylene and 1,2- dichloroethylene of measurement in 10 days.
2 (blank) are tested, 5.0L simulated wastewater solution is prepared, wherein sodium sulfate concentration 100mg/L, trichloro ethylene
Concentration is about 50ug/L, and thermophilic organic methane producing strains (organophilum) are added into solution, and bacterial concentration control exists
1.0*109CFU/mL-2.0*109CFU/mL is uniformly mixed.The concentration (for 50.5ug/L) of trichloro ethylene is measured first and with 1,
The concentration (49.7ug/L) of 2- dichloroethylene, then every the concentration of a trichloro ethylene and 1,2-dichloroethene of measurement in 10 days.
As a result with phenomenon: for experiment 1, after ferric citrate addition after, produced rapidly in solution pyrite precipitating, it is quiet
After setting 2h, pyrite precipitating is completed.Take supernatant liquor using the surplus of gas chromatograph for determination trichloro ethylene and 1,2- dichloroethylene
Remaining concentration is respectively 23.8ug/L (removal rate 51.9%) and 22.7ug/L (removal rate 54.5%).After reacting 40 days, measurement
The residual concentration of trichloro ethylene and 1,2- dichloroethylene is respectively 3.8ug/L (removal rate 92.3%) and 1.2ug/L (removal rate
97.6%).For experiment 2, after reaction 40 days, the residual concentration for measuring trichloro ethylene and 1,2-dichloroethene is respectively
44.3ug/L (removal rate 12.3%) and 42.6ug/L (removal rate 14.3%), removal rate are significantly lower than the removal rate in experiment 1,
Illustrate that ferric citrate and iron ammonium oxalate play key effect to the removal of trichloro ethylene.
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (6)
1. weak acid ferric ammonium repairs the application in chlorohydrocarbon polluted underground water in microorganism in situ, which is characterized in that described is weak
Sour ferric ammonium is selected from one or more of ferric citrate, iron ammonium oxalate or ferric ammonium ethylene diamine tetraacetate；The chlorine
Content for sulfate in hydrocarbon polluted underground water is 10~500mg/L.
2. a kind of method of enhancement microbiological in-situ immobilization chlorohydrocarbon polluted underground water, which is characterized in that be by weak acid ferric ammonium
It injects in the underground water polluted by chlorohydrocarbon, promotes the removal of chlorohydrocarbon by physics chemical action and microbiological deterioration,
Usage amount of the weak acid ferric ammonium in underground water is 10~1000mg/L；The weak acid ferric ammonium is selected from ironic citrate
One or more of ammonium, iron ammonium oxalate or ferric ammonium ethylene diamine tetraacetate；Sulfuric acid in the chlorohydrocarbon polluted underground water
The content of salt is 10~500mg/L.
3. according to the method described in claim 2, it is characterized in that, usage amount of the weak acid ferric ammonium in underground water is 100-
500mg/L。
4. according to the method described in claim 2, it is characterized in that, the injection is adopted by the method realization of high-pressure injection
Channel is interim stick or permanent well, and the high pressure is realized by liquid pump.
5. according to the method described in claim 2, it is characterized in that, in the chlorohydrocarbon polluted underground water chlorohydrocarbon concentration
For 0.1~200ug/L.
6. according to the method described in claim 5, it is characterized in that, the chlorohydrocarbon is trichloro ethylene or 1, bis- chloroethene of 2-
Alkene.
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| CN106145306A (en) * | 2016-08-05 | 2016-11-23 | 上海市环境工程设计科学研究院有限公司 | A kind of method using slag to purify Polluted Groundwater |
| CN108373199A (en) * | 2018-03-23 | 2018-08-07 | 桂林理工大学 | A method of improving pesticide pyrazon biodegradation efficiency |
| CN114534682B (en) * | 2022-03-23 | 2024-04-19 | 福建农林大学 | Composition for removing adsorbable organic halide in industrial sludge and method thereof |
| CN114853146B (en) * | 2022-04-25 | 2023-10-31 | 武汉理工大学 | Water treatment agent and water treatment method for magnetic recyclable pyrite catalyst |
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| CN1195373A (en) * | 1996-04-22 | 1998-10-07 | 丰田自动车株式会社 | Microorganisms that decompose halogenated hydrocarbons and their use |
| CN1909983A (en) * | 2003-12-04 | 2007-02-07 | 苹果花许可有限公司 | Electricity enhancing original position restoring for contaminated soil |
| CN103011465A (en) * | 2012-12-07 | 2013-04-03 | 常州大学 | Method for removing chloride ion in sewage |
| CN105399193A (en) * | 2015-12-14 | 2016-03-16 | 中国科学院南京土壤研究所 | Method for degrading heavy non-aqueous phase liquid component composite hydrochloric ether pollutants in underground water |
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| JP3899304B2 (en) * | 2002-09-25 | 2007-03-28 | 独立行政法人科学技術振興機構 | Chelating agent-degrading bacteria and treating agent for chelating agent contamination using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195373A (en) * | 1996-04-22 | 1998-10-07 | 丰田自动车株式会社 | Microorganisms that decompose halogenated hydrocarbons and their use |
| CN1909983A (en) * | 2003-12-04 | 2007-02-07 | 苹果花许可有限公司 | Electricity enhancing original position restoring for contaminated soil |
| CN103011465A (en) * | 2012-12-07 | 2013-04-03 | 常州大学 | Method for removing chloride ion in sewage |
| CN105399193A (en) * | 2015-12-14 | 2016-03-16 | 中国科学院南京土壤研究所 | Method for degrading heavy non-aqueous phase liquid component composite hydrochloric ether pollutants in underground water |
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