CN104492804B - The system and method for ozone pretreatment enhancement microbiological degraded repairing polluted soil - Google Patents
The system and method for ozone pretreatment enhancement microbiological degraded repairing polluted soil Download PDFInfo
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Abstract
The invention provides the system and method for ozone pretreatment enhancement microbiological degraded repairing polluted soil, contaminated soil is polycyclic aromatic hydrocarbon pollution, and main step of repairing includes collection and the pretreatment of sample, prepares and mix slurry liquid, assembly and connection repair system, ozone pretreatment, adding biosurfactant and liquid culture medium, carrying out combined degradation and period sampling measuring until having repaired in reaction vessel.System for use in carrying configuration is simple and convenient to operate, safety is high, the features such as, pollution history deep for Pollution of Polycyclic Aromatic Hydrocarbons in Soil is lasting, ozone pretreatment and biosurfactant solubilization technique is used to carry out enhancement microbiological degraded United Technologies, overcome the limitation of monotechnics, and it is easy and simple to handle, with low cost, cycle of operation is short, removal effect is good, and the clearance of polycyclic aromatic hydrocarbon reaches more than 93%, and does not produce secondary pollution, largely reducing polycyclic aromatic hydrocarbon pollution to human body and the harm of environment, provide new thinking for soil remediation.
Description
Technical field
The present invention relates to technical field of soil remediation, particularly relate to a kind of system and method utilizing ozone pretreatment enhancement microbiological degradation technique to repair polycyclic aromatic hydrocarbon pollution.
Background technology
China advance rapidly industrialized during, owing to the shortage of people's environmental consciousness causes environment that we depend on for existence by serious destruction, the soil natural resources lived of relying as the mankind also fails to escape by luck, and Soil Environmental Pollution problem is more and more sharp-pointed.Wherein, there is polycyclic aromatic hydrocarbon (Polycyclicaromatichydrocarbons, polycyclic aromatic hydrocarbon) contamination phenomenon the most carcinogenic, teratogenesis, mutagenic action the most universal.The four groups of rice terraces in Fushun three essentials-essence village in irrigated area are comforted in Shen, and because the petroleum waste waters irrigations of more than 30 years form contaminated land of attaching most importance to, nineteen eighty-two records polycyclic aromatic hydrocarbon total amount and is up to 631.9mg/kg(topsoil 0～20cm), 602.95mg/kg(underearth 20～35cm).Except causing agricultural land soil by addition to polycyclic aromatic hydrocarbons contaminated because dirt fills, carry out the coal chemical industry enterprises of production activity with coal for primary raw material and coking enterprise be also soil by one of polycyclic aromatic hydrocarbons contaminated factor, more and more places being once engaged in similar production activity have been diagnosed as polycyclic aromatic hydrocarbon heavily contaminated place.Result of study in recent years shows, polycyclic aromatic hydrocarbon is the most typical organic pollution in China's chemical products contaminated site soil, and the total content of PAHs in soil is more than 1%.Such as, in the soil of genuine location, Beijing coke-oven plant, the maximum concentrations of 16 kinds of polycyclic aromatic hydrocarbon total contents is 14363.7mg/kg, and mean concentration is 190.4mg/kg；Wherein, benzo (a) pyrene maximum detected level exceeds standard 430 times than Beijing " place soil environmental risk assessment screening value ", the polycyclic aromatic hydrocarbon pollution bulky to be repaired finally determined.More than 1300 family's coking enterprises (not including illegal coking workshop) are had in view of current nationwide, by 2008, the coal chemical enterprise closed down because of a variety of causes reaches 1061, and smelting iron and steel enterprise (major part exists coking subsidiary factory) only 2010 makes superseded enterprise because production capacity falls behind just reaches 175 simultaneously, the polycyclic aromatic hydrocarbon pollution enormous amount that China need to repair.The reparation of polycyclic aromatic hydrocarbon pollution, during utilizing for guarantee places polluted by polynuclear aromatic hydrocarbons redevelopment, the healthy and preventing secondary environmental pollution of resident has great importance.
At present, domestic and international polycyclic aromatic hydrocarbon pollution recovery technique mainly includes physical technique, chemical technology and biotechnology.
Physical technique is the physical characteristic according to polycyclic aromatic hydrocarbon, utilize the method such as extraction, eluting, adsorption and desorption by its from gas, liquid, solid mutually separate, quantities involved by this technology is big, costly, being applicable to contaminated area situation little, with serious pollution, the pollutant that this technology fails thoroughly to remove simultaneously can produce certain exposure to environment；Certain chemical reaction is there is with organic pollution in chemical technology mainly by chemical agent (such as strong oxidizer), make pollutant polycyclic aromatic hydrocarbon be degraded, toxicity is removed or reduces, it is preferable that this technology removes soil polycyclic aromatic hydrocarbon effect, but frequently result in Soil structure destruction, biological activity of soil decline, soil fertility degeneration and produce secondary pollution；Biotechnology refers mainly to microbial technology, its rehabilitation cost is low, operational management simply, does not produce secondary pollution, but the later stage in biological restoration, the degraded of pollutant changes inconspicuous with the prolongation of repair time, repair " hangover " stage of entrance, substantially prolongs the time reaching to repair target, study simultaneously and also find, for the contour ring polycyclic aromatic hydrocarbon of benzo [a] pyrene, the effect of biological restoration is unsatisfactory.
Summary of the invention
Present invention aim at providing the system and method for a kind of ozone pretreatment enhancement microbiological degraded repairing polluted soil, solve the limitation of single recovery technique in prior art, as peripheral doses physical technique quantities greatly, costly, problem that the scope of application is little, chemical technology is easily caused Soil structure destruction, biological activity declines, Fertility Degeneration and produce the problem of secondary pollution, and the biotechnology later stage repair speed slow down, length overall repair time, the problem that clearance is low, remediation efficiency is the highest to high ring polycyclic aromatic hydrocarbon.
For realizing above-mentioned technical purpose, the present invention adopts the following technical scheme that:
A kind of system of ozone pretreatment enhancement microbiological degraded repairing polluted soil, described contaminated soil is polycyclic aromatic hydrocarbon pollution, it is characterised in that: include ozone generating-device, reaction vessel and the tail gas absorption bottle sequentially connected by gas conduit；The wet flow indicator being provided with monitoring ozone flow on gas conduit between described ozone generating-device and reaction vessel and the check-valves avoiding ozone to reflux；Described reaction vessel is placed in water bath chader；The slurry liquid being mixed into equipped with polycyclic aromatic hydrocarbon pollution and deionized water in described reaction vessel, it can input with the container of the container containing biosurfactant and Sheng liquid culture medium container and be connected；Equipped with tail gas absorption liquid in described tail gas absorption bottle.
As preferred technical scheme, described gas conduit is the ozone proof silica gel tube of aging resistance；Described reaction vessel is the standard-sized Drexel bottle of diameter d=70mm or h:d air-tightness vial between 4:1～6:1 at the bottom of height h=280mm, bottle.
It is further preferred that in described reaction vessel, the deionized water of every 50g polycyclic aromatic hydrocarbon pollution corresponding 200～300mL.
It is furthermore preferred that the tail gas absorption liquid in described tail gas absorption bottle is KI solution.KI solution concentration is 200g/L, concrete configuration method is: dissolve in the distilled water that 200g potassium iodide (analytical pure) cools down after 1000mL boils, it is stored in refrigerator with brown bottle, at least stores after one day use, every 1.00mL solution potassium iodide Han 0.20g again.
The method that the invention still further relates to the ozone pretreatment enhancement microbiological degraded repairing polluted soil that a kind of system utilizing above-mentioned ozone pretreatment enhancement microbiological degraded repairing polluted soil is carried out, described contaminated soil is polycyclic aromatic hydrocarbon pollution, comprises the following steps:
Step one, the collection of sample and pretreatment: gather by polycyclic aromatic hydrocarbons contaminated soil, In Shade air-dried, process of sieving after rejecting the impurity such as root system of plant and chad, place standby；
Step 2, preparation slurry liquid: correct amount amount polycyclic aromatic hydrocarbon pollution sample and sterilizing deionized water, be placed in reaction vessel, be made into Tu Shui than the slurry liquid that scope is 1:4～1:6；
Step 3, the mixing of slurry liquid: be placed in water bath chader by reaction vessel, open water bath chader, and temperature is 30～38 DEG C, and vibration 10～20min makes the slurry liquid mix homogeneously in reaction vessel；
Step 4, assembly and connection repair system: be sequentially connected with ozone generating-device, reaction vessel and tail gas absorption bottle with gas conduit, wet flow indicator and check-valves is connected on gas conduit between ozone generating-device and wet flow indicator, reaction vessel is placed in water bath chader, tail gas absorption bottle fills tail gas absorption liquid；
Step 5, carry out ozone pretreatment: ozone concentration and the pretreatment time of pretreatment are set in ozone generating-device, open ozone generating-device and water bath chader, in the slurry liquid of reaction vessel, it is passed through ozone carries out pretreatment, after pretreatment completes, close ozone generating-device；
Step 6, in reaction vessel, add biosurfactant: adding biosurfactant in reaction vessel, the biosurfactant of every 50g polycyclic aromatic hydrocarbon pollution corresponding 0.5～1.5g, for realizing the solubilising of the polycyclic aromatic hydrocarbon in slurry liquid；
Step 7, in reaction vessel add liquid culture medium: continue in reaction vessel, add the liquid culture medium rich in nutrient, the liquid culture medium of every 50g polycyclic aromatic hydrocarbon pollution corresponding 40～60mL, the indigenous microorganism being contaminated in soil for enrichment culture；
Step 8, carrying out combined degradation: carry out United Technologies degradation reaction in continuing reaction vessel to be placed in water bath chader, the temperature range in water bath chader is 30～38 DEG C, concussion mixing；
Step 9, period sampling measuring are until having repaired: be sampled week about, analyze the concentration remaining polycyclic aromatic hydrocarbon in slurry liquid, until the clearance of polycyclic aromatic hydrocarbon reaches stable, so far, the reparation of polycyclic aromatic hydrocarbon pollution completes.
Wherein, preferably, in described step 5, the time of ozone pretreatment and the concentration of ozone are obtained by preliminary experiment, by experiment of single factor, change time or the concentration of ozone of ozone pretreatment, analyze clearance and the number change of microorganism of polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon pollution, draw optium concentration and the Best Times of ozone pretreatment, as the concentration of ozone in actual ozone pretreatment and the pretreatment time of ozone.
It is further preferred that in described step 5 ozone preprocessing process, the concentration of ozone is 1.70～1.80mg/L, the time of ozone pretreatment is 3～6min.
Preferably, in described step 6, kind and the concentration of biosurfactant are obtained by preliminary experiment, pass through experiment of single factor, change the kind of biosurfactant or concentration or the concentration of biosurfactant, conciliate adsorption effect by analyzing critical micelle concentration, draw optimal kind and the optium concentration of biosurfactant, as the kind of biosurfactant and the concentration of reality application.
Further preferred, in described step 6, biosurfactant is saponin, and its concentration is 3～5g/L.
Preferred, in described step 7, the preparation method of liquid culture medium is: take 10g tryptone, 5g yeast extract, 5gNaCl, 0.1g compound vitamin are substantially soluble in the deionized water of 800mL, add deionized water and be settled to 1L, adjust pH value to 7.0, put into high-pressure sterilizing pot, sterilizing 20 minutes at 121 DEG C, can use after natural cooling.According to this kind of weight, can be widely used in actual soil remediation engineering.
Compared with prior art, the present invention has a techniques below advantage:
1, the limitation of monotechnics is effectively overcome: with polycyclic aromatic hydrocarbon pollution as object, take full advantage of being combined of ozone pretreatment, the strengthening of biosurfactant solubilising and indigenous microorganism auto-degradation effect, various technology is complemented one another, ozone pretreatment makes the biodegradable repairing effect in rear end be improved, the clearance of polycyclic aromatic hydrocarbon reaches more than 93%, shortens repairing efficiency simultaneously；The strengthening of biosurfactant solubilising then utilizes the solubilization of biosurfactant, is eluted out by polycyclic aromatic hydrocarbon, improves its bioavailability, to promote biodegradation from soil；And compare chemical surfactant, natural biological surfactant has many good qualities, such as hypotoxicity, high biological degradability, good environment compatibility, therefore, natural biological surfactant is used for environment remediation, secondary pollution will not be brought, and can reach intended solubilization.
2, easy and simple to handle, with low cost, removal effect is good, and cycle of operation is short, does not produce secondary pollution；
3, the liquid culture medium rich in nutrient is used, this liquid culture medium is in ventilation or under conditions of vibration, the nutrition of beneficially growth of microorganism can be provided with, thus the further indigenous microorganism in this polycyclic aromatic hydrocarbon pollution of enrichment culture, enhancement microbiological degradation capability, improves the degradation efficiency of polycyclic aromatic hydrocarbon further.
To sum up, the advantage of the comprehensive recovery technique the most of the same race of the present invention, ozone pretreatment, biosurfactant solubilization technique and three kinds of monotechnicses of microbial degradation are joined together, shorten cycle of operation to greatest extent, control secondary pollution, save rehabilitation expense, effectively raise polycyclic aromatic hydrocarbon in chemical products contaminated soil, the clearance of the highest ring polycyclic aromatic hydrocarbon.
Accompanying drawing explanation
Fig. 1 is the overall structure schematic diagram of the system of the ozone pretreatment enhancement microbiological degraded repairing polluted soil that the present invention relates to；
Fig. 2 is the schematic flow sheet of the method for the ozone pretreatment enhancement microbiological degraded repairing polluted soil that the present invention relates to.
Reference: 1-ozone generating-device, 2-check-valves, 3-wet flow indicator, 4-gas conduit, 5-reaction vessel, 6-water bath chader, 7-tail gas absorption bottle, 8-contain the container of biosurfactant, the container of 9-Sheng liquid culture medium.
Detailed description of the invention
Below in conjunction with the accompanying drawings present invention is made further explanation and description.
The present embodiment method is the soil on certain manufacturing enterprise of comprehensive coke-oven plant contaminated site for examination soil, this enterprise is with coal as primary raw material, start to produce coal gas, coke and Coal Chemical Industry product from the fifties in last century, in its each workshop of this enterprise, the imperfect combustion of Fossil fuel and the course of processing of the chemical products such as coal gas, coke all may cause the discharge of multiring aromatic hydrocarbon substance, this enterprise stops production the beginning of this century, polycyclic aromatic hydrocarbon was retained for more than 50 years in the soil of place, was the most polycyclic aromatic hydrocarbons contaminated " aging " soil.In the case of constant according to the flow process in present system and method and fixing material proportion, i.e. can be applicable to after expansion doses in the reparation of large-scale polycyclic aromatic hydrocarbon pollution.
First detecting the content for examination Determination of Polycyclic Aromatic Hydrocarbons in Soil, its detection method is as follows:
First carry out sample pretreatment, precise 4.00g soil sample, add 8.00gNa2SO4(impurity metal oxide is removed with dilute HCI washing that volume fraction is 10% with 0.28g copper powder, then with distilled water cyclic washing until not showing acidity, again with methanol and normal hexane washing) grind dehydration mix homogeneously, divide and be separately added into 16mL, 12mL, 12mL dichloromethane for 3 times: the mixing organic extractant of acetone (1:1) (v/v), each ultrasonic extraction 20min(power 70%)；Collect extract, under Rotary Evaporators, be concentrated into about 1mL after being sufficiently mixed, add 4mL normal hexane, ultrasonic extraction 10min(power 70%)；Crossing silica gel column chromatography, collect eluent, nitrogen purging is concentrated into 1mL, crosses 0.45 μm organic facies filter membrane, loads sample injection bottle, to be measured.Then GC-MS analysis is carried out, GC-MS instrument condition: Agilent7890-5975 type gas chromatograph-mass spectrometer.Chromatographic condition: DB-5MS type capillary chromatographic column (30m × 0.25mm × 0.25 μm).Heating schedule: initial temperature 60 DEG C, keeps 2min, then with the ramp of 15 DEG C/min to 290 DEG C, stops 5min；Injector temperature 250 DEG C, Splitless injecting samples, sample size 1 μ L；200 DEG C of EI source, electron energy 70eV, detects voltage 350V, transmission line temperature 250 DEG C.
Content for polycyclic aromatic hydrocarbon total in examination pedotheque is 4452.19 ± 394.11mg/kg after measured.
Being illustrated in figure 1 the system of the ozone pretreatment enhancement microbiological degraded repairing polluted soil that the present invention relates to, the direction of arrow is stream of ozone direction, and it includes ozone generating-device 1, reaction vessel 5 and the tail gas absorption bottle 7 sequentially connected by gas conduit 4；The wet flow indicator 3 being provided with monitoring ozone concentration on gas conduit 4 between described ozone generating-device 1 and reaction vessel 5 and the check-valves 2 avoiding ozone to reflux；Described reaction vessel 5 is placed in water bath chader 6；The slurry liquid being mixed into equipped with polycyclic aromatic hydrocarbon pollution and deionized water in described reaction vessel 5, it can input with the container 9 of the container 8 containing biosurfactant and Sheng liquid culture medium container and be connected, the deionized water of every 50g polycyclic aromatic hydrocarbon pollution corresponding 200～300mL during slurry liquid configuration；Equipped with tail gas absorption liquid in described tail gas absorption bottle 7, tail gas absorption liquid is KI solution, its effect is that residual exhaust is passed through the recovery of KI solution, prevention ozone tail gas overflows the secondary pollution being likely to result in, concentration is 200g/L, concrete configuration method is: dissolves in the distilled water that 200g potassium iodide (analytical pure) cools down after 1000mL boils, is stored in refrigerator with brown bottle, uses after at least storing one day again.This solution 1.00mL potassium iodide Han 0.20g.
In this system, ozone generating-device 1, check-valves 2, wet flow indicator 3 and gas conduit 4, together constitute with the air supply system of ozone pretreatment；The inlet gas ozone concentration of ozone generating-device 1 can set by arranging ozone charge flow rate and regulation operating current；Check-valves 2 is dependent on the ozone self of ozone generating-device 1 generation and flows and automatic open and close flap, is used for the valve preventing ozone from flowing backwards；Wet flow indicator 3 can measure the ozone volume in the reaction phase, and then calculates ozone concentration by iodine number chemical method；Gas conduit 4 uses the ozone proof silica gel tube of aging resistance, plays the effect of transmission ozone gas.
Reaction vessel 5 is placed in water bath chader 6, constitutes main body response system；Reaction vessel 5 is by selecting Drexel bottle after many experiments screening verification, Drexel bottle a size of h=280mm, d=7mm, the slender structure of Drexel bottle, make its gas conduit 4 that can ensure to transmit ozone as reaction vessel go deep into the middle and lower part to the reaction vessel slurry liquid water surface, can at utmost ensure that ozone fully reacts with slurry liquid；And the airtight performance of Drexel bottle is better than general vial；Placing the reaction vessel having installed slurry liquid 1:5 Tu Shui ratio in water bath chader 6, regulation rotating speed is the maximum (top) speed 220r/min at water bath chader, to guarantee the slurry liquid mix homogeneously in reaction vessel.Water bath chader 6 can be placed multiple reaction vessel simultaneously and carry out United Technologies process, it can be ensured that the operating mode of each reaction vessel is consistent so that result has comparability.
The present invention also provides for the method for the ozone pretreatment enhancement microbiological degraded repairing polluted soil that a kind of system utilizing above-mentioned ozone pretreatment enhancement microbiological degraded repairing polluted soil is carried out, wherein contaminated soil is polycyclic aromatic hydrocarbon pollution, comprises the following steps:
Step one, the collection of sample and pretreatment: gather by polycyclic aromatic hydrocarbons contaminated soil, In Shade air-dried, process of sieving after rejecting the impurity such as root system of plant and chad, obtain the soil particle that particle diameter is not more than 5mm, preferably no greater than 2mm；Place standby；
Step 2, preparation slurry liquid: correct amount amount polycyclic aromatic hydrocarbon pollution sample and sterilizing deionized water, be placed in reaction vessel 5, be made into Tu Shui than the slurry liquid that scope is 1:4～1:6；
Step 3, the mixing of slurry liquid: be placed in water bath chader 6 by reaction vessel 5, open water bath chader 6, and regulation rotating speed is 150r/min～220r/min, and temperature is 30～38 DEG C, and vibration 10～20min makes the slurry liquid mix homogeneously in reaction vessel 5；
Step 4, assembly and connection repair system: be sequentially connected with ozone generating-device 1, reaction vessel 5 and tail gas absorption bottle 7 with gas conduit 4, wet flow indicator 3 and check-valves 2 is connected on gas conduit 4 between ozone generating-device 1 and wet flow indicator 3, for ensureing the air-tightness of system, appropriate vaseline is smeared in all joints, reaction vessel 5 is placed in water bath chader 6, tail gas absorption bottle 7 fills tail gas absorption liquid；
Step 5, carry out ozone pretreatment: ozone concentration and the pretreatment time of pretreatment are set in ozone generating-device 1, open ozone generating-device 1 and water bath chader 6, in the slurry liquid of reaction vessel 5, it is passed through ozone carries out pretreatment, after pretreatment completes, close ozone generating-device 1；Wherein, the time of ozone pretreatment and the concentration of ozone are obtained by preliminary experiment, pass through experiment of single factor, change time or the concentration of ozone of ozone pretreatment, analyze clearance and the number change of microorganism of polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon pollution, draw optium concentration and the Best Times of ozone pretreatment, as the concentration of ozone in actual ozone pretreatment and the pretreatment time of ozone, the concentration of ozone is 1.70～1.80mg/L, the time of ozone pretreatment is 3～6min, the concentration of the ozone that optimum is selected is 1.74mg/L, the time of ozone pretreatment is 5min；
Concrete Pre-testing procedure is as follows:
Ozone pretreatment factor of influence factorial experiment, two factor of influence ozone concentrations and response time on affecting course of reaction are estimated, and explore more excellent reaction condition for subsequent experimental.It is respectively provided with the ozone three groups of experiments under 0.79,1.74 and 4.50mg/L tri-kinds of variable concentrations, what often group was tested is specifically provided that arranging ozone charge flow rate is 14.6L/min, regulation operating current sets inlet gas ozone concentration, arranges water bath chader temperature 35 DEG C, rotating speed 220r/min；Question response plant running is stable, will be equipped with in the reaction vessel placement water bath chader that slurry liquid is mixed by 50.00g Polluted Soil and 250.00mL sterilizing deionized water, connecting airway and be passed through ozone to slurry liquid, residual exhaust is passed through KI solution and reclaims, by titration measuring ozone residual concentration；Respectively 5,10,20,30,40,50, respectively take two Duplicate Samples analyses at 60min, measure remaining polycyclic aromatic hydrocarbon content in soil, calculate the clearance of polycyclic aromatic hydrocarbon, and average.
Such as table 1, often group arranges 2 Duplicate Samples；Orthogonal experiment results shows, ozone pretreatment can not be by degradable for soil polycyclic aromatic hydrocarbon, and ozone concentration is that the polycyclic aromatic hydrocarbon removal effect under the conditions of 1.74g/L is best, and in soil, the polycyclic aromatic hydrocarbon of 46.00% is removed.Further by 95% confidence interval or standardization effect normal state figure, response time and ozone concentration are the key factors affecting ozone pretreatment soil polycyclic aromatic hydrocarbon, i.e. the response time is the longest, and ozone pretreatment soil polycyclic aromatic hydrocarbon effect is the best；Ozone concentration is the highest, and ozone pretreatment soil polycyclic aromatic hydrocarbon effect is the best.
Tested by ozone pretreatment soil polycyclic aromatic hydrocarbon single-factor variable, analytical table 1, it can be deduced that to draw a conclusion:
1 after the ozone of three kinds of variable concentrations processes, and in 5min, the clearance of the total polycyclic aromatic hydrocarbon of soil is the highest, and respectively 11.01%, 32.48%, 34.65%；Along with logical ozonation time extends further, soil total polycyclic aromatic hydrocarbon clearance continues to increase, but increasing degree gradually slows down, and last polycyclic aromatic hydrocarbon concentration tends towards stability state.
After 2 ozone pretreatment 60min, soil total polycyclic aromatic hydrocarbon clearance is respectively 39.58%, 52.84%, 53.79%, and soil microorganism colony counts is respectively from the 3.07 × 10 of original soil8CFU/g is reduced to 1.73 × 106CFU/g、1.02×105CFU/g、1.49×103CFU/g。
3 ozone Financial cost aspects, consider from removal efficiency and micro organism quantity, increase with concentration, clearance increases, but the removal efficiency that 1.74 and 4.50mg/L ozone are after pretreatment 60min is more or less the same, on in the impact of micro organism quantity, the ozone of 4.50mg/L reduces 2 orders of magnitude than 1.74mg/L micro organism quantity.
Therefore, considering three factors such as polycyclic aromatic hydrocarbon clearance, micro organism quantity and ozone Financial cost, find that ozone concentration is suitable for the actual polycyclic aromatic hydrocarbon pollution in this coke-oven plant of pretreatment when 1.74mg/L, optimal pretreatment time is 5min.
Step 6, in reaction vessel 5, add biosurfactant: in reaction vessel 5, add biosurfactant, for realizing the solubilising of polycyclic aromatic hydrocarbon in slurry liquid；Wherein, kind and the concentration of biosurfactant are obtained by preliminary experiment, pass through experiment of single factor, change the kind of biosurfactant or concentration or the concentration of biosurfactant, adsorption effect is conciliate by analyzing critical micelle concentration, draw optimal kind and the optium concentration of biosurfactant, as the kind of biosurfactant and the concentration of reality application.The biosurfactant preferably gone out is saponin, the preferred 4g/L of its concentration 3～5g/L.
Biosurfactant preliminary experiment method particularly includes: use the biosurfactant of two kinds of industrialized production: the saponin of powder and the rhamnolipid of paste, test to determine optimal biosurfactant by desorption.Biosurfactant desorption experimental result shows, the desorption efficiency of saponin and rhamnolipid extends in time and is continuously increased, after continuing desorption 80h, 32h, desorption is in dynamic balance state, and after eventually passing through 5d desorption, the desorption efficiency of saponin and rhamnolipid is respectively 16.48%, 3.76%.Either desorption efficiency or desorption continuous action time, the saponin of same concentrations is better than rhamnolipid.In the experiment of this desorption, saponin concentration is 4g/L.
Step 7, in reaction vessel 5 add liquid culture medium: continue in reaction vessel 5, add the liquid culture medium rich in nutrient, the indigenous microorganism being contaminated in soil for enrichment culture；The preparation method of liquid culture medium is: take 10g tryptone, 5g yeast extract, 5gNaCl, 0.1g compound vitamin are substantially soluble in the deionized water of 800mL, add deionized water and be settled to 1L, adjust pH value to 7.0, put into high-pressure sterilizing pot, sterilizing 20 minutes at 121 DEG C, can use after natural cooling；This liquid culture medium is in ventilation or under conditions of vibration, it is possible to provide is conducive to the nutrition of growth of microorganism, thus improves indigenous microorganism quantity；
Step 8, carrying out combined degradation: carry out United Technologies degradation reaction in continuing reaction vessel 5 to be placed in water bath chader 6, the temperature range in water bath chader 6 is 30～38 DEG C, rotating speed is set to 150r/min～220r/min；
Step 9, period sampling measuring are until having repaired: be sampled week about, analyze the concentration remaining polycyclic aromatic hydrocarbon in slurry liquid, until the clearance of polycyclic aromatic hydrocarbon reaches stable, so far, the reparation of polycyclic aromatic hydrocarbon pollution completes.After testing, polycyclic aromatic hydrocarbon pollution sample in the present embodiment, the Combined Treatment total polycyclic aromatic hydrocarbon clearance after a week is 69.61%, the Combined Treatment total polycyclic aromatic hydrocarbon clearance after two weeks is 77.08%, the Combined Treatment total polycyclic aromatic hydrocarbon clearance after three weeks is 91.62%, and the total polycyclic aromatic hydrocarbon clearance after Combined Treatment surrounding is 93.26%；After surrounding, proceeding with Combined Treatment, total polycyclic aromatic hydrocarbon clearance almost no longer changes.
Pollutant polycyclic aromatic hydrocarbon in the soil to be repaired that this method relates to, is the most typical organic pollution in China's chemical products contaminated site soil.The repair system of the present invention and method with polycyclic aromatic hydrocarbons contaminated " aging " soil as object, deep for " aging " Pollution of Polycyclic Aromatic Hydrocarbons in Soil, the features such as pollution history is lasting, use with ozone pretreatment, biosurfactant solubilising enhancement microbiological degraded United Technologies fast and effeciently remove the polycyclic aromatic hydrocarbon in actual soil, the most domestic there is not yet relevant report, although abroad having ozone pretreatment, or the research of surface active agent solubilization etc., but there is not yet ozone pretreatment, report in the middle of repairing with microbial technology use in conjunction to actual polycyclic aromatic hydrocarbon pollution while of surface active agent solubilization.Repair for places polluted by polynuclear aromatic hydrocarbons is provided a kind of new technological reserve by the present invention.Develop efficiently, the combined remediation technology of low cost there is great Significance for Environment and economic implications, particularly significant for promoting the overall technology level that China repairs field at polycyclic aromatic hydrocarbon pollution.
Claims (9)
1. the system of an ozone pretreatment enhancement microbiological degraded repairing polluted soil, described contaminated soil is polycyclic aromatic hydrocarbon pollution, it is characterised in that: include ozone generating-device (1), reaction vessel (5) and the tail gas absorption bottle (7) sequentially connected by gas conduit (4)；The wet flow indicator (3) being provided with monitoring ozone flow on gas conduit (4) between described ozone generating-device (1) and reaction vessel (5) and the check-valves (2) avoiding ozone to reflux；Described reaction vessel (5) is placed in water bath chader (6)；The slurry liquid being mixed into equipped with polycyclic aromatic hydrocarbon pollution and deionized water in described reaction vessel (5), it can input with the container (9) of the container (8) containing biosurfactant and Sheng liquid culture medium container and be connected；Equipped with tail gas absorption liquid in described tail gas absorption bottle (7)；Described gas conduit (4) is the ozone proof silica gel tube of aging resistance；Described reaction vessel (5) is the standard-sized Drexel bottle of diameter d=70mm or h:d air-tightness vial between 4:1～6:1 at the bottom of height h=280mm, bottle.
The system of ozone pretreatment enhancement microbiological the most according to claim 1 degraded repairing polluted soil, it is characterised in that: in described reaction vessel (5), the deionized water of every 50g polycyclic aromatic hydrocarbon pollution corresponding 200～300mL.
The system of ozone pretreatment enhancement microbiological the most according to claim 1 degraded repairing polluted soil, it is characterised in that: the tail gas absorption liquid in described tail gas absorption bottle (7) is KI solution.
4. the method for the ozone pretreatment enhancement microbiological degraded repairing polluted soil that the system of the ozone pretreatment enhancement microbiological degraded repairing polluted soil that a kind utilizes described in claim 1～3 any one is carried out, described contaminated soil is polycyclic aromatic hydrocarbon pollution, it is characterized in that, comprise the following steps:
Step one, the collection of sample and pretreatment: gather by polycyclic aromatic hydrocarbons contaminated soil, In Shade air-dried, process of sieving after rejecting the impurity such as root system of plant and chad, place standby；
Step 2, preparation slurry liquid: accurately measure polycyclic aromatic hydrocarbon pollution sample and sterilizing deionized water, be placed in reaction vessel (5), be made into Tu Shui than the slurry liquid that scope is 1:4～1:6；
Step 3, the mixing of slurry liquid: be placed in water bath chader (6) by reaction vessel (5), open water bath chader (6), and temperature is 30～38 DEG C, and vibration 10～20min makes the slurry liquid mix homogeneously in reaction vessel (5)；
Step 4, assembly and connection repair system: be sequentially connected with ozone generating-device (1), reaction vessel (5) and tail gas absorption bottle (7) with gas conduit (4), wet flow indicator (3) and check-valves (2) is connected on gas conduit (4) between ozone generating-device (1) and wet flow indicator (3), for ensureing the air-tightness of system, appropriate vaseline is smeared in all joints, reaction vessel (5) is placed in water bath chader (6), dress tail gas absorption liquid in tail gas absorption bottle (7)；
Step 5, carry out ozone pretreatment: ozone concentration and the pretreatment time of pretreatment are set in ozone generating-device (1), open ozone generating-device (1) and water bath chader (6), in the slurry liquid of reaction vessel (5), it is passed through ozone carries out pretreatment, after pretreatment completes, close ozone generating-device (1)；
Step 6, add biosurfactant in the reaction vessel (5): in reaction vessel (5), add biosurfactant, the biosurfactant of every 50g polycyclic aromatic hydrocarbon pollution corresponding 0.5～1.5g, for realizing the solubilising of the polycyclic aromatic hydrocarbon in slurry liquid；
Step 7, add liquid culture medium in the reaction vessel (5): continue to add the liquid culture medium rich in nutrient in reaction vessel (5), the liquid culture medium of every 50g polycyclic aromatic hydrocarbon pollution corresponding 40～60mL, the indigenous microorganism being contaminated in soil for enrichment culture；
Step 8, carry out combined degradation: carrying out United Technologies degradation reaction in continuing to be placed in water bath chader (6) by reaction vessel (5), the temperature range in water bath chader (6) is 30～38 DEG C, concussion mixing；
Step 9, period sampling measuring are until having repaired: be sampled at set intervals, analyze the concentration remaining polycyclic aromatic hydrocarbon in slurry liquid, until the clearance of polycyclic aromatic hydrocarbon reaches stable, so far, the reparation of polycyclic aromatic hydrocarbon pollution completes.
The method of ozone pretreatment enhancement microbiological the most according to claim 4 degraded repairing polluted soil, it is characterized in that: in described step 5, the time of ozone pretreatment and the concentration of ozone are obtained by preliminary experiment, by changing time or the concentration of ozone of ozone pretreatment, analyze clearance and the number change of microorganism of polycyclic aromatic hydrocarbon in polycyclic aromatic hydrocarbon pollution, draw optium concentration and the Best Times of ozone pretreatment, as the concentration of ozone in actual ozone pretreatment and the pretreatment time of ozone.
The method of ozone pretreatment enhancement microbiological the most according to claim 4 degraded repairing polluted soil, it is characterised in that: in described step 5 ozone preprocessing process, the concentration of ozone is 1.70～1.80mg/L, and the time of ozone pretreatment is 3～6min.
The method of ozone pretreatment enhancement microbiological the most according to claim 4 degraded repairing polluted soil, it is characterized in that: in described step 6, kind and the concentration of biosurfactant are obtained by preliminary experiment, adsorption effect is conciliate by analyzing critical micelle concentration, draw optimal kind and the optium concentration of biosurfactant, as the kind of biosurfactant and the concentration of reality application.
The method of ozone pretreatment enhancement microbiological the most according to claim 4 degraded repairing polluted soil, it is characterised in that: in described step 6, biosurfactant is saponin, and its concentration is 3～5g/L.
The method of ozone pretreatment enhancement microbiological the most according to claim 4 degraded repairing polluted soil, it is characterized in that, in described step 7, the preparation method of liquid culture medium is: take 10g tryptone, 5g yeast extract, 5gNaCl, 0.1g compound vitamin are substantially soluble in the deionized water of 800mL, adding deionized water and be settled to 1L, regulation PH is 7.0, puts into high-pressure sterilizing pot, sterilizing 20 minutes at 121 DEG C, can use after natural cooling.
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| CN106140810B (en) * | 2015-04-02 | 2022-07-05 | 中环循环境技术有限责任公司 | Composite biological treatment system for repairing soil polluted by high-ring polycyclic aromatic hydrocarbon |
| CN108580543A (en) * | 2018-06-28 | 2018-09-28 | 四川省天晟源环保股份有限公司 | A kind of new-type mortar reactor and its operating method for soil remediation |
| CN112620342A (en) * | 2020-10-20 | 2021-04-09 | 广西博世科环保科技股份有限公司 | Method for synergistic remediation of soil polluted by high-ring polycyclic aromatic hydrocarbon by using biosurfactant |
| CN117236528B (en) * | 2023-11-15 | 2024-01-23 | 成都信息工程大学 | Ozone concentration forecasting method and system based on combined model and factor screening |
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