CN104690084A - Electrochemical and microbial synergetic restoration integrated equipment for organic contaminated soil and restoration method thereof - Google Patents
Electrochemical and microbial synergetic restoration integrated equipment for organic contaminated soil and restoration method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of restoration of organic contaminated soil, and in particular relates to electrochemical and microbial synergetic restoration integrated equipment for organic contaminated soil and a restoration method thereof. The electrochemical and microbial synergetic restoration integrated equipment comprises a direct-current power supply, a positive electrode, a negative electrode, a reactor, a spiral stirrer, a motor and a slurry storage tank, wherein a sample inlet and a sample outlet are formed in the side wall of the reactor; the sample inlet is connected with the slurry storage tank through a peristaltic pump I and a sampling pipeline; the spiral stirrer is inserted into the reactor and connected with the motor arranged outside the reactor; and the positive electrode and the negative electrode are arranged in the reactor at intervals and connected with the direct-current power supply. The organic contaminated soil is integrally processed by adopting the synergetic action of electrochemical oxidation and microbial degradation; solid-liquid mass transfer in the electrochemical reaction process is enhanced through the fluid state characteristics of soil to be restored; molecular structures of organic macromolecular pollutants can be damaged rapidly; and a suitable condition is provided for optimizing the microbial degradation effect.
Description
Technical field
The invention belongs to the technical field that organic polluted soil is repaired, specifically a kind of electrochemistry and microorganism of organic polluted soil are worked in coordination with and repair integration apparatus and restorative procedure.
Background technology
Microbial degradation one common are one of machine contaminated soil remediation technology, and have and be easy to regulation and control, the advantage that treatment effect is good, is at home and abroad used widely.But the problem that microbial technology long processing period, efficiency are low, constrains the remediation efficiency of organic polluted soil.And electrochemical oxidation technology is by direct current, anode is captured electronics and makes oxidation operation or first make low-valent metal be oxidized to high volence metal ion, then high volence metal ion makes the method for oxidation operation again.At present, the advanced electrochemical oxidation process in electrochemical oxidation has manifested efficient feature in the improvement of process hardly degraded organic substance.
Two kinds of technology have requirement to dissolved oxygen content, and dissolved oxygen can be microbial degradation and creates aerobic environment on the one hand, and the increase of dissolved oxygen content, also can improve the intensity of electrochemical oxidation reactions on the other hand.This provide the new approaches of process organic polluted soil, electrochemical oxidation technology is combined with microbial technology, sets up heterogeneous integrated integrated reactor, associated treatment organic polluted soil, improve treatment effect.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind of electrochemistry of organic polluted soil and microorganism to work in coordination with and repair integration apparatus and restorative procedure.
To achieve these goals, the present invention is by the following technical solutions:
A kind of electrochemistry of organic polluted soil and microorganism are worked in coordination with and repair integration apparatus, comprise dc source, positive electrode, negative electrode, reactor, spiral agitator, motor and mud reservoir, wherein the sidewall of reactor is provided with injection port and outlet, described injection port is connected with mud reservoir with sample channel by peristaltic pump I, be connected with the motor being arranged at reactor outside in described spiral agitator intercalation reaction device, described positive electrode and negative electrode to be spaced in reactor and to be all connected with dc source.
Be provided with aerator near negative electrode in described reactor, described aerator is connected with air compressor.Described positive electricity very iron electrode, described negative electricity very graphite electrode, described iron electrode and graphite electrode are symmetricly set in the both sides of spiral agitator.
Described reactor is autoclave structure.Injection port and the sample outlet position of described reactor are equipped with valve.In described reactor, sample outlet position is provided with filter screen.
A kind of method of renovation of organic pollution soil, add pending organic polluted soil in described reactor and add immobilized microorganism, by regulating dissolved oxygen content in reactor, on the basis meeting microbiological deterioration, improve electrochemical oxidation intensity in reactor; Electrochemical oxidation is by pollutant mineralising or be degraded to small molecule contaminants, and pollutant or electrochemical oxidation product are degraded by microorganism further, thus realize the organic pollution in efficient degradation soil.
Positive electrode in described reactor and negative electrode carry out electrochemical reaction, and described spiral agitator rotates and makes organic polluted soil be monophasic fluid, utilizes the synergy of electrochemical oxidation and microbial degradation, degraded organic contaminants in soil.
Advantage of the present invention and beneficial effect are:
The one process organic polluted soil that the present invention adopts electrochemical oxidation and microbial degradation to work in coordination with, the characteristics of fluid state of soil to be repaired enhances the solid-liquid mass transfer in electrochemical reaction process, quick crashing organic macromolecule pollutant, for the degradation optimization of microorganism provides suitable condition.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
Fig. 2 is embodiment 1 pyrene degradation rate figure under electrochemical oxidation of the present invention and microbial degradation act synergistically;
Fig. 3 is embodiment 2 pyrene degradation rate figure under electrochemical oxidation of the present invention and microbial degradation act synergistically.
Wherein: 1 is dc source, 2 is iron anode, and 3 is graphite cathode, 4 is autoclave structural response device main body, and 5 is motor and spiral agitator, and 6 is air compressor, 7 is filter screen, and 8 is injection port, and 9 is outlet, 10 is peristaltic pump II, 11 is valve, and 12 is mud reservoir, and 13 is mud, 14 is immobilized microorganism, and 15 is peristaltic pump I.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described.
As shown in Figure 1, the electrochemistry of a kind of organic polluted soil of the present invention and microorganism are worked in coordination with and repair integration apparatus, comprise dc source 1, positive electrode 2, negative electrode 3, reactor 4, spiral agitator 5, motor and mud reservoir 12, wherein reactor 4 adopts autoclave structure, sidewall is arranged with injection port 8 and outlet 9, in reactor 4, outlet 9 place is provided with filter screen 7.Described injection port 8 is connected with mud reservoir 12 with sample channel by peristaltic pump I15, and outlet 9 is connected with peristaltic pump II10 by produce kinds of pipeline, and injection port 8 and outlet 9 place are equipped with valve 11.Be connected with the motor being arranged at reactor 4 outside in described spiral agitator 5 intercalation reaction device 4, described positive electrode 2 and negative electrode 3 to be spaced in reactor 4 and to be all connected with dc source, and positive electrode 2 and negative electrode 3 carry out electrochemical reaction.Be provided with aerator near negative electrode 3 in described reactor 4, described aerator is connected with air compressor 6.By continuous aeration, strengthening electrochemical reaction, thus degradable organic pollutant.Described positive electrode 2 is iron electrode, and described negative electrode 3 is graphite electrode, and described iron electrode and graphite electrode are symmetricly set in the both sides of spiral agitator 5.Described reactor 4 is autoclave structure.
The electrochemistry of described organic polluted soil and microorganism work in coordination with the method for repairing integration apparatus process organic polluted soil: add pending organic polluted soil and add immobilized microorganism 14 in described reactor 4, by regulating dissolved oxygen content in reactor 4, on the basis meeting microbiological deterioration, improve electrochemical oxidation intensity in reactor 4; Electrochemical oxidation is by pollutant mineralising or be degraded to small molecule contaminants, and pollutant or electrochemical oxidation product are degraded by microorganism further, thus realize the organic pollution in efficient degradation soil.
Positive electrode 2 in described reactor 4 and negative electrode 3 carry out electrochemical reaction, and described spiral agitator 5 rotates and makes organic polluted soil be monophasic fluid, accelerates the mass-transfer efficiency of dissolved oxygen, increases the reaction rate of electrochemical reaction.Utilize the synergy of electrochemical oxidation and microbial degradation, degraded organic contaminants in soil.
Embodiment 1
(1) preparation of electrochemical oxidation and microbial degradation concerted reaction device: the main body of reactor 4 adopts PVC autoclave structure, volume 1L, motor-operated spiral agitator 5 is put in centre, two electrodes are symmetrically placed in spiral agitator 5 both sides, two electrode distance 6cm, by air compressor 6 aeration near negative electrode, injection port 8 is distributed in reactor 4 both sides respectively with outlet 9 and is connected with peristaltic pump respectively, for sample introduction and go out sample.
(2) operational factor of electrochemical oxidation and microbiological deterioration: soil is that pyrene pollutes loam, loam air-dry mistake 60 mesh sieve, takes wind desiceted soil 200g, pyrene concentration is 100mg/kg, mud soil ratio is 3:1,10g/L anhydrous sodium sulfate is supporting electrolyte, and pH is 6.8, agitator speed 380r/min, aeration rate 1000ml/min, voltage gradient 2v/cm, immobilized microorganism addition is 2%, the cycle of operation is once 3d, and preference temperature is provided by electrochemical reaction heat production.
(3) operation of renovation of organic pollution soil is worked in coordination with in electrochemical oxidation and microbial degradation: 1) conditioning of mud soil ratio remains on setting ratio, conditioning of mud pH is under near-neutral sulfite deinking, open peristaltic pump I15, mud 13 is made to enter reactor 4 from mud reservoir 12, add a certain amount of immobilized microorganism 14, place two electrode positions.Start spiral agitator 5 and make rotating speed remain on predetermined value, preaeration simultaneously, after 15 minutes, applies voltage and carries out constant current degraded between negative electrode and positive electrode, and timing sampling measures organic matter degradation index; 2) after one-period terminates, by the peristaltic pump II10 of outlet 9, mud 13 after process is extracted out, immobilized microorganism 14 is retained by filter screen 7 and waits in the reactor 4 to continue to use simultaneously, open the peristaltic pump I15 at injection port 8 place again, repeat above operation, realize the continuous process to organic polluted soil.
Described electrochemical oxidation process is: in the electric field, and passing into dissolved oxygen can promote electrochemical oxidation process, effectively by various poisonous and unmanageable oxidation operation, can have good removal effect to the soil of multiring aromatic hydrocarbon bio-refractory.Test ferroelectric very anode, graphite electrode is negative electrode, is the columnar electrode of diameter 1cm, aeration near negative electrode, and 10g/L anhydrous sodium sulfate is supporting electrolyte.
The preparation of described immobilized microorganism: material comprises this laboratory seed selection degradation bacteria Pseudomonas fluorescens (Pseudomonas fluorescens, this bacterial strain is preserved in China typical culture collection center on July 19th, 2011, be called for short CCTCC, address is: Luo Jia Shan, wuchang, wuhan, Wuhan University, preservation registration number is CCTCC No:M2011260), polyvinyl alcohol, sodium alginate, calcium chloride, glutaraldehyde and hexamethylene diamine.10% polyvinyl alcohol water solution and 2% sodium alginate aqueous solution are mixed and made into embedding medium solution, after 1% degradation germ liquid is mixed with embedding medium, be added drop-wise in the saturated BAS containing 2% calcium chloride, after glue connection is solidified into bead, with hexamethylene diamine and glutaraldehyde, process is cured to bead surface again, obtain the embedded immobilization microbial bead that diameter is about 3mm, save backup in 0-4 DEG C of biochemical cultivation case.
In the integrated prosthetic appliance that electrochemical oxidation of the present invention is collaborative with microbial degradation, the degradation rate of pyrene contaminated soil first stage 3d pyrene under the synergy of electrochemical oxidation and microbial degradation reaches 86.55%, and process 12h after degradation rate namely close to 50%, mud is entered again by spoil disposal after first stage terminates, continuous second and the 3rd two stage degraded, the degradation rate of twice is all more than 80%, but degradation rate will lower than the first stage, and the phase III is less than second stage, as shown in Figure 2, microbial activity slightly reduces, but still keeps active.It can be said that this restorative procedure bright and reactor can realize the continuous high-efficient reparation to organic polluted soil.
Described microbial degradation and electrochemical oxidation technology all need dissolved oxygen content to a certain degree, and dissolved oxygen can be microbial degradation and creates aerobic environment on the one hand, and the increase of dissolved oxygen content, also can improve the intensity of electrochemical oxidation reactions on the other hand.Electrochemical oxidation technology is combined with microbial technology, sets up heterogeneous integrated integrated reactor, associated treatment organic polluted soil.Reactor 4 can be electrochemical oxidation reactions and provides required fluid and homogenization conditions, electrochemical oxidation can be microorganism and provides suitable temperature and effective electro photoluminescence, and not biodegradable pollutant is oxidized to biodegradable Small molecular organic pollution, thus improves overall treatment effect.
Embodiment 2
Reactor, immobilized microorganism, mud, reaction condition and course of reaction etc. are as described in Example 1, difference is to test ferroelectric very anode, graphite electrode is negative electrode, is plate electrode, and it is 5cm × 3cm × 0.2cm that electrode size is set to length x width x thickness.
In the integrated prosthetic appliance that the electrochemical oxidation and the microbial degradation that increase electrode surface area are collaborative, pyrene contaminated soil will height to the effect of the degradation capability pyrene columnar electrode of pyrene under the synergy of electrochemical oxidation with microbial degradation.The degradation rate of first stage 3d pyrene reaches 92.31%, and process 12h after degradation rate namely close to 65%, and second and the 3rd two stage degradation rate all more than 80%, but degradation rate will lower than the first stage, and the phase III is less than second stage, as shown in Figure 3, increase electrode surface area is described, increase electrochemical strengths thus the generation of hydroxyl radical free radical (.OH) is increased, accelerating the degraded of pollutant.
Claims (8)
1. the electrochemistry of an organic polluted soil and microorganism is collaborative repairs integration apparatus, it is characterized in that: comprise dc source (1), positive electrode (2), negative electrode (3), reactor (4), spiral agitator (5), motor and mud reservoir (12), wherein the sidewall of reactor (4) is provided with injection port (8) and outlet (9), described injection port (8) is connected with mud reservoir (12) with sample channel by peristaltic pump I (15), in described spiral agitator (5) intercalation reaction device (4), and the motor outside with being arranged at reactor (4) is connected, described positive electrode (2) and negative electrode (3) are spaced in reactor (4), and be all connected with dc source.
2. work in coordination with by electrochemistry and the microorganism of organic polluted soil according to claim 1 and repair integration apparatus, it is characterized in that: be provided with aerator near negative electrode (3) in described reactor (4), described aerator is connected with air compressor (6).
3. work in coordination with by electrochemistry and the microorganism of organic polluted soil according to claim 1 and repair integration apparatus, it is characterized in that: described positive electrode (2) is iron electrode, described negative electrode (3) is graphite electrode, and described iron electrode and graphite electrode are symmetricly set in the both sides of spiral agitator (5).
4. work in coordination with by electrochemistry and the microorganism of organic polluted soil according to claim 1 and repair integration apparatus, it is characterized in that: described reactor (4) is autoclave structure.
5. work in coordination with by electrochemistry and the microorganism of organic polluted soil according to claim 1 and repair integration apparatus, it is characterized in that: injection port (8) and outlet (9) place of described reactor (4) are equipped with valve (11).
6. work in coordination with by electrochemistry and the microorganism of organic polluted soil according to claim 1 and repair integration apparatus, it is characterized in that: described reactor (4) interior outlet (9) place is provided with filter screen (7).
7. the method by the equipment renovation of organic pollution soil described in any one of claim 1-6, it is characterized in that: add pending organic polluted soil in described reactor (4) and add immobilized microorganism (14), by regulating dissolved oxygen content in reactor (4), on the basis meeting microbiological deterioration, improve electrochemical oxidation intensity in reactor (4); Electrochemical oxidation is by pollutant mineralising or be degraded to small molecule contaminants, and pollutant or electrochemical oxidation product are degraded by microorganism further, thus realize the organic pollution in efficient degradation soil.
8. by method according to claim 7, it is characterized in that: the positive electrode (2) in described reactor (4) and negative electrode (3) carry out electrochemical reaction, described spiral agitator (5) rotates and makes organic polluted soil be monophasic fluid, utilize the synergy of electrochemical oxidation and microbial degradation, degraded organic contaminants in soil.
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CN104907324A (en) * | 2015-06-26 | 2015-09-16 | 西安工程大学 | Oil polluted soil degrading method based on combination of zoogloearesiniphila, bacillus and electric field |
CN104923559A (en) * | 2015-06-26 | 2015-09-23 | 西安工程大学 | Oily soil degradation method based on combination of pseudomonas, zoogloea and electric field |
CN105290100A (en) * | 2015-11-23 | 2016-02-03 | 河海大学 | Method for remedying facility continuous cropping acidized soil through microorganism-electric combination |
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CN104907324A (en) * | 2015-06-26 | 2015-09-16 | 西安工程大学 | Oil polluted soil degrading method based on combination of zoogloearesiniphila, bacillus and electric field |
CN104923559A (en) * | 2015-06-26 | 2015-09-23 | 西安工程大学 | Oily soil degradation method based on combination of pseudomonas, zoogloea and electric field |
CN104923559B (en) * | 2015-06-26 | 2018-03-23 | 西安工程大学 | Based on pseudomonad, dynamic glue bacterium and the united petroleum-contaminated soil biodegrading process of electric field |
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CN105290100A (en) * | 2015-11-23 | 2016-02-03 | 河海大学 | Method for remedying facility continuous cropping acidized soil through microorganism-electric combination |
CN105290100B (en) * | 2015-11-23 | 2018-08-21 | 河海大学 | A kind of method of the electronic joint restoration facilities continuous cropping acidified soil of microorganism- |
CN106269842A (en) * | 2016-09-13 | 2017-01-04 | 山东师范大学 | Electrochemical oxidation drip washing Cr contaminated soil processes integrated apparatus and processing method |
CN109317506A (en) * | 2018-09-05 | 2019-02-12 | 上海大学 | The method repaired the electric device of As polluted soil and repair As polluted soil |
CN109513739A (en) * | 2018-11-02 | 2019-03-26 | 江苏澳洋生态园林股份有限公司 | A kind of electrochemical oxidation soil restoring device |
CN110193514A (en) * | 2019-07-09 | 2019-09-03 | 北京石油化工学院 | Repair the electronic and intensified by ultrasonic wave mud bioreactor of oily sludge and soil |
CN110681693A (en) * | 2019-11-27 | 2020-01-14 | 唐君 | Soil remediation device for treating heavy metal pollutants |
CN111545563A (en) * | 2020-05-19 | 2020-08-18 | 华东理工大学 | Slurry reaction method for treating petroleum-polluted soil by coupling electroactive persulfate with microorganisms |
CN112090952B (en) * | 2020-08-29 | 2021-07-27 | 山西大学 | Boiling type micro-foam soil pollution desorption device and method suitable for coking field |
CN112547790A (en) * | 2020-12-28 | 2021-03-26 | 苏州精英环保有限公司 | Device for repairing organic contaminated soil through microbial combined chemical oxidation |
CN112872014A (en) * | 2021-01-08 | 2021-06-01 | 南开大学 | Stackable recyclable microbial electrochemical reactor and degradation method of petroleum hydrocarbon polluted soil |
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