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ELECTROCHEMICAL REMEDIATION Achille De Battisti Laboratory of Elettrochemistry Department of Chemistry of the University of Ferrara ESSEE 4 Palić, Serbia,

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Presentation on theme: "ELECTROCHEMICAL REMEDIATION Achille De Battisti Laboratory of Elettrochemistry Department of Chemistry of the University of Ferrara ESSEE 4 Palić, Serbia,"— Presentation transcript:

1 ELECTROCHEMICAL REMEDIATION Achille De Battisti Laboratory of Elettrochemistry Department of Chemistry of the University of Ferrara ESSEE 4 Palić, Serbia, 17 – 22 Sept., 2006

2 Targets: Non-destructive removal of pollutants from soils - Detoxification/sterilization of industrial wastewaters, landfill leachates, swimming-pool water, water in food industry. - Cold incineration of organic wastes and disgregation of radioactive residuals. - Quality improvement of potable water, detoxification/sterilization of groundwaters

3 Methods: Imposition of potential gradients across the soil portion to be remediated polarizing suitably positioned electrodes Soils: Electrochemical (electrokinetic) extraction of pollutants Primary effects : displacement of charged species (electromigration, electro-osmosis), and neutral species (electro-osmosis). Secondary effects : Accumulation of pollutants in electrodic spaces, followed by abatement.

4 Advantages: in situ methods, substantially non-destructive, no chemicals used, low energy consumption (e.g..: few tens of Volts and currents of the order of few Amperes); flexibility (e.g.: D.C., A.C. polarization), Disadvantages: possible incompatibility with the specific features of the site to be reclamated, problems of stability for metallic structures in the soil. Soils: Electrochemical (electrokinetic) remediation

5 Electrokinetic phenomena: some general aspects ------------------------ + + + + + + + + + + + + + S 0 2 Outer Helmholtz Plane Sharing plane Solution flow

6 Further information on an electrified interfase interphase or = potential at the distance x from the charged wall 0 = potential at the charged wall 2 = potential at the Outer Helmholtz Plane (OHP) = permittivity of the liquid phase -1 = diffuse-layer thickness

7 - - - - - - - - - - - + + ++ + + + + surface of the immobile solid with charge density -q d transit plane charge plane (q d ) veve

8 Flow of electrolyte solutions through capillary channels with charged surface Elettro-osmosis Phenomenological equation V e =electro-osmotic flow rate; P=pressure gradient; E=campo elettrico Electrode Electrolyte solution Electro- osmotic flow

9 Electrode Electrolyte solution Electrokinetic current Flow of electrolyte solutions through capillary channels with charged surface Streaming currents and potentials Phenomenological equation: j = current density; P=pressure gradient; E=electric field

10 ------------- ------------- v E Qualitative representation of the profile of the electro-osmotic flow rate in a capillary channel +++++++++++++ +++++++++++++

11 + + + + + + + + + + + + ++ + + + + ++ + + + + ++ ++ - - - - - - - -- - - - - -- - - -- - - - - - - - - - + + + - - - - - - - + + + - - - - - + + + - + + + Simplified scheme of a particle plug with surface ionogenic groups: fixed solid-mobile solution Hydrostatic pressure gradients across the plug, cause a displacement of a fraction of the volume-charge in the direction of the fluid flow. As a consequence, streaming currents and potentials are measured

12 In the hypotesis that the shear plane and capillary surface cohincide: From former definitions and developments we have also:

13 Transport due to the electric field: electro-osmosis V e = electro-osmotic flow rate u e = electro-osmotic velocity K e = electro-osmotic permeability coefficient E = electric field A = total cross-sectional area

14 Some considerations on the electro-osmotic permeability coefficient The electro-osmotic permeability coefficient, k e is independent from the pore diameter, at variance with the hydraulic permeability coefficient, k h. The experimental values of k e do not depend on soil nature and change within a very narrow range, between 10 -9 e 10 -8 m 2 V -1 s -1, while k h ranges between 10 -13 e 10 -5 m s -1. An electric gradient is more effective than an hydraulic one in fine-grained soils. Electro-osmotic flow is well controlled, being confined within the area across which electric field is active Being for a given soil negative, the electro-osmotic flow is addressed toward the cathode.

15 Transport under the effect of electric field: electromigration The dependence of ion elettromigration on potential gradient, in a capillary: Where v m is the ion velocity, is the ionic mobility, assuming values typically around 3.10 -8 m 2 v -1 s -1 (about one order of magnitude higher for H + e OH - ) Electromigration is affected by electric field, and ionic strength.

16 Soil chemistry, or soil-contaminant interaction: The kinetics of the removal of contaminants is bound to adsorption phenomena, ion-exchange, buffering capacity Water content : inhomogeneous distribution of humidiy and consolidation may take place during an electrokinetic Soil structure : clogging of the soil porous texture and blocking of the electro-osmotic flow may take place due to hydroxide (presence of heavy metals). Positioning of the electrodes and electrode structure : Solidity of the structure, easy workability, chemical stability, costs, are major actors. graphite, activated Titanium are electrode materials of practical interest. Important factors in electrokinetic remediation

17 Optimization of the electro-osmotic process -use of washing liquids, like water, diluite NaCl solutions. -control of soil pH by means of buffering substances. -washing of electrodic compartments, by addition of water/water solutions. -addition of complexing agents, for heavy-metal removal -weak alkalinization and/or adition of surfactants for the removal of strongly adsorbed organic contaminants

18 Simple equipment for Studies in electrokinetic soil remediation

19 Electrode distribution (bench scale to commercial installations


21 Electrokinetic soil remediation: time required/1 V = rate of species transport (or velocity: LT -1 ) i *= effective ionic mobility L 2 T -1 V -1 K e = coefficient of electroosmotic permeability L 2 T -1 V -1 R dc = delaying factor (dimensionless, depends on soil type, pH, and contaminant nature. Accounts for contaminant desorption and dissolution. E = the electric gradient V L -1

22 Electrokinetic soil remediation: time required/2 The remediation time T E required for a given contaminant in a soil may be expressed as: L E /v, where L E is the spacing between electrodes of opposite polarity σ* = effective soil conductivity (siemens m -1 ) β is a lumped property of the contaminant and of the soil (L 3 C -1 ), similar to transference numbers in electrochemistry, but it also accounts for electroosmosis, soil conditions and retardation caused by geochemical reaction:

23 Electrokinetic soil remediation: time required/3 β is a fundamental parameter in electrokinetic soil remediation. Its values typically range within 1.10 -9 and 1.10 -6 m 3 C -1 If the remediation time has to be calculated on the basis of current density applied across the soil, then we have: Where I d is the electric current density = I/A (amp L -2 ), I is the total current and A the cross-sectional area of the soil treated.

24 PERMEABLE REACTIVE BARRIERS Groundwater treatment Definition and methodologyDefinition and methodology PRB normal with respect to groundwater flow. PRB normal with respect to groundwater flow. Containing reactive material Containing reactive material Veduta schematica dellinstallazione di una PRB Funnel-and-gate and continuous PRB

25 Encouraging number of commercial installations: the situation in USA

26 PERMEABLE REACTIVE BARRIERS Reductive degradation of organochloro componds with oxidation of Fe 0 a Fe 2+ Fe 0 + RCl + H + Fe 2+ + RH + Cl - 2Fe 0 + O 2 + 2 H 2 O 2 Fe 2+ + 4 OH – Fe 3+ + 3 OH – Fe(OH) 3 (S) Aerobic environment important!! Hydraulic permeability and reactivity of the barrier Anaerobic environment Fe 0 + 2H 2 O Fe 2+ + H 2 + 2OH – Fe 2+ + 2OH – Fe(OH) 2 (S)

27 from PRB to Electrochemical Reactor Possible efficiency problem: Barrier aging and degradation Electrochemically generated Fenton reactant Reazione di Fenton Oxidative attack to organic substrates O 2 cathodic reduction in presence of Fe 2+ CATHODE ANODE Further oxidation Fe² + + H 2 O 2 Fe³ + +. OH + OH - Fe³ + + H 2 O 2 Fe² + +. OOH + H +

28 Hybrid Processes - Synergism has been observed in the application of electric fields and hydraulic pressure gradients (removal of heavy metals from da mixtures sand/process-sludge -Similar observations in the use of acoustic treatments coupled with the electro-osmotic one (removal of decane, Zn, Cd, from clays) -Electrodialysis: The efficiency of removal of heavy metals and maintenance of treated soil pH can be improved making use of ion-exchange membranes. -Bioremediation: The displacement of nutrients and colonies of microorganisms under the action of electric fields may favour the removal of complex organic species. -Fitoremediation: the transfer of the pollutant to the treated area accelerates the removal process.

29 Suggested reference: I.K. Iskander, Environmental Restoration of Metals-Contaminated Soils Lewis Publ., London, 2001

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