Journal of Molecular Liquids 220 (2016) 657664

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Review

Electrootation process: A review

George Z. Kyzas, Kostas A. Matis
Division of Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki GR-541 24, Greece

a r t i c l e

i n f o

a b s t r a c t

Article history:
Received 20 January 2016
Received in revised form 4 April 2016
Accepted 18 April 2016
Available online 17 May 2016

Flotation is a known gravity separation process originated from mineral processing; concerning the used bubble
generation method, this could be typically by dispersed-air otation, dissolved-air otation or electrootation.
The later technique constitutes the scope of the present review article, commenting recent selected papers published in the literature, and focusing on applications such as waters, heavy metals, biological wastes, etc. Examples given (from our lab) are, among others, minerals like magnesite and pyrite, and pollutant metal ions, as
Cd(II) and Cr(VI). The process advantages were discussed in-depth, such as the electric eld gradient and the
ne gas bubbles; and also, certain design aspects (as kinetics, hydrodynamics, electrolytic cell). Electrootation
was shown to contribute well for the recycling of by-products and waste materials, including water.
2016 Elsevier B.V. All rights reserved.

Keywords:
Water
Wastewater
Minerals
Flotation techniques
Electrootation

Contents
1.
2.
3.
4.
5.
6.
7.

Introduction . . . . . . . . . . . .
Waters . . . . . . . . . . . . . .
Minerals . . . . . . . . . . . . . .
Heavy metals. . . . . . . . . . . .
Biological wastes . . . . . . . . . .
Various applications . . . . . . . .
Design aspects . . . . . . . . . . .
7.1.
Work at Newcastle-upon-Tyne
8.
Conclusions . . . . . . . . . . . .
References . . . . . . . . . . . . . . .

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1. Introduction
Flotation constitutes a gravity separation process that certainly originated from minerals processing (termed froth otation). The importance of otation to economy of the whole industrial world is
considered to be enormous. Without this separation process, many familiar metals and inorganic raw materials would be exceedingly scarce
and costly. The process involves the removal of hydrophobic/surface-inactive ions or particles from aqueous solutions, usually by adding surfactants or collectors, and the subsequent passage of gas bubbles
through the solution [1,2].
However, otation has nowadays found wide applications, particularly to industrial wastewater treatment (i.e. metal ions recovery). A
Corresponding author.
E-mail address: kamatis@chem.auth.gr (K.A. Matis).

http://dx.doi.org/10.1016/j.molliq.2016.04.128
0167-7322/ 2016 Elsevier B.V. All rights reserved.

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657
658
658
659
660
660
661
662
662
662

wide variety of heavy metals bearing waste streams requires drastic

treatment. It has been established, beyond any doubt, that dissolved
heavy metals escaping into the environment pose a serious health hazard. The food-chain pyramid receives metals through man's activities;
on top of the pyramid, man receives pre-concentrated metal toxicity
[3,4]. Many separation techniques were used for heavy metals removal
and adsorption process is one of the most applied one [523].
One of the alternative but effective otation techniques, mainly in
smaller scale, is electrootation or perhaps, should be correctly called
electrolytic otation, owing its name to the bubbles generation method
it uses, i.e., electrolysis of the aqueous medium. Certain advantages of
this technique may be stressed: the electrode grids can be arranged to
provide good coverage of the whole surface area of the otation tank,
so uniform mixing between the wastewater and the gas bubbles is
achieved. A large amount of very small bubbles is formed with minimum turbulence, with result that clarication can be effected with

658

G.Z. Kyzas, K.A. Matis / Journal of Molecular Liquids 220 (2016) 657664

efuents that previously would not have been considered suitable for
treatment by otation. Gas production, residence time and the other operating conditions of electrootation can be checked quickly and are
easily controlled. The equipment is reliable and safe in operation since
only low voltage (in the range 520 V) is used. The relative quantities
of gases produced are a function of current density and salinity of the solution. A simple blower system would eliminate any hazard from the
predominant escaping gas (hydrogen). Finally, electrootation can be
used in cases where air could be difcult to dissolve in a particular efuent [24,25].
Also, the electric eld gradient between the electrodes aids occulation of suspended matter. In the case of using a sacricial iron or aluminum anode, this dissolves and produces coagulant ions; so,
electrocoagulation precedes otation (although the relative costs of
the former are a drawback). Various designs of the electrootation cell
were proposed (in the ex-USSR (Union of Soviet Socialist Republics)),
including the idea of consumable anodes. The operation of other electrochemical processes accompanying electrootation and taking place
simultaneously with the main process, namely electrodialysis, electrophoresis, electrocoagulation etc., was presented during a summer
school [26].
Before a viable electrootation process could be developed, it is necessary to nd electrode materials of adequate mechanical and electrical
properties with an extended lifetime [27]. The basic information desired
from batch electrootation tests and the relative questions to be answered were stressed. In this article, the old work conducted by one of
the authors (for his postgraduate studies) was also discussed, including
design aspects. The scope of the present work is to review the given scientic area of electrootation in some detail for the last ve years.
2. Waters
Water is a natural product that is needed in many industrial uses, but
some processes like washing or cooling do not require drinking water;
the efciency of electrocoagulation-electrootation treatment of surface waters (from a river) was investigated, in order to increase their
quality [28]. Vital nutriments for the bacteria development were consumed during the electrolysis. This treatment led to great decreases of
molecular oxygen, phosphate and nitrate anions, and dissolved organic
compounds, which may explain the disinfection effect that was observed for the total ora.
An excess amount of uoride anions in drinking water has been
known to cause adverse effects on human health. Hence, an airlift reactor was applied for that [29]. The comparison of energy consumption
demonstrated that this removal process was advantageous for carrying
out deuoridation. A variable-order kinetic model derived from the
Langmuir-Freundlich equation was used to determine the kinetics of
uoride removal reaction by electrocoagulation.
Another work was concerned with the treatment of liquid efuents
rich in anionic surfactant by electrootation, in batch mode [30]; anionic
surfactants are extensively used in many elds of technology and research, due to their favorable physicochemical characteristics. The oxygen transfer was studied, considering its importance for the abatement
of the dissolved organic matter in the industrial efuents.
Electrootation, was employed for microltration pretreatment by
skimming off the surfacial oc layer and drawing water from near the
bottom of an electrootation cell; this approach signicantly increased
permeate uxes during surface water dead-end microltration, by reducing both the cake mass and the cumulative hydraulic resistance
[31]. The results were compared with electrocoagulation (a closely related process), wherein the entire destabilized suspension was sent to
microltration. Electrocoagulation pretreatment also improved
microltration uxes compared with raw water, but not as much as
electrootation.
One of the most serious problems encountered in membrane separation processes is known to be fouling during their use, and gas sparging

was used, among other, to overcome this obstacle. An innovative hybrid

cell was investigated that combines the advantages of both (dispersedair) otation and membrane separation, while overcoming their limitations [32].
For centuries, water has been a manufacturing tool that industry has
taken for granted, because it is inexpensive and plentiful. But population
growth, globalization, and climate change are shepherding in a new
water-constrained era. Good, clean water just cannot be replaced and
it is becoming harder to come by.

3. Minerals
Due to advances in grinding lately, the exploitation of low grade
mineral deposits has become economically viable, which in turn enhances the importance of ne particle otation [33]. In the case of
salt-type minerals, otation separation is difcult [34]. The collector
ions (i.e. oleate) may react with different other ions in solution (as
Ca(II)) giving insoluble salts and resulting in lowering of the available
collector. This is the reason why, except of collector concentration,
other parameters usually should be controlled (pH, modiers addition),
so that the desired separation is possible.
Electrootation, a rather unconventional otation technique used in
efuent treatment, has been examined for the recovery and separation
of magnesium carbonate nes [35]; in this category belong magnesite
MgCO3 and dolomite CaMg(CO3)2. It was found that that
carboxymethyl-cellulose and sodium hexametaphosphate as modiers
reduced the recovery, whereas sodium silicate did not affect the process, at the applied conditions. Better depression results were obtained
using the modiers before conditioning with the collector (commercial
fatty acid). Typical results are shown for magnesite in Fig. 1; the case
was similar for dolomite, too.
The electrootation cell, constructed in the laboratory, was essentially of a modied Hallimond-type with electrodes, in place of the porous diffuser (of the original); the electrodes were connected to a
direct current power supply of low voltage. The content of the cell
was 270 cm3, and the tests were conducted in deionized water, working
with 3 g of material. A stirring of 15 rpm by a mechanical stirrer was applied to keep the particles in suspension.
Fine particles typically show slow recovery rates, owing to decreased
particle-bubble collision efciency. Moreover, very small particles tend
to have large specic areas and low mass [36]. So, the treatment of

Fig. 1. Electrootation of magnesite: the effect of solution pH. (a) 20 mg/L collector, no
modier; (b) 40 mg/L concentration, both of fatty acid collector and carboxymethyl
cellulose modier; current density 100 A/m2. Reprinted with permission by
Butterworth-Heinemann [34].

G.Z. Kyzas, K.A. Matis / Journal of Molecular Liquids 220 (2016) 657664

mineral nes treatment continues to be one of the major technical challenges for the mineral processing area.
The electrootation of cassiterite ne ranges (of 37 m) using
Rhodococcus opacus, as bioreagent, was carried out [37]. The interaction
between microorganism cells and mineral surface was valued through
zeta-potential, contact angle measurements, and adsorption studies;
the resulting particles exhibited hydrophobic characters. The contribution of physical chemistry to otation has been recently reviewed in
depth [38]. The use of microorganisms in mineral beneciation has
been elucidated with the development in biotechnology, and these efforts may be further viewed as a green chemistry approach.
The hydrogen bubble electrootation (of 315 m diameter) silica
particles was investigated [39]. As it was said, in typical electrootation
operations it is the hydrogen bubbles produced at the cathode surface
that are utilized in the collection of the valuable mineral. It was found
that, for this study at least, otation recovery was controlled by either
the bubble-particle aggregate rise velocity being greater than zero or
the bubble-particle aggregate projected area being less than that of
just the bubble. A recovery model based largely on a modeling work
[40] was applied.
In fact, the two electrodes of an horizontal electrodes set, usually applied in electrootation, could be separated by a cation exchange membrane, as only one of the produced gases is often necessary [41]. In the
lower part/separated electrode, an electrolyte was circulated to remove
the created gas and in the meantime, increase the conductivity; hence,
having power savings (as the electric eld is built up between the electrodes through the use of the suspension conductivity). Attention
should be paid in this case to anode corrosion, mainly by the chloride
ion (i.e. seawater).
Electrootation has been investigated on pyrite (FeS2); the process
was enhanced by xanthate (i.e. 0-alkyl-dithiocarbonate), and also a cationic collector. This was then compared with classical oatability experiments [42]. Pyrite, formerly used in sulphuric acid production, is
nowadays considered to be an unwanted sulphide admixture, due to
its low economic value.
For instance, from pH 6 to 10 no change in otation was observed
and a small activation was shown at pH 11. With lime used to control
pH, different behaviour was observed (Fig. 2).
Pyrite remained activated from pH 5 to 8 (at 80% recovery), while it
was depressed at the pH range from 9 to 12. Zeta-potential measurements, under similar pulp conditions, were also conducted to explain
the process mechanism of the aforementioned. In order to explain the
difference in otation behaviour, thermodynamic calculations for the

Fig. 2. Electrootation of pyrite: effect of the pH regulator (conditioning: 30 min in the

presence of modier alone and further 15 min after the addition of xanthate). Reprinted
with permission by the Society of Chemical Industry [42].

659

system Fe-EX-H2O have been done (i.e. pe-pH predominance diagrams

for iron and ethyl xanthate species). Among the limited papers in the
eld, work on pyrite and other minerals, such as cassiterite, manganese
and diamonds is notable [43].

4. Heavy metals
The electrootation method allowed the extraction of suspended
compounds of heavy and non-ferrous metals and emulsions of organic
substances. The effect of various surfactants on the physicochemical parameters (particle size and zeta-potential) of the disperse phase of copper, nickel, and zinc hydroxides was studied [44]. The efciency of their
extraction into froth was determined, in a laboratory electrootation
module with antiwear oxide electrodes, with efciency of higher than
95%.
3
and S2 ions as precipitants in soluThe introduction of CO2
3 , PO4
tions containing non-ferrous ions led to a decrease of the average values
of the hydrodynamic diameter of disperse phase particles, relative to
those in solutions containing the OH precipitant [45]; the introduction
of occulants in the solution led to enlargement of particles. The surface
characteristics of the particles of the disperse phase of various slightly
soluble copper, nickel, cobalt, and manganese compounds were found
to affect the electrootation of these compounds in aqueous solutions.
The electrootation efciency could be improved by varying the surface characteristics of the dispersed phase by varying the pH and redox
potential of the medium, as well as using different reagents [46]. Also,
precipitate electrootation was examined (by addition of orthophosphate ions); a method commonly used in wastewater treatment to remove nonferrous metal cations, based on chemical precipitation of
metal compounds via reacting metal cations with suitable alkaline
agents [47]. To isolate the resulting compounds, electrootation with
insoluble anodes was employed.
Some methods for intensifying wastewater treatment processes
without using chemical reagents (i.e. not only acceleration of the process, but also improvement of the treatment quality) were also interesting; so , the exposure of the aqueous system to magnetic eld was tried,
allowing in the meantime the reduction in capital and operational costs
[48]. Electrocoagulation was fundamentally reviewed for improved organic and inorganic matters removal, together with two induced phenomena: electrophoresis and electrootation [49]. This perhaps is one
of the few papers commenting on electrophoresis, i.e. the migration of
a charged particle under the inuence of an electric eld.
The feasibility of simultaneous removal of heavy metals and ethylenediaminetetraacetic acid in an electrolytic undivided cell (equipped
with Ti/RuO2 as anode and stainless steel as cathode) was demonstrated, involving the combination of two techniques electrochlorination
and electrootation [50]. A combined two-step process was also designed to simultaneously remove Cr(VI) and uoride from pretreated
acidic semiconductor efuents; in the electrocoagulation step a hybrid
Fe-Al was used as sacricial anode and stainless steel as cathode [51].
Fig. 3 presents some of the earlier work of the Lab (laboratory of
General and Inorganic Chemical Technology, Department of Chemistry,
Aristotle University of Thessaloniki, Greece) on hexavalent chromium
ions removal from dilute aqueous solutions, at bench-scale experiments. The two collectors applied, dodecylamine and cetyl-trimethyl
ammonium bromide (CTABr), gave similar results, as shown. Cr(VI) is
extensively hydrolyzed in water, giving only neutral or anionic species.
The water chemistry and the aqueous speciation of heavy metals are
considered of specic importance during the performed experiments.
The investigated parameters were: otation time, current density,
type of electrodes (from iron, aluminum and aluminum alloy), initial
chromium content, additional agitation, concentration and type of collector, frother (ethyl alcohol) concentration, pH of solution, ionic
strength, and temperature. Very good results with removals near 100%
were obtained, but at high current densities [52].

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G.Z. Kyzas, K.A. Matis / Journal of Molecular Liquids 220 (2016) 657664

Non-living, anaerobically digested, activated sludge (AS) was examined as a possible biosorbent for the electrootation of cadmium from
dilute aqueous solution [60]. Removals over 90% were achieved for
both metal and biomass, during one separation stage, in laboratoryscale experiments (Fig. 4).
Elsewhere, Cd(II) removal was investigated by precipitate otation
techniques, of the rst and second kind, employing potassium ethyl
xanthate as the precipitating/collecting agent [61].
A more logical approach to the treatment of metal-contaminated
waters is certainly to combine metal removal for clean-up purposes
with metal recovery, the metal then being available for reuse in industry. A process, previously studied, initially utilized biosorption onto a
free cell suspension of dead bacterial biomass for cadmium removal
[62]; the biomass was then separated from the metal-depleted aqueous
phase (i.e. by otation), and the bound metal was concentrated through
an elution or desorption step. Finally, cadmium metal was recovered
from the eluate by electrolysis using a rotating cathode cell. The biomass
and eluant (desorption liquor) could be both recycled within the
process.
Fig. 3. Flotation removal of chromates: effect of applied current density with different
collectors (in tap water); (1) RNH2, (2) CTABr. Reprinted with permission by Taylor &
Francis [52].

Chromium considered as a toxic water pollutant, is usually found in

liquid wastes from etching and machining operations, metal plating and
electroplating, chrome tanning, etc.; chromates were used as a corrosion inhibitor in cooling towers. The adsorptive removal of Cr(VI)
from aqueous solutions by Mg-Al-CO3 hydrotalcite sorbent was elsewhere published [53]. Removal of Cr(VI) ions from aqueous solution
on Aeromonas caviae biomass particles was also investigated, in a
well-stirred batch reactor [54]. A detailed analysis was conducted testing several chemical reaction kinetic models in order to identify a suitable kinetic equation, assuming that biosorption was chemical
sorption controlled. The ability of microorganisms to remove metal
ions is a well-known phenomenon. Biosorption was called the process
that makes use of dead biomass, in comparison to bioaccumulation [55].
5. Biological wastes
The biomass separation of the microalgae Desmodesmus subspicatus
by electrootation, with a spiral-shaped electrode using aluminum or
iron tubes, was evaluated [56]; the contribution to the concentration
of iron or aluminum ions in the treated wastewater by the system was
signicant. Microalgae are essential components of the global ecosystem because they are the major oxygen producers. They play a large
role in the task of mitigating the effects of pollution (in CO2 capture)
caused by humans, too. Some species of microalgae have high productivity and lipid content, which also make them good candidates for biodiesel production. In that, biomass separation and cell disruption are
important steps. So, the fundamentals of electrootation were explored,
by alternating current with non-consumable electrodes, to simultaneously harvest microalgae and disrupt cells from mixed microalgae,
obtained from waste stabilization ponds [57].
A combined electrocoagulation-electrootation process was investigated, in a bench test, for the total separation of the loaded powdered
activated carbon from wastewater [58]; the separation efciency
reached values above 95%. According to these authors, some separation
methods (such as sedimentation, ltration, air otation and
hydrocyclone) have low efciency or high construction cost, noting
that in order to eliminate micro-pollutants from efuent of urban
wastewater treatment plant, adsorption by powdered activated carbon
became a promising solution. The literature, over the past decade, of the
application of activated carbon (microporous or mesoporous) as adsorbents for the removal of heavy metals from the aqueous phase has been
systematically reviewed, focusing especially on lead and arsenic ions
[59].

6. Various applications
The oil wells drilling have been one source of soil contamination by
lead, barium, zinc, etc. Electrootation for the treatment of synthetic solutions, simulating wastewater from washing soil contaminated by drilling uids from oil wells, was investigated [63]. The experimental
results showed that it is possible to remove these heavy metals by
electrocoagulation/electrootation attaining 97% of removal, using
stainless steel mesh electrodes with a power consumption of 14 kWh/
m3.
Biodiesel wastewater treatment using a combined electrootation
and electrooxidation process in bench-scale was elsewhere published
[64]. The results showed that electrootation pre-treatment was efcient in removing turbidity, total solids, and oils and greases concentration; on the other hand, this process showed average and poor
reduction and removal efciencies for COD and methanol, respectively
(using aluminum electrodes and applying a current density of 8.0 mA/
cm2, for a reaction time of 60 min). Noting that in the nal process of
biodiesel production, the former undergoes a washing process with
water, which is used to remove impurities from the biodiesel for
purication.
A wastepaper furnish, which contains exographic old newspaper or
newsprint, is difcult to deink by the conventional otation process; the
problem with exographic inks is related to their composition and

Fig. 4. Cadmium removal onto biomass: effect of solution pH values (using aluminum alloy
electrodes, 10 min otation time) current density of 130 A/m2. Reprinted with permission
by Inderscience Enterprises [60].

G.Z. Kyzas, K.A. Matis / Journal of Molecular Liquids 220 (2016) 657664

properties. Flexographic inks consist of carbon black pigments and

acrylic resin binders that disperse the pigments in water. A semi-continuous otation cell, which incorporates an electrolytic cell, was used to
collect inks from newsprint pulp slurry [65]. The use of electric eld improved deinking efciency.
The Taguchi method [66] was applied in the process of
electrocoagulation-electrootation of vinasse from distillery to remove
the contents of BOD, TOC, COD and turbidity. The process was seen as favorable, achieving high percentages [67]. Fourier Transform Infrared
was used to identify possible compounds that were formed on the
electrodes.
The cooking industry nally discharges millions of tons of wastewater every year, and the discharge of wastewater continues to increase.
Electrocoagulation and electrootation were effective technologies for
restaurant wastewater treatment, especially for the removal of oil and
grease. The response surface methodology was used to establish a
model of restaurant wastewater treatment and to provide the optimum
operation conditions [68]. When the wastewater conductivity was
above 3500 s/cm, electrootation played the dominant role and its
contribution rates ranged from 52 to 66%.
7. Design aspects
Restaurant wastewater was treated in another paper [69] by the
combined electrocoagulation-electrootation process, on a pilot scale
with a design capacity of 25 L/min, scaling-up a previously tested
bench equipment. The experimental results showed that the efuent
quality indices, under the optimized operating conditions (and following the aforementioned methodology), met the environmental requirements, and the resulting trade efuent surcharge could be waived.
Since 1970s, numerous studies were focused on the otation of ne
mineral particles, due mainly to the increasingly complex mineralogy
and lower grade of many current ore reserves [70]. During an Advanced
Study Institute (with an ominous title), it was proposed that the ne
particle recovery may be enhanced by using ne bubbles generated by
the then unconventional techniques [71]. Knowledge, therefore, of the
size distribution of bubbles in a otation system is highly important.
For electrootation, reagent and electrolyte concentrations, current
density, and cathode aperture were the found important factors in controlling bubble size and nucleation [72].
An electrootation column was used in order to study the process
hydrodynamics. The effect of both liquid phase physicochemical characteristics and current density on bubbles diameter characteristics and gas
hold-up were studied [73]. Models predicting bubble diameters, Reynolds number, and gas hold-up were established.
The performance of a continuous bipolar reactor designed for simultaneous removal of ammonia and phosphate from wastewater efuent
was investigated [74]. The reactor was comprised of two distinct units:
electrochemical and separation. The unit was able to decrease the concentrations of phosphate, ammonia, and COD under actual wastewater
conditions by 98, 98, and 72%, respectively.
A bipolar arrangement is characterized by the fact that only the terminal electrodes are connected to the source of electric current, while
the rest of the electrodes conduct each other through the solution conductivity; the optimum plate thickness of the electrodes and their spacing should be determined in order to improve this cell's design [27].
Olive mill wastewater is also considered as one of the most polluting
efuents of the food industry and constitutes a source of important environmental problems for instance, in the Mediterranean area. The removal of pollutants (i.e. COD, BOD, polyphenols, turbidity, color, total
suspended solids, oil and grease) from olive oil mill processing wastewater by peroxi-electrocoagulation/electrooxidation-electrootation
process was evaluated, using a pilot continuous reactor with bipolar aluminum electrodes [75]. This process was considered effective and feasible for pre-treating the wastewater, making possible a post-treatment
of the efuent in a biological system.

661

Stringent water treatment criteria and rapidly growing pollutant

loads provoke the demand for retrotting wastewater treatment plants
towards a higher capacity. So, a two-stage alternating aeration bioreactor, equipped with an electrootation clarier, was assessed, for nitrogen removal within a short hydraulic retention time [76].
Electrootation under steady solids loading required a minimum unit
height, and a gas/solids ratio of 0.006 for efcient clarication.
Perhaps, the most common form of water pollution is that caused by
sewage and garbage dumped into aquatic reservoirs. A study was carried out on the decontamination of domestic sewage efuent by
electrootation in a (homemade) pilot-scale unit, with a capacity of

Table 1
Experimental electrootation results from selected published papers.
Separation application

Comments

Reference

Microalgae biomass

Spiral-shaped electr., 3 A/20 min for Al

electrode
ec, Hybrid Fe-Al anode

[56]

[45]

Microalgae

3
CO2
& S2 Precipitants,
3 , PO4
-potential
pH 4, c.d. 40 mA/m2, 30 min, H2O2, NaCl,
Bipolar Al electr.
Stainless steel, ~100% Re, 170 A/m2, 15

Oil and grease

min, pH 7.8
ec, Anode Al, stainless steel cathode, 43

[68]

A/m2, 34 min, 95% Re, 3.6 cm

interelectrode gap
ec, Stainless steel, 350 A/m2, 97% Re, SDS

[63]

Hexavalent chromium and

uoride
Slightly soluble
non-ferrous metals
Olive mill wastewater

Washing soil & heavy

metals
Copper, nickel, zinc
hydroxides and
phosphates
PAC urban wastewater
Microalgae, cell disruption
Sparingly-soluble heavy
metals and iron, nickel,
cobalt
Sparingly-soluble heavy
metals and iron, nickel,
cobalt
Oxygen transfer
Liquid phase
(physicochemical
characteristics)
Non-ferrous metals (sh
industry reservoirs)
Condition-induced
bubbles
Cassiterite nes
Biodiesel wastewater
Heavy metals
Restaurant wastewater
N2 removal
Sewage pilot study
Microltration of surface
water
Ammonia and phosphate
removal
Vinasse from distillery
Silica particles
Deuoridation of drinking
water
Surface water
Deinking

Various surfactants, pH ~10, volumetric

c.d. 0.2 A/L

[51]

[75]
[49]

[44]

[58]
ec, 100 A/m2, 10 min, 95% Re
Alternating current, N95% Re, 140 min,
[57]
biodiesel production
Magnetic treatment, -potential, particles [48]
size
Medium composition, dispersity,
solubility, redox potential

[47]

Anionic surfactants, critical micelle

concentration, mass transfer
Gas hold-up, bubble diameters, Reynolds

[30]
[73]

Precipitation, hydroxyphosphate

[46]

Size and distribution, nucleation, cathode [72]

apertures, 20 A/m2
Rhodococcus opacus, contact angle,
[37]
adsorption, -potential
Electrooxidation, conductivity, 8
[64]
mA/cm2, 1 h
EDTA, electrochlorination, current
intensity
ec, Pilot plant, cost effective, zero trade
efuent discharge
Continuous bioreactor, thickening, short
retention time, gas/solids ratio
$ 0.63 m3, 14.18 A/m2, NaCl
(Conductivity)
Pretreatment, permeate ux, fouling, ec,
H2 bubbles, hybrid
ec, Bipolar, electrooxidation, actual
conditions
ec, Taguchi method, stirring, FTIR
H2 Bubbles, agitation, recovery model
ec, airlift reactor, kinetics (variable order)
ec, Industrial use, disinfection
Semi-continuous, electric eld assisting
otation

[50]
[69]
[76]
[77]
[31]
[74]
[67]
[39]
[29]
[28]
[65]

662

G.Z. Kyzas, K.A. Matis / Journal of Molecular Liquids 220 (2016) 657664

The tracer input signal was an electrolyte and had the form of a step
function. Assuming that the ow regime was composed of various
ow types, a theoretical multiparameter model, known from Levenspiel
(existing even in the front cover of the latest edition of Chemical Reaction Engineering, by Wiley), was applied and the experimental data of
electrootation were tted accordingly; the age distribution function
I was used as given by:
I

Fig. 5. Internal age distribution function of the efuent during electrolytic otation.
Reprinted with permission by Taylor & Francis [78].




Q1
Q V
VP Q
exp 1

Q
Q VB
V Q1

where Q1 is the owrate of the dispersion (efuent) passing through the

tank, Q is the total volumetric owrate of the feed, V is the total volume
of the otation cell, VB is the backmix ow volume, VP is the plug ow
volume, and is the dimensionless time, i.e., the time divided by the
mean residence time of the efuent in the vessel; the above equation
can then be rearranged (see Fig. 5).
A simple equation was used to describe the process in continuous
operation, based also on the assumption of a rst-order kinetics equation. Under steady-state conditions, a mass balance was computed
around the electrootation vessel:
r Q in C i Q out C i kl CV

approximately 134 L; Al electrodes were used for the simultaneous

electrocoagulation and electrootation treatment [77].
Table 1 gives a brief summary of the recent literature in the area in
tabular form as described in the previous section.
7.1. Work at Newcastle-upon-Tyne
It was observed that for most of the experimental time, except perhaps for the initial period, the rst-order equation (as known from
chemical reaction kinetics) could satisfactorily describe the process:
ln C=C0 kt

where k denotes the otation rate coefcient, C is the concentration at

time t = t, and C0 at time t = 0 [25,27].
An investigation of hydrodynamics was also undertaken, as the efciency is expected to be a function of the residence time distribution.
The stimulus-response technique was used in this experimentation.

where r is the overall otation rate, Q is the volumetric owrate, Ci and C

are the inlet and exit concentrations, respectively, and kl is the otation
rate constant; the latter is really a complex function of various parameters, e.g., the particle and bubble size, the particle characteristics, the
concentration of collector, if applied, etc.
This equation, which was suitably rearranged, gave promising results in comparison with the experimental data (Fig. 6).
8. Conclusions
With the recent progress in electrochemistry and hence, the design
of a suitable (for electrootation) electrolytic cell having the appropriate electrode materials, the process perhaps could be no more an unconventional one - as it has been earlier argued. Although this separation
technique originated in mineral processing, some very interesting applications in water and wastewater treatment have recently appeared in
the literature. Pilot plants were constructed and tried with success for
different wastes, as commented above.
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Fig. 6. Continuous-mode electrolytic otation of paint suspension. Reprinted with

permission by Taylor & Francis [78].

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