CN106269843A - The in-situ remediation method of one heavy metal species organic co-contaminated soil - Google Patents
The in-situ remediation method of one heavy metal species organic co-contaminated soil Download PDFInfo
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- CN106269843A CN106269843A CN201610943531.3A CN201610943531A CN106269843A CN 106269843 A CN106269843 A CN 106269843A CN 201610943531 A CN201610943531 A CN 201610943531A CN 106269843 A CN106269843 A CN 106269843A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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Abstract
The present invention relates to the in-situ remediation method of a heavy metal species organic co-contaminated soil, this method is that a set of electro reclamation device increases Power transfer system, electrode heating technology is combined with electro reclamation and chemical oxidation techniques, i.e. first with DC source, by electrokinetic process, oxidant sodium peroxydisulfate is migrated into soil, realize migration and the removal of heavy metal in soil ion simultaneously.Then switch alternating current power supply, by heated by electrodes mode, soil is increased to uniform temperature and carrys out the sodium peroxydisulfate in Activation And Transportation entrance soil, thus realize the ira situ degradation of organic contaminants in soil.Electrode is applied simultaneously in heated by electrodes system and electro reclamation system by this method, simplify prosthetic appliance, save system energy consumption, solve the difficult problem that oxidant cannot migrate and activate in soil simultaneously, improve remediation efficiency, be a kind of associating soil restoring technology having application prospect.
Description
Technical field
The present invention designs the in-situ remediation method of one heavy metal species-organic co-contaminated soil, adds especially by electrode
Hometown earth combines with electro reclamation and chemical oxidation, and utilizing electrokinetic process to promote, sodium peroxydisulfate migrates into the same of soil
Time, it is achieved the electro reclamation of heavy metal in soil ion, then the mode by heated by electrodes soil carrys out Activation And Transportation entrance soil
Sodium peroxydisulfate in earth, thus realize the efficient oxidation degraded of organic contaminants in soil, belong to technical field of soil remediation.
Background technology
Along with China " move back two and enter three ", the enforcement of " Tui Chengjin garden " policy, large-scale industrial undertaking resettlement cause city
Occurring in that and leave in a large number, abandon industrial pollution place, the place of leaving over after these resettlements creates pole to environmental and human health impacts
Big risk, it would be highly desirable to repair and administer.
At present, the technology that soil remediation is conventional have excavation, landfill, stabilisation solidification, chemical leaching, chemistry redox,
Cement kiln synergic processing, thermal desorption, phytoremediation and microorganism remediation etc., but these technology are to be excavated by pollutant mostly
Carry out dystopy process, it is easy to cause secondary pollution.And plant and microorganism remediation technology are faced with that repairing efficiency is short, repair
Multiple inefficient problem.Therefore, it is badly in need of development soil remediation new technique and solves these problems.
Electric repairing technique is a kind of in-situ soil remediation technology risen the eighties in last century, by executing at soil two ends
Adding direct current weak electric field, the pollutant in soil move to electrode district by the way of electromigration, EOF and electrophoresis and are enriched with.
Electric repairing technique can be particularly well-suited to the reparation of hypotonicity soil with remediating heavy metal, organic and combined contamination soil.
Along with soil restoring technology from dystopy to the development of based technique for in-situ remediation, electric repairing technique advantage in soil remediation is also got over
Come the most obvious.
When processing organic pollution, generally electric repairing technique is combined with other technologies and improves remediation efficiency,
As electro reclamation combines with chemical oxidation, electric field can promote oxidant migration in soil, so that it arrives target
Polluted area, it is achieved the in-situ oxidation of organic pollution.Sodium peroxydisulfate is a kind of new oxidants, and it has higher chemical oxygen
Change current potential.But due to the preferable chemical stability of sodium peroxydisulfate, itself occur redox speed very slow, through overactivation
The higher potentiometric titrations of rear generation oxidisability can significantly improve remediation efficiency.Thus the pass implemented is repaired in sodium peroxydisulfate oxidation
Key is the activation being sodium peroxydisulfate.
The activation method of sodium peroxydisulfate has thermal activation, alkali activation, ironwork and hydrogen peroxide activation, beyond heat extraction activation,
After all there is activator in other activation methods and sodium peroxydisulfate ratio cannot regulate and control problem, activator and sodium peroxydisulfate mixing,
Sodium peroxydisulfate arrives before Polluted area and can inevitably decompose, it is impossible to realize after sodium peroxydisulfate is transferred to Polluted area
In-situ activation.Comparatively speaking, as long as soil is heated to uniform temperature by thermal activation, (about 50 DEG C) can realize sodium peroxydisulfate
Activation and the degraded of pollutant.Therefore, associating original position soil heating technique and chemical oxidation techniques can solve the problem that sodium peroxydisulfate
The problem of activation.
Original position soil mode of heating mainly includes resistance heating, conduction of heat heating, steam/heat air injected with heated and microwave
Heating.Wherein ohmic heating technology is to insert electrodes in soil, produces electromotive force and voltage difference, applies 100-400V on electrode
Voltage because soil is conductive, electric current can conduct in soil so that soil heating.Due at resistance heating process
In, the moisture in soil aperture serves the effect of conduction electric current, and therefore subsurface temperature is not above water under local atmospheric pressure
Boiling point, i.e. 100 DEG C, and soil can not be oven-dried.
The document that relevant hot repair at present is answered and electro reclamation combines is little, and China Patent No. CN103286120B authorizes
A kind of Microwave electric soil in-situ prosthetic device and restorative procedure, this invention is imbedded microwave absorbing material in soil, is first passed through
Some organic pollutants and heavy metal in Electroremediation and microwave heating combine d bioremediation soil, when temperature is higher than 200 DEG C, stop
Only Electroremediation system, continue to use high temperature microwave Soil Thermal recovery technique difficulty to be volatilized, the organic pollution of difficult degradation and
Residual heavy metal carries out vitrification to be fixed.The method uses microwave heating technique too high, inevitably to soil moisture heating
It is evaporated soil moisture, thus suppresses the migration of Electroremediation process heavy metal ion.Application number
The repair system of the application for a patent for invention of 201510745350.5 one heavy metal species-organic co-contaminated soil and method.Should
Ohmic heating technology, soil air stripping technology and Electroremediation technology are combined by method, first use resistance to add by alternating current power supply
Soil is heated to 50-100 DEG C and organic pollution carries out thermal desorption final vacuum extracting process by hot systems, then uses unidirectional current
Source carries out the heavy metal in electro reclamation soil.Although this repair system simplifies equipment, but is also heated to by soil higher
Temperature, repairing efficiency is long, and energy consumption is the most of a relatively high, additionally for some high boiling organic pollutions, the heating less than 100 DEG C
Temperature also cannot realize these organic thermal desorptions.
Summary of the invention
Therefore, during the technical problem to be solved in the present invention overcomes existing in situ chemical oxidation exactly, oxidant cannot
Move to Polluted area, and the problem that oxidant and activator ratio cannot regulate and control, use electro reclamation and resistance heating phase
In conjunction with mode realize migration and the activation of sodium peroxydisulfate, utilize electrokinetic process to realize the removal of heavy metal in soil simultaneously.
For reaching above-mentioned purpose, the solution that the present invention takes is: one heavy metal species-organic co-contaminated soil former
Position restorative procedure, it is characterised in that: comprise the following steps:
(1) building the in-situ remediation system of one heavy metal species-organic co-contaminated soil, described system includes: electro reclamation system
System, including the anode being connected with DC source and negative electrode；Oxidative agent injection system；Resistive heating system, including with alternating current power supply
The anode connected and negative electrode；Power transfer system, including be connected with DC power system first switch and with alternating current power supply system
The second switch that system is connected；
(2) injection of sodium peroxydisulfate solution: sodium peroxydisulfate solution is injected in anode well by oxidative agent injection system；
(3) operation of direct current drive repair system: Guan Bi the first switch, utilizes DC source to carry out electrokinetic process, persulfate
With heavy metal ion under electric field action to cathodic migration；Simultaneously for avoiding negative electrode generation heavy metal precipitation, use citric acid solution
Controlling catholyte pH is faintly acid；
(4) AC resistance heating system is run: disconnects the first switch, closes second switch, utilize resistive heating system to soil
Heat, until the two electrode centre position soil moistures are increased to 40-50 DEG C, after maintaining a period of time, close closed system.
Anode described in step one and negative electrode are stainless steel electrode or graphite electrode or metal-oxide inert electrode, two electricity
Distance between pole is 1-2 m.
Alternating current power supply described in step one connects adjustable resistance, is used for regulating the voltage on electrode.
Described in step one, voltage x current monitor is connected with the outfan of D.C. regulated power supply, and described temperature detector is arranged
Near electrode part soil and electrode centre position cold end soil in soil region to be repaired, temperature detector probe is inserted
Soil.
The set-up mode of electrode described in step one includes be arrangeding in parallel or regular hexagon setting of anode and cathode.
Described in step one, the voltage gradient between power driven system anode and cathode is 10-150 V/m.
In oxidative agent injection system described in step 2, medicament is added from anode well by high-pressure pump, makes sodium peroxydisulfate concentration
For in this Polluted area 5-15 times of soil organic matter content.
Controlling catholyte pH scope described in step 3 is 4.5-5.0.
The operation time of direct current drive repair system described in step 3 is 15-90 days.
Described in step 4, the AC resistance heating system operation time is 15-90 days.
The inventive method, first uses DC source, makes sodium peroxydisulfate migrate into soil by electrokinetic process, simultaneously soil
In heavy metal migrate in catholyte under electric field action.It is then turned off DC power system, connects alternating current power supply
System, makes soil warming to uniform temperature to activate sodium peroxydisulfate during resistance heats, thus realizes organic pollution
Ira situ degradation.
One heavy metal species of the present invention-organic co-contaminated soil in-situ remediation method, has the advantage that
(1) electrode is applied simultaneously in electro reclamation system and resistive heating system by the method for the present invention, and utilizes power supply to cut
Electrode is switched between electro reclamation and resistance heat by system of changing, it is achieved that electric repairing technique and resistance heat treated skill
The combination of art, simplifies system equipment, and on this basis, it is achieved that the migration of sodium peroxydisulfate and in-situ heat activation and
The migration of heavy metal in soil ion, improves the removal efficiency of organic contaminants in soil and heavy metal.
(2) the method profit of the present invention is heated by resistive and the soil moisture is increased to 40-50 DEG C, is possible not only to for activating
Sodium sulfate, it is also possible to improve the saturated vapour pressure of pollutant in soil, dissolubility, diffusion coefficient, desorption rate, and biological fall
Solution rate, these movement and degradeds of both contributing to improve pollutant.
(3) method of the present invention, range is wide, and repairing effect is good, and repairing efficiency is short, and rehabilitation cost is relatively low, and method is grasped
Making simple, reliability is high, has good promotion potential, in particular for heavy metal and the combined contamination soil of organic pollution
Gather around and have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the system structure signal of the in-situ remediation method of the one heavy metal species-organic co-contaminated soil of the present invention
Figure.
Fig. 2 is the inventive method first stage and second stage repairing effect comparison diagram.
In Fig. 1, concrete parts are as follows:
1. alternating current power supply, 2. the first switch, 3. adjustable resistance, 4. DC source, 5. second switch, 6. voltage x current prison
Survey instrument, 7. anode, 8. negative electrode, 9. anode well, 10. negative electrode well, 11. oxidant storage tanks, 12. high-pressure pumps, 13. electricity
Solve liquid treating system, 14. first peristaltic pumps, 15. industrial digital pH meters, 16. second peristaltic pumps, 17. acid solution storage tanks.
Detailed description of the invention
The present invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Choosing 2m*2m scope in a certain contaminated site to process, the soil pollution degree of depth about 2m, pollutant are predominantly
Cu, Cd and chlorobenzene.
The system utilizing above-mentioned heavy metal-organic co-contaminated soil in-situ immobilization carries out the method repaired, including as follows
Step:
(1) building the in-situ remediation system of one heavy metal species-organic co-contaminated soil, described system includes: electro reclamation system
System, including the anode 7 being connected with DC source 4 and negative electrode 8, electrode is respectively placed in electrode wells 9 and 10；Oxidant injects system
System, including the high-pressure pump 12 being connected with medicament storage tank 11；Resistive heating system, including the anode 7 being connected with alternating current power supply 1 and the moon
Pole 8；Power transfer system, including the first switch 5 being connected with DC power system and be connected with AC power supply system second
Switch 2；Automatic monitoring system, including voltage x current monitor 6 and temperature detector 18, described voltage x current monitor 6 is with straight
The outfan of stream regulated power supply 4 is connected, and described temperature detector 18 is arranged in soil region to be repaired near electrode part soil
Earth and electrode centre position cold end soil, inserts soil by temperature detector probe；PH automatic control system, including Techno-Industrial
PH meter 15, single channel peristaltic pump 16 and acid solution storage tank 17, described industrial digital pH meter 15 is placed in negative electrode well 10, compacted by second
Dynamic pump 16 is connected with acid solution storage tank 17.Described electro reclamation system, also includes electrolyte processing system 13, by the first peristaltic pump 14
The electrolyte that negative electrode contains heavy metal is drawn to reuse after electrolyte processing system 13 processes.Above-mentioned alternating current power supply 1 is also
Connect and have adjustable resistance 3, be used for regulating the voltage on electrode, to control soil heating-up temperature.
(2) selection of electrode and installation: using graphite electrode to be fit in making holes in soil, anode and cathode parallel divide
Cloth, the distance between two electrodes is 2 m, electrode length 2 m, and restoring area arranges 4 electrodes altogether.
(3) injection of sodium peroxydisulfate solution: use high-pressure pump that the sodium peroxydisulfate solution in oxidant storage tank is injected anode
In electrode hole, the concentration values of sodium peroxydisulfate is its dissolubility maximum 400g/L, uses high-pressure pump to be noted by sodium peroxydisulfate solution
Entering in anode well pollution depth, making this Polluted area sodium peroxydisulfate concentration is in this Polluted area the 15 of soil organic matter content
Times.Oxidant injects in three times, injects electronic beginning the 1st day, the 10th day and the 20th day respectively.
(4) operation of direct current drive repair system: Guan Bi the first switch, utilizes DC source to carry out electro reclamation, voltage
Gradient is set to 50 V/m, and cycle of operation is 30 days.Control catholyte pH with the citric acid solution of 0.5M is 5.0 simultaneously,
Persulfate and heavy metal ion are to cathodic migration under electric field action, and the electrolyte extracted out in negative electrode well for every 10 days is to processing dress
Put and process.
(5) AC resistance heating system is run: disconnects the first switch, closes second switch, utilize resistive heating system pair
Soil carries out heating 30 days, until the two electrode centre position soil moistures are increased to 40-50 DEG C, after maintaining 15 days, closes closed system.
Effect after first stage and second stage reparation is compared, as in figure 2 it is shown, electronic repair through the first stage
After multiple, the clearance of heavy metal in soil reaches 75%, and the clearance of organic pollution has reached 45%.Through second stage resistance
After heating is repaired, the clearance of heavy metal in soil reaches 90%, and the clearance of organic pollution has reached 85%.
Claims (9)
1. the in-situ remediation method of one heavy metal species-organic co-contaminated soil, it is characterised in that: comprise the following steps:
Step one, building the in-situ remediation system of one heavy metal species-organic co-contaminated soil, described system includes: electronic repair
Complex system, including the anode being connected with DC source and negative electrode；Oxidative agent injection system；Resistive heating system, including with exchange
The anode of power supply connection and negative electrode；Power transfer system, including the first switch and and the alternating current being connected with DC power system
The second switch that origin system is connected；
Step 2, the injection of sodium peroxydisulfate solution: sodium peroxydisulfate solution is injected in anode well by oxidative agent injection system；
Step 3, the operation of direct current drive repair system: Guan Bi the first switch, utilize DC source to carry out electrokinetic process, over cure
Acid group and heavy metal ion under electric field action to cathodic migration；Simultaneously for avoiding negative electrode generation heavy metal precipitation, use citric acid
It is faintly acid that solution controls catholyte pH；
Step 4, AC resistance heating system are run: disconnect the first switch, close second switch, utilize resistive heating system pair
Soil heats, until the two electrode centre position soil moistures are increased to 40-50 DEG C, after maintaining a period of time, closes closed system.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
Anode described in rapid one and negative electrode are stainless steel electrode, graphite electrode or metal-oxide inert electrode, between two electrodes away from
From for 1-2 m.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
Alternating current power supply described in rapid one connects adjustable resistance, is used for regulating the voltage on electrode.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
Described in rapid one, voltage x current monitor is connected with the outfan of D.C. regulated power supply, and described temperature detector is arranged on earth backing to be repaired
Near electrode part soil and electrode centre position cold end soil in earth region, temperature detector probe is inserted soil.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
The set-up mode of electrode described in rapid one includes be arrangeding in parallel or regular hexagon setting of anode and cathode.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
Described in rapid one, the voltage gradient between power driven system anode and cathode is 10-150 V/m.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
In oxidative agent injection system described in rapid two, medicament is added from anode well by high-pressure pump, and making sodium peroxydisulfate concentration is this contaminated area
In territory 5-15 times of soil organic matter content.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
Controlling catholyte pH scope described in rapid three is 4.5-5.0.
The in-situ remediation method of heavy metal-organic co-contaminated soil the most according to claim 1, it is characterised in that: step
The operation time of direct current drive repair system described in rapid three is 15-90 days；When AC resistance heating system described in step 4 is run
Between be 15-90 days.
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