CN107470339A - The method and system of polycyclic aromatic hydrocarbon pollution is repaired in class Fenton and microorganism combination - Google Patents

The method and system of polycyclic aromatic hydrocarbon pollution is repaired in class Fenton and microorganism combination Download PDF

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Publication number
CN107470339A
CN107470339A CN201710917281.0A CN201710917281A CN107470339A CN 107470339 A CN107470339 A CN 107470339A CN 201710917281 A CN201710917281 A CN 201710917281A CN 107470339 A CN107470339 A CN 107470339A
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CN
China
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aromatic hydrocarbon
polycyclic aromatic
contaminated soil
soil
porous foam
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CN201710917281.0A
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Chinese (zh)
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张小梅
吴娟
马东
柴超
郑永权
柳修楚
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青岛农业大学
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Priority to CN201710917281.0A priority Critical patent/CN107470339A/en
Publication of CN107470339A publication Critical patent/CN107470339A/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes

Abstract

The method and system of polycyclic aromatic hydrocarbon pollution is repaired in one species Fenton and microorganism combination, and this method comprises the following steps:(1)Charcoal bag is covered into porous foam iron subparticle and is sprinkled into polluted soil with sodium perborate or the mixture of carbamide peroxide and citrate;(2)Hydrogen peroxide solution is uniformly sprayed into polluted soil, is enriched with and removes polycyclic aromatic hydrocarbon pollutant, reclaims foamed iron subparticle;(3)Plastc ring is sprayed into polluted soil.The system includes material-strewing device and retracting device;Material-strewing device includes spreading track conveyor and spreading fixed mount, and mixture hopper, hydrogen peroxide solution storage tank and shower nozzle are provided with spreading fixed mount;Retracting device includes recovery track conveyor and recovery fixed mount, reclaims and is provided with magnetic retracting device, accumulator tank, plastc ring storage tank and shower nozzle on fixed mount.Process of the present invention is simple, and cost is low, and sustainability is strong, avoids the destruction to edaphon and organic matter, the risk of non-secondary pollution.

Description

The method and system of polycyclic aromatic hydrocarbon pollution is repaired in class Fenton and microorganism combination

Technical field

It is used to repair the method by polycyclic aromatic hydrocarbons contaminated soil the present invention relates to a kind of, belongs to contaminated soil remediation skill Art field.

Background technology

Polycyclic aromatic hydrocarbon has carcinogenic, teratogenesis, a mutagenesis characteristic, hydrophobicity it is strong and it is extremely difficult be degraded by microorganisms, therefore in richness It is widely present in soil containing organic matter, the polycyclic aromatic hydrocarbon in soil accounts for more than the ninety percent of its all environment gross reserves.With work The quickening of industry process, a large amount of of polycyclic aromatic hydrocarbon use and discharged, and the content of PAHs in soil is constantly accumulated, to the mankind Health and ecological environment cause great threat, repair polycyclic aromatic hydrocarbon pollution as the research heat in ecological environment field Point.

The restorative procedure of polycyclic aromatic hydrocarbon pollution mainly has physics, chemistry, biological three major types.Common Physical has gas Mutually extracting, thermal desorption etc., this kind of method is higher to the low ring polycyclic aromatic hydrocarbon repair process efficiency of high volatile, but can destroy soil Structure, and energy consumption and cost are higher, practicality is not strong.Chemistry, the biological renovation method of polycyclic aromatic hydrocarbon pollution use more Extensively, common chemical restoration has chemical leaching, chemical oxidation etc., has the advantages that cost is low, treating capacity is big, quick, But secondary pollution may be caused, thereby increases and it is possible to which irreversible destruction is caused to soil texture and composition.Bioremediation technology has plant Reparation and microorganism remediation, there is low, the environment-friendly advantage of rehabilitation cost, but repairing efficiency is longer.

In recent years, Fenton (or class Fenton) oxidizing process, which repairs polycyclic aromatic hydrocarbon pollution, turns into soil chemistry reparation field One focus.The principle of Fenton (or class Fenton) oxidizing process is that the reaction based on ferrous iron and hydrogen peroxide forms strong oxidizer hydroxyl The principle of free radical carrys out Quick Oxidation decomposing organic pollutant.But during contaminated soil remediation, due to answering for soil constitution Polygamy, low mass transfer, this method still suffer from many bottlenecks urgently to be resolved hurrily.First, divalence source of iron, oxidation reaction needs stabilization, held Continuous ferrous iron source is to ensure its sustainability;Second, the concentration and stability problem of hydrogen peroxide, the too high meeting of hydrogen peroxide concentration Irreversible destruction is caused to edaphon and organic matter, too low, oxidability dies down, and hydrogen peroxide itself is easy to send out Raw decomposition production oxygen and water;Third, secondary pollution problem caused by soil remediation.

At present, repair the technology of polycyclic aromatic hydrocarbon polluted farmland soil have it is a variety of.As Chinese patent literature CN10155943 is public Open《Plants interplanting method for continuous repair polycyclic aromatic hydrocarbon polluted farmland soil in situ》, disclosed in CN101947542A 《The method for repairing polycyclic aromatic hydrocarbon polluted farmland soil using ganoderma lucidum and interplanting corn》, disclosed in CN10129140140《One kind is used In the agricultural method for repairing polycyclic aromatic hydrocarbon polluted farmland soil》, disclosed in CN103691734A《Live on a kind of cloudy-non-mixed surface Property rye grass is strengthened in agent, rhizosphere microorganism repairs the method for polycyclic aromatic hydrocarbon polluted farmland soil》And CN1017975141A is public Open《A kind of ecological method for repairing polycyclic aromatic hydrocarbon polluted farmland soil》.These methods are repaired by Planting Crops Polycyclic aromatic hydrocarbons contaminated agricultural land soil, though not producing secondary pollution, repairing efficiency is long, remediation efficiency is low, and labor intensity is big, When repairing by polycyclic aromatic hydrocarbons contaminated agricultural land soil, there is certain limitation.

It can be seen that a kind of cleaning of exploitation, polycyclic aromatic hydrocarbon pollution restorative procedure pole efficiently, inexpensive are necessary.

The content of the invention

For secondary pollution existing for existing polycyclic aromatic hydrocarbon pollution recovery technique, efficiency is low, cost is high the defects of, this Invention proposes that a kind of good repairing effect, efficiency high, cost are low, will not secondary pollution class Fenton and microorganism combination repair it is polycyclic The method of aromatic hydrocarbons contaminated soil, while a kind of system for realizing this method is provided.

The method that polycyclic aromatic hydrocarbon pollution is repaired in the class Fenton of the present invention and microorganism combination, comprises the following steps:

(1) charcoal bag is covered into porous foam iron subparticle and sodium perborate or carbamide peroxide and citrate (citric acid Sodium or potassium citrate) powder is 70-90 in mass ratio:5-15:5-15 ratio is well mixed, with resulting mixture, by mixture Polluted soil uniformly is sprinkled into, every kilogram of contaminated soil is sprinkled into mixture 20-60g;

(2) ratio that the hydrogen peroxide solution that mass concentration is 0.05% is sprayed in every kilogram of contaminated soil to 40-100mL is equal Even penetrating polluted soil, by absorption, light electrolysis and redox, the polycyclic aromatic hydrocarbon pollutant in soil is enriched with simultaneously Remove;Charcoal bag is covered the recovery of porous foam iron subparticle by pollutant in soil by after fully degraded 5-8 days;

(3) will oxidation microbacterium (Microbacterium oxydans) Ji 2 and Rhodococcus sp (Rhodococcus sp.) Lxb-6 bacteria suspension by volume 1:1-1:Plastc ring is made in 3 compound proportion, and is sprayed by every kilogram of contaminated soil 20-60mL ratio uniform sprays into polluted soil, the side that the polycyclic aromatic hydrocarbon still residued in soil is passed through into microbial degradation Formula removes.

Oxidation 2 and Rhodococcus sp lxb-6 of microbacterium Ji is purchased from China Committee for Culture Collection of Microorganisms's commonly micro- life Thing center, deposit number are respectively CGMCC NO.9072 and CGMCC No.3715.

Charcoal bag covers the preparation method of porous foam iron subparticle in the step (1), is:

According to the ratio of 1-2.5g glucose, 5-15g porous foam iron subparticles and 40mL water, first glucose is dissolved Yu Shuizhong, glucose solution is made, then porous foam iron subparticle is put into glucose solution, be made into mixed liquor;Will be upper State mixed liquor to be placed in hydrothermal reaction kettle, heat 2-6 hours at 120-180 DEG C, take porous foam iron subparticle after reaction Go out, dried after being washed with deionized, that is, charcoal bag is made and covers porous foam iron subparticle.

The particle diameter of the porous foam iron subparticle is 200-500 microns.

In the step (3), the preparation method of 2 or Rhodococcus sp lxb-6 of oxidation microbacterium Ji bacteria suspension, it is:

Fermented and cultured is carried out to logarithmic phase to oxidation microbacterium or Rhodococcus sp, abandoning supernatant after centrifugation, adds phosphate Buffer solution is washed, and supernatant is abandoned after centrifuging again, is collected thalline and is resuspended in it in phosphate buffer respectively, to every milliliter Contain viable bacteria 10 in buffer solution5~106It is individual, obtain lucky 2 bacteria suspensions of oxidation microbacterium or Rhodococcus sp lxb-6 bacteria suspensions.

In the step (3), as polycyclic aromatic hydrocarbon content≤0.6mg/kg in contaminated soil, every kilogram of contaminated soil sprays Plastc ring 20-40mL;In contaminated soil during polycyclic aromatic hydrocarbon content > 0.6mg/kg, every kilogram of contaminated soil sprays Mixed Microbes Suspension 40-60mL.

In the step (3), when in contaminated soil >=4 ring high ring polycyclic aromatic hydrocarbon mass fraction >=50% when, oxidation 2 and Rhodococcus sp lxb-6 of microbacterium Ji bacteria suspension by volume 1:2-1:Plastc ring is made in 3 compound proportion;Work as pollution In soil during the mass fraction > 50% of the low ring polycyclic aromatic hydrocarbon of the rings of < 4,2 and Rhodococcus sp lxb-6 of oxidation microbacterium Ji bacterium is hanged Liquid by volume 1:1-1:Plastc ring is made in 2 compound proportion.

The principle that handles contaminated soil of the above method of the present invention is:

Porous foam iron subparticle is covered as source of iron using charcoal bag, due to the layer of charcoal of porous foam iron external sheath have compared with Strong hydrophobicity, after charcoal bag covers porous foam iron subparticle input polycyclic aromatic hydrocarbon pollution, charcoal bag covers porous foam Iron subparticle in soil electrolyte solution can a large amount of hydrophobic polycyclic aromatic hydrocarbon pollutant of adsorption and enrichment, by itself and soil Electrolyte solution separates;A large amount of miniature galvanic cells are formed between the iron and charcoal on porous foam iron subparticle surface simultaneously, Iron is constantly oxidized to ferrous ion as galvanic cell anode and slowly released during micro-electrolysis reaction, with applying soil The hydrogen peroxide of earth forms Fenton oxidation system, will be adsorbed in the ironing surface polycyclic aromatic hydrocarbon pollutant oxidation Decomposition of porous foam and goes Remove;The polycyclic aromatic hydrocarbon still residued in soil, is further degraded by polycyclic aromatic hydrocarbon-degrading bacteria;Aoxidize lucky 2 Hes of microbacterium Rhodococcus sp lxb-6 has efficient degradation effect to low ring and high ring polycyclic aromatic hydrocarbon respectively, polycyclic for low ring and epipodium in soil The mass fraction of aromatic hydrocarbons, compound proportion of the two kinds of degradation bacterias of regulation in suspension, polycyclic aromatic hydrocarbon is thoroughly removed.

The class Fenton of the above method and the system that polycyclic aromatic hydrocarbon pollution is repaired in microorganism combination are realized, using following skill Art scheme:

The system, including material-strewing device and retracting device;Material-strewing device includes spreading track conveyor and spreading fixed mount, Spreading fixed mount setting is provided with mixture hopper and hydrogen peroxide solution on the top of spreading track conveyor, spreading fixed mount Storage tank, hydrogen peroxide solution shower nozzle is provided with hydrogen peroxide solution storage tank;Retracting device includes recovery track conveyor and recovery is solid Determine frame, recovery fixed mount setting is disposed with magnetic on the top of recovery track conveyor, recovery fixed mount and returned from front to back Receiving apparatus, accumulator tank and plastc ring storage tank, plastc ring shower nozzle is provided with plastc ring storage tank.

The spreading track conveyor and recovery track conveyor can be a set of track conveyor.

The bottom of the mixture hopper is provided with gate valve, is fallen with control material.

Mixture hopper covers porous foam iron subparticle, sodium perborate or carbamide peroxide and lemon for holding charcoal bag The mixture of hydrochlorate.Hydrogen peroxide solution storage tank is used to hold and spray hydrogen peroxide solution.Magnetic retracting device is used to inhale by magnetic force Lead back receipts charcoal bag and cover porous foam iron subparticle.The charcoal bag that accumulator tank is used to hold recovery covers porous foam iron subparticle. Plastc ring storage tank is used to hold and spray the polycyclic aromatic hydrocarbon plastc ring of compounding.

Spreading track conveyor drives contaminated soil movement, passes sequentially through mixture hopper and hydrogen peroxide solution shower nozzle, presses Order first scatters mixture on contaminated soil first, then hydrogen peroxide solution is sprayed to the contaminated soil for being sprinkled into mixture On.After pollutant in soil is by fully degraded, starts recovery track conveyor, the contaminated soil after fully degraded is passed through successively Magnetic retracting device and plastc ring shower nozzle are crossed, attracts recovery charcoal bag to cover porous foam iron subparticle by magnetic force and is contained in In accumulator tank, then the plastc ring in plastc ring storage tank is sprayed into the contaminated soil of fully degraded.

The present invention utilizes " light electrolysis+class Fenton+magnetic recovery+microbial degradation " pattern, and process is simple, and cost is low;Have Following characteristics:

(1) charcoal bag covers porous foam iron subparticle and provides stabilization, lasting ferrous iron source for oxidation reaction to protect Demonstrate,prove its sustainability;

(2) sodium perborate (or carbamide peroxide) plays oxidation and activation in Fenton oxidation course of reaction, effectively The concentration and amount of application of hydrogen peroxide are reduced, avoids the destruction to edaphon and organic matter;

(3) citrate (sodium citrate or potassium citrate) can be used as hydrogen peroxide stabilizer during Fenton's reaction, have Effect delays the decomposition of hydrogen peroxide itself, improves the lasting effectiveness and utilization ratio of hydrogen peroxide;

(4) reacted source of iron (charcoal bag covers porous foam iron subparticle) is reclaimed by magnetic retracting device, solved The secondary pollution problem of soil, the risk of non-secondary pollution, and source of iron can be recycled;

(5) by the compounding of difference in functionality polycyclic aromatic hydrocarbon-degrading bacteria, further strengthen the removal of residual polycyclic aromatic hydrocarbon, can incite somebody to action Contaminated soil is thoroughly repaired.

Brief description of the drawings

Fig. 1 is that the structural principle of the system that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton and microorganism combination in the present invention shows It is intended to.

In figure:1. contaminated soil;2. spreading track conveyor;3. mixture hopper;4. hydrogen peroxide solution storage tank;5. dioxygen Aqueous solution shower nozzle;6. spreading fixed mount;7. magnetic retracting device;8. accumulator tank;9. plastc ring storage tank;10. plastc ring Shower nozzle;11. reclaim fixed mount;12. reclaim track conveyor;13. fully degraded contaminated soil.

Embodiment

The system that class Fenton and microorganism combination in the present invention repair polycyclic aromatic hydrocarbon pollution, as shown in figure 1, including Material-strewing device and retracting device, material-strewing device and retracting device are one in front and one in back set.Material-strewing device includes spreading track conveyor 2 With spreading fixed mount 6, spreading fixed mount 6 is arranged on the top of spreading track conveyor 2, on spreading fixed mount 6 from front to back according to Secondary to be provided with mixture hopper 3 and hydrogen peroxide solution storage tank 4, hydrogen peroxide solution shower nozzle is distributed with the bottom of hydrogen peroxide solution storage tank 5.The bottom of mixture hopper 3 is provided with gate valve, is fallen with control material.Retracting device includes recovery track conveyor 12 and returned Receive fixed mount 11, recovery fixed mount 11 be arranged on recovery track conveyor 12 top, reclaim fixed mount 11 on from front to back according to Secondary to be provided with magnetic retracting device 7, accumulator tank 8 and plastc ring storage tank 9, Mixed Microbes are distributed with the bottom of plastc ring storage tank Suspension shower nozzle 10.Material-strewing device and retracting device can also share a set of track conveyor.

Mixture hopper 3 covers porous foam iron subparticle, Boratex or carbamide peroxide and lemon for holding charcoal bag The mixture of silicate powder.Hydrogen peroxide solution storage tank 4 is used to hold and spray the hydrogen peroxide solution of mass concentration 0.05%.Magnetic returns Receiving apparatus 7 is used to attract recovery charcoal bag to cover porous foam iron subparticle by magnetic force.Accumulator tank 8 is used for the charcoal bag for holding recovery Cover porous foam iron subparticle.Plastc ring storage tank 9 is used for the polycyclic aromatic hydrocarbon plastc ring for holding compounding, and by mixed Close bacteria suspension shower nozzle 10 and degradation bacteria is sprayed into soil.

Magnetic retracting device 7 can use prior art, the distributed magnet on tilted-putted conveyer belt, by attraction charcoal Coated porous foamed iron subparticle, charcoal bag are covered porous foam iron subparticle and risen with conveyer belt, fall under gravity into Accumulator tank 8.As disclosed in CN106904701A《A kind of magnetic recovery and sewage water treatment method》In magnetic retracting device, one the back of the body Face be provided with field region belt it is domatic on, the magnetic kind recovery zone set using top of the slope bottom part down will be because of gravity and from skin Take the magnetic kind recovery to come off.

Contaminated soil 1 is contained on the belt of track conveyor 2, and the back kick under the drive of spreading track conveyor 2 Send.Mixture in mixture hopper 3 scatters on contaminated soil 1 first, controls belt gait of march, and binding mixture falls Doses, the mixture for being sprinkled into every kilogram of contaminated soil are 20-60g.Then, the hydrogen peroxide solution in hydrogen peroxide solution storage tank 4 It is sprayed at by hydrogen peroxide solution shower nozzle 5 on the contaminated soil for being sprinkled into mixture.After pollutant in soil is by fully degraded, then It is secondary to start recovery track conveyor 12, the contaminated soil after fully degraded 13 is passed through successively in the case where recovery track conveyor 12 conveys Cross magnetic retracting device 7 and plastc ring shower nozzle 10, it is micro- that magnetic retracting device 7 by magnetic force attracts recovery charcoal bag to cover porous foam iron Fine grained, and being contained in accumulator tank 8, while plastc ring shower nozzle 10 is by the plastc ring in plastc ring storage tank 9 Spray on fully degraded contaminated soil 13, the belt gait of march of track conveyor 12 is controlled, with reference to the compound proportion of degradation bacteria With the amount of spraying, it is 20-60mL every kilogram of contaminated soil is sprayed plastc ring.

The deposit number for being purchased from China Committee for Culture Collection of Microorganisms's common micro-organisms center is respectively CGMCC No.9072 and CGMCC No.3715 oxidation microbacterium 2 and Rhodococcus sp lxb-6 of Ji, can be as disclosed in CN101974445A《It is high The strain of molecular weight polycyclic aromatic hydrocarbon-degrading bacteria and its mixed culture》In operating method prepare two kinds of bacteria suspensions, respectively by after activation Inoculation is cultivated to logarithmic phase, abandoning supernatant after centrifugation into beef extract-peptone fluid nutrient medium, adds 20mL phosphoric acid W salt buffer washes 2 times, abandoning supernatant after centrifuging again, thalline is harvested, and thalline is resuspended to every milli with phosphate buffer Rise bacterium solution and contain viable bacteria 105~106It is individual, the bacteria suspension of oxidation microbacterium Ji 2 and Rhodococcus sp lxb-6 bacteria suspension are obtained respectively;Then By 2 and bacterial strain lxb-6 of bacterial strain Ji bacteria suspension by volume 1:1-1:Plastc ring is made in 3 compound proportion.Specific volume Than the quality of high ring polycyclic aromatic hydrocarbon or low ring polycyclic aromatic hydrocarbon point in polycyclic aromatic hydrocarbon content and contaminated soil can be pressed in contaminated soil Number determines.Specifically as polycyclic aromatic hydrocarbon content≤0.6mg/kg in contaminated soil, every kilogram of contaminated soil sprays Mixed Microbes and hanged Liquid 20-40mL;In contaminated soil during polycyclic aromatic hydrocarbon content > 0.6mg/kg, every kilogram of contaminated soil sprays plastc ring 40- 60mL;When high ring polycyclic aromatic hydrocarbon (>=4 ring) mass fraction in contaminated soil >=50%, oxidation microbacterium Ji 2 and Rhodococcus sp Lxb-6 by volume 1:2-1:Plastc ring is made in 3 compound proportion;Low ring polycyclic aromatic hydrocarbon (rings of < 4) matter in contaminated soil When measuring fraction > 50%, oxidation microbacterium Ji 2 and Rhodococcus sp lxb-6 by volume 1:1-1:Mixed Microbes are made in 2 compound proportion Suspension.

Oxidation microbacterium (Microbacterium oxydans) Ji 2 refers to Chinese patent literature CN104342392A public affairs Open《A kind of oxidation microbacterium of degrading polycyclic aromatic hydrocarbons and its application》, deposit number is CGMCC No.9072.Rhodococcus sp (Rhodococcus sp.) lxb-6 is referred to disclosed in CN101974445A《Polycyclic aromatic hydrocarbon with high molecular weight degradation bacteria strains and its mixed Close fungus strain》, deposit number is CGMCC No.3715.

Embodiment 1

In the ratio of 1g glucose, 10g porous foam iron subparticles and 40mL water, first glucose is dissolved in the water, Glucose solution is made, then porous foam iron subparticle is put into glucose solution, is made into mixed liquor;By above-mentioned mixed liquor It is placed in high-pressure hydrothermal reaction kettle, 6 hours (pressure is 1.0~2.0MPa in hydrothermal reaction kettle) is heated at 120 DEG C, will after reaction Porous foam iron subparticle takes out, and is dried after being washed with deionized, that is, charcoal bag is made and covers porous foam iron subparticle.

It is 70 in mass ratio that charcoal bag is covered into porous foam iron subparticle, sodium perborate and sodium citrate powder:15:15 Ratio is well mixed, with resulting mixture.

Obtained charcoal bag is covered into porous foam iron subparticle, sodium perborate and sodium citrate mixture and loads mixed material In bucket 3.The hydrogen peroxide solution that mass concentration is 0.05% is fitted into hydrogen peroxide solution storage tank 4.Mixture is pressed into every kilogram of dirt The ratio uniform that dye soil is sprinkled into 40g is sprinkled into polluted soil, then hydrogen peroxide solution is sprayed into 70mL by every kilogram of contaminated soil Ratio polluted soil is uniformly sprayed into by atomizing and spraying apparatus.

Pollutant in soil starts retracting device by after fully degraded 5 days, and fully degraded contaminated soil 13 is returned by magnetic Charcoal bag is covered the recovery of porous foam iron subparticle and is contained in retracting device accumulator tank 8 by receiving apparatus 7.

Detect the mass fraction of the polycyclic aromatic hydrocarbon content and each ring in fully degraded contaminated soil 13.First according to fully drop The mass fraction configuration plastc ring of each ring of polycyclic aromatic hydrocarbon in contaminated soil 13 is solved, is specifically:High ring polycyclic aromatic hydrocarbon (>=4 ring) Mass fraction >=50% when, 2 and Rhodococcus sp lxb-6 of oxidation microbacterium Ji by volume 1:Mixed Microbes are made in 2 compound proportion Suspension;During the mass fraction > 50% of low ring polycyclic aromatic hydrocarbon (rings of < 4), by volume 1:1 compound proportion is made Mixed Microbes and hanged Liquid.

Then plastc ring is sprayed according to polycyclic aromatic hydrocarbon content in fully degraded contaminated soil 13, is specifically:Fully drop When solving polycyclic aromatic hydrocarbon content≤0.6mg/kg in contaminated soil 13, the plastc ring in plastc ring storage tank 5 is pressed every thousand Gram fully degraded contaminated soil 13 sprays plastc ring 30mL;In contaminated soil during polycyclic aromatic hydrocarbon content > 0.6mg/kg, press Every kilogram of fully degraded contaminated soil 13 sprays plastc ring 40mL.

Embodiment 2

According to the ratio of 2.5g glucose, 5g porous foam iron subparticles and 40mL water, glucose is first dissolved in water In, glucose solution is made, then porous foam iron subparticle is put into glucose solution, it is made into mixed liquor;Will be above-mentioned mixed Close liquid to be placed in high-pressure hydrothermal reaction kettle, heat 4 hours (pressure is 1.0~2.0MPa in hydrothermal reaction kettle) at 160 DEG C, reaction Porous foam iron subparticle is taken out afterwards, dried after being washed with deionized, that is, charcoal bag is made and covers fine of porous foam iron Grain.

It is 80 in mass ratio that charcoal bag is covered into porous foam iron subparticle, carbamide peroxide and potassium citrate powder:10:10 Ratio be well mixed, with resulting mixture.

Fill this blend into mixture hopper 3.It is water-soluble that the hydrogen peroxide solution that mass concentration is 0.05% is loaded into dioxygen In liquid storage tank 4.The ratio uniform that mixture is first sprinkled into 60g by every kilogram of contaminated soil is sprinkled into polluted soil, then by dioxygen The ratio that the aqueous solution is sprayed 100mL in every kilogram of contaminated soil uniformly sprays into polluted soil by atomizing and spraying apparatus.

Pollutant in soil is started retracting device, fully degraded contaminated soil is reclaimed by magnetic by after fully degraded 8 days Charcoal bag is covered the recovery of porous foam iron subparticle and is contained in accumulator tank 8 by device 7.

Detect the mass fraction of the polycyclic aromatic hydrocarbon content and each ring in fully degraded contaminated soil 13.First according to fully drop The mass fraction configuration plastc ring of each ring of polycyclic aromatic hydrocarbon in contaminated soil 13 is solved, is specifically:Fully degraded contaminated soil 13 During middle high ring polycyclic aromatic hydrocarbon (>=4 ring) mass fraction >=50%, 2 and Rhodococcus sp lxb-6 of oxidation microbacterium Ji by volume 1:3 Plastc ring is made in compound proportion;During low ring polycyclic aromatic hydrocarbon (rings of < 4) mass fraction > 50%, by volume 1:2 compounding Plastc ring is made in ratio.

Then plastc ring is sprayed according to polycyclic aromatic hydrocarbon content in fully degraded contaminated soil 13, is specifically:Fully drop When solving polycyclic aromatic hydrocarbon content≤0.6mg/kg in contaminated soil 13, the plastc ring in plastc ring storage tank 5 is pressed every thousand Gram fully degraded contaminated soil 13 sprays plastc ring 20mL;In contaminated soil during polycyclic aromatic hydrocarbon content > 0.6mg/kg, press Every kilogram of fully degraded contaminated soil 13 sprays plastc ring 60mL.

Embodiment 3

According to the ratio of 2g glucose, 15g porous foam iron subparticles and 40mL water, glucose is first dissolved in water In, glucose solution is made, then porous foam iron subparticle is put into glucose solution, it is made into mixed liquor;Will be above-mentioned mixed Close liquid to be placed in high-pressure hydrothermal reaction kettle, heat 2 hours (pressure is 1.0~2.0MPa in hydrothermal reaction kettle) at 180 DEG C, reaction Porous foam iron subparticle is taken out afterwards, dried after being washed with deionized, that is, charcoal bag is made and covers fine of porous foam iron Grain.

It is 90 in mass ratio that charcoal bag is covered into porous foam iron subparticle, sodium perborate and sodium citrate powder:5:5 ratio Example is well mixed, with resulting mixture.

Fill this blend into mixture hopper 3.It is water-soluble that the hydrogen peroxide solution that mass concentration is 0.05% is loaded into dioxygen In liquid storage tank 4.The ratio uniform that mixture is first sprinkled into 20g by every kilogram of contaminated soil is sprinkled into polluted soil, then by dioxygen The ratio that the aqueous solution is sprayed 40mL in every kilogram of contaminated soil uniformly sprays into polluted soil by atomizing and spraying apparatus.

Pollutant in soil starts retracting device by after fully degraded 7 days, and fully degraded contaminated soil 13 is returned by magnetic Charcoal bag is covered the recovery of porous foam iron subparticle and is contained in retracting device accumulator tank 8 by receiving apparatus 7.

Detect the mass fraction of the polycyclic aromatic hydrocarbon content and each ring in fully degraded contaminated soil 13.First according to fully drop The mass fraction configuration plastc ring of each ring of polycyclic aromatic hydrocarbon in contaminated soil 13 is solved, is specifically:Fully degraded contaminated soil 13 During middle high ring polycyclic aromatic hydrocarbon (>=4 ring) mass fraction >=50%, 2 and Rhodococcus sp lxb-6 of oxidation microbacterium Ji by volume 1:3 Plastc ring is made in compound proportion;During low ring polycyclic aromatic hydrocarbon (rings of < 4) mass fraction > 50%, by volume 1:1 compounding Plastc ring is made in ratio.

Then plastc ring is sprayed according to polycyclic aromatic hydrocarbon content in fully degraded contaminated soil 13, is specifically:Fully drop When solving polycyclic aromatic hydrocarbon content≤0.6mg/kg in contaminated soil 13, the plastc ring in plastc ring storage tank 5 is pressed every thousand Gram fully degraded contaminated soil 13 sprays plastc ring 40mL;In contaminated soil during polycyclic aromatic hydrocarbon content > 0.6mg/kg, press Every kilogram of fully degraded contaminated soil 13 sprays plastc ring 50mL.

Claims (9)

1. the method that polycyclic aromatic hydrocarbon pollution is repaired in a species Fenton and microorganism combination, it is characterized in that, comprise the following steps:
(1) charcoal bag is covered into porous foam iron subparticle and sodium perborate or carbamide peroxide and citrate powder in mass ratio For 70-90:5-15:5-15 ratio is well mixed, and with resulting mixture, mixture is uniformly sprinkled into polluted soil, every kilogram Contaminated soil is sprinkled into mixture 20-60g;
(2) by mass concentration be 0.05% hydrogen peroxide solution by every kilogram of contaminated soil spray 40-100mL ratio uniform spray Enter polluted soil, by absorption, light electrolysis and redox, the polycyclic aromatic hydrocarbon pollutant in soil is enriched with and gone Remove;Charcoal bag is covered the recovery of porous foam iron subparticle by pollutant in soil by after fully degraded 5-8 days;
(3) 2 and Rhodococcus sp lxb-6 of microbacterium Ji bacteria suspension by volume 1 will be aoxidized:1-1:Mixing is made in 3 compound proportion Bacteria suspension, and by every kilogram of contaminated soil spray 20-60mL ratio uniform spray into polluted soil, still will residue in soil Polycyclic aromatic hydrocarbon removed by way of microbial degradation.
2. the method that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton according to claim 1 and microorganism combination, its feature It is that charcoal bag covers the preparation method of porous foam iron subparticle in the step (1), is:
According to the ratio of 1-2.5g glucose, 5-15g porous foam iron subparticles and 40mL water, glucose is first dissolved in water In, glucose solution is made, then porous foam iron subparticle is put into glucose solution, it is made into mixed liquor;Will be above-mentioned mixed Close liquid to be placed in hydrothermal reaction kettle, heat 2-6 hours at 120-180 DEG C, take out porous foam iron subparticle after reaction, use Dried after deionized water washing, that is, charcoal bag is made and covers porous foam iron subparticle.
3. the method that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton according to claim 2 and microorganism combination, its feature It is that the particle diameter of the porous foam iron subparticle is 200-500 microns.
4. the method that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton according to claim 1 and microorganism combination, its feature It is in the step (3), the preparation method of 2 or Rhodococcus sp lxb-6 of oxidation microbacterium Ji bacteria suspension, to be:
Fermented and cultured is carried out to logarithmic phase to oxidation microbacterium or Rhodococcus sp, abandoning supernatant after centrifugation, adds phosphate-buffered Liquid is washed, and supernatant is abandoned after centrifuging again, is collected thalline and is resuspended in it in phosphate buffer respectively, to every milliliter of buffering Contain viable bacteria 10 in liquid5~106It is individual, obtain lucky 2 bacteria suspensions of oxidation microbacterium or Rhodococcus sp lxb-6 bacteria suspensions.
5. the method that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton according to claim 1 and microorganism combination, its feature It is that in the step (3), as polycyclic aromatic hydrocarbon content≤0.6mg/kg in contaminated soil, every kilogram of contaminated soil sprays mixing Bacteria suspension 20-40mL;In contaminated soil during polycyclic aromatic hydrocarbon content > 0.6mg/kg, every kilogram of contaminated soil sprays plastc ring 40-60mL。
6. the method that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton according to claim 1 and microorganism combination, its feature Be, in the step (3), when in contaminated soil >=4 ring high ring polycyclic aromatic hydrocarbon mass fraction >=50% when, aoxidize microbacterium 2 and Rhodococcus sp lxb-6 of Ji bacteria suspension by volume 1:2-1:Plastc ring is made in 3 compound proportion;When in contaminated soil During the mass fraction > 50% of the low ring polycyclic aromatic hydrocarbon of the rings of < 4,2 and Rhodococcus sp lxb-6 of oxidation microbacterium Ji bacteria suspension presses body Product ratio 1:1-1:Plastc ring is made in 2 compound proportion.
7. the system that polycyclic aromatic hydrocarbon pollution is repaired in a species Fenton and microorganism combination, it is characterized in that, including material-strewing device And retracting device;Material-strewing device includes spreading track conveyor and spreading fixed mount, and spreading fixed mount setting is defeated in spreading crawler belt The top of machine is sent, mixture hopper and hydrogen peroxide solution storage tank are provided with spreading fixed mount, is set on hydrogen peroxide solution storage tank There is hydrogen peroxide solution shower nozzle;Retracting device includes recovery track conveyor and recovery fixed mount, and recovery fixed mount setting is reclaiming The top of track conveyor, reclaim and be disposed with magnetic retracting device, accumulator tank and plastc ring from front to back on fixed mount Storage tank, plastc ring shower nozzle is provided with plastc ring storage tank.
8. the system that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton according to claim 7 and microorganism combination, its feature It is that the spreading track conveyor and recovery track conveyor are a set of track conveyor.
9. the system that polycyclic aromatic hydrocarbon pollution is repaired in class Fenton according to claim 7 and microorganism combination, its feature It is that the bottom of the mixture hopper is provided with gate valve.
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