CN104492804A - System and method for repairing polluted soil by pre-processing through ozone and enhancing micro-biological degradation - Google Patents
System and method for repairing polluted soil by pre-processing through ozone and enhancing micro-biological degradation Download PDFInfo
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Abstract
The invention provides a system and a method for repairing polluted soil by pre-processing through ozone and enhancing micro-biological degradation; the polluted soil is polycyclic aromatic hydrocarbon polluted soil. The method provided by the invention comprises the following main repairing steps of: collecting and pre-processing a sample, preparing and uniformly mixing slurry, connecting to a repairing system, pre-processing through ozone, adding a biological surfactant and a liquid culture medium into a reaction container, and carrying out combination degradation and regular sampling and measuring till completing repairing. The system provided by the invention is simple to configure, convenient to operate and high in safety; aiming at the characteristics of being high in pollution degree of polycyclic aromatic hydrocarbon in soil, durable in pollution history, the micro-biological degradation combination technology is enhanced by adopting ozone pre-processing and biological surfactant solubilizing technologies; the limitation of the single technology is overcome; furthermore, the method provided by the invention is simple and convenient to operate, low in cost, short in operation period and good in eliminating effect; the eliminating rate of polycyclic aromatic hydrocarbon is above 93%; furthermore, secondary pollution cannot be generated; harm of polycyclic aromatic hydrocarbon polluted soil to human bodies and environments is greatly reduced; and a novel concept is provided for repairing soil.
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 reinforcing microorganism to degrade technology to repair polycyclic aromatic hydrocarbon pollution.
Background technology
Advance rapidly in industrialized process in China, the environment that the shortage due to people's environmental consciousness causes us to depend on for existence is subject to serious destruction, and soil also fails to escape by luck as mankind's natural resources lived of relying, and Soil Environmental Pollution problem is more and more sharp-pointed.Wherein, have strongly carcinogenic, teratogenesis, mutagenesis polycyclic aromatic hydrocarbon (Polycyclicaromatichydrocarbons, polycyclic aromatic hydrocarbon) contamination phenomenon very general.The Fushun Triratna that irrigated area is comforted in Shen collects four groups of rice terraces, because of more than 30 years petroleum waste waters irrigate form contaminated land of attaching most importance to, nineteen eighty-two records polycyclic aromatic hydrocarbon total amount up to 631.9mg/kg(topsoil 0 ~ 20cm), 602.95mg/kg(underearth 20 ~ 35cm).Except because of dirt fill with cause agricultural land soil be subject to polycyclic aromatic hydrocarbons contaminated except, be that primary raw material carries out the coal chemical industry enterprises of activity in production and coking enterprise is also that soil is subject to one of polycyclic aromatic hydrocarbons contaminated factor with coal, more and more place of being once engaged in similar activity in production has 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, the maximum detected level of benzo (a) pyrene exceeds standard 430 times, the polycyclic aromatic hydrocarbon pollution finally determined bulky to be repaired than Beijing " place soil environmental risk assessment screening value ".Consider that current nationwide has more than 1300 family's coking enterprises (not comprising illegal coking workshop), by 2008, the coal chemical enterprise of closing down because of a variety of causes reaches 1061, and smelting iron and steel enterprise (major part exists coking subsidiary factory) only makes superseded enterprise just reach 175, the polycyclic aromatic hydrocarbon pollution enormous amount that China need repair because production capacity falls behind for 2010 simultaneously.The reparation of polycyclic aromatic hydrocarbon pollution, utilizes the healthy and preventing secondary environmental pollution of resident in process to have great importance for the redevelopment of guarantee places polluted by polynuclear aromatic hydrocarbons.
At present, domestic and international polycyclic aromatic hydrocarbon pollution recovery technique mainly comprises physical technique, chemical technology and biotechnology.
Physical technique is the physical characteristic according to polycyclic aromatic hydrocarbon, utilize the method such as extraction, wash-out, adsorption and desorption by its from gas, liquid, solid mutually separate, quantities involved by this technology is large, costly, be applicable to little, the with serious pollution situation of contaminated area, the pollutant that this technology fails thoroughly to remove simultaneously can produce certain exposure to environment; Chemical technology mainly utilizes chemical agent (as strong oxidizer) and organic pollution that certain chemical reaction occurs, make that pollutant polycyclic aromatic hydrocarbon is degraded, toxicity is removed or reduce, it is better that this technology removes soil polycyclic aromatic hydrocarbon effect, but usually cause that soil texture destroys, biological activity of soil declines, soil fertility degeneration and produce secondary pollution; Biotechnology mainly refers to microbial technology, its rehabilitation cost is low, operational management simply, not produces secondary pollution, but in the biological prosthetic later stage, the degraded of pollutant is not obvious with the prolongation change of repair time, reparation enters " hangover " stage, substantially prolongs the time reaching and repair target, studies simultaneously and also find, for the contour ring polycyclic aromatic hydrocarbon of benzo [a] pyrene, biological prosthetic effect is unsatisfactory.
Summary of the invention
The object of the invention is the system and method providing a kind of ozone pretreatment reinforcing microorganism to degrade 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 easily causes that soil texture destroys, biologically active declines, Fertility Degeneration and produce the problem of secondary pollution, and the problem that biotechnology later stage speed of repairing slows down, overall repair time is long, low to the clearance of high ring polycyclic aromatic hydrocarbon, remediation efficiency is not high.
For realizing above-mentioned technical purpose, the present invention takes following technical scheme:
A system for ozone pretreatment reinforcing microorganism to degrade repairing polluted soil, described contaminated soil is polycyclic aromatic hydrocarbon pollution, it is characterized in that: comprise the ozone generating-device, reaction vessel and the tail gas absorption bottle that are communicated with in turn by gas conduit; Wet flow indicator gas conduit between described ozone generating-device and reaction vessel being provided with monitoring ozone flow and the check-valves avoiding ozone to reflux; Described reaction vessel is placed in water bath chader; The slurry liquid that polycyclic aromatic hydrocarbon pollution and deionized water are mixed into is housed in described reaction vessel, its with the container containing biosurfactant and the container containing liquid culture medium container can input and be connected; In described tail gas absorption bottle, tail gas absorption liquid is housed.
As preferred technical scheme, described gas conduit is anti-aging ozone proof silicone tube; Described reaction vessel is the standard-sized Drexel bottle of diameter d=70mm or the air-tightness vial of h:d between 4:1 ~ 6:1 at the bottom of height h=280mm, bottle.
Preferred further, in described reaction vessel, the deionized water of every 50g polycyclic aromatic hydrocarbon pollution correspondence 200 ~ 300mL.
Preferred, 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 200g KI (analyzing pure) and boil in 1000mL in the distilled water of rear cooling, be stored in refrigerator with brown bottle, at least to store after one day use again, every 1.00mL solution is containing 0.20g KI.
The invention still further relates to a kind of method of the ozone pretreatment reinforcing microorganism to degrade repairing polluted soil utilizing the system of above-mentioned ozone pretreatment reinforcing microorganism to degrade repairing polluted soil to carry out, described contaminated soil is polycyclic aromatic hydrocarbon pollution, comprises the following steps:
The collection of step one, sample and pretreatment: gather by polycyclic aromatic hydrocarbons contaminated soil, In Shade air-dry, process of sieving after rejecting the impurity such as root system of plant and chad, places for subsequent use;
Step 2, preparation slurry liquid: correct amount amount polycyclic aromatic hydrocarbon pollution sample and sterilizing deionized water, be placed in reaction vessel, and being made into Tu Shui than scope is the slurry liquid of 1:4 ~ 1:6;
The mixing of step 3, slurry liquid: reaction vessel is placed in water bath chader, open water bath chader, temperature is 30 ~ 38 DEG C, and vibration 10 ~ 20min, makes the slurry liquid in reaction vessel mix;
Step 4, assembly and connection repair system: connect ozone generating-device, reaction vessel and tail gas absorption bottle in turn with gas conduit, gas conduit between ozone generating-device and wet flow indicator connects wet flow indicator and check-valves, reaction vessel is placed in water bath chader, in tail gas absorption bottle, fills tail gas absorption liquid;
Step 5, carry out ozone pretreatment: pretreated ozone concentration and pretreatment time are set in ozone generating-device, open ozone generating-device and water bath chader, in the slurry liquid of reaction vessel, pass into ozone carry out pretreatment, after pretreatment completes, close ozone generating-device;
Step 6, in reaction vessel, add biosurfactant: in reaction vessel, add biosurfactant, the biosurfactant of every 50g polycyclic aromatic hydrocarbon pollution correspondence 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 being rich in nutrient, the liquid culture medium of every 50g polycyclic aromatic hydrocarbon pollution correspondence 40 ~ 60mL, for the indigenous microorganism in the contaminated soil of enrichment culture;
Step 8, carry out combined degradation: continued to be placed in water bath chader by reaction vessel and carry out United Technologies degradation reaction, the temperature range in water bath chader is 30 ~ 38 DEG C, concussion mixing;
Step 9, period sampling measuring are until repaired: sample week about, and 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 concentration of ozone pretreated time and ozone is obtained by preliminary experiment, by experiment of single factor, change the concentration of ozone pretreated time or ozone, analyze the clearance of polycyclic aromatic hydrocarbon and the number change of microorganism in polycyclic aromatic hydrocarbon pollution, draw the pretreated optium concentration of ozone and Best Times, as the concentration of ozone and the pretreatment time of ozone in actual ozone pretreatment.
Preferred further, in described step 5 ozone preprocessing process, the concentration of ozone is 1.70 ~ 1.80mg/L, and the ozone pretreated time 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 the concentration of concentration or biosurfactant, conciliating adsorption effect by analyzing critical micelle concentration, drawing best kind and the optium concentration of biosurfactant, as kind and the concentration of the biosurfactant of practical 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: get 10g tryptone, 5g yeast extract, 5gNaCl, 0.1g B B-complex be fully dissolved in the deionized water of 800mL, add deionized water again and be settled to 1L, adjust pH to 7.0, put into high-pressure sterilizing pot, sterilizing 20 minutes at 121 DEG C, can use after naturally cooling.According to this kind of weight, can be widely used in actual soil remediation engineering.
Compared with prior art, the present invention has following technical advantage:
1, the limitation of monotechnics is effectively overcome: take polycyclic aromatic hydrocarbon pollution as object, take full advantage of ozone pretreatment, the strengthening of biosurfactant solubilising and being combined of 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, and polycyclic aromatic hydrocarbon wash-out from soil out, is improved its bioavailability, to promote biodegradation; And compare chemical surfactant, natural biological surfactant has many good qualities, as hypotoxicity, high biological degradability, good environment compatibility, therefore, natural biological surfactant is used for environment remediation, can not secondary pollution be brought, and the solubilization of expection can be reached.
2, easy and simple to handle, with low cost, removal effect is good, and the cycle of operation is short, does not produce secondary pollution;
3, the liquid culture medium being rich in nutrient is adopted, this liquid culture medium is in ventilation or under the condition of vibration, the nutrition being beneficial to growth of microorganism can be provided, thus the indigenous microorganism in further this polycyclic aromatic hydrocarbon pollution of enrichment culture, reinforcing microorganism to degrade ability, improves the degradation efficiency of polycyclic aromatic hydrocarbon further.
To sum up, the advantage of the comprehensive recovery technique not of the same race of the present invention, ozone pretreatment, biosurfactant solubilization technique and microbial degradation three kinds of monotechnicses are joined together, shorten the cycle of operation to greatest extent, control secondary pollution, save rehabilitation expense, effectively raise the clearance of polycyclic aromatic hydrocarbon in chemical products contaminated soil, especially high ring polycyclic aromatic hydrocarbon.
Accompanying drawing explanation
Fig. 1 is the overall structure schematic diagram of the system of the ozone pretreatment reinforcing microorganism to degrade repairing polluted soil that the present invention relates to;
Fig. 2 is the schematic flow sheet of the method for the ozone pretreatment reinforcing microorganism to degrade repairing polluted soil that the present invention relates to.
Reference numeral: 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 accompanying drawing, content of the present invention is made further explanation and description.
The confession examination soil of the present embodiment method is the soil on certain manufacturing enterprise of comprehensive coke-oven plant contaminated site, this enterprise take coal as primary raw material, coal gas, coke and Coal Chemical Industry product is produced the fifties from last century, in its each workshop of this enterprise, the imperfect combustion of fossil fuel and the process 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 retained for more than 50 years in the soil of place, was typical polycyclic aromatic hydrocarbons contaminated " aging " soil.When according to the flow process in present system and method and fixing material proportion constant, namely can be applicable to after expansion doses in the reparation of large-scale polycyclic aromatic hydrocarbon pollution.
First detect 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, adds 8.00gNa
2sO
4(impurity metal oxide is removed with rare HCI washing that volume fraction is 10% with 0.28g copper powder, then distilled water cyclic washing is used until aobvious acid, use methyl alcohol and n-hexane again) grind dehydration and mix, divide and add 16mL, 12mL, 12mL carrene respectively 3 times: the mixing organic extractant of acetone (1:1) (v/v), each ultrasonic extraction 20min(power 70%); Collect extract, fully under Rotary Evaporators, be concentrated into about 1mL after mixing, then add 4mL n-hexane, ultrasonic extraction 10min(power 70%); Cross silica gel column chromatography, collect eluent, nitrogen purges and is concentrated into 1mL, crosses 0.45 μm of organic phase 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 to 290 DEG C of 15 DEG C/min, stops 5min; Injector temperature 250 DEG C, Splitless injecting samples, sample size 1 μ L; 200 DEG C, EI source, electron energy 70eV, detects voltage 350V, transmission line temperature 250 DEG C.
Content after measured for polycyclic aromatic hydrocarbon total in examination pedotheque is 4452.19 ± 394.11mg/kg.
Be illustrated in figure 1 the system of the ozone pretreatment reinforcing microorganism to degrade repairing polluted soil that the present invention relates to, the direction of arrow is stream of ozone direction, and it comprises the ozone generating-device 1, reaction vessel 5 and the tail gas absorption bottle 7 that are communicated with in turn by gas conduit 4; The wet flow indicator 3 gas conduit 4 between described ozone generating-device 1 and reaction vessel 5 being provided with monitoring ozone concentration and the check-valves 2 avoiding ozone to reflux; Described reaction vessel 5 is placed in water bath chader 6; The slurry liquid that polycyclic aromatic hydrocarbon pollution and deionized water are mixed into is housed in described reaction vessel 5, its with the container 8 containing biosurfactant and the container 9 containing liquid culture medium container can input and be connected, the deionized water of every 50g polycyclic aromatic hydrocarbon pollution correspondence 200 ~ 300mL when slurry liquid configures; In described tail gas absorption bottle 7, tail gas absorption liquid is housed, tail gas absorption liquid is KI solution, its effect is that residual exhaust passes into the recovery of KI solution, prevention ozone tail gas overflows the secondary pollution that may cause, concentration is 200g/L, concrete configuration method is: dissolve 200g KI (analyzing pure) and boil in 1000mL in the distilled water of rear cooling, be stored in refrigerator with brown bottle, use after at least storing one day again.This solution 1.00mL is containing 0.20g KI.
In this system, ozone generating-device 1, check-valves 2, wet flow indicator 3 and gas conduit 4, together constitute the pretreated air supply system of ozone; The inlet gas ozone concentration of ozone generating-device 1 is by arranging ozone charge flow rate and regulating operating current to set; Check-valves 2 is ozone self flowing that relies on ozone generating-device 1 to produce and automatic open and close flap, is used for the valve preventing ozone from flowing backwards; Wet flow indicator 3 can ozone volume in the assaying reaction phase, and then calculates ozone concentration by iodine number chemical method; Gas conduit 4 adopts anti-aging ozone proof silicone tube, plays the effect of transmission ozone gas.
Reaction vessel 5 is placed in water bath chader 6, constitutes main body reaction system; Reaction vessel 5 is by selecting Drexel bottle after many experiments screening verification, Drexel bottle is of a size of h=280mm, d=7mm, the slender structure of Drexel bottle, make it can ensure to transmit the gas conduit 4 of ozone deeply to the middle and lower part of the reaction vessel slurry liquid water surface as reaction vessel, at utmost can ensure that ozone and slurry liquid are fully reacted; And the airtight performance of Drexel bottle is better than general vial; Place the reaction vessel having installed slurry liquid 1:5 Tu Shui ratio in water bath chader 6, adjusting rotary speed is the maximum (top) speed 220r/min of water bath chader, to guarantee that the slurry liquid in reaction vessel mixes.Water bath chader 6 can be placed multiple reaction vessel simultaneously and carry out United Technologies process, can guarantee that the operating mode of each reaction vessel is consistent, make result have comparativity.
The present invention also provides a kind of method of the ozone pretreatment reinforcing microorganism to degrade repairing polluted soil utilizing the system of above-mentioned ozone pretreatment reinforcing microorganism to degrade repairing polluted soil to carry out, wherein contaminated soil is polycyclic aromatic hydrocarbon pollution, comprises the following steps:
The collection of step one, sample and pretreatment: gather by polycyclic aromatic hydrocarbons contaminated soil, In Shade air-dry, process of sieving after rejecting the impurity such as root system of plant and chad, obtains the soil particle that particle diameter is not more than 5mm, is preferably not more than 2mm; Place for subsequent use;
Step 2, preparation slurry liquid: correct amount amount polycyclic aromatic hydrocarbon pollution sample and sterilizing deionized water, be placed in reaction vessel 5, and being made into Tu Shui than scope is the slurry liquid of 1:4 ~ 1:6;
The mixing of step 3, slurry liquid: reaction vessel 5 is placed in water bath chader 6, open water bath chader 6, adjusting rotary speed is 150r/min ~ 220r/min, and temperature is 30 ~ 38 DEG C, and vibration 10 ~ 20min, makes the slurry liquid in reaction vessel 5 mix;
Step 4, assembly and connection repair system: connect ozone generating-device 1, reaction vessel 5 and tail gas absorption bottle 7 in turn with gas conduit 4, gas conduit 4 between ozone generating-device 1 and wet flow indicator 3 connects wet flow indicator 3 and check-valves 2, for ensureing the air-tightness of system, appropriate vaseline is smeared in all joints, reaction vessel 5 is placed in water bath chader 6, in tail gas absorption bottle 7, fills tail gas absorption liquid;
Step 5, carry out ozone pretreatment: pretreated ozone concentration and pretreatment time 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, pass into ozone carry out pretreatment, after pretreatment completes, close ozone generating-device 1, wherein, the concentration of ozone pretreated time and ozone is obtained by preliminary experiment, pass through experiment of single factor, change the concentration of ozone pretreated time or ozone, analyze the clearance of polycyclic aromatic hydrocarbon and the number change of microorganism in polycyclic aromatic hydrocarbon pollution, draw the pretreated optium concentration of ozone and Best Times, as the concentration of ozone and the pretreatment time of ozone in actual ozone pretreatment, the concentration of ozone is 1.70 ~ 1.80mg/L, the ozone pretreated time is 3 ~ 6min, the concentration of the ozone that optimum is selected is 1.74mg/L, the ozone pretreated time is 5min,
Concrete Pre-testing procedure is as follows:
The factorial experiment of ozone pretreatment factor of influence, assesses two the factor of influence ozone concentrations and reaction time affecting course of reaction, for subsequent experimental explores more excellent reaction condition.The three group experiments of ozone under 0.79,1.74 and 4.50mg/L tri-kinds of variable concentrations are set respectively, specifically arranging that often group is tested is as follows: arranging ozone charge flow rate is 14.6L/min, regulate operating current setting inlet gas ozone concentration, water bath chader temperature 35 DEG C, rotating speed 220r/min are set; Question response plant running is stablized, place in water bath chader by being equipped with the reaction vessel that slurry liquid is mixed by 50.00g Polluted Soil and 250.00mL sterilizing deionized water, connect wireway and pass into ozone to slurry liquid, residual exhaust passes into KI solution and reclaims, by titration measuring ozone residual concentration; Respectively 5,10,20,30,40,50,60min place respectively gets two Duplicate Samples analyses, measure remaining polycyclic aromatic hydrocarbon content in soil, calculate the clearance of polycyclic aromatic hydrocarbon, and average.
As table 1, often group arranges 2 Duplicate Samples; Orthogonal experiment results shows, and ozone pretreatment can not by degradable for soil polycyclic aromatic hydrocarbon, and ozone concentration is that the polycyclic aromatic hydrocarbon removal effect under 1.74g/L condition is best, and in soil, the polycyclic aromatic hydrocarbon of 46.00% is removed.Further by 95% confidential interval or standardization effect normal state figure known, reaction time and ozone concentration are the key factors affecting ozone pretreatment soil polycyclic aromatic hydrocarbon, and namely the reaction time is longer, and ozone pretreatment soil polycyclic aromatic hydrocarbon effect is better; Ozone concentration is higher, and ozone pretreatment soil polycyclic aromatic hydrocarbon effect is better.
By the test of ozone pretreatment soil polycyclic aromatic hydrocarbon single-factor variable, analytical table 1, can draw to draw a conclusion:
1 after the ozone treatment of three kinds of variable concentrations, and in 5min, the clearance of the total polycyclic aromatic hydrocarbon of soil is the highest, is respectively 11.01%, 32.48%, 34.65%; Along with logical ozonation time extends further, the total polycyclic aromatic hydrocarbon clearance of soil continues to increase, but increasing degree slows down gradually, and last polycyclic aromatic hydrocarbon concentration tends towards stability state.
After 2 ozone pretreatment 60min, the total polycyclic aromatic hydrocarbon clearance of soil is respectively 39.58%, 52.84%, 53.79%, and edaphon colony counts is respectively from 3.07 × 10 of original soil
8cFU/g is reduced to 1.73 × 10
6cFU/g, 1.02 × 10
5cFU/g, 1.49 × 10
3cFU/g.
3 ozone financial cost aspects, consider from removal efficiency and micro organism quantity, increase with concentration, clearance increases, but 1.74 and the removal efficiency of 4.50mg/L ozone after pretreatment 60min be 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, consider three factors such as polycyclic aromatic hydrocarbon clearance, micro organism quantity and ozone financial cost, find that ozone concentration is applicable to the actual polycyclic aromatic hydrocarbon pollution in this coke-oven plant of pretreatment when 1.74mg/L, best pretreatment time is 5min.
Step 6, in reaction vessel 5, add biosurfactant: in reaction vessel 5, add biosurfactant, for realizing the solubilising of the 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 the concentration of concentration or biosurfactant, adsorption effect is conciliate by analyzing critical micelle concentration, draw best kind and the optium concentration of biosurfactant, as kind and the concentration of the biosurfactant of practical application.The biosurfactant optimized is saponin, the preferred 4g/L of its concentration 3 ~ 5g/L.
The concrete grammar of biosurfactant preliminary experiment is: the biosurfactant adopting two kinds of suitability for industrialized production: the rhamnolipid of pulverous saponin and paste, tests to determine best biosurfactant by desorption.Biosurfactant desorption experimental result shows, the desorption efficiency of saponin and rhamnolipid extends in time and constantly increases, 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%.No matter be 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, to add the liquid culture medium being rich in nutrient, for the indigenous microorganism in the contaminated soil of enrichment culture; The preparation method of liquid culture medium is: get 10g tryptone, 5g yeast extract, 5gNaCl, 0.1g B B-complex be fully dissolved in the deionized water of 800mL, add deionized water again and be settled to 1L, adjust pH to 7.0, put into high-pressure sterilizing pot, sterilizing 20 minutes at 121 DEG C, can use after naturally cooling; This liquid culture medium, in ventilation or under the condition of vibration, can provide the nutrition being beneficial to growth of microorganism, thus improves indigenous microorganism quantity;
Step 8, carry out combined degradation: continued to be placed in water bath chader 6 by reaction vessel 5 and carry out United Technologies degradation reaction, 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 repaired: sample week about, and 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 total polycyclic aromatic hydrocarbon clearance of Combined Treatment after one week is 69.61%, the total polycyclic aromatic hydrocarbon clearance of Combined Treatment after two weeks is 77.08%, the total polycyclic aromatic hydrocarbon clearance of Combined Treatment after three weeks is 91.62%, and the total polycyclic aromatic hydrocarbon clearance after Combined Treatment surrounding is 93.26%; After surrounding, with the proceeding of 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.Repair system of the present invention and method with polycyclic aromatic hydrocarbons contaminated " aging " soil for object, deep for " aging " Pollution of Polycyclic Aromatic Hydrocarbons in Soil, the features such as pollution history is lasting, adopt with ozone pretreatment, biosurfactant solubilising reinforcing microorganism to degrade United Technologies fast and effeciently remove the polycyclic aromatic hydrocarbon in actual soil, domesticly at present there is not yet relevant report, although have ozone pretreatment abroad, or the research of surface active agent solubilization etc., but there is not yet ozone pretreatment, report in the middle of repairing to actual polycyclic aromatic hydrocarbon pollution with microbial technology use in conjunction 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 combined remediation technology that is efficient, low cost and there is great Significance for Environment and economic implications, very important in the overall technology level in polycyclic aromatic hydrocarbon pollution reparation field for promoting China.
Claims (10)
1. the system of an ozone pretreatment reinforcing microorganism to degrade repairing polluted soil, described contaminated soil is polycyclic aromatic hydrocarbon pollution, it is characterized in that: comprise the ozone generating-device (1), reaction vessel (5) and the tail gas absorption bottle (7) that are communicated with in turn by gas conduit (4); The wet flow indicator (3) gas conduit (4) between described ozone generating-device (1) and reaction vessel (5) being provided with monitoring ozone flow and the check-valves (2) avoiding ozone to reflux; Described reaction vessel (5) is placed in water bath chader (6); The slurry liquid that polycyclic aromatic hydrocarbon pollution and deionized water are mixed into is housed in described reaction vessel (5), its with the container (8) containing biosurfactant and the container (9) containing liquid culture medium container can input and be connected; In described tail gas absorption bottle (7), tail gas absorption liquid is housed.
2. the system of ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 1, is characterized in that: described gas conduit (4) is anti-aging ozone proof silicone tube; Described reaction vessel (5) is the standard-sized Drexel bottle of diameter d=70mm or the air-tightness vial of h:d between 4:1 ~ 6:1 at the bottom of height h=280mm, bottle.
3. the system of ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 1, is characterized in that: in described reaction vessel (5), the deionized water of every 50g polycyclic aromatic hydrocarbon pollution correspondence 200 ~ 300mL.
4. the system of ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 1, is characterized in that: the tail gas absorption liquid in described tail gas absorption bottle (7) is KI solution.
5. the method for the ozone pretreatment reinforcing microorganism to degrade repairing polluted soil utilizing the system of the ozone pretreatment reinforcing microorganism to degrade repairing polluted soil described in claim 1 ~ 4 any one to carry out, described contaminated soil is polycyclic aromatic hydrocarbon pollution, it is characterized in that, comprise the following steps:
The collection of step one, sample and pretreatment: gather by polycyclic aromatic hydrocarbons contaminated soil, In Shade air-dry, process of sieving after rejecting the impurity such as root system of plant and chad, places for subsequent use;
Step 2, preparation slurry liquid: correct amount amount polycyclic aromatic hydrocarbon pollution sample and sterilizing deionized water, be placed in reaction vessel (5), and being made into Tu Shui than scope is the slurry liquid of 1:4 ~ 1:6;
The mixing of step 3, slurry liquid: reaction vessel (5) is placed in water bath chader (6), open water bath chader (6), temperature is 30 ~ 38 DEG C, and vibration 10 ~ 20min, makes the slurry liquid in reaction vessel (5) mix;
Step 4, assembly and connection repair system: connect ozone generating-device (1), reaction vessel (5) and tail gas absorption bottle (7) in turn with gas conduit (4), gas conduit (4) between ozone generating-device (1) and wet flow indicator (3) connects wet flow indicator (3) and check-valves (2), 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: pretreated ozone concentration and pretreatment time 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), pass into ozone carry out pretreatment, after pretreatment completes, close ozone generating-device (1);
Step 6, add biosurfactant in reaction vessel (5): in reaction vessel (5), add biosurfactant, the biosurfactant of every 50g polycyclic aromatic hydrocarbon pollution correspondence 0.5 ~ 1.5g, for realizing the solubilising of the polycyclic aromatic hydrocarbon in slurry liquid;
Step 7, add liquid culture medium in reaction vessel (5): continue in reaction vessel (5), add the liquid culture medium being rich in nutrient, the liquid culture medium of every 50g polycyclic aromatic hydrocarbon pollution correspondence 40 ~ 60mL, for the indigenous microorganism in the contaminated soil of enrichment culture;
Step 8, carry out combined degradation: continued to be placed in water bath chader (6) by reaction vessel (5) and carry out United Technologies degradation reaction, the temperature range in water bath chader (6) is 30 ~ 38 DEG C, concussion mixing;
Step 9, period sampling measuring are until repaired: sample at set intervals, and 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.
6. the method for ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 5, it is characterized in that: in described step 5, the concentration of ozone pretreated time and ozone is obtained by preliminary experiment, by changing the concentration of ozone pretreated time or ozone, analyze the clearance of polycyclic aromatic hydrocarbon and the number change of microorganism in polycyclic aromatic hydrocarbon pollution, draw the pretreated optium concentration of ozone and Best Times, as the concentration of ozone and the pretreatment time of ozone in actual ozone pretreatment.
7. the method for ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 5, it is characterized in that: in described step 5 ozone preprocessing process, the concentration of ozone is 1.70 ~ 1.80mg/L, and the ozone pretreated time is 3 ~ 6min.
8. the method for ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 5, 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 best kind and the optium concentration of biosurfactant, as kind and the concentration of the biosurfactant of practical application.
9. the method for ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 5, it is characterized in that: in described step 6, biosurfactant is saponin, and its concentration is 3 ~ 5g/L.
10. the method for ozone pretreatment reinforcing microorganism to degrade repairing polluted soil according to claim 5, it is characterized in that, in described step 7, the preparation method of liquid culture medium is: get 10g tryptone, 5g yeast extract, 5gNaCl, 0.1g B B-complex be fully dissolved in the deionized water of 800mL, add deionized water again and be settled to 1L, regulate PH to be 7.0, put into high-pressure sterilizing pot, sterilizing 20 minutes at 121 DEG C, can use after naturally cooling.
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