CN103011349A - Device and method for repairing chromium contaminated underground water through electromotive force - Google Patents
Device and method for repairing chromium contaminated underground water through electromotive force Download PDFInfo
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- CN103011349A CN103011349A CN2012105919850A CN201210591985A CN103011349A CN 103011349 A CN103011349 A CN 103011349A CN 2012105919850 A CN2012105919850 A CN 2012105919850A CN 201210591985 A CN201210591985 A CN 201210591985A CN 103011349 A CN103011349 A CN 103011349A
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Abstract
The invention belongs to the field of underground water pollution repair, and particularly relates to a device and a method for repairing chromium contaminated underground water through electromotive force. The device comprises a water feeding system, a main body reaction system and a water discharging system which are sequentially connected; contaminated underground water enters the main body reaction system through a hydraulic system and is subjected to organic acid reinforced electromotive force treatment; simulated contaminated dynamic underground water generates hydraulic gradient in a reaction region through a water level difference between overflowing water tanks at two sides so that the flow rate is controlled; after entering the reaction region, the chromium contaminated underground water stands, then serves as an electrolyte to pass through the reaction region and is mixed with a citric acid solution, chromium ions in the contaminated underground water are ceaselessly desorbed out from the underground water in the repairing process under the effect of constant direct currents and are removed from the underground water under the effect of electric field force, so that the treatment of the chromium contaminated underground is realized. The technology of the device has the characteristics of high heavy metal removal rate of above 95%, no secondary pollution, easiness in pollution and the like.
Description
Technical field
The invention belongs to the Remedy Technology of Contaminated Groundwater field, particularly a kind of device and restorative procedure of Electroremediation pollution of chromium underground water.
Background technology
Underground water is the important component part of nature water cycle, and is closely bound up with mankind's activity and existence.Along with the development of producing, the problem of underground water heavy metal contamination is day by day serious, has become one of the most urgent problem of environmental pollution that current mankind faces.During 118 Urban Underground quality estimated to the whole nation, 64% urban groundwater that has was subject to serious pollution, and 33% urban groundwater is subject to slight pollution, and only 3% urban groundwater is substantially clean, and wherein the underground water pollution of chromium is especially noticeable.Underground water is present in interstices of soil and the subsurface rock crack, because the physics chemical action process of underground water and its heavy metal pollutants is very complicated, its pollution process is often very hidden and slow, both be not easy to find early, be difficult to again administer within a short period of time and prove effective, therefore the Pollution abatement of underground environment is more more complicated and difficult than ground surface environment, thereby recovery technique is also had relatively high expectations.
Generally the soil and groundwater of heavy metal contamination adopted the technology such as phytoremediation more, but the cycle of this type reparation is long and take effect slow because heavy metal contaminants mainly is combined with the Humus natural organic matter in soil and is adsorbed on the soil particle, and stable existence, be difficult for being absorbed by plant efficient, so increased the difficulty that heavy metal contaminants is removed from soil, make traditional phytoremediation Efficiency Decreasing, the extraction processing of groundwater pollution then expends larger, and application is restricted.
Electronic reparation is a kind of based technique for in-situ remediation, its Basic Mechanism is: water saturation soil is under the effect of electric field, steeping in water for reconstitution is given birth to electrolytic reaction, negative electrode produces hydrogen and hydroxide ion, anode produces oxygen and hydrogen ion, the hydrogen ion that anode produces is under the effect of electric field and concentration gradient, to soil internal migration and diffusion, hydrogen ion is in the process of migration and diffusion, heavy metal contaminants in displacement and the dissolving soil, heavy metal contaminants after dissolved under the effect of electric field and concentration gradient, in the mode of ion migration and electric osmose towards the cathode direction directional migration, thereby reach the purpose of removing soil pollutant.In the electronic repair process
Topmost electrode reaction following (E0 is standard potential):
Anodic reaction 2H
2O-4e
-→ O2 ↑+4H
+, E
0=-1.229 V;
Cathodic reaction 2H
2O+2e
-→ H2 ↑+2OH
-, E
0=-0.828 V;
Because electrolytic reaction, anode produces hydrogen ion, and negative electrode produces hydroxide ion, and the hydrogen ion that anode produces is conducive to the activation of heavy metal, makes it migrate to negative electrode and enrichment.The hydroxide ion that negative electrode produces makes the heavy metal ion precipitation, blocks the dummy space, is unfavorable for electromigration and electroosmotic flow.Compare with chemical reduction method with chemical cleaning method, have that labor intensive is few, maintenance management is simple, chemical reagent uses the basic structure of less, not destroying dummy and characteristic, basic non-secondary pollution, economic benefit advantages of higher; Comparing with the chemosetting method, is the recovery technique that a kind of cost is low, can realize the thorough removing of pollution substance; Compare with the physics reparation, labor intensive is few, does not need construction and affects extraneous view and surrounding environment; Compare with bioremediation technology, have advantages of less investment, instant effect.In addition, electric recovery technique can also form combined pollution with other technology and administer technique.
Simultaneously, also there are some limitation in electric repairing technique: 1. be not suitable for the low dummy of water ratio, in water ratio 10% following deleterious; 2. owing to the component difference of same dummy, local mineral substance is high, and electric conductivity is good, causes current anomaly, also may affect the original proterties of dummy; 3. electrolytic reaction produces secondary pollutant, produces by product chlorine etc. such as redox reaction; 4. etching problem is as remaining in the dummy behind the electrode corrosions such as carbon, graphite, platinum.
In addition, in the electronic repair process, the pH value of dummy and the extreme change of redox potential also can cause the repairing effect variation.In fact, because the constantly migration under electric field action of a large amount of hydrogen ions of anode electrolysis generation causes the pH value of soil to descend, although be conducive to the heavy metal ion dissolving, if crossing to hang down, the pH value will make the Zeta of soil change to zero potential, even reindexing.Will cause like this electroosmotic flow to weaken, seriously can cause the RO phenomenon to occur.
Many researchers utilizes organic acid as the reinforcer of electronic reparation, and has realized the clearance higher to pollutent.Organic acid not only can be used for regulating the pH value, but also has certain buffering and huge legendary turtle is closed function, thereby can impel pollutant dissolution to be conducive to removal of pollutants.Organic acid commonly used mainly contains acetic acid, citric acid, lactic acid etc., and it is best that wherein the huge legendary turtle of citric acid is closed performance, is most widely used.Organic acid is a kind of biodegradable, environment amenable reinforcer, its strengthening effect mainly contains two aspects: the one, and control pH value, make repair system maintain more stable sour environment, near the alkalization precipitation of negative electrode is removed and is prevented in the dissolving that is conducive to heavy metal; The 2nd, huge legendary turtle cooperation usefulness promotes the heavy metal huge legendary turtle to close and is dissolved in aqueous phase, has improved the transportable property of heavy metal.But the impact that organic acid is used electroosmotic flow also merits attention, because the excessive use of organic acid also can cause the dummy negatively charged ion to increase and reduce Zeta potential, directly affects size even the direction of electroosmotic flow.
Summary of the invention
The present invention is directed to the impact that the electrolyte PH value that occurs in the traditional electrical power repair process changes repairing effect and improve, select citric acid as chemical intensifier, a kind of device and restorative procedure of Electroremediation pollution of chromium underground water is provided.Citric acid is used for regulating the pH value on the one hand, also has in addition certain buffering and huge legendary turtle and closes function, thereby can impel pollutant dissolution to be conducive to removal of pollutants.
A kind of device of Electroremediation pollution of chromium underground water, this device is connected to form in turn by water inlet system, main body reactive system and outlet system; Inlet chest links to each other with the water inlet overflow groove in the described water inlet system, and the top of water inlet overflow groove arranges the water inlet overflow weir; Reaction unit is divided into inhalant region, reaction zone and exhalant region three parts by two vertical clapboards in the described main body reactive system, the positive pole of direct supply links to each other with exhalant region with the inhalant region of reaction unit respectively with negative pole, anode citric acid deposit chamber links to each other with negative electrode citric acid input tube with anode citric acid input tube by a peristaltic pump respectively with negative electrode citric acid deposit chamber, and anode citric acid input tube links to each other with exhalant region with inhalant region respectively with negative electrode citric acid input tube; Described outlet system is the water outlet overflow groove, and its top arranges the water outlet overflow weir; Described water inlet overflow groove links to each other with exhalant region with inhalant region by pipeline respectively with the water outlet overflow groove.
Described dividing plate is the synthetic glass material, and a plurality of circular holes are set on it, and the both sides of each dividing plate arrange one deck non-woven geotextile respectively, makes the uniform liquid infiltration of dividing plate both sides, and prevents that sand from outwards flowing out.
Described anode citric acid input tube and negative electrode citric acid input tube are the synthetic glass material, and it evenly arranges respectively a plurality of circular holes on the tube wall of reaction unit inside, and its outside all arranges one deck non-woven geotextile, prevents that sand from entering.
The positive pole of described direct supply and negative pole are cylindric pure Graphite Electrodes, and inhomogeneous field is provided in reaction unit.
A kind of method of Electroremediation pollution of chromium underground water, the dynamic underground water of its simulating pollution comes coutroi velocity by water inlet overflow groove and the waterhead between the water outlet overflow groove of both sides in reaction zone generation hydraulic gradient, and concrete steps are as follows:
A. at first, the citric acid solution that in anode citric acid deposit chamber and negative electrode citric acid deposit chamber, adds according to demand;
B. with wire reaction unit and direct supply are coupled together;
C. the heavy metal contamination underground water that contains the high chromium concentration ion is intake by water inlet system, and the reaction zone of flowing through carries out electrolytic reaction; Meanwhile, the anode citric acid solution mixes with the underground water that is subjected to heavy metal contamination that is flowed into by inhalant region by anode citric acid input tube, enters together reaction zone, then by DC power supply, and the beginning electrolytic reaction, reaction is flowed out by exhalant region after finishing; In the whole reaction process, the citric acid solution in anode citric acid deposit chamber and the negative electrode citric acid deposit chamber replenishes in reaction unit by peristaltic pump with certain speed respectively;
D. the chromium ion concentration of exhalant region is measured.
The concentration of the citric acid solution of described negative electrode citric acid deposit chamber is 0.3 mol/L ~ 0.5 mol/L, and the citric acid solution concentration of anode citric acid deposit chamber is 0.03 mol/L ~ 0.05 mol/L.
The water intake velocity of described water inlet system is 10 L/h.
Citric acid solution in the described negative electrode citric acid storage room replenishes in reaction unit with the speed of 1 mL/d ~ 5 mL/d, and the citric acid solution in the anode citric acid deposit chamber replenishes with the speed of 0.1 mL/d ~ 0.6 mL/d.
The positive pole of described direct supply and negative pole are cylindric pure Graphite Electrodes, and inhomogeneous field is provided in reaction unit, and direct supply applies the constant current of 20 mA ~ 50 mA to reaction unit.
Beneficial effect of the present invention is:
1, combines with electric power chemical enhanced, improved greatly the removal efficient to heavy metal ion, organic acid not only can be used for regulating the pH value, but also has certain buffering and huge legendary turtle is closed function, thereby can impel pollutant dissolution to be conducive to removal of pollutants;
2, this method is applicable to repair far away, and is less to eco-environmental impact, can prevent heavy metal contaminants contaminated soil in transfer process;
3, high to the removal efficient of heavy metal, effluent quality is good, can reach more than 95%, and the underground water of exhalant region reaches state sewage emission standard;
4, compare than traditional restorative procedure, this method embodies: cost is low, and is simple for process, convenient operation, the outstanding advantages such as non-secondary pollution; And compare with general mineral acid treatment, clearance has greater advantage;
Description of drawings
Fig. 1 is apparatus of the present invention structural representation;
Number in the figure: 1-inlet chest; The 2-overflow weir of intaking; The 3-overflow groove of intaking; The 4-reaction unit; 5-water outlet overflow groove; 6-water outlet overflow weir; 7-is direct supply; 8-anode citric acid input tube; 9-negative electrode citric acid input tube; 10-anode citric acid deposit chamber; 11-negative electrode citric acid deposit chamber; The 12-peristaltic pump; The 13-water inlet system; 14-main body reactive system; The 15-outlet system; The 16-dividing plate; The 17-inhalant region; The 18-reaction zone; The 19-exhalant region.
Embodiment
The invention provides a kind of device and restorative procedure of Electroremediation pollution of chromium underground water, the present invention will be further described below in conjunction with the drawings and specific embodiments.
A kind of device of Electroremediation pollution of chromium underground water, this device is connected to form in turn by water inlet system 13, main body reactive system 14 and outlet system 15; Inlet chest 1 links to each other with water inlet overflow groove 3 in the described water inlet system 13, and the top of water inlet overflow groove 3 arranges water inlet overflow weir 2; Reaction unit 4 is divided into inhalant region 17, reaction zone 18 and exhalant region 19 3 parts by two vertical clapboards 16 in the described main body reactive system 14, the positive pole of direct supply 7 links to each other with exhalant region 19 with the inhalant region 17 of reaction unit 4 respectively with negative pole, anode citric acid deposit chamber 10 links to each other with negative electrode citric acid input tube 9 with anode citric acid input tube 8 by a peristaltic pump 12 respectively with negative electrode citric acid deposit chamber 11, and anode citric acid input tube 8 links to each other with exhalant region 19 with inhalant region 17 respectively with negative electrode citric acid input tube 9; Described outlet system 15 is water outlet overflow groove 5, and its top arranges water outlet overflow weir 6; Described water inlet overflow groove 3 links to each other with exhalant region 19 with inhalant region 17 by pipeline respectively with water outlet overflow groove 5.
Described dividing plate 16 is the synthetic glass material, and a plurality of circular holes are set on it, and the both sides of each dividing plate 16 arrange one deck non-woven geotextile respectively, makes dividing plate 16 both sides uniform liquid infiltrations, and prevents that sand from outwards flowing out.
Described anode citric acid input tube 8 and negative electrode citric acid input tube 9 are the synthetic glass material, and it evenly arranges respectively a plurality of circular holes on the tube wall of reaction unit 4 inside, and its outside all arranges one deck non-woven geotextile, prevents that sand from entering.
The positive pole of described direct supply 7 and negative pole are cylindric pure Graphite Electrodes, provide inhomogeneous field in reaction unit 4.
A kind of method of Electroremediation pollution of chromium underground water, the dynamic underground water of its simulating pollution comes coutroi velocity by water inlet overflow groove and the waterhead between the water outlet overflow groove of both sides in reaction zone generation hydraulic gradient, and concrete steps are as follows:
A. at first, the citric acid solution that in anode citric acid deposit chamber and negative electrode citric acid deposit chamber, adds according to demand;
B. with wire reaction unit and direct supply are coupled together;
C. the heavy metal contamination underground water that contains the high chromium concentration ion is intake by water inlet system, and the reaction zone of flowing through carries out electrolytic reaction; Meanwhile, the anode citric acid solution mixes with the underground water that is subjected to heavy metal contamination that is flowed into by inhalant region by anode citric acid input tube, enters together reaction zone, then by DC power supply, and the beginning electrolytic reaction, reaction is flowed out by exhalant region after finishing; In the whole reaction process, the citric acid solution in anode citric acid deposit chamber and the negative electrode citric acid deposit chamber replenishes in reaction unit by peristaltic pump with certain speed respectively;
D. the chromium ion concentration of exhalant region is measured.
The concentration of the citric acid solution of described negative electrode citric acid deposit chamber is 0.3 mol/L ~ 0.5 mol/L, and the citric acid solution concentration of anode citric acid deposit chamber is 0.03 mol/L ~ 0.05 mol/L.
The water intake velocity of described water inlet system is 10 L/h.
Citric acid solution in the described negative electrode citric acid storage room replenishes in reaction unit with the speed of 1 mL/d ~ 5 mL/d, and the citric acid solution in the anode citric acid deposit chamber replenishes with the speed of 0.1 mL/d ~ 0.6 mL/d.
The positive pole of described direct supply and negative pole are cylindric pure Graphite Electrodes, and inhomogeneous field is provided in reaction unit, and direct supply applies the constant current of 20 mA ~ 50 mA to reaction unit.
The present invention combines with electric power chemical enhanced, improved greatly the removal efficient to heavy metal ion, organic acid not only can be used for regulating the pH value, but also has certain buffering and huge legendary turtle is closed function, thereby can impel pollutant dissolution to be conducive to removal of pollutants this method is applicable to repair far away, less to eco-environmental impact, can prevent heavy metal contaminants contaminated soil in transfer process.Removal efficient to heavy metal is high, and effluent quality is good, can reach more than 95%, and the underground water of exhalant region reaches state sewage emission standard.Compare than traditional restorative procedure, this method embodies: cost is low, and is simple for process, convenient operation, the outstanding advantages such as non-secondary pollution.And compare with general mineral acid treatment, clearance has greater advantage.
Claims (9)
1. the device of an Electroremediation pollution of chromium underground water, it is characterized in that: this device is connected to form in turn by water inlet system (13), main body reactive system (14) and outlet system (15); Inlet chest (1) links to each other with water inlet overflow groove (3) in the described water inlet system (13), and the top of water inlet overflow groove (3) arranges water inlet overflow weir (2); Reaction unit (4) is divided into inhalant region (17) by two vertical clapboards (16) in the described main body reactive system (14), reaction zone (18) and exhalant region (19) three parts, the positive pole of direct supply (7) links to each other with exhalant region (19) with the inhalant region (17) of reaction unit (4) respectively with negative pole, anode citric acid deposit chamber (10) links to each other with negative electrode citric acid input tube (9) with anode citric acid input tube (8) by a peristaltic pump (12) respectively with negative electrode citric acid deposit chamber (11), and anode citric acid input tube (8) links to each other with exhalant region (19) with inhalant region (17) respectively with negative electrode citric acid input tube (9); Described outlet system (15) is water outlet overflow groove (5), and its top arranges water outlet overflow weir (6); Described water inlet overflow groove (3) links to each other with exhalant region (19) with inhalant region (17) by pipeline respectively with water outlet overflow groove (5).
2. device according to claim 1, it is characterized in that: described dividing plate (16) is the synthetic glass material, and a plurality of circular holes are set on it, and the both sides of each dividing plate (16) arrange one deck non-woven geotextile respectively, make the uniform liquid infiltration of dividing plate (16) both sides, and prevent that sand from outwards flowing out.
3. device according to claim 1, it is characterized in that: described anode citric acid input tube (8) and negative electrode citric acid input tube (9) are the synthetic glass material, it evenly arranges respectively a plurality of circular holes on the inner tube wall of reaction unit (4), its outside all arranges one deck non-woven geotextile, prevents that sand from entering.
4. device according to claim 1, it is characterized in that: the positive pole of described direct supply (7) and negative pole are cylindric pure Graphite Electrodes, provide inhomogeneous field in reaction unit (4).
5. the method for an Electroremediation pollution of chromium underground water is characterized in that, the dynamic underground water of simulating pollution comes coutroi velocity by water inlet overflow groove and the waterhead between the water outlet overflow groove of both sides in reaction zone generation hydraulic gradient, and concrete steps are as follows:
A. at first, the citric acid solution that in anode citric acid deposit chamber and negative electrode citric acid deposit chamber, adds according to demand;
B. with wire reaction unit and direct supply are coupled together;
C. the heavy metal contamination underground water that contains the high chromium concentration ion is intake by water inlet system, and the reaction zone of flowing through carries out electrolytic reaction; Meanwhile, the anode citric acid solution mixes with the underground water that is subjected to heavy metal contamination that is flowed into by inhalant region by anode citric acid input tube, enters together reaction zone, then by DC power supply, and the beginning electrolytic reaction, reaction is flowed out by exhalant region after finishing; In the whole reaction process, the citric acid solution in anode citric acid deposit chamber and the negative electrode citric acid deposit chamber replenishes in reaction unit by peristaltic pump with certain speed respectively;
D. the chromium ion concentration of exhalant region is measured.
6. method according to claim 5 is characterized in that: the concentration of the citric acid solution of described negative electrode citric acid deposit chamber is 0.3 mol/L ~ 0.5 mol/L, and the citric acid solution concentration of anode citric acid deposit chamber is 0.03 mol/L ~ 0.05 mol/L.
7. method according to claim 5, it is characterized in that: the water intake velocity of described water inlet system is 10 L/h.
8. method according to claim 5, it is characterized in that: the citric acid solution in the described negative electrode citric acid storage room replenishes in reaction unit with the speed of 1 mL/d ~ 5 mL/d, and the citric acid solution in the anode citric acid deposit chamber replenishes with the speed of 0.1 mL/d ~ 0.6 mL/d.
9. method according to claim 5, it is characterized in that: the positive pole of described direct supply and negative pole are cylindric pure Graphite Electrodes, and inhomogeneous field is provided in reaction unit, and direct supply applies the constant current of 20 mA ~ 50 mA to reaction unit.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776444A (en) * | 2016-04-25 | 2016-07-20 | 青岛理工大学 | Method for strengthening Cr(VI) electroreduction by virtue of small molecular inorganic acid |
| CN109900596A (en) * | 2019-02-14 | 2019-06-18 | 河海大学 | A kind of experimental provision for simulating Shallow Groundwater Pollution regulation effect |
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| KR20060036963A (en) * | 2004-10-27 | 2006-05-03 | 한상재 | Development of electrode compartment for enhanced electrokinetic remediation and post-treatment of waste water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776444A (en) * | 2016-04-25 | 2016-07-20 | 青岛理工大学 | Method for strengthening Cr(VI) electroreduction by virtue of small molecular inorganic acid |
| CN109900596A (en) * | 2019-02-14 | 2019-06-18 | 河海大学 | A kind of experimental provision for simulating Shallow Groundwater Pollution regulation effect |
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| CN103011349B (en) | 2014-08-06 |
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