CN103232096A - In-situ repairing system and repairing method capable of continuously removing Cr in underground water - Google Patents
In-situ repairing system and repairing method capable of continuously removing Cr in underground water Download PDFInfo
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- CN103232096A CN103232096A CN2013101502566A CN201310150256A CN103232096A CN 103232096 A CN103232096 A CN 103232096A CN 2013101502566 A CN2013101502566 A CN 2013101502566A CN 201310150256 A CN201310150256 A CN 201310150256A CN 103232096 A CN103232096 A CN 103232096A
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Abstract
The invention relates to an in-situ repairing system and a repairing method capable of continuously removing Cr in underground water; the repairing system comprises one or more layers of iron nets, one or more layers of PVC (Polyvinyl Chloride) nets, an iron filling material and an iron brush type electrode, wherein one or more layers of iron nets are put in a caisson of a permeable reactive barrier (PRB); one or more layers of PVC nets are put in the iron nets; the iron filling material is put in the PVC nets; the iron brush type electrode is inserted into the iron filling material; the iron brush type electrode is put on the sharp part at one end in the caisson of the PRB and contacted with the iron nets; and a power supply is connected with the iron nets and the iron brush type electrode. The repairing method disclosed by the invention comprises the following steps that: after the iron filling material is passivated, one corner of the iron net is selected as the anode; the iron brush type electrode is selected as the cathode; the iron net and the iron brush type electrode are electrified through the power supply; then, the other corner of the iron net is selected as the anode; the iron net is electrified for the same time; finally, the anode and the cathode are reversed and electrified for the same time; a lot of hydrogen is separated on the surface at one side of the cathode; the hydrogen has the functions of stripping and eliminating an adhesive layer on the cathode, so that the passivated layer on the surface of iron is stripped; and a lot of iron ions are dissolved at one side of the anode and used for stripping sediment on the surface of the iron filling material. The in-situ repairing system and the repairing method disclosed by the invention are capable of continuously removing Cr pollution and effectively solving the passivation problem of application of the traditional PRB.
Description
Technical field
The present invention relates to the removal technical field of Cr in the underground water, be specifically related to a kind of sustainable removal underground water Cr Pollution in Situ repair system and restorative procedure.
Background technology
At present, the underground water in the many areas of China and even the world all is subjected to Cr in various degree and pollutes, serious threat resident's drinking water safety, and Cr pollutes and more and more is subjected to extensive concern in the underground water.Cr is listed in one of eight kinds of maximum chemical substances of human body harm, is one of internationally recognized three kinds of carcinogenic metals, also is simultaneously one of 129 kinds of generally acknowledged priority pollutants of U.S. EPA.The World Health Organization's " water quality standard for drinking water " and China's " drinking water sanitary standard " all regulation sexavalence Cr standard are 0.05mg/L.Extraction-facture is adopted in the underground water reparation that polluted by Cr usually, comprises the compound integrated method of physico-chemical process, chemical method, biological process and these technology.Extraction-facture is handled after underground pollution water is extracted again, cost height, cycle length, energy consumption cause secondary pollution greatly, easily, can not carry out the original position reparation and effectively solve the problem of directly using of extracting out, more can not be from the long-term drinking water safety that ensures China resident on the macroscopic view.PRB(infiltration type reaction wall) technology is a kind of emerging based technique for in-situ remediation of efficient economy, this technology need not additionaling power, ground stores treatment measures, operation and maintenance cost are lower, can remove multiple pollutent simultaneously, comprise heavy metal, organism, radionuclide and nutritive substance.This technology has successfully applied in the polluted underground water reparation on the spot the America and Europe, and this technology also is in the starting stage in China.Zero-valent Iron because have inexpensive, high reduction potential, speed of response is fast, become PRB and use maximum reaction medium material.
A lot of scenes and laboratory applications Fe-PRB remove Cr (VI) and have obtained effect preferably.Cr in the Fe-PRB system (VI) at first is reduced to Cr (III), follows Zero-valent Iron to be oxidized to Fe (II) or Fe (III), and then Cr precipitates with the form of Cr (III) oxyhydroxide or Fe (III)/Cr (III) oxyhydroxide.In the PRB operational process, Zero-valent Iron or ferrous iron are oxidized to ferric iron by Cr (VI), cause that the pH value raises.Simultaneously, Zero-valent Iron by dioxygen oxidation, under anaerobic can all be accompanied by the rising of pH value by the water oxidation under aerobic condition.This makes in PRB long-time running process, forms alkaline condition, causes the Zero-valent Iron surface to generate the precipitations such as oxide compound, oxyhydroxide of iron.At present, the bottleneck problem in the PRB application process be occur in the long-time running process because the problem that the passivation of Zero-valent Iron causes processing power to reduce.The Zero-valent Iron surface precipitation can cover the iron surface avtive spot in various degree according to thickness is different with composition, and causing electronics to transmit resistance increases, and the Zero-valent Iron surface reaction activity reduces.Henderson and Demond have collected the original position PRB service data of a plurality of contaminated sites, identify the parameter that influences the PRB operation, think that the activity of Zero-valent Iron is the main factor of the permanently effective operation of restriction PRB than the perviousness reduction.Flurry etc. carry out research in 4 years to Switzerland Cr contaminated site PRB, find that the major cause that causes the PRB treatment effect to reduce is the passivation of Zero-valent Iron, and the while is blockage phenomenon not.The mineral ion of polluted water is formed the generation that can influence precipitation, in laboratory and on-the-spot operation PRB, find multiple sedimentable matter, Cr (III)-Fe (III) precipitation of hydroxide as Fe (III) and Cr (III) co-precipitation formation, the oxide compound of various iron, the oxyhydroxide of iron and carbonate deposition etc.The Zero-valent Iron solution passivating method of report comprises pickling and supersound process etc. at present, but there are problems such as processing costs height, workload is big, operability is not strong in varying degrees in these means.Therefore, need at present that a kind of cost is low, efficient is high badly, easy handling, can be used for the technology in actual treatment place, thereby effectively solve the problem of passivation that influence the PRB application.
The field engineering of infiltration type reaction wall has following several field engineering usually: the conventional groove formula is installed, caisson type is installed, landfill is installed and excavated continuously to the mandrel formula.Plough groove type is installed the mode that hollows out backfill that adopts, and squeezes into sheet pile with bracing reinforcement, the method that adopts equipment such as backhoe and clampshell dredging shovel to dig out a groove afterwards around the reaction member of intending excavation.Caisson type is installed as and utilizes prefabricated steel caisson to help excavation, when caisson reaches the set degree of depth its inner soil is removed, and fills out the reflection medium.The mandrel formula is installed and is utilized a hollow steel axle or mandrel to open up a packaged space of filling out reaction medium, then medium is filled into.Continous way excavation can excavate the narrow groove of 40cm-60cm continuously, simultaneously immediately with the reaction medium backfill or put into the continuous barrier film of high-density polyvinyl chloride of antiseepage.Polluting local many water proof funnel-wicket gate systems with caissons that pinniform is wideer, concentration is higher, flow velocity is bigger, the caisson general diameter is 2.4m or littler, and diameter is more little more easily to be pushed and keep vertical state.
Summary of the invention
In order to solve the problem that above-mentioned prior art exists, the object of the present invention is to provide a kind of sustainable removal underground water Cr Pollution in Situ repair system and restorative procedure, this original position repair system can be removed Cr sustainably and pollute, solve the problem of passivation that conventional P RB uses effectively, after traditional PRB system filler Zero-valent Iron passivation, need not more conversion materials, realize the former bit recovery of ironwork, prolonged the operation life of PRB system.
For reaching above purpose, the present invention adopts following technical scheme:
A kind of sustainable removal underground water Cr Pollution in Situ repair system, comprise one or more layers iron net 2 of putting into infiltration type reaction wall caisson 1 and being close to its inwall, place one or more layers PVC net 3 in the iron net 2, place the iron filler 4 in the PVC net 3, insert the iron brush electrode 5 in the infiltration type reaction wall caisson 1 central position iron filler 4, described iron brush electrode 5 places the tip of an end in the infiltration type reaction wall caisson 1 to touch the iron net, also comprises the power supply 6 that is connected with iron brush electrode 5 with iron net 2.
Comprise that also the ionogen that is communicated with infiltration type reaction wall caisson 1 adds stirred vessel 7.
The virtual voltage of described power supply 6 is 0-50V, and watt current is 0-5A.
The restorative procedure of original position repair system described above at first flows into synthetic Cr polluted water from infiltration type reaction wall caisson 1 water-in, water outlet flows out, when reaction reaches Preset Time, and 4 couples of Cr of iron filler
6+Clearance when being lower than the clearance of setting, after being 4 passivation of iron filler, choose the iron net and be a positive pole for 2, iron brush electrode 5 is negative pole, behind power supply 6 energising 1-30min, choose iron net 2 another angles again for anodal, switch on the same time, put upside down positive and negative electrode at last again, switch on the same time, by adding certain electric field, one side of negative electrode, a large amount of hydrogen can be separated out in the surface, and a large amount of bubbles break loose from iron filler 4 surfaces, adhesion layer on it is peeled off and scavenging(action), the iron surface passivation layer is peeled off; The precipitation on iron filler 4 surfaces is peeled off in a large amount of strippings of one side iron ion of anode;
In electrochemistry solution passivating process, when iron as negative electrode and when certain potential value is arranged, following electrochemical reaction takes place, separate out a large amount of hydrogen:
Anode: 2H
2O → O
2+ 4H
++ 4e
-
Negative electrode: 2H
2O+2e
-→ H
2+ 2OH
-
When iron during as anode, following electrochemical reaction takes place, anode has iron ion and produces:
Anode: Fe → Fe
2++ 2e
-
Negative electrode: 2H
2O+2e-→ H
2+ 2OH
-(2) O
2+ 2H
2O+4e
-→ 4OH
-
In when energising, by ionogen add stirred vessel (7 to the iron filler (add anhydrous sodium sulphate in 4 as ionogen, the dosage of anhydrous sodium sulphate is 0.5g/L.
Cr is 25mg/L in the described synthetic Cr polluted water; Na
2SO
4Be 0.5g/L.
The present invention compares with prior art, has following advantage:
(1) all processing are finished in single reaction unit, need not more conversion materials, escapable cost;
(2) separating the passivation post-reactor removes Cr efficient height and can not cause secondary pollution
(3) be applicable to PRB caisson type field engineering, it is simple, easy to operate to construct, the level of automation height.
Description of drawings
Fig. 1 is original position repair system skeleton view of the present invention.
Fig. 2 is original position repair system simulated slot of the present invention (caisson volume device) skeleton view.
Fig. 3 is iron brush electrode synoptic diagram, and wherein Fig. 3 a is front view, and Fig. 3 b is vertical view.
Fig. 4 is Cr change curve in time in the original position repair system.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail.
As depicted in figs. 1 and 2, a kind of sustainable removal underground water Cr Pollution in Situ repair system of the present invention, comprise one or more layers iron net 2 of putting into infiltration type reaction wall caisson 1 and being close to its inwall, place one or more layers PVC net 3 in the iron net 2, place the iron filler 4 in the PVC net 3, insert the iron brush electrode 5 in the infiltration type reaction wall caisson 1 central position iron filler 4, described iron brush electrode 5 places the tip of an end in the infiltration type reaction wall caisson 1 to touch PVC net 3, also comprises the power supply 6 that is connected with iron brush electrode 5 with iron net 2.Comprise that also the ionogen that is communicated with infiltration type reaction wall caisson 1 adds stirred vessel 7.
As preferred implementation of the present invention, the virtual voltage of described power supply 6 is 0-50V, and watt current is 0-5A.
As shown in Figure 3, be iron brush electrode synoptic diagram, wherein Fig. 3 a is front view, and Fig. 3 b is vertical view.
Embodiment
Adopt a 6x4x3=72cm
3The organic plastics reactive tank.A direct current stabilizer is as power supply, and its virtual voltage is 0-50V, and watt current is 0-5A.Adopt synthetic Cr polluted water (Cr, 25mg/L in the experiment; Na
2SO
4; 0.5g/L the experiment water inlet adopts the mode of upwelling to carry out, and contains the Cr polluted water and flows into from reactor bottom with the 4mL/min flow velocity, and flow out from reactor head.Be about 198min when the reaction times, find the iron filler to the clearance of Cr (VI) and initially clearance compare significantly and reduce.Power up with 10v voltage, choose respectively the iron net wherein one jiao for anodal, the iron brush electrode is negative pole electrolysis 5min, chooses another angle again for the operation before anodal the repetition, puts upside down positive and negative electrode then.As shown in Figure 4, the clearance recovery rate is initial clearance 108.2% after electrolysis as can be seen, and the life-span of PRB is effectively prolonged.
As the optimal way of present embodiment, when energising, add stirred vessel 7 by ionogen and in iron filler 4, add anhydrous sodium sulphate as ionogen, the dosage of anhydrous sodium sulphate is 0.5g/L.By adding anhydrous sodium sulphate, make solution have certain specific conductivity, if the treatment soln specific conductivity is enough big, can not add sodium sulfate, specifically can add with the actual treatment water condition.
Claims (6)
1. sustainable removal underground water Cr Pollution in Situ repair system, it is characterized in that: comprise one or more layers iron net (2) of putting into infiltration type reaction wall caisson (1) and being close to its inwall, place one or more layers PVC net (3) in the iron net (2), place the iron filler (4) in the PVC net (3), insert the iron brush electrode (5) in infiltration type reaction wall caisson (1) the central position iron filler (4), described iron brush electrode (5) places the tip of an end in the infiltration type reaction wall caisson (1) to touch the iron net, also comprises the power supply (6) that is connected with iron brush electrode (5) with iron net (2).
2. a kind of sustainable removal underground water Cr Pollution in Situ repair system according to claim 1 is characterized in that: comprise that also the ionogen that is communicated with infiltration type reaction wall caisson (1) adds stirred vessel (7).
3. a kind of sustainable removal underground water Cr Pollution in Situ repair system according to claim 1 and 2, it is characterized in that: the virtual voltage of described power supply (6) is 0-50V, watt current is 0-5A.
4. the restorative procedure of each described original position repair system of claim 1 to 3 is characterized in that:
At first synthetic Cr polluted water is flowed into from infiltration type reaction wall caisson (1) water-in, water outlet flows out, and when reaction reaches Preset Time, iron filler (4) is to Cr
6+Clearance when being lower than the clearance of setting, after being iron filler (4) passivation, choose the iron net and be a positive pole for (2), iron brush electrode (5) is negative pole, behind power supply (6) energising 1-30min, choose another angle of iron net (2) again for anodal, switch on the same time, put upside down positive and negative electrode at last again, switch on the same time, by adding certain electric field, one side of negative electrode, a large amount of hydrogen can be separated out in the surface, and a large amount of bubbles break loose from iron filler (4) surface, adhesion layer on it is peeled off and scavenging(action), the iron surface passivation layer is peeled off; The precipitation on iron filler (4) surface is peeled off in a large amount of strippings of one side iron ion of anode;
In electrochemistry solution passivating process, when iron as negative electrode and when certain potential value is arranged, following electrochemical reaction takes place, separate out a large amount of hydrogen:
Anode: 2H
2O → O
2+ 4H
++ 4e
-
Negative electrode: 2H
2O+2e
-→ H
2+ 2OH
-
When iron during as anode, following electrochemical reaction takes place, anode has iron ion and produces:
Anode: Fe → Fe
2++ 2e
-
Negative electrode: 2H
2O+2e-→ H
2+ 2OH
-(2) O
2+ 2H
2O+4e
-→ 4OH
-
5. method according to claim 4 is characterized in that: when energising, add stirred vessel (7) by ionogen and add anhydrous sodium sulphate as ionogen in iron filler (4), the dosage of anhydrous sodium sulphate is 0.5g/L.
6. method according to claim 4, it is characterized in that: Cr is 25mg/L in the described synthetic Cr polluted water; Na
2SO
4Be 0.5g/L.
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| CN201310150256.6A CN103232096B (en) | 2013-04-26 | 2013-04-26 | In-situ repairing system and repairing method capable of continuously removing Cr in underground water |
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| CN201310150256.6A CN103232096B (en) | 2013-04-26 | 2013-04-26 | In-situ repairing system and repairing method capable of continuously removing Cr in underground water |
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| CN103232096B CN103232096B (en) | 2014-07-23 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105414160A (en) * | 2015-12-18 | 2016-03-23 | 江苏维尔利环保科技股份有限公司 | Device and method for repairing hexavalent chromium-polluted groundwater by virtue of up-flow PRB technology |
| CN113929206A (en) * | 2021-11-22 | 2022-01-14 | 重庆大学 | Method and device for in-situ remediation of underground water pollution by electrically driven biological PRB |
| WO2022061797A1 (en) * | 2020-09-23 | 2022-03-31 | 北京高能时代环境技术股份有限公司 | Permeable reactive wall and restoration method |
| CN115231649A (en) * | 2022-07-11 | 2022-10-25 | 南京格洛特环境工程股份有限公司 | Method for removing perfluorinated compounds in underground water by photoelectrocatalysis and PRB (physical resource block) method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105414160A (en) * | 2015-12-18 | 2016-03-23 | 江苏维尔利环保科技股份有限公司 | Device and method for repairing hexavalent chromium-polluted groundwater by virtue of up-flow PRB technology |
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| CN115231649A (en) * | 2022-07-11 | 2022-10-25 | 南京格洛特环境工程股份有限公司 | Method for removing perfluorinated compounds in underground water by photoelectrocatalysis and PRB (physical resource block) method |
| CN115231649B (en) * | 2022-07-11 | 2023-09-15 | 南京格洛特环境工程股份有限公司 | Method for removing perfluorinated compounds in underground water by photoelectrocatalysis synergistic PRB method |
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| CN103232096B (en) | 2014-07-23 |
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