CN101172732A - Method for renovating groundwater in situ with chemical and biological composite reaction wall - Google Patents

Method for renovating groundwater in situ with chemical and biological composite reaction wall Download PDF

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Publication number
CN101172732A
CN101172732A CNA2007100561701A CN200710056170A CN101172732A CN 101172732 A CN101172732 A CN 101172732A CN A2007100561701 A CNA2007100561701 A CN A2007100561701A CN 200710056170 A CN200710056170 A CN 200710056170A CN 101172732 A CN101172732 A CN 101172732A
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aniline
reaction wall
biological
degradation
mirbane
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张兰英
刘娜
赵勇胜
高松
张玉玲
孙立波
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Jilin University
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Jilin University
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Abstract

The invention discloses a method for treating underground sewage, in particular for the underground water which is polluted by nitrobenzene and aniline. The original restoration of the underground water with chemical and biological combination reaction wall is adopted in the method. The upper reach of the flowing underground water is provided with a chemical reaction wall, and a biological reaction wall is arranged below the chemical reaction wall with a certain distance away. The chemical reaction wall consists of nonvalent ferrum and active carbon at a certain proportion, and the biological reaction wall consists of the attached nitrobenzene degradation bacteria and the attached aniline degradation bacteria biological active carbon. The nitrobenzene is reduced to be the degradable nitrobenzene through the chemical reaction wall, and the nonvalent ferrum is good in the removal of the nitrobenzene organism which is difficult in degradation, so the chemical reaction wall has good applicability and can achieve 120-minute reaction time and the 97.4 percent of the reduction rate for the nitrobenzene. The production of the biological reaction wall with the biological active carbon is good in the removal of the target pollutant. The work of the biological reaction wall for 36 days can achieve more than 98.83 percent of the degradation rate for the nitrobenzene with the preliminary density of 300.89mg/L, and the work of the biological reaction wall for 71 days can achieve more than 99.6 percent of degradation rate.

Description

Chemistry is repaired phreatic method with the biological composite reaction wall original position
Technical field
The present invention relates to a kind of treatment process of groundwater pollution, especially pass through chemistry and the reparation of the anti-wall original position of life assemblage type by the phreatic method of oil of mirbane and aniline pollution.
Background technology
Existing multiple at present groundwater pollution is administered technology and recovery scenario, concludes to get up to mainly contain: physics method, chemical method, biological process; Come the decomposing biological repairing method can be divided into heterotopic biological repairing method and biology in situ repairing method and associating biological restoration method again according to processing feature.
The physics method: extracting facture out is the very general a kind of traditional dystopy recovery technique of current application, and this technology is one of groundwater pollution recovery technique that occurs the earliest, also is the representative art that the underground water dystopy is repaired.Carry out the groundwater pollution reparation so far from the eighties in 20th century, groundwater pollution is administered still with P﹠amp; The T technology is main.P﹠amp; The T technology is that the underground water that pollutes is released, and handles on the ground then.In recent years, along with deepening continuously of Pollution abatement research, this technology has had implication widely, as long as in the groundwater pollution governance process underground water has been implemented extraction or injection process, all classifies as P﹠amp; The T technology.P﹠amp; The repair process of T technology generally can be divided into the two parts: underground water power control process and ground Pollutant Treatment process.This technology, will be come in the polluted groundwater mining by water pump and well at the pumped well of contaminated site laying some amount according to the underground water pollution range, utilize the ground treating plant to carry out groundwater pollution then and administer.The improvement method mainly contains 1. air stripping, is to handle the method that volatile organic matter often adopts.2. charcoal absorption almost can be adsorbed any organic pollutant.3. chemical oxidation comprises that mainly ultraviolet ray adds hydrogen peroxide, ultraviolet adds ozone, and ultraviolet adds hydrogen peroxide and adds strong oxidizer combinations such as ozone, and reaction process produces the hydroxyl free radical with strong oxidation capacity, makes organic contamination obtain decomposing; 4. biological degradation utilizes activated sludge process or biomembrane process, carries out bio-oxidation and decomposes extracting organism in the underground water come up; 5. precipitation normally utilizes lime or alkali soda that heavy metal ion is converted into insoluble oxyhydroxide, removes through precipitation; 6. membrane sepn is to utilize the selectivity semipermeable partition, can separate from underground water and remove organism or heavy metal ion.In extraction process, because the decline of well water level, around well, form the ground descending water funnel that falls, make on every side that underground water continues to flow to well, reduced contamination.According to the practical situation of contaminated site, the underground water of handling is discharged at last, can enter rainwash, recharge underground or be used for local water supply etc.P﹠amp; The T technology is applied widely, and is big for pollution range, pollute and dizzyly bury dark contaminated site and also be suitable for.But also there are some limitation in himself: 1. when non-aqueous solution occurs, owing to the almost unlikely way of taking out by pump of non-aqueous solution that capillary tension is detained is removed; 2. this technology excavation treatment project expense costliness, and relate to phreatic extracting or recharge, disturb big to repairing the district; If 3. do not seal source of pollution, when stopping pumping, hangover and rebound phenomena are serious; 4. the energy that needs to continue is supplied with, and to guarantee the operation of phreatic extraction and water treatment system, also requires simultaneously system is carried out regular maintenance and monitoring.
Chemical method: set up the active reaction zone in contaminated area, simultaneously will around pollution substance migrate to the active reaction district with underground water and decompose and remove or passivation is fixed.Generally need suitable reactive material of injection and the pollutent that migration comes to react in the active reaction zone, but the reactive behavior material that injects to can relatively be evenly distributed in the active zone, and reactive material itself or product environmental sound.The advantage of setting up the active reaction district is that pollutent is disposed on the spot and degraded, do not need to set up expensive ground infrastructure, the installation ratio is easier to simple, Operation and Maintenance is also both economical, can be used for reparation and disposal that deep layer is polluted, reaction active region can be used for holding back the pollutent in the underground water that is in flow state, avoids it to spread and move to farther distance, pollutes bigger scope.
Biological restoration method: be broadly divided into biology in situ reparation (in-situ bioremediation) and heterotopic biological reparation (ex-situ bioremediation) and associating biological restoration (combined remediation).The biology in situ reparation is meant under the condition of not destroying soil and underground water physical environment substantially, contaminated environment is not done carrying or conveying, and directly carry out biological restoration in former field.This technology be applied to by petroleum like hydrocarbon institute zone of pollution underground water administer had historical for many years, but be directly used in improvement by the underground water of other contaminants also in recent years thing just.The heterotopic biological reparation is that mobile pollutent carries out in contiguous place or reactor, concentrates reparation.The associating biological restoration can be divided into the reparation of different modes biology in situ and combine.
The permeable reaction wall method: the permeability response wall is a kind of subterranean groundwater treatment system that is built in, and is called for short PRB technology (Permeable Reactive Barrier).The permeability response wall is a kind of underground water based technique for in-situ remediation that occurs for 20 end of the centurys, is that present underground water is repaired the focus in the research field.Definition according to EPA (EPA): " PRB is a dependent response district that is filled with the active reaction dielectric material, and when contaminated underground water passed through the permeability response wall, pollutent mass-energy was degraded or is fixing.When pollution substance relied on the nature hydrotransport to pass through pre-designed reaction medium, medium can degrade, adsorb, precipitate or remove dissolved organism, metal, nucleic and other pollutents ".Reaction contain within the walls the reductive agent of degradable volatile organic matter, the chela of fixing metal (network) mixture, in addition can provide microorganism growth breed needed nutrition and oxygen, in order to other materials of strengthening biological treatment etc.The permeability response wall generally is installed in the underground storage layer, perpendicular to the groundwater flow direction.When underground current under self hydraulic gradient effect during by the permeability response wall, the pollution substance that discharges from source of pollution forms one and pollutes and swoon flow event downwards.PRB is provided with body of wall one on the cross section that pollutes dizzy flowing-path, fill different dielectric materials in the body of wall.When polluting dizzy flowing through within the walls, when contacting with the body of wall dielectric material, a series of physics, chemistry, bioprocesss such as the reduction reaction of process materials for wall, degraded, absorption, leaching, the pollution components of polluting in swooning obtains degraded, perhaps be trapped in the body of wall, thereby reach the purpose that underground water surrounding is repaired.In a single day the permeability response wall installs, and needs to change the body of wall reaction medium material under some situation, needs other operation and maintenance costs hardly.Existing permeable reaction wall all is single wall, and it is thorough that some pollutent can't react.
Oil of mirbane has high stability in water, because its density is greater than water, the oil of mirbane that enters water body can sink under water, and remains unchanged for a long time.Because it has certain solubleness in water, boiling point is higher, and the velocity of evaporation under the natural condition is slower, above-mentioned prior art is difficult to effectively repair by the underground water of oil of mirbane and aniline pollution again.
Summary of the invention
The objective of the invention is at above-mentioned the deficiencies in the prior art, provide a kind of chemistry and biological composite reaction wall original position to repair phreatic method.
Another purpose of the present invention provides the screening and the acclimation method of a kind of nitrobenzene degradation bacterium and microphenomenon of degradation of aniline.
Another purpose of the present invention provides the method for a kind of gac appendix nitrobenzene degradation bacterium and microphenomenon of degradation of aniline.
The objective of the invention is to realize in the following manner:
The composite reaction wall is included in the thick chemical reaction wall 2 of provided upstream 30-50Cm of direction of groundwater flow, establishes the thick biological respinse wall 4 of 20-30Cm at 50Cm place, the downstream of chemical reaction wall 2.
The screening of nitrobenzene degradation bacterium and microphenomenon of degradation of aniline and domestication comprise following method and step:
The screening of a, bacterial classification, get two parts of chemical plant sewage draining exit bed muds, each 10ml, place the 250ml triangular flask that granulated glass sphere and 90ml distilled water are housed respectively, the vibration aeration is after 24 hours in 10C ° of constant temperature oscillator, respectively get 10ml and be inoculated in respectively and contain in aniline or the oil of mirbane nutrient solution, cultivated again 48 hours, be the bacterial classification of aniline or oil of mirbane;
B, the microphenomenon of degradation of aniline domestication, bacterial classification is placed the 250ml triangular flask, add the 45ml enrichment medium that contains aniline 200mg/l, add bed mud 5g again, place under 10 ℃, the 120r/min shaking table, training amine concentration reaches 500mg/L, and after taming a week, replace rich supporting with the basic medium that contains aniline 50mg/L, 7 days is an acclimation period, and the inoculum size with 10% inserts in the fresh enrichment medium, to tame bacterium liquid every other day and place mutagenesis under the ultraviolet light, the pH value is controlled between 7.0~7.2 in the domestication process, cultivated for two weeks after, enrichment culture liquid is diluted, with coating method on the basic medium (containing aniline 200mg/L) that with aniline is sole carbon source and nitrogenous source, 28 ℃ of cultivations, picking list bacterium colony, the purifying of ruling repeatedly, obtained strains is inoculated on the beef extract-peptone inclined-plane that contains aniline, and 4 ℃ of refrigerators are preserved; Through being accredited as: Pseudomonas asplenii (Pseudomonas asplenii); [preservation date: on 07 24th, 2007, depositary institution: China Committee for Culture Collection of Microorganisms common micro-organisms center, deposit number: CGMCC No.2119]
The oil of mirbane bacterial classification 1ml of a step screening is got in c, the domestication of nitrobenzene degradation bacterium, coats on the culture dish, inserts the filter paper that dips in oil of mirbane respectively and tame in culture dish, and acclimation period is 3 days, carries out 4 domestications, and acclimation temperature is 10 ℃;
D, get the oil of mirbane bacterial classification 2ml of a step screening, insert and be equipped with in the triangular flask of 200ml beef-protein medium, simultaneously nitro phenenyl concentration in the substratum is adjusted to 400ppm, tame, acclimation period is 3 days, carries out four domestications, and acclimation temperature is 10 ℃;
E, treat that domestication finishes after, two kinds of domestication gained bacterial classifications are merged, 4 ℃ of refrigerators are preserved; Through being accredited as: cured shape genus bacillus (Bacillus cereus) .[preservation date: on 07 24th, 2007, depositary institution: China Committee for Culture Collection of Microorganisms common micro-organisms center, deposit number: CGMCC No.2118]
The appendix method of oil of mirbane biological activated carbon and aniline biological activated carbon: granulated active carbon water or distilled water flushing is clean, 105 ℃ of oven dry down, and place the cylinder agitator, adding the bacterium amount is 2.06 * 10 9The nitrobenzene degradation bacterium of individual/L or microphenomenon of degradation of aniline liquid nutrient medium are fixed 3 hours and are oil of mirbane biological activated carbon or aniline biological activated carbon in 110r/min cylinder agitator.
Purpose of the present invention can also realize in the following manner:
Chemical reaction wall 2 is made up of Zero-valent Iron and gac; Biological respinse wall 4 is that the biological activated carbon by appendix nitrobenzene degradation bacterium and appendix microphenomenon of degradation of aniline constitutes; Oil of mirbane bioactive carbon and aniline bioactive carbon are that equal proportion is mixed.
Beneficial effect:
The chemical reaction wall is handled and shown by the phreatic experiment of nitrobenzene contamination: the dominant mechanism of reacting with Zero-valent Iron and oil of mirbane is Fe ° reductive action, oil of mirbane is biodegradable aniline by the main reduzate of chemical reaction wall, Zero-valent Iron is better to the nitrobenzene removal effect of organic matter of difficult for biological degradation, and adaptability is strong.When the reaction times was 120min, the reduction of nitrobenzene rate can reach 97.4%.
Biological respinse wall experimental result shows: make the biological respinse wall with the immobilized microorganism of gac, can good removal effect be arranged to target contaminant.36 days results show for biological respinse wall operation: to starting point concentration is that the degradation rate of the oil of mirbane of 300.89mg/L reaches more than 98.83%, and degradation rate reaches 99.63% in 71 days.
Description of drawings
Accompanying drawing: chemistry is repaired phreatic method structure iron with the biological composite reaction wall original position
1,3,5 sandy soil layers, 2 chemical reactions are strong, and 4 biological respinses are strong.
Classification name: cured shape genus bacillus
Latin literary fame: Bacillus cereus
Depositary institution: China Committee for Culture Collection of Microorganisms common micro-organisms center
Address: Datun Road, Chaoyang District, Beijing City
Preservation date: on July 24th, 2007
Deposit number: CGMCC No.2118
Classification name: Pseudomonas asplenii
Latin literary fame: Pseudomonas asplenii
Depositary institution: China Committee for Culture Collection of Microorganisms common micro-organisms center
Address: Datun Road, Chaoyang District, Beijing City
Preservation date: on July 24th, 2007
Deposit number: CGMCC No.2119
Embodiment
Be described in further detail below in conjunction with drawings and Examples:
Embodiment 1
The composite reaction wall is included in the thick chemical reaction wall 2 of provided upstream 50Cm of direction of groundwater flow, establishes the thick biological respinse wall 4 of 30Cm at 50Cm place, the downstream of chemical reaction wall 2.
The screening of nitrobenzene degradation bacterium and microphenomenon of degradation of aniline and domestication comprise following method and step:
The screening of a, bacterial classification, get two parts of chemical plant sewage draining exit bed muds, each 10ml, place the 250ml triangular flask that granulated glass sphere and 90ml distilled water are housed respectively, the vibration aeration is after 24 hours in 10C ° of constant temperature oscillator, respectively get 10ml and be inoculated in respectively and contain in aniline or the oil of mirbane nutrient solution, cultivated again 48 hours, be the bacterial classification of aniline or oil of mirbane;
B, the microphenomenon of degradation of aniline domestication, bacterial classification is placed the 250ml triangular flask, add the 45ml enrichment medium that contains aniline 200mg/l, add bed mud 5g again, place under 10 ℃, the 120r/min shaking table, training amine concentration reaches 500mg/L, and after taming a week, replace rich supporting with the basic medium that contains aniline 50mg/L, 7 days is an acclimation period, and the inoculum size with 10% inserts in the fresh enrichment medium, to tame bacterium liquid every other day and place mutagenesis under the ultraviolet light, the pH value is controlled between 7.0~7.2 in the domestication process, cultivated for two weeks after, enrichment culture liquid is diluted, with coating method on the basic medium (containing aniline 200mg/L) that with aniline is sole carbon source and nitrogenous source, 28 ℃ of cultivations, picking list bacterium colony, the purifying of ruling repeatedly, obtained strains is inoculated on the beef extract-peptone inclined-plane that contains aniline, and 4 ℃ of refrigerators are preserved; Through being accredited as: Pseudomonas asplenii (Pseudomonas asplenii)
The oil of mirbane bacterial classification 1ml of a step screening is got in c, the domestication of nitrobenzene degradation bacterium, coats on the culture dish, inserts the filter paper that dips in oil of mirbane respectively and tame in culture dish, and acclimation period is 3 days, carries out 4 domestications, and acclimation temperature is 10 ℃;
D, get the oil of mirbane bacterial classification 2ml of a step screening, insert and be equipped with in the triangular flask of 200ml beef-protein medium, simultaneously nitro phenenyl concentration in the substratum is adjusted to 400ppm, tame, acclimation period is 3 days, carries out four domestications, and acclimation temperature is 10 ℃;
E, treat that domestication finishes after, two kinds of domestication gained bacterial classifications are merged, 4 ℃ of refrigerators are preserved; Through being accredited as: cured shape genus bacillus (Bacillus cereus).
The appendix method of oil of mirbane biological activated carbon and aniline biological activated carbon: granulated active carbon water or distilled water flushing is clean, and oven dry places the cylinder agitator under 105 ℃, and adding the bacterium amount is 2.06 * 10 9The nitrobenzene degradation bacterium of individual/L or microphenomenon of degradation of aniline liquid nutrient medium are fixed 3 hours and are oil of mirbane biological activated carbon or aniline biological activated carbon in 110r/min cylinder agitator.
Chemical reaction wall 2 is made up of Zero-valent Iron and gac, and the mass ratio of Zero-valent Iron and gac is mixed for the ratio in 5: 1; Biological respinse wall 4 is that the biological activated carbon by appendix nitrobenzene degradation bacterium and appendix microphenomenon of degradation of aniline constitutes; The oil of mirbane biological activated carbon is that equal proportion is mixed with the aniline biological activated carbon.
The screening of bacterial classification:
Get end mud (two parts of each 10mL) and place the 250mL triangular flask that granulated glass sphere and 90mL sterile distilled water are housed, the empty aeration of vibration is after 24 hours in 10 ℃ of constant temperature oscillators, respectively get the 10mL bacterial suspension inoculation in the stand-by seed culture fluid of sterilizing, oil of mirbane or aniline are pressed sole carbon source and the energy of a certain amount of adding as microorganism growth, cultivated 48 hours, with the bacterium that grows under this condition purpose bacterial classification as oil of mirbane and aniline.Respectively with above bacterial classification inoculation (before culture medium inoculated all high pressure steam sterilization) in the pH value is 7.0 fresh oil of mirbane or aniline liquid nutrient medium.Through enrichment culture, with dilution or the single bacterium colony of streak culture acquisition.These bacterial strains are cultivated in the oil of mirbane that contains different oil of mirbane or aniline concentration (10.0mg/L, 20.0mg/L, 30.0mg/L, 40.0mg/L, 50.0mg/L) or the vibration of aniline inoculation of medium, sealing, lucifuge (for the no solar light irradiation situation of simulated groundwater), oscillator temperature is made as 10 ℃, every the residual concentration of 72h sampling and measuring oil of mirbane or aniline, picking out p-nitrophenyl or aniline thus has the bacterial strain of degradation capability as oil of mirbane or microphenomenon of degradation of aniline.
The domestication of microphenomenon of degradation of aniline:
In the triangular flask of 250mL, add 45mL enrichment medium (containing aniline 200mg/L), add bed mud 5g again, place under 10 ℃, after 120r/min shaking table training amine concentration reaches 500mg/L and tames a week, replace rich supporting with the basic medium that contains aniline 50mg/L, 7d is an acclimation period, inoculum size with 10% behind each end cycle inserts in the fresh enrichment medium, aniline concentration is by 10.0mg/L simultaneously, 50.0mg/L, 100.0mg/L, 150.0mg/L, 200.0mg/L, also will tame bacterium liquid during this period every other day and place the mutagenesis some time under the ultraviolet light of doses.Well grow for the assurance thalline, in the domestication process, want regularly to detect every day the pH value changing conditions of domestication liquid, and in time the pH value is transferred between 7.0~7.2.Treat the aniline substratum in the enrichment culture liquid, after cultivating for two weeks, enrichment culture liquid is suitably diluted, with diluent with coating method on the basic medium (containing aniline 200mg/L) that with aniline is sole carbon source and nitrogenous source, 28 ℃ of cultivations, picking list bacterium colony, the purifying of ruling repeatedly, obtained strains is inoculated on the beef extract-peptone inclined-plane that contains aniline, and 4 ℃ of refrigerators are preserved.
The domestication of nitrobenzene degradation bacterium:
The domestication of solid medium: get two culture dish that are assembled with the beef extract-peptone solid medium, get the original bacterium liquid 1ml in bacterium source, two places respectively, coat on the culture dish, in culture dish, insert the filter paper that dips in oil of mirbane respectively, tame.Acclimation period is 3 days, carries out 4 domestications.
Domestication in the liquid nutrient medium: respectively get the original bacterium liquid 2ml in two bacterium sources, insert and be equipped with in the triangular flask of 200ml beef-protein medium, simultaneously nitro phenenyl concentration in the substratum is adjusted to 400ppm, tame then.Acclimation period is 3 days, carries out four domestications.After treating that domestication finishes, will mix bacterium from the domestication gained in two bacterium sources and merge.
The evaluation of bacterial classification:
Colonial morphology is observed: inoculation bacterium liquid is rule on the beef-protein medium flat board, puts 10 ℃ and observes colonial morphology behind the cultivation 24h down.Microscopic examination: on bacterium liquid inoculation beef-protein medium. put sample preparation when being cultured to logarithmic phase under 10 ℃, with microscopic examination and take pictures.
Strain identification adopts Biolog strain identification system and fluorescent PCR method that two kinds of bacterium are identified: microphenomenon of degradation of aniline is a Pseudomonas asplenii, the Latin literary fame: Pseudomonas asplenii; The nitrobenzene degradation bacterium is cured shape genus bacillus, Latin literary fame: Bacillus cereus.
Gac appendix nitrobenzene degradation bacterium and microphenomenon of degradation of aniline:
It is clean to get 200g granulated active carbon water or distilled water flushing, dries down at 105 ℃ and places the cylinder agitator, is sub-packed in the glassware of 2 2L, and adding 1L bacterium amount respectively is 2.06 * 10 9The nitrobenzene degradation bacterium of individual/L or microphenomenon of degradation of aniline liquid nutrient medium, (institute gets and adds glucose 5g/L in the underground water, NH4Cl0.2g/L, buffering 0.5mL/L), 10 ℃ of controlled temperature are fixed 3 hours and are oil of mirbane biological activated carbon or aniline biological activated carbon in 110r/min cylinder agitator.
The preparation of Zero-valent Iron:
1 kilogram of iron filings is put into the 2L beaker, pouring 1.5L concentration into is that 0.1mol/L NaOH solution soaking was removed oil film in 5 hours, be washed with distilled water to neutrality again, pouring 1.5L concentration after the seasoning again into is 0.1mol/LHCl, and stir repeatedly, table impurity and zone of oxidation are removed in cleaning, treat that the pickling time reaches to pour out pickle solution behind the 0.5h and be Zero-valent Iron.
Simulation is loaded:
It is wide to dig a 50Cm in the upstream of direction of groundwater flow, and the degree of depth reaches the zanjon of water-resisting layer under the underground water, and Zero-valent Iron and gac are mixed case in 5: 1 ratio, inserts after stirring is mixed, and is chemical reaction wall 2.The original concentration of oil of mirbane is 300.87mg/L, run to the 10th talent behind the after chemical reaction wall and detect oil of mirbane, this explanation oil of mirbane is all adsorbed by Zero-valent Iron reduction and gac in 10 days, increase along with the time, the concentration of oil of mirbane slightly increases, and the charcoal absorption of this explanation iron charcoal layer has reached saturated, and the reducing property of iron decreases, thereby the appearance of oil of mirbane is arranged, oil of mirbane has reached 1.597mg/L-1.756mg/L during by the 71st day.The transformation efficiency that experimental results show that chemical reaction wall p-nitrophenyl is 99.44%.
At 50Cm place, the downstream of chemical reaction wall 2, it is wide to dig a 30Cm, and the degree of depth reaches the zanjon of water-resisting layer under the underground water, and the biological activated carbon of appendix nitrobenzene degradation bacterium and appendix microphenomenon of degradation of aniline is mixed in the ditch of packing into by equal proportion, is biological respinse wall 4.The degradation capability of immobilized thalline p-nitrophenyl is extremely strong, concentration is that the nitrobenzene solution of 20mg/L sharply descends preceding 4 days concentration, this mainly is due to the adsorption of gac, after absorption reached balance, the microorganism that is fixed on the gac just demonstrated its degradation property, reached 55.10% at the 8th day degradation rate, reached 70.31% on the 20th day, reach 79.83%, the 50 day at 36 days and reach 94.71%, the 71 day degradation rate and reach 95.63%.The biological activated carbon p-nitrophenyl that appendix nitrobenzene degradation bacterium and appendix microphenomenon of degradation of aniline are described has good effect of removing.Concentration is that the aniline solution of 87.35mg/L sharply descends preceding 8 days concentration, this mainly is due to the adsorption of gac, after absorption reaches balance, the microorganism that is fixed on the gac just demonstrates its degradation property, at 16 days degradation rates up to 77.37%, reached 91.92%, the 36 day on the 20th day and reach that degradation rate reaches 97.61% in 95.49%, the 71 day.
Embodiment 2
It is wide to dig a 30Cm in the upstream of direction of groundwater flow, and the degree of depth reaches the zanjon of water-resisting layer under the underground water, and Zero-valent Iron and gac are mixed case in 5: 1 ratio, inserts after stirring is mixed, and is chemical reaction wall 2.The original concentration of oil of mirbane is 300.87mg/L, run to the 10th talent behind the after chemical reaction wall and detect oil of mirbane, this explanation oil of mirbane is all adsorbed by Zero-valent Iron reduction and gac in 10 days, increase along with the time, the concentration of oil of mirbane slightly increases, and the charcoal absorption of this explanation iron charcoal layer has reached saturated, and the reducing property of iron decreases, thereby the appearance of oil of mirbane is arranged, oil of mirbane has reached 1.4mg/L-1.6mg/L during by the 71st day.The transformation efficiency that experimental results show that chemical reaction wall p-nitrophenyl is 99%.
At 50Cm place, the downstream of chemical reaction wall 2, it is wide to dig a 20Cm, and the degree of depth reaches the zanjon of water-resisting layer under the underground water, and the biological activated carbon of appendix nitrobenzene degradation bacterium and appendix microphenomenon of degradation of aniline is mixed in the ditch of packing into by equal proportion, is biological respinse wall 4.The degradation capability of immobilized thalline p-nitrophenyl is extremely strong, and concentration is that the nitrobenzene solution of 20mg/L sharply descends preceding 4 days concentration, and this mainly is due to the adsorption of gac.After absorption reached balance, the microorganism that is fixed on the gac just demonstrated its degradation property, reached 50%, the 20 day at the 8th day degradation rate and reached 65.31%, reached 75.83%, the 50 day at 36 days and reach 90.71%, the 70 day degradation rate to reach 94.63%.The biological activated carbon p-nitrophenyl that appendix nitrobenzene degradation bacterium and appendix microphenomenon of degradation of aniline are described has good effect of removing.Concentration is that the aniline solution of 87.35mg/L sharply descends preceding 8 days concentration, and this mainly is due to the adsorption of gac.After absorption reached balance, the microorganism that is fixed on the gac just demonstrated its degradation property, reached 90%, the 36 day up to 75.37%, the 20 day and reach that degradation rate reaches 96% in 94%, the 71 day at 16 days degradation rates.

Claims (7)

1. chemistry and biological composite reaction wall original position are repaired phreatic method, it is characterized in that, the composite reaction wall is included in the thick chemical reaction wall (2) of provided upstream 30-50Cm of direction of groundwater flow, establishes the thick biological respinse wall (4) of 20-30Cm at the 50Cm place, downstream of chemical reaction wall (2).
2. according to the described biological respinse wall of claim 1 (4), it is characterized in that the screening of nitrobenzene degradation bacterium and microphenomenon of degradation of aniline and domestication comprise following method and step:
The screening of a, bacterial classification, get two parts of chemical plant sewage draining exit bed muds, each 10ml, place the 250ml triangular flask that granulated glass sphere and 90ml distilled water are housed respectively, the vibration aeration is after 24 hours in 10C ° of constant temperature oscillator, respectively get 10ml and be inoculated in respectively and contain in aniline or the oil of mirbane nutrient solution, cultivated again 48 hours, be the bacterial classification of aniline or oil of mirbane;
B, the microphenomenon of degradation of aniline domestication, bacterial classification is placed the 250ml triangular flask, add the 45ml enrichment medium that contains aniline 200mg/l, add bed mud 5g again, place under 10 ℃, the 120r/min shaking table, training amine concentration reaches 500mg/L, and after taming a week, replace rich supporting with the basic medium that contains aniline 50mg/L, 7 days is an acclimation period, and the inoculum size with 10% inserts in the fresh enrichment medium, to tame bacterium liquid every other day and place mutagenesis under the ultraviolet light, the pH value is controlled between 7.0~7.2 in the domestication process, cultivated for two weeks after, enrichment culture liquid is diluted, with coating method on the basic medium (containing aniline 200mg/L) that with aniline is sole carbon source and nitrogenous source, 28 ℃ of cultivations, picking list bacterium colony, the purifying of ruling repeatedly, obtained strains is inoculated on the beef extract-peptone inclined-plane that contains aniline, and 4 ℃ of refrigerators are preserved; Through being accredited as: Pseudomonas asplenii (Pseudomonas asplenii)
The oil of mirbane bacterial classification 1ml of a step screening is got in c, the domestication of nitrobenzene degradation bacterium, coats on the culture dish, inserts the filter paper that dips in oil of mirbane respectively and tame in culture dish, and acclimation period is 3 days, carries out 4 domestications, and acclimation temperature is 10 ℃;
D, get the oil of mirbane bacterial classification 2ml of a step screening, insert and be equipped with in the triangular flask of 200ml beef-protein medium, simultaneously nitro phenenyl concentration in the substratum is adjusted to 400ppm, tame, acclimation period is 3 days, carries out four domestications, and acclimation temperature is 10 ℃;
E, treat that domestication finishes after, two kinds of domestication gained bacterial classifications are merged, 4 ℃ of refrigerators are preserved; Through being accredited as: cured shape genus bacillus (Bacillus cereus).
3. it is characterized in that according to the described chemical reaction wall of claim 1 (2) that chemical reaction wall (2) is made up of Zero-valent Iron and gac.
4. according to the described chemical reaction wall of claim 3 (2), it is characterized in that Zero-valent Iron and gac are mixed in 5: 1 ratio of quality.
5. repair phreatic method according to described chemistry of claim 1 and biological composite reaction wall original position, it is characterized in that, biological respinse wall (4) is that the biological activated carbon by appendix nitrobenzene degradation bacterium and appendix microphenomenon of degradation of aniline constitutes.
6. according to the appendix method of described oil of mirbane biological activated carbon of claim 5 and aniline biological activated carbon, it is characterized in that, granulated active carbon water or distilled water flushing is clean, 105 ℃ of oven dry down, and place the cylinder agitator, adding the bacterium amount is 2.06 * 10 9The nitrobenzene degradation bacterium of individual/L or microphenomenon of degradation of aniline liquid nutrient medium are fixed 3 hours and are oil of mirbane biological activated carbon or aniline biological activated carbon in 110r/min cylinder agitator.
7. it is characterized in that according to the described biological respinse wall of claim 1 (4) that oil of mirbane bioactive carbon and aniline biological activated carbon are that equal proportion is mixed.
CNA2007100561701A 2007-10-15 2007-10-15 Method for renovating groundwater in situ with chemical and biological composite reaction wall Pending CN101172732A (en)

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