CN107413837A - Device and the application of oil heavy-metal composite pollution soil are repaired with electronic microbial association - Google Patents

Device and the application of oil heavy-metal composite pollution soil are repaired with electronic microbial association Download PDF

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CN107413837A
CN107413837A CN201710786110.9A CN201710786110A CN107413837A CN 107413837 A CN107413837 A CN 107413837A CN 201710786110 A CN201710786110 A CN 201710786110A CN 107413837 A CN107413837 A CN 107413837A
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electrolytic cell
pond
soil
positive
electronic
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CN107413837B (en
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李琋
马永松
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Southwest Petroleum University
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    • 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
    • B09C1/085Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
    • 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Soil Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Molecular Biology (AREA)
  • Mycology (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention belongs to environment preventing and treating with administering field, it is related to the prosthetic device of oil heavy-metal composite pollution soil, it is characterised in that:Described device includes electro reclamation pool structure, microorganism remediation module and electrode pH monitoring system structures, the electro reclamation pool structure is provided with soil sample filling pond and the cloudy electrolytic cell positioned at soil sample filling pond both ends and positive electrolytic cell, and it is additionally provided with and is inserted respectively in cloudy electrolytic cell and positive electrolytic cell by the connected negative electrode of dc source and positive electrode, negative electrode and positive electrode;Electrolyte inlet is provided with the outside of the upper end of cloudy electrolytic cell and positive electrolytic cell, end portion outside is provided with electrolyte outlet;Soil sample, which fills use between pond and electrolytic cell, can make the interlayer of separation of solid and liquid.There are electrolyte inlet and outlet on the outside of electrolytic cell, electrolyte is carried out to update and circulate in real time.Ensure the activity of microorganism and stable degradation property;Make up the deficiency of simple microorganism remediation technology, and it is easy to operate, cost is low, remediation efficiency is high, does not destroy original natural environment.

Description

With it is electronic-microbial association repair restoration of petroleum-heavy metal soil device and Using
Technical field
The invention belongs to environment preventing and treating with administering field, it is related to the prosthetic device of restoration of petroleum-heavy metal soil, especially It is related to a kind of device that restoration of petroleum-heavy metal soil is repaired with electronic-microbial association.
Background technology
Oil is the main energy sources of the world today, and with the development and prosperity of human social economy, countries in the world are to oil Demand also constantly increasing.But the defects of technology and management, oil exploration and exploitation, accumulating, transport, refining, processing and The leakage of oil and its petroleum product or spilling can cause serious environmental pollution during its use, especially with oil and again Combined contamination soil is serious caused by metal, compromises the living environment of the mankind.Heavy metal pollution of soil compared to atmosphere pollution and For water pollution, there is chronicity, disguise, irreversibility and can not decompose or disappear completely, and directly with Agricultural production is related, therefore endangers serious, improvement difficulty.How effectively to prevent and treat and solve soil oil-compound dirt of heavy metal Dye problem increasingly by countries in the world attention and how highly effective and safe low cost reparation oil-heavy-metal contaminated soil Have become one of important topic of environmental area.
Microorganism remediation technology has that cost is low in recovery technique, does not destroy the soil environment needed for plant growth, dirty Contaminate thing oxidative safety, non-secondary pollution, high treating effect, it is simple to operate the features such as, therefore be always biolith greasy dirt in recent years Contaminate the emphasis of recovery technique research.But due to the nutrition numerous imbalances in oil-polluted soils, indigenous microbes are insufficient, so, It is low there is rate of contaminant degradation in the repair process of microbiological petroleum contaminated soil, soil remediation cycle length, more cyclophanes Hydrocarbons pollutant is difficult to the shortcomings of degraded.
Electrokinetic technique is the new soil recovery technique carried out first in Holland and the U.S. the 1970s, in early days Reparation for heavy-metal contaminated soil.Also many methods and related device on electro reclamation are generated, are also had electronic With the experimental provision of technology.For example CN201454977U discloses a kind of dynamic absorption composite heavy metal pollution soil restoration Device, described device include being made electrode using graphite, and electrode includes negative electrode and anode, negative electrode and anode respectively with dc source Both ends be connected, anode is placed in anode and taken, and negative electrode is placed in cathodic region, and by anode region to cathodic region, device prevents pollution weight successively The dividing plate of metal ion diffusion, porous material activated carbon, the heavy-metal contaminated soil that need to be handled for adsorbing heavy metal, and use and cut Changing the method for electrode prevents cathode zone pH rising and anode region pH decline.CN102896143A has published one kind Powered surface activating agent combines the experimental provision of repairing polluted soil, and described device includes main body and eluent regulating reservoir, and it is led Body top half loads untainted soil, and the side of main body is provided with eluent outlet, main-body electrode room perforated baffle and main body Two electrode chambers are formed between medial surface, two electrodes are connected with dc source respectively.The eluent regulating reservoir being placed on above main body Through valve injecting electrode room.This device ensure that surfactant add homogeneity, solve eluent under ooze pollution problem.
It is united repairing heavy metal polluted that also such as CN1899717B discloses a kind of point power and iron permeable reactive barrier The technique of soil, the technique are to install graphite electrode in soil both sides, and iron wall is laid between two electrodes and pending soil, is connected Power supply, anionic metal is moved near anode under electric field action, and metal cation is moved near negative electrode, when a huge sum of money React therewith when category is through iron wall and be able to adsorb, reduce and precipitate.CN102500610A discloses a kind of electrodynamics Joint drip irrigation restoration of soil polluted by heavy metal method, this method is to install positive and negative electrode at heavy-metal contaminated soil both ends, just Adsorbent is placed between negative electrode and contaminated soil respectively, near adsorbent soil top set drip irrigation appliance, by electrolyte, Buffer solution or complexing agent etc. are slowly dropped in the contaminated soil of both sides, and periodical anode and cathode polarity switching, heavy metal are carried out to electrode By electrokinetic migration action and it is adsorbed by adsorbent so as to reduce its concentration in soil.CN204710408047145U A kind of electronic joint prosthetic device of elution of heavy-metal contaminated soil is disclosed, described device includes elution circuit and electro reclamation System;The elution circuit is connected by peristaltic pump with contaminated soil soil box;Leacheate tank inside is provided with mixer;Leaching The contaminated soil reservoir bottom washed in system is connected by slush pump with electro reclamation room.Using described device, first heavy metal Contaminated soil carries out chemical leaching, then carries out electric reparation to soil after elution.
As described above, although electronic combination prosthetic device and method are a lot, the effect having had, there is repair into This height, repair the technical problem such as single.
Also begin to occur entering restoration of petroleum-heavy metal soil using electronic-microbial association reparation in recent years Row is repaired, and electronic and microorganism combination repair technology is the technical research newly risen at present, the method be considered as at present most before One of soil restoring technology of scape, there is certain frontier nature and novelty, but both at home and abroad in electric field-enhanced microorganism remediation Correlative study is considerably less.And on electro reclamation with experimental provision associated with microorganism renovation agent is rare is related to, and because most The electronic experimental provision of number only sets anode pool and cathode pool, and without adding electrolyte, sour environment caused by electrolytic cell anode is unfavorable In the growth and breeding of microorganism, the alkaline environment of negative electrode causes heavy metal precipitation, and clearance reduces, while is unfavorable for micro- life again The growth of thing.
Therefore, the apparatus and method for being adapted to electronic-microbial association reparation oil-heavy-metal contaminated soil are now required Want.
The content of the invention
In order to solve the above problems, the present invention provides a kind of with electronic-microbial association reparation oil-heavy metal polluted soil The device of earth, it can be very good to simulate the situation that electronic-microbial association technology repairs combined contamination soil, ensure microorganism Activity and stable degradation property;Make up the deficiency of simple microorganism remediation technology, and it is easy to operate, cost is low, remediation efficiency is high, Original natural environment is not destroyed.
Solve a kind of with electronic-microbial association technology reparation oil-heavy metal in the present invention of above technical problem The device of contaminated soil, it is characterised in that:Described device includes electro reclamation pool structure, microorganism remediation module and electrode pH prisons System architecture is controlled, the electro reclamation pool structure is provided with soil sample filling pond and the cloudy electrolytic cell and sun positioned at soil sample filling pond both ends Electrolytic cell, and be additionally provided with and negative electricity is inserted by the connected negative electrode of dc source and positive electrode, negative electrode and positive electrode respectively In Xie Chi and positive electrolytic cell;Electrolyte inlet is provided with the outside of the upper end of cloudy electrolytic cell and positive electrolytic cell, end portion outside is set There is electrolyte outlet;Soil sample, which fills use between pond and electrolytic cell, can make the interlayer of separation of solid and liquid.There is electrolyte on the outside of electrolytic cell Inlet and outlet, electrolyte is carried out to update and circulate in real time
The electrode pH monitoring systems structure is provided with pH Real- time monitors and electrolysis fluid exchange pond, pH Real- time monitors one end and electricity Xie Yegenghuanchi connections, electrolysis fluid exchange pond are provided with anode electrolysis fluid exchange pond and catholyte fluid exchange pond;It is additionally provided with import Peristaltic pump and outlet peristaltic pump, peristaltic pump one end are connected with electrolyte inlet, and one end is stretched into electrolysis fluid exchange pond, and outlet is wriggled Pump one end is connected with electrolyte outlet, and one end is stretched into electrolysis fluid exchange pond;With pH Real- time monitor real-time displays pH change.
The microorganism remediation module includes N number of microorganism remediation block being located in electro reclamation pond.
The electro reclamation pool structure is additionally provided with top cover, cloudy positioned at soil sample filling pond, cloudy electrolytic cell and positive electrolytic cell upper end Electrode and positive electrode insert in cloudy electrolytic cell and positive electrolytic cell respectively through top cover.
The top cover has stomata, stomata quantity >=1.
Top cover is beneficial to the holding of temperature, has stomata thereon, breathing and gas exchanges beneficial to microorganism.
The soil sample filling pond is divided into N number of small soil chamber, N >=1;If N>More than 1, then use film between each small soil chamber (11)Separate.
N=5, film are inorganic ceramic membrane, negative electrode and positive electricity extremely graphite.It is used for using inorganic ceramic membrane as dividing plate Separation of solid and liquid.
The microorganism remediation block specific surface area is 1000 m2/g, pore size 2-50nm.Microorganism remediation block is micro- life Thing remediating heavy metal passivator, using Novel environment-friendlymaterial material fixation of microbe, it has, and specific surface area is big, and porosity is high, to stone Oil contaminants have good suction-operated, while heavy metal has absorption and passivation well again, make the reduction of its toxicity, have Beneficial to the absorption and degraded of microorganism.Porosity is high can to provide good habitat for microorganism again, accelerate microorganism Growth, improve the degradation rate of combined pollutant.
The microorganism remediation block preparation method is as follows:
Step 1:Porous silica is added in the fluid nutrient medium containing high efficient petroleum degrading bacteria, culture medium is containing whetheing there is The beef extract culture medium of machine salt, composition are beef extract 15-25%, NaCl 0.5-3%, NH4SO4 0.1-5%, NaH2PO4 1%, Na2HPO4 0.5%, pH 7-7.5, mass fraction is 0.1-1% in porous silica liquid medium within;
Step 2:Incubated 7 days, centrifuge, be drying to obtain the microorganism remediation block for being loaded with high efficient petroleum degrading bacteria.
The preparation process of the porous oxidation silicon nano material is as follows:
(1) with tetraethyl orthosilicate(TEOS)For silicon source, with cetyl trimethylammonium bromide(CATB), it is template;By 2.1 The mol/L of ml 2 NaoH solution and 0.6 g CATB are added in 288 ml distilled water, then in 80 DEG C in the state of stirring Heating, until solution becomes clarification;
(2)Then 3 ml TEOS are added dropwise, and stir, are reacted two hours at 80 DEG C;After reaction terminates, by resulting solution Centrifugation, dry, grinding, obtain white powdery solids;
(3)Template agent removing is removed with calcination method, detailed process is:By 1.0 g acrylamides, 0.1 mg crosslinking agents under stirring N-N methylene-bisacrylamides and 25 mg(NH4)2S2O8(Ammonium peroxydisulfate)It is suspended containing 5% nano-particle to be added to 10 g In liquid, 15 min of ultrasound make nano particle be fully dispersed in solution;Then, 50 DEG C are warming up to, sends out the organic monomer of addition Raw polymerisation, resulting solution is dried overnight in 80-100 DEG C;Afterwards, calcining obtains good dispersion property at 550 DEG C Porous oxidation silicon nano material.
The application of oil-heavy-metal contaminated soil device is repaired in the present invention with electronic-microbial association, i.e. microorganism is repaiied Multiple heavy metal deactivator and electronic joint reparation, 5-10% is added in the oil after grinding-heavy metal pollution mixed soil The porous silica for being loaded with petroleum efficient degradation bacteria is heavy metal deactivator, rearmounted through inorganic salt loading 24 hours after being sufficiently mixed Filled in soil sample in pond, compacting, after 28 days, the composite pollution soil after being repaired, specifically include following steps:
(1) erecting device:Electro reclamation pool structure is installed;
(2) collection pollution soil sample, dry, be granular, being sieved after removing tree root and stone, then nothing is used after being mixed with microorganism remediation block Machine salt saturated solution saturation 22-26 hours, it is put into soil sample filling pond and is compacted;Wherein inorganic salt saturated solution composition includes following The composition of mass parts:0.1 part of 0.9 part of KH2PO4, K2HPO4,0.1 part of 0.1 part of NH4NO3, MgSO4 7H2O, CaCl2 0.08 part and 0.01 part of FeCl3 6H2O.
(3) negative electrode and positive electrode are inserted in cloudy electrolytic cell and positive electrolytic cell respectively, while connects electrolysis fluid exchange Pond, import peristaltic pump, export peristaltic pump and pH Real- time monitor parts;
(4) switch on power, the voltage is 1V/cm;
(5) pH Real- time monitors are opened, prevent pH from having larger fluctuation;
(6)Measure observation:A sample is removed within 7 days, then determines the content and heavy metal lead of total petroleum hydrocarbon(Pb)Content.
The step(5)In make pH5.6 in catholyte pond, 8.0 in anode electrolysis pond.
The beneficial effects of the present invention are:
A, by adding electrolyte, real-time circulation and regularly update, can avoid because pH caused by electrolysis water is reduced extremely or Person raises, and is preferably advantageous to the removal of oil and heavy metal.
B, by setting pH real-time monitoring systems, be advantageous to timely carry out the renewal of electrolyte, save manpower and financial resources.
C, by adding microorganism remediation heavy metal deactivator, pH larger fluctuation can be avoided to the shadow of microbial activity Ring, so as to influence degradation efficiency, can guarantee that the lasting progress of electro reclamation.Metal toxicity can be adsorbed and reduce again simultaneously, profit In the absorption and degraded of microorganism heavy metal.
D, the situation of microorganism-electronic United Technologies processing contaminated soil can be simulated by this device, to single before this Electro reclamation and the effect of microorganism remediation contaminated soil have greatly improved, solve before this that clearance is low, microorganism lives Property it is inadequate, heavy metal because pH it is elevated be easy to precipitation and be difficult to the problem that removes.There is application prospect and promotional value simultaneously.
The electro reclamation device provided in the present invention, can be very good to simulate electronic-microbial association technology repair it is compound The situation of contaminated soil, ensure the activity of microorganism and stable degradation property, be for oil-heavy metal polluted soil in recent years Earth recovery technique has experimental value and a kind of device of application prospect very much, while has good application value again.With it is micro- Biotechnology combines, and establishes electronic-microbial association recovery technique, starts the reparation for organic contamination.It is electric field-enhanced micro- Bioremediation technology can make up the deficiency of simple microorganism remediation technology, and it is easy to operate, cost is low, remediation efficiency is high, does not break Bad original natural environment.Novel microbial remediating heavy metal passivator and electro reclamation are joined together to combined contamination soil Administer, the problem being had no way of doing it before can effectively solving to combined pollution.
Brief description of the drawings
Fig. 1 is apparatus structure schematic diagram in the present invention.
Wherein it is specifically identified as follows:
1. dc source, 2.pH Real- time monitors, 3 import peristaltic pumps, 4. outlet peristaltic pumps, 5. anode electrolysis fluid exchange ponds(5-1 Anode electrolysis fluid exchange pond, 5-2 catholyte fluid exchanges pond), 6. microorganism renovation agents, 7. electrolyte inlets, 8. electrolyte go out Mouthful, 9. anode electrolysis ponds, 10. catholyte ponds, 11. inorganic ceramic membranes, 12. top covers, 13. anode electrodes, 14. cathode electrodes, 15. soil sample fills pond, 16. stomatas
Embodiment
Below in conjunction with the accompanying drawings and embodiment does further detailed description to the present invention:
Embodiment 1
The present invention is further described with reference to specification drawings and specific embodiments:
Apparatus of the present invention are described in further detail with specific embodiment below in conjunction with the accompanying drawings, but this is to this practicality Exemplary description is made in type device and operation, and not this practical usage range of explanation is only limitted to this.
Embodiment 1
Described device includes electro reclamation pool structure, microorganism remediation module and electrode pH monitoring system structures, described electronic to repair Multiple pool structure is provided with soil sample filling pond and the cloudy electrolytic cell positioned at soil sample filling pond both ends and positive electrolytic cell, and is additionally provided with and passes through The connected negative electrode of dc source and positive electrode, negative electrode and positive electrode insert in cloudy electrolytic cell and positive electrolytic cell respectively;Negative electricity Electrolyte inlet is provided with the outside of the upper end of Xie Chi and positive electrolytic cell, end portion outside is provided with electrolyte outlet;Soil sample is filled Use can make the interlayer of separation of solid and liquid between pond and electrolytic cell.
Electrode pH monitoring systems structure is provided with pH Real- time monitors and electrolysis fluid exchange pond, pH Real- time monitors one end and electricity Xie Yegenghuanchi connections, electrolysis fluid exchange pond are provided with anode electrolysis fluid exchange pond and catholyte fluid exchange pond;It is additionally provided with import Peristaltic pump and outlet peristaltic pump, peristaltic pump one end are connected with electrolyte inlet, and one end is stretched into electrolysis fluid exchange pond, and outlet is wriggled Pump one end is connected with electrolyte outlet, and one end is stretched into electrolysis fluid exchange pond;With pH Real- time monitor real-time displays pH change. Microorganism remediation module includes N number of microorganism remediation block being located in electro reclamation pond.
PH Real- time monitors are 2, are connected respectively with anode electrolysis fluid exchange pond and catholyte fluid exchange pond.Anode electricity Xie Yegenghuanchi and positive electrolytic cell are located at the same side, and catholyte fluid exchange pond and cloudy electrolytic cell are located at the same side.
Embodiment 2
With reference to figure 1, described device includes electro reclamation pool structure, microorganism remediation module and electrode pH monitoring system structures, institute Cloudy electrolytic cell and positive electrolytic cell of the electro reclamation pool structure provided with soil sample filling pond and positioned at soil sample filling pond both ends are stated, and also Cloudy electrolytic cell and positive electrolytic cell are inserted respectively provided with the negative electrode and positive electrode, negative electrode and positive electrode being connected by dc source In;Electrolyte inlet is provided with the outside of the upper end of cloudy electrolytic cell and positive electrolytic cell, end portion outside is provided with electrolyte outlet;Soil Sample, which fills use between pond and electrolytic cell, can make the interlayer of separation of solid and liquid.
Electrode pH monitoring systems structure is provided with pH Real- time monitors and electrolysis fluid exchange pond, pH Real- time monitors one end and electricity Xie Yegenghuanchi connections, electrolysis fluid exchange pond are provided with anode electrolysis fluid exchange pond and catholyte fluid exchange pond;It is additionally provided with import Peristaltic pump and outlet peristaltic pump, peristaltic pump one end are connected with electrolyte inlet, and one end is stretched into electrolysis fluid exchange pond, and outlet is wriggled Pump one end is connected with electrolyte outlet, and one end is stretched into electrolysis fluid exchange pond;With pH Real- time monitor real-time displays pH change. Microorganism remediation module includes N number of microorganism remediation block being located in electro reclamation pond.
Wherein, electro reclamation pond top cover is additionally provided with, positioned at soil sample filling pond, cloudy electrolytic cell and positive electrolytic cell upper end, negative electricity Pole and positive electrode insert in cloudy electrolytic cell and positive electrolytic cell respectively through top cover.Soil sample fills pond between negative and positive electrolytic cell, Be divided into five small soil chambers, facilitate sampling analysis, between each soil chamber and electrolytic cell with the inorganic ceramic membrane of penetrability every Open, there are electrolyte inlet and outlet on the outside of electrolytic cell, electrolyte is carried out to update and circulate in real time;Top cover is beneficial to the holding of temperature, There is stomata thereon, breathing and gas exchanges beneficial to microorganism.
PH real-time monitoring systems include electrolysis fluid exchange pond, and pH Real- time monitors are inserted into electrolysis fluid exchange pond, to electricity Solution liquid is detected in real time, prevents removal generation shadow of the big ups and downs due to pH to oil degradation microbial activity and heavy metal Ring.After microorganism remediation heavy metal deactivator nano material should be sufficiently mixed with restoration of petroleum-heavy metal thing, then add Filled to soil sample in pond.
Embodiment 3
The preparation method of microorganism remediation heavy metal deactivator is as follows:Porous oxidation silicon nano material is made first, then solid High efficient petroleum degrading bacteria is determined as microorganism remediation heavy metal deactivator.
Microorganism remediation block specific surface area is 1000 m2/g, pore size 2-50nm.
The preparation process of porous oxidation silicon nano material is as follows:
(1) with tetraethyl orthosilicate(TEOS)For silicon source, with cetyl trimethylammonium bromide(CATB), it is template;By 2.1 The mol/L of ml 2 NaoH solution and 0.6 g CATB are added in 288 ml distilled water, then in 80 DEG C in the state of stirring Heating, until solution becomes clarification;
(2)Then 3 ml TEOS are added dropwise, and stir, are reacted two hours at 80 DEG C;After reaction terminates, by resulting solution Centrifugation, dry, grinding, obtain white powdery solids;
(3)Template agent removing is removed with calcination method, detailed process is:By 1.0 g acrylamides, 0.1 mg crosslinking agents under stirring N-N methylene-bisacrylamides and 25 mg(NH4)2S2O8(Ammonium peroxydisulfate)It is suspended containing 5% nano-particle to be added to 10 g In liquid, 15 min of ultrasound make nano particle be fully dispersed in solution;Then, 50 DEG C are warming up to, sends out the organic monomer of addition Raw polymerisation, resulting solution is dried overnight in 80-100 DEG C;Afterwards, calcining obtains good dispersion property at 550 DEG C Porous oxidation silicon nano material.
Microorganism remediation block(Microorganism remediation heavy metal deactivator)Preparation method is as follows:
Step 1:Porous silica is added in the fluid nutrient medium containing high efficient petroleum degrading bacteria, culture medium is containing whetheing there is The beef extract culture medium of machine salt, composition are beef extract 15-25%, NaCl 0.5-3%, NH4SO4 0.1-5%, NaH2PO4 1%, Na2HPO4 0.5%, pH 7-7.5, mass fraction is 0.1-1% in porous silica liquid medium within;
Step 2:Incubated 7 days, centrifuge, be drying to obtain the microorganism remediation block for being loaded with high efficient petroleum degrading bacteria.
Exemplified by handling oil-heavy-metal contaminated soil using this device, electronic microbial association reparation is carried out.
Embodiment 4
The step of electronic-microbial association reparation of restoration of petroleum-heavy metal thing is carried out in the present invention, i.e. microorganism remediation Heavy metal deactivator and electronic joint reparation, 5-10% loads are added in the oil after grinding-heavy metal pollution mixed soil The porous silica for having petroleum efficient degradation bacteria is heavy metal deactivator, is placed in after being sufficiently mixed through inorganic salt loading after 24 hours In soil sample filling pond, compacting, after 28 days, the composite pollution soil after being repaired.
Comprise the following steps that:
(1) the described device of installation invention, the size of device will with handled soil sample number depending on, it is ensured that at dividing plate Connection it is closed, prevent the particle seepage such as soil.The structure of this device for picking is:The size in soil sample filling pond is 20 cm The cm of × 4 cm × 4, it is divided into 5 soil chambers, convenient sampling, the size of electrolytic cell be 1L, and it is 2L to be electrolysed fluid exchange pond size.
(2) will pick up from for many years by oil and heavy metal lead(Pb)The soil sample of pollution, through drying it is granular, remove tree root and 2mm sieves are crossed after stone, then weighs after 600g pollution soil sample and microorganism remediation heavy metal deactivator fully relax, uses inorganic salts Saturated solution saturation, inorganic salts ingredients:KH2PO4 0.9, K2HPO4 0.1, NH4NO3 0.1, MgSO4 7H2O 0.1, CaCl2 0.08, FeCl3 6H2O 0.01, saturation averagely assign to 5 small soil chambers after 24 hours, by soil sample, compacting.
(3) parts such as electrolytic cell, connection electrolysis fluid exchange pond, peristaltic pump, pH Real- time monitors are inserted electrodes into;It is described Electrode is graphite electrode, and specification is the cm of the cm of 4 cm × 4 × 4.
(4) switch on power, the voltage is 1V/cm.
(5) pH Real- time monitors are opened, prevent pH from having larger fluctuation.
(6) apparatus of the present invention, can directly be read on the size dc source of electric current in experimentation, EOF it is big It is small to be calculated with the height of electrolyte in electrolytic cell.
Experiment one
The designed soil chamber of this experiment is five fractions, removes a sample within each 7 days, then determines the content of total petroleum hydrocarbon And heavy metal lead(Pb)Content.Specific steps and device use the content in embodiment 1, dirty by the experiment process of 28 days Contaminate thing concentration(mg/kg)Change as shown in Table:
Handled above by 28 day, the soil pollutant content after processing is respectively less than national regulation, achieves extraordinary effect Fruit.
The filling of electrolyte, periodic replacement are carried out in the present invention to electrolytic cell;By sorbing material be arranged on contact anode or The position of person's negative electrode, using addition microorganism remediation heavy metal deactivator, not only can in soil chamber can to pollutant Effectively degraded, but also pollutant can be migrated;The filling of electrolyte, real-time circulation and is regularly updated, again PH change in polarity can be controlled, so as to improve the clearance of oil and heavy metal.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to is assert The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention, On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's Protection domain.

Claims (9)

  1. A kind of 1. device that oil-heavy-metal contaminated soil is repaired with electronic-microbial association, it is characterised in that:Described device Including electro reclamation pool structure, microorganism remediation module and electrode pH monitoring system structures, the electro reclamation pool structure are provided with Soil sample fills pond (15) and fills pond positioned at soil sample(15)The cloudy electrolytic cell at both ends(10)With positive electrolytic cell(9), and be additionally provided with Pass through dc source(1)Connected negative electrode(14)And positive electrode(13), negative electrode(14)And positive electrode(13)Insertion is cloudy respectively Electrolytic cell(10)With positive electrolytic cell(9)In;Cloudy electrolytic cell(10)With positive electrolytic cell(9)Upper end on the outside of be provided with electrolyte inlet (7), be provided with electrolyte outlet on the outside of end portion(8);
    The electrode pH monitoring systems structure is provided with pH Real- time monitors(2)With electrolysis fluid exchange pond(5), pH Real- time monitors (2)One end and electrolysis fluid exchange pond(5)Connection, electrolysis fluid exchange pond(5)Provided with anode electrolysis fluid exchange pond(5-1)With negative electrode electricity Xie Yegenghuanchi(5-2);It is additionally provided with import peristaltic pump(3)With outlet peristaltic pump(4), peristaltic pump(3)One end and electrolyte inlet (7)Electrolysis fluid exchange pond is stretched into connection, one end(5)In, export peristaltic pump(4)One end and electrolyte outlet(8)Connection, one end is stretched Enter to be electrolysed fluid exchange pond(5)In;
    The microorganism remediation module includes N number of microorganism remediation block being located in electro reclamation pond(6).
  2. 2. the device according to claim 1 that oil-heavy-metal contaminated soil is repaired with electronic-microbial association, it is special Sign is:The electro reclamation pool structure is additionally provided with top cover(12), positioned at soil sample filling pond (15), cloudy electrolytic cell(10)And positive electricity Xie Chi(9)Upper end, negative electrode(14)And positive electrode(13)Through top cover(12)Cloudy electrolytic cell is inserted respectively(10)With positive electrolytic cell (9)In.
  3. 3. the device according to claim 2 that oil-heavy-metal contaminated soil is repaired with electronic-microbial association, it is special Sign is:The top cover(12)There is stomata(16), stomata(16)Quantity >=1.
  4. 4. the device according to claim 1 that oil-heavy-metal contaminated soil is repaired with electronic-microbial association, it is special Sign is:Soil sample filling pond (15) is divided into N number of small soil chamber, N >=1;If N>More than 1, then used between each small soil chamber Film(11)Separate.
  5. 5. the device according to claim 4 that oil-heavy-metal contaminated soil is repaired with electronic-microbial association, it is special Sign is:N=5, film(11)For inorganic ceramic membrane, negative electrode(14)And positive electrode(13)For graphite.
  6. 6. the device according to claim 1 that oil-heavy-metal contaminated soil is repaired with electronic-microbial association, it is special Sign is:The microorganism remediation block specific surface area is 1000 m2/ g, pore size 2-50nm.
  7. 7. the device according to claim 1 that oil-heavy-metal contaminated soil is repaired with electronic-microbial association, it is special Sign is:The microorganism remediation block preparation method is as follows:
    Step 1:Porous silica is added in the fluid nutrient medium containing high efficient petroleum degrading bacteria, culture medium is containing whetheing there is The beef extract culture medium of machine salt, composition are beef extract 15-25%, NaCl 0.5-3%, NH4SO40.1-5%, NaH2PO41%, Na2HPO40.5%, pH 7-7.5, mass fraction is 0.1-1% in porous silica liquid medium within;
    Step 2:Incubated 7 days, centrifuge, be drying to obtain the microorganism remediation block for being loaded with high efficient petroleum degrading bacteria.
  8. 8. the application according to claim 1 that oil-heavy-metal contaminated soil device is repaired with electronic-microbial association, It is characterized in that:Comprise the following steps:
    (1) erecting device:Electro reclamation pool structure is installed;
    (2) collection pollution soil sample, dry, be granular, being sieved after removing tree root and stone, then nothing is used after being mixed with microorganism remediation block Machine salt saturated solution saturation 22-26 hours, it is put into soil sample filling pond and is compacted;Wherein inorganic salt saturated solution composition includes following The composition of mass parts:0.1 part of 0.9 part of KH2PO4, K2HPO4,0.1 part of 0.1 part of NH4NO3, MgSO4 7H2O, CaCl2 0.08 part and 0.01 part of FeCl3 6H2O;
    (3) negative electrode and positive electrode are inserted in cloudy electrolytic cell and positive electrolytic cell respectively, while connects electrolysis fluid exchange pond, enters Mouth peristaltic pump, exports peristaltic pump and pH Real- time monitor parts;
    (4) switch on power, the voltage is 1V/cm;
    (5) pH Real- time monitors are opened, prevent pH from having larger fluctuation;
    (6)Measure observation:A sample is removed within 7 days, then determines the content and heavy metal lead of total petroleum hydrocarbon(Pb)Content.
  9. 9. the application according to claim 8 that oil-heavy-metal contaminated soil device is repaired with electronic-microbial association, It is characterized in that:The step(5)In make pH5.6 in catholyte pond, 8.0 in anode electrolysis pond.
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CN114378111A (en) * 2021-11-30 2022-04-22 西安建筑科技大学 Device and method for removing loess heavy metal pollution based on electrodynamics and mineralogy
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CN108405580A (en) * 2018-02-09 2018-08-17 浙江安淡环保科技有限公司 A kind of the electro reclamation system and its restorative procedure in mine
CN110870407A (en) * 2018-09-04 2020-03-10 郭英强 High-efficient broken soil improvement prosthetic devices
CN109317511A (en) * 2018-12-06 2019-02-12 中电建路桥集团有限公司 The device and method of AC field enhancement microbiological reparation petroleum hydrocarbon contaminated soil
CN110434168A (en) * 2019-08-28 2019-11-12 枣庄学院 A kind of closed soil electro reclamation experimental tank of volume adjustable
CN112658028A (en) * 2020-12-30 2021-04-16 森特士兴集团股份有限公司 Electrochemical-microbial coupling repair system and application thereof
CN112692051A (en) * 2021-01-25 2021-04-23 明志科技大学 Method and equipment for removing pollutants by using beneficial microorganism mixed bacterial liquid
CN113548778A (en) * 2021-08-19 2021-10-26 中交四航工程研究院有限公司 Biological remediation system and method for heavy metal-organic composite polluted river sediment
CN113548778B (en) * 2021-08-19 2022-07-26 中交四航工程研究院有限公司 Bioremediation method of heavy metal-organic composite polluted river sediment
CN114378111A (en) * 2021-11-30 2022-04-22 西安建筑科技大学 Device and method for removing loess heavy metal pollution based on electrodynamics and mineralogy
CN115069756A (en) * 2022-06-07 2022-09-20 常州大学 Method and device for degrading petroleum hydrocarbon polluted soil

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