Electrochemical Technologies in Wastewater Treatment PDF

Separation and Purification Technology 38 (2004) 11–41
Electrochemical technologies in wastewater treatment

Guohua Chen∗
Department of Chemical Engineering, Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China
Received 19 September 2003; accepted 13 October 2003
Abstract
This paper reviews the development, design and applications of electrochemical technologies in water and wastewater treat-
ment. Particular focus was given to electrodeposition, electrocoagulation (EC), electroflotation (EF) and electrooxidation. Over
300 related publications were reviewed with 221 cited or analyzed. Electrodeposition is effective in recover heavy metals from
wastewater streams. It is considered as an established technology with possible further development in the improvement of
space-time yield. EC has been in use for water production or wastewater treatment. It is finding more applications using either
aluminum, iron or the hybrid Al/Fe electrodes. The separation of the flocculated sludge from the treated water can be accomplished
by using EF. The EF technology is effective in removing colloidal particles, oil & grease, as well as organic pollutants. It is proven
to perform better than either dissolved air flotation, sedimentation, impeller flotation (IF). The newly developed stable and active
electrodes for oxygen evolution would definitely boost the adoption of this technology. Electrooxidation is finding its application
in wastewater treatment in combination with other technologies. It is effective in degrading the refractory pollutants on the surface
of a few electrodes. Titanium-based boron-doped diamond film electrodes (Ti/BDD) show high activity and give reasonable
stability. Its industrial application calls for the production of Ti/BDD anode in large size at reasonable cost and durability.
© 2003 Elsevier B.V. All rights reserved.
Keywords: Advanced oxidation; Anode; Electrocoagulation; Electrodeposition; Electroflotation; Electrooxidation; Oxygen evolution; Water
1. Introduction electricity supply, electrochemical water or wastewater

technologies did not find wide application worldwide
Using electricity to treat water was first proposed then. Extensive research, however, in the US and the
in UK in 1889 [1]. The application of electrolysis in former USSR during the following half century has
mineral beneficiation was patented by Elmore in 1904 accumulated abundant amount of knowledge. With
[2]. Electrocoagulation (EC) with aluminum and iron the ever increasing standard of drinking water supply
electrodes was patented in the US in 1909. The elec- and the stringent environmental regulations regarding
trocoagulation of drinking water was first applied on the wastewater discharge, electrochemical technolo-
a large scale in the US in 1946 [3,4]. Because of the gies have regained their importance worldwide during
relatively large capital investment and the expensive the past two decades. There are companies supplying
facilities for metal recoveries, for treating drinking
∗ Tel.: +852-23587138; fax: +852-23580054. water or process water, treating various wastewaters
E-mail address: [email protected] (G. Chen). resulting from tannery, electroplating, diary, textile
1383-5866/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2003.10.006
12 G. Chen / Separation and Purification Technology 38 (2004) 11–41
such as electrophotooxidation, electrodisinfection will

Nomenclature not be discussed. In addition, I shall focus more on
a specific electrode area (m2 /m3 ) the technologies rather than analyzing the sciences
A area of electrode (m2 ) or mechanisms behind them. For books dealing with
CE current efficiency environmentally related electrochemistry, the readers
d net distance between electrodes (m) are referred to other publications [5–8].
E constant in Eqs. (16) and (17) (V) Before introducing the specific technologies, let us
Eeq equilibrium potential difference between review a few terminologies that are concerned by elec-
an anode and a cathode (V) trochemical process engineers. The most frequently
F Faraday constant (C/mol) referred terminology besides potential and current may
i current density (A/m2 ) be the current density, i, the current per area of elec-
I current (A) trode. It determines the rate of a process. The next pa-
K1 constant in Eqs. (16) and (17) rameter is current efficiency, CE, the ratio of current
K2 constant in Eq. (17) consumed in producing a target product to that of to-
m constant in Eq. (17) tal consumption. Current efficiency indicates both the
M molecular mass (g/mole) specificity of a process and also the performance of
n constant in Eq. (17) the electrocatalysis involving surface reaction as well
N total electrode number of an as mass transfer. The space–time yield, YST , of a re-
electrocoagulation unit actor is defined as the mass of product produced by
U total required electrolysis voltage of an the reactor volume in unit time with
electrocoagulation process (V) iaM
U0 electrolysis voltage between electrodes (V) YST = CE. (1)
1000 zF
YST space–time yield
z charge number The space–time yield gives an overall index of a reac-
tor performance, especially the influence of the spe-
Greek letters cific electrode area, a.
α constant in Eq. (20)
ηa,a anode activation overpotential (V)
ηa,c anode concentration overpotential (V) 2. Electrochemical reactors for metal recovery
ηa,p anode passive overpotential (V)
ηc,a cathode activation overpotential (V) The electrochemical recovery of metals has been
ηc,c cathode concentration overpotential (V) practiced in the form of electrometallurgy since long
κ conductivity of water/wastewater treated time ago [9]. The earliest reported application of elec-
(S/m) trochemical phenomena in chemical subjects was sup-
posed to be carried out by Pliny in protecting iron with
lead electroplating [10]. The first recorded example of
electrometallurgy was in mid-17th century in Europe
processing, oil and oil-in-water emulsion, etc. Nowa- [11]. It involved the recovery of copper from cuprifer-
days, electrochemical technologies have reached such ous mine water electrochemically. During the past two
a state that they are not only comparable with other and half centuries, electrochemical technologies have
technologies in terms of cost but also are more effi- grown into such areas as energy storage, chemical syn-
cient and more compact. For some situations, elec- thesis, metal production, surface treatment, etc. [12].
trochemical technologies may be the indispensable The electrochemical mechanism for metal recovery is
step in treating wastewaters containing refractory very simple. It basically is the cathodic deposition as
pollutants. In this paper, I shall examine the estab- Mn+ + ne → M. (2)
lished technologies such as electrochemical reactors
for metal recovery, electrocoagulation, electroflota- The development of the process involves the improve-
tion and electrooxidation. The emerging technologies ment of CE as well as YST .
G. Chen / Separation and Purification Technology 38 (2004) 11–41 13
Fig. 1. Tank cell.

-
(a) monopolar
2.1. Typical reactors applied
There are quite a few types of reactors found ap- +

plications in metal recovery, from very basic reactors
such as tank cells, plate and frame cells, rotating cells,
to complicated three-dimensional reactor systems like
fluidized bed, packed bed cell, or porous carbon pack-
ing cells. Tank cells, Fig. 1, are one of the simplest
and hence the most popular designs. It can be easily
scaled up or down depending on the load of a pro-
(b) -
cess. The electrode can be arranged in mono-polar or
bi-polar mode, Fig. 2. The main application of this Fig. 2. Electrode arrangements.
type of reactor system is the recovery of metals from
high concentration process streams such as effluents
from the electroplating baths, ethants, and eluates of simple [13]. In order to enhance mass transfer from
an ion-exchange unit [11]. The number of electrodes the bulk to the electrode surface and also to remove
in a stack may vary from 10 to 100. The water flow is the deposited metal powders from the cathode, the ro-
usually induced by gravity. tating cathode cell was designed and employed, Fig. 4
The plate and frame cell or sometimes called filter [14]. It was found that this system can reduce copper
press, Fig. 3, is one of the most popular electrochem- content from 50 to 1.6 ppm by using the systems in a
ical reactor designs. It conveniently houses units with cascade version [15]. The pump cell is another vari-
an anode, a cathode, and a membrane (if necessary) ant of rotating cathode cell, Fig. 5. By having a static
in one module. This module system makes the design, anode and a rotating disk cathode, the narrow spac-
operation and maintenance of the reactor relatively ing between the electrodes allows the entrance of the
Fig. 3. Filter press reactor.

trical contact is not always maintained thus the current

distribution is not always uniform and the ohmic drop
within the cell is high. In order or improve the contact
between the electrode feeder and cathode particles, a
large number of additional rod feeders was used [21].
Inert particles were also employed in fluidized bed
reactor to improve mass transfer rate in a ChemElec
commercial design. Tumbling bed electrodes, Fig. 7,
are also available.
The packed bed cell overcomes the sometimes
non-contacting problem met in fluidized bed, Fig. 8
[22,23]. Carbon granules were packed in a cell. The
anode was separated by a diaphragm. The recently
developed packed bed reactor by EA Technology
Ltd. (UK) and marketing by Renovare Interna-
tional Inc. (US), RenoCell, Fig. 9, claims to excel
Fig. 4. Rotating cylinder electrode. in competition with many existing technologies.
This three-dimensional porous, carbon cathode pro-
effluent. The metals were electrically won and scraped vides 500 times more plating area than conventional
as powders [16–18]. Another design employs rotating two-dimensional cells [24]. In order for dilute metal
rod cathodes in between inner and outer anodes. Be- pollutants to deposit properly on the cathode, it is
sides metal recovery, it is also possible to have the suggested to seed metal powders by having concen-
anodic destruction of cyanides if necessary [19]. trated metal solution at the beginning of the recovery
Since the metal deposition happens at the surface process. Control of pH in the feed tank of a recircu-
of the cathode, it is necessary to increase the specific lating electrolyte is important to avoid precipitation
surface area in order to improve the space–time yield. of the metal.
Fluidized bed electrode was therefore designed, Fig. 6 For example, “100 l of a solution containing 19 ppm
[20]. The cathode was made of conductive particles in nickel in a 0.1 M Na2 SO4 matrix were electrolyzed in
contact with a porous feeder electrode. The electrode the cell under conditions at 40 ◦ C and pH 4 and using
can give a specific area of 200 m2 /m3 . Because of the a current density of 200 A/m2 (based on geometric
fluidization of the particles by the water flow, the elec- area). The nickel concentration was reduced from 19
Fig. 5. Pump cell.

Fig. 6. Fluidized bed reactor.
to 5 ppm in 120 min.” The circulation flowrate was may be applied. The RenoCell unit can be used alone,
20 l/min. Four grams per liter of boric acid was added or in series or parallel depending on the quantity and
as buffer agent [24]. The deposited metals can be quality of the effluent.
removed from a felt cathode in a stripping cell using
the carbon felt electrode as an anode. This system 2.2. Electrode materials
can work on single metal as well as metal mixtures.
The circulating flowrate can vary between 15 and The anode electrode materials for metal recovery
30 l/min. The current density is preferably between can be steel or dimensionally stable anodes (DSA® ).
100 and 300 A/m2 based on geometric area. In ex- The latter was made of a thin layer of noble metal
ceptional cases where very high acidity or alkalinity oxides on titanium substrate [25]. It has been used
exists, a current density between 300 and 800 A/m2 extensively in electrochemical industry. More on this
material will be discussed later on in Section 4. The
Cleaned
water
Metal solution Carbon granules
(a) side view
(b) end view
Fig. 7. Tumbling bed electrodes. Fig. 8. Fixed bed reactor.

Fig. 9. Design of a RenoCell.
cathode materials can be the metal to be recovered 3. Electrocoagulation

or graphite, carbon fibers, etc. The cathode electrode
feeder can be steel or titanium. Electrocoagulation involves the generation of co-
agulants in situ by dissolving electrically either alu-
2.3. Application areas minum or iron ions from respectively aluminum or
iron electrodes. The metal ions generation takes place
The electrochemical recovery of metals can be used at the anode, hydrogen gas is released from the cath-
in the metal surface finishing industry. It has to bear ode. The hydrogen gas would also help to float the
in mind that it is unable to provide a complete solu- flocculated particles out of the water. This process
tion to the industry’s waste management problems be- sometimes is called electrofloculation. It is schemati-
cause it cannot treat all the metals either technically cally shown in Fig. 10. The electrodes can be arranged
or economically. The electrolytic recovery of metals in a mono-polar or bi-polar mode. The materials can
here involves two steps: collection of heavy metals be aluminum or iron in plate form or packed form of
and stripping of the collected metals. The collection scraps such as steel turnings, millings, etc.
step involves plating and the stripping can be accom- The chemical reactions taking place at the anode
plished chemically or electrochemically. Nowadays, are given as follows.
metal powders can be formed on the surface of car- For aluminum anode:
bon cathodes. Therefore, physical separation is suf-
Al − 3e → Al3+ , (3)
ficient. The metals recovered can be of quite high
purity. at alkaline conditions
Another application is in the printed circuit board
manufacturing industry. Because of the well-defined Al3+ + 3OH− → Al(OH)3 , (4)
process, the treatment can be accomplished rela- at acidic conditions
tively easily for this industry. For dilute effluent, an
ion-exchange unit can be used to concentrate the Al3+ + 3H2 O → Al(OH)3 + 3H+ . (5)
metal concentration. For high concentration streams, For iron anode:
they can be treated directly using a recovery system
as in metal surface finishing industry. Application Fe − 2e → Fe2+ , (6)
of metal recovery should be very much useful in
at alkaline conditions
metal winning in mining industry especially in the
production of precious metals such as gold [11]. Fe2+ + 3OH− → Fe(OH)2 , (7)
(a) Horizontal flow

(b) Vertical flow
Fig. 10. Electrocoagulation units.
at acidic conditions high chance of wasting electrical energy in heating

up the water. More importantly, a too large current
4Fe2+ + O2 + 2H2 O → 4Fe3+ + 4OH− . (8)
density would result in a significant decrease in cur-
In addition, there is oxygen evolution reaction rent efficiency. In order for the electrocoagulation
system to operate for a long period of time without
2H2 O − 4e → O2 + 4H+ . (9)
maintenance, its current density is suggested to be
The reaction at the cathode is 20–25 A/m2 unless there are measures taken for a
periodical cleaning of the surface of electrodes. The
2H2 O + 2e → H2 + 2OH− . (10)
current density selection should be made with other
The nascent Al3+ or Fe2+ ions are very effi- operating parameters such as pH, temperature as
cient coagulants for particulates flocculating. The well as flowrate to ensure a high current efficiency.
hydrolyzed aluminum ions can form large networks The current efficiency for aluminum electrode can
of Al–O–Al–OH that can chemically adsorb pollu- be 120–140% while that for iron is around 100%.
tants such as F− [26]. Aluminum is usually used for The over 100% current efficiency for aluminum is
water treatment and iron for wastewater treatment. attributed to the pitting corrosion effect especially
The advantages of electrocoagulation include high when there are chlorine ions present. The current
particulate removal efficiency, compact treatment fa- efficiency depends on the current density as well
cility, relatively low cost and possibility of complete as the types of the anions. Significantly enhanced
automation. current efficiency, up to 160%, was obtained when
low frequency sound was applied to iron electrodes
3.1. Factors affecting electrocoagulation [27].
The quality of the treated water depends on the
3.1.1. Current density or charge loading amount of ions produced (mg) or charge loading,
The supply of current to the electrocoagulation the product of current and time (Ah). Table 1 gives
system determines the amount of Al3+ or Fe2+ the values of the required Al3+ for treating some
ions released from the respective electrodes. For typical pollutants in water treatment [28]. The oper-
aluminum, the electrochemical equivalent mass is ating current density or charge loading can be deter-
335.6 mg/(Ah). For iron, the value is 1041 mg/(Ah). mined experimentally if there are not any reported
A large current means a small electrocoagulation unit. values available. There is a critical charge loading
However, when too large current is used, there is a required. Once the charge loading reaches the critical
Table 1
The aluminum demand and power consumption for removing pollutants from water
Pollutant Unit quantity Preliminary purification Purification
Al3+ (mg) E (W h/m3 ) Al3+ (mg) E (W h/m3 )
Turbidity 1 mg 0.04–0.06 5–10 0.15–0.2 20–40

Color 1 unit 0.04–0.1 10–40 0.1–0.2 40–80
Silicates 1 mg/SiO2 0.2–0.3 20–60 1–2 100–200
Irons 1 mg Fe 0.3–0.4 30–80 1–1.5 100–200
Oxygen 1 mg O2 0.5–1 40–200 2–5 80–800
Algae 1000 0.006–0.025 5–10 0.02–0.03 10–20
Bacteria 1000 0.01–0.04 5–20 0.15–0.2 40–80
value, the effluent quality does not show significant neutral pH due to the variation of conductivity. When
improvement for further current increase [29]. conductivity is high, pH effect is not significant.
The effluent pH after electrocoagulation treatment
3.1.2. Presence of NaCl would increase for acidic influent but decrease for al-
Table salt is usually employed to increase the con- kaline influent. This is one of the advantages of this
ductivity of the water or wastewater to be treated. process. The increase of pH at acidic condition was
Besides its ionic contribution in carrying the electric attributed to hydrogen evolution at cathodes, reaction
charge, it was found that chloride ions could signifi- [10] by Vik et al. [31]. In fact, besides hydrogen evolu-
cantly reduce the adverse effect of other anions such tion, the formation of Al(OH)3 near the anode would
as HCO3 − , SO4 2− . The existence of the carbonate or release H+ leading to decrease of pH. In addition,
sulfate ions would lead to the precipitation of Ca2+ there is also oxygen evolution reaction leading to pH
or Mg2+ ions that forms an insulating layer on the decrease. When there are chlorine ions, there are fol-
surface of the electrodes. This insulating layer would lowing chemical reactions taking place:
sharply increase the potential between electrodes and 2Cl− − 2e → Cl2 . (11)
result in a significant decrease in the current efficiency.
It is therefore recommended that among the anions Cl2 + H2 O → HOCl + Cl− + H+ . (12)
present, there should be 20% Cl− to ensure a nor-
HOCl → OCl− + H+ . (13)
mal operation of electrocoagulation in water treatment.
The addition of NaCl would also lead to the decrease Hence, the increase of pH due to hydrogen evolution
in power consumption because of the increase in con- is more or less compensated by the H+ release reac-
ductivity. Moreover, the electrochemically generated tions above. For the increase in pH at acidic influent,
chlorine was found to be effective in water disinfec- the increase of pH is believed to be due to CO2 re-
tions [30]. lease from hydrogen bubbling, due to the formation of
precipitates of other anions with Al3+ , and due to the
3.1.3. pH effect shift of equilibrium towards left for the H+ release re-
The effects of pH of water or wastewater on elec- actions. As for the pH decrease at alkaline conditions,
trocoagulation are reflected by the current efficiency it can be the result of formation of hydroxide precip-
as well as the solubility of metal hydroxides. When itates with other cations, the formation of Al(OH)4 −
there are chloride ions present, the release of chlo- by [29].
rine also would be affected. It is generally found that Al(OH)3 + OH− → Al(OH)4 − . (14)
the aluminum current efficiencies are higher at either
acidic or alkaline condition than at neutral. The treat- The pollutants removal efficiencies were found to be
ment performance depends on the nature of the pol- the best near neutral pH using aluminum electrode.
lutants with the best pollutant removal found near pH When iron electrode was used in textile printing and
of 7. The power consumption is, however, higher at dying wastewater treatment, alkaline influent was
found to give better color as well as COD removals for old passivated electrodes,
[32]. d K 2 in
U0 = E + i + K1 ln i + m . (17)
κ κ
3.1.4. Temperature
On the right-hand side of Eqs. (16) and (17), both
Although electrocoagulation has been around for
K1 and K2 are constants. Although E is related to
over 100 years, the effect of temperature on this
the transport number of Al3+ and OH− , it approaches
technology was not very much investigated. For wa-
constant when κ is large, the case for electrocoagula-
ter treatment, the literatures from former USSR [33]
tion. Eqs. (16) and (17) indicate that U0 is indepen-
show that the current efficiency of aluminum increases
dent on pH and it does not change significantly with
initially with temperature until about 60 ◦ C where a
flowrate. For new aluminum electrodes, E = −0.76,
maximum CE was found. Further increase in temper-
K1 = 0.20. For passivated aluminum electrodes, E =
ature results in a decrease in CE. The increase of CE
−0.43, K1 = 0.20, K2 = 0.016 and m = 0.47, n =
with temperature was attributed to the increased activ-
0.75 [35].
ity of destruction of the aluminum oxide film on the
With U0 obtained, the total required electrolysis
electrode surface. When the temperature is too high,
voltage U of an electrocoagulation process can be
there is a shrink of the large pores of the Al(OH)3 gel
calculated easily. For the mono-polar mode, the to-
resulting in more compact flocs that are more likely
tal required electrolysis voltage is the same as the
to deposit on the surface of the electrode. Similar to
electrolysis voltage between electrodes, that is
the current efficiency, the power consumption also
gives a maximum at slightly lower value of temper- U = U0 . (18)
ature, 35 ◦ C, for treating oil-containing wastewater For the bi-polar mode, the total required electrolysis
[34]. This was explained by the opposite effects of voltage is U0 times the number of total cell which is
temperature on current efficiency and the conductivity the number of electrodes minus one. Thus:
of the wastewater. Higher temperature gives a higher
conductivity hence a lower energy consumption. U = (N − 1)U0 . (19)
N is usually less than 8 in order to maintain high
3.1.5. Power supply current efficiency for each electrode plate. Usually,
When current passes through an electrochemical DC power supply is employed. In order to minimize
reactor, it must overcome the equilibrium potential the electrode surface oxidation or passivation, the di-
difference, anode overpotential, cathode overpotential rection of power supply is changed at a certain time
and ohmic potential drop of the solution [7]. The an- interval. Fifteen minutes were found to be optimal for
ode overpotential includes the activation overpotential water treatment using aluminum electrodes. A three
and concentration overpotential, as well as the possi- phase AC power supply was also used with six alu-
ble passive overpotential resulted from the passive film minum electrodes (three pairs) in treating colloidal
at the anode surface, while the cathode overpotential wastewaters from petrochemical industries. Alternat-
is principally composed of the activation overpotential ing current was also explored [36].
and concentration overpotential. Therefore,
3.2. Electrode materials
U0 = Eeq + ηa,a + ηa,c + ηa,p + |ηc,a |
d As stated earlier, the materials employed in electro-
+ |ηc,c | + i. (15) coagulation are usually aluminum or iron. The elec-
κ
trodes can be made of Al or Fe plates or from scraps
It should be noted that the passive overpotential highly such as Fe or Al millings, cuttings, etc. When the waste
depends on the electrode surface state. For the new materials are used, supports for the electrode materials
non-passivated electrodes, the passive overpotential have to be made from insert materials. Care needs to be
can be neglected and Eq. (15) simplifies to: taken to make sure that there are no deposits of sludges
d in between the scraps. It is also necessary to rinse regu-
U0 = E + i + K1 ln i, (16) larly of the surface of the electrode plates or the scraps.
κ
+
-
+
-
+
-
+
-
(a) multiple channels
+
-
+
-
+
-
+
-
(b) Single channel
Fig. 11. Mode of water flow.
Because there are a definite amount of metal ions re-

quired to remove a given amount of pollutants, it is
usually to use iron for wastewater treatment and alu-
minum for water treatment because iron is relatively
cheaper. The aluminum plates are also finding applica- Fig. 12. Electrocoagulation unit with cylindrical electrodes.
tions in wastewater treatment either alone or in com-
bination with iron plates due to the high coagulation
efficiency of Al3+ [26]. When there are a significant suspended solids (SS) from water. In order to prevent
amount of Ca2+ or Mg2+ ions in water, the cathode any blockings, scraper blades are installed inside the
material is recommended to be stainless steel [28]. cylinder. The electrodes are so fitted that they are at
the open space of the teeth of the comb. An alternative
3.3. Typical design of cylindrical design is given in Fig. 13 where a ven-
turi is placed in the center of the cylinder with water
Depending on the orientation of the electrode and coagulants flowing inside it to give a good mix-
plates, the electrocoagulation cell can be horizontal ing. The electrocoagulation reactor can be operating
or vertical, Fig. 10. To keep the electrocoagulation in continuous as well as in batch operation. For batch
system simple, the electrode plates are usually con- operation such as the cases for treating small amount
nected in bi-polar mode. The water flow through the of laundry wastewater or for the water supply of con-
space between the plates can be multiple channels or struction site, the automation is an important issue.
a single channel, Fig. 11. Multiple channels are sim- The electrocoagulation has to be followed by a sludge
ple in the flow arrangement but the flowrate in each removal process. It is either a sedimentation unit or a
channel is also small. When the electrode surface flotation unit.
passivation cannot be minimized otherwise, increas-
ing the flowrate by using a single channel flow is 3.4. Effluents treated by electrocoagulation
recommended.
For water treatment, a cylindrical design can be used Electrocoagulation is efficient in removing sus-
as shown in Fig. 12. It can be efficiently separate the pended solids as well as oil and greases. It has been
Water inlet Chemicals Table 2

The range of gas bubbles at different pH and electrode materials
pH Hydrogen (␮m) Oxygen (␮m)
Pt Fe C Pt
2 45–90 20–80 18–60 15–30

7 5–30 5–45 5–80 17–50
12 17–45 17–60 17–60 30–70
electrolysis [53]. Therefore, the electrochemical reac-

tions at the cathode and anode are hydrogen evolution
and oxygen evolution reactions, respectively. EF was
first proposed by Elmore in 1904 for flotation of valu-
able minerals from ores [2].
air
4.1. Factors affecting electroflotation
Fig. 13. Rod electrodes in a cylinder electrocoagulation unit. The performance of an electroflotation system is
reflected by the pollutant removal efficiency and the
power and/or chemical consumptions. The pollutant
proven to be effective in water treatment such as removal efficiency is largely dependent on the size of
drinking water supply for small or medium sized the bubbles formed. For the power consumption, it re-
community, for marine operation and even for boiler lates to the cell design, electrode materials as well as
water supply for industrial processes where a large the operating conditions such as current density, wa-
water treatment plant is not economical or necessary. ter conductivity, etc. If the solid particles are charged,
It is very effective in coagulating the colloidal found the opposite zeta-potential for the bubbles are recom-
in natural water so that reduces the turbidity and mended [54].
color. It is also used in the removal or destruction of
algeas or microorganisms. It can be used to remove 4.1.1. pH effect
irons, silicates, humus, dissolved oxygen, etc. [28]. The size variation of the bubbles depends on wa-
Electrocoagulation was found particularly useful ter pH as well as the electrode material as shown in
in wastewater treatment [37]. It has been employed Table 2 [55]. The hydrogen bubbles are smallest at
in treating wastewaters from textile [38–41], catering neutral pH. For oxygen bubbles, their sizes increase
[29,42], petroleum, tar sand and oil shale wastewater with pH. It should be noted, however, the cathode ma-
[43], carpet wastewater [44], municipal sewage [45], terials affect the size of the hydrogen bubbles, so do the
chemical fiber wastewater [46], oil–water emulsion anode materials. The bubble sizes obey a log-normal
[47,48], oily wastewater [34] clay suspension [49], distribution [54].
nitrite [50], and dye stuff [51] from wastewater. Cop- Using buffer solution, Llerena et al. [56] found that
per reduction, coagulation and separation was also the recovery of sphalerite is optimal at pH between
found effective [52]. 3 and 4. They also documented that during this pH
range, the hydrogen bubbles are the smallest, about
16±2 ␮m. Decrease or increase pH from 3 to 4 results
4. Electroflotation in the increase of hydrogen bubbles. At pH of 6, the
mean hydrogen bubbles is 27 ␮m. At pH of 2, the
Electroflotation is a simple process that floats pol- hydrogen bubbles are about 23 ␮m when the current
lutants to the surface of a water body by tiny bubbles density was all fixed at 500 A/m2 using a 304 SS wire.
of hydrogen and oxygen gases generated from water Oxygen and hydrogen were separated in their research
Table 3 Table 4
The mean gas bubble size at different current density and electrode The mean gas bubble size at different conditions (polished graphite
materials, pH 9 electrodes, DI water, Na2 SO4 )
Electrode Current density (A/m2 ) Ionic strength Current density Gas Mean size
(A/m2 ) (␮m)
125 200 250 300 375
0.1 52.3 O2 18.6
Hydrogen gas bubbles diameter (␮m) 98.5 21.2
SS plate 34 32 29 26 22 129.2 23.3
200 mesh 39 35 32 31 28 196.7 17.1
100 mesh 45 40 38 30 32 212.3 37.9
60 mesh 49 45 42 40 37 295.4 20.0
393.8 20.7
Oxygen gas bubbles diameter (␮m)
492.3 28.7
Pt plate 48 46 42
590.8 26.2
200 mesh 50 45 38
689.2 20.7
787.7 25.3
886.1 31.5
and it was found that the increase of pH in the cathode 55.4 H2 29.7
chamber and pH decrease in the anode chamber are 98.5 37.7
196.9 19.3
very quick when no buffer solutions were used. The
recovery efficiency of oxygen is about half of that of 0.01 33.8 O2 27.0
hydrogen proportional to the amount of gas generated 46.2 24.7
58.5 22.0
at a given current. This was also confirmed by O2 and 36.9 H2 37.6
H2 gas sparging. 43.1 s 37.3
55.4 22.0
4.1.2. Current density
The gas bubbles depends also on the current density
[57,58]. The surface condition affects the particle size, energy consumption will be unacceptably high due to
too. The polished mirror surface of the stainless steel the large inter-electrode spacing required for prevent-
plate gives the finest bubbles, Table 3. Besides size ing the short-circuit between the upper flexible screen
of bubble, the bubble flux, defined as the number of cathode and the bottom anode.
gas bubbles available per second per unit cross-section Chen et al. [62] proposed and tested the novel
area of the flotation cell, also plays a role in mineral arrangement of electrodes with anode and cathode
flotation, recovery of different sized particles [58]. A placed on the same plane as shown in Fig. 15. Effective
decrease of gas bubble sizes was found with the in- flotation was obtained because of quick dispersion of
crease of current intensity, Table 3. Burns et al. [59] the small bubbles generated into the wastewater flow.
found that such a decrease of bubble size with increase Quick bubble dispersion is essentially as important
in current density was true only at the low end of cur- as the generation of tiny bubbles. For a conventional
rent densities. When the current density is higher than electrode system, only the upper screen cathode faces
200 A/m2 , no clear trend can be observed with gas the wastewater flow, while the bottom anode does not
bubbles ranging from 20 to 38 ␮m, Table 4.
4.1.3. Arrangement of the electrodes

Usually, an anode is installed at the bottom, while
a stainless steel screen cathode is fixed at 10–50 mm
above the anode [56,60,61], Fig. 14. Such an elec-
trode arrangement cannot ensure quick dispersion of
the oxygen bubbles generated at the bottom anode
into wastewater flow, affecting flotation efficiency.
Moreover, if the conductivity of wastewater is low, Fig. 14. Conventional electrodes arrangement for electroflotation.
Cathode
A
A
Plexiglas
A-A
Anode
Fig. 15. Novel electrodes arrangement for electroflotation.
interact with the flow directly. Therefore, the oxygen Meanwhile, the open configuration has been proven
bubbles generated at the bottom anode cannot be dis- quite effective in the flotation of oil and suspended
persed immediately into the wastewater being treated. solids. Significant electrolysis energy saving has also
Consequently, some oxygen bubbles may coalesce to been obtained due to the small inter-electrode gap
form useless large bubbles. This not only decreases used in the novel electrode system. It is useful to
the availability of the effective small bubbles, but also point out that the electrolysis voltage required in
increases the possibility of breaking the flocs formed an EF process is mainly from the ohmic potential
previously, affecting the flotation efficiency. When drop of the solution resistance, especially when the
the anode and the cathode are leveled, such an open conductivity is low and the current density is high.
configuration allows both the cathode and the anode Since the ohmic potential drop is proportional to the
to contact the wastewater flow directly. Therefore, the inter-electrode distance, reducing this distance is of
bubbles generated at both electrodes can be dispersed great importance for reducing the electrolysis energy
into wastewater rapidly and attach onto the flocs ef- consumption. For a conventional electrode system,
fectively, ensuring high flotation efficiency. Another due to the easy short-circuit between the upper flex-
arrangement of the electrodes is shown in Fig. 16. ible screen electrode and the bottom electrode, use of
It has the advantage of the uniform property of the a very small spacing is technically difficult. But for
surface of an electrode. It is also very much efficient the electrode system shown in Figs. 15 and 16, the
[26]. inter-electrode gap can be as small as 2 mm.
Fig. 16. Alternative electrode arrangement for electroflotation.

4.2. Comparison with other flotation technologies available, and able to fulfill the simultaneous EC
and EF, they are anodically soluble [29,56,59,67]. To
The effective electroflotation obtained is primarily make matters worse, the bubbles generated at partially
attributed to the generation of uniform and tiny bub- dissolved electrodes usually have large sizes due to
bles. It is well known that the separation efficiency of the coarse electrodes surfaces [42]. Graphite and lead
a flotation process depends strongly on bubble sizes. oxide are among the most common insoluble anodes
This is because smaller bubbles provide larger sur- used in EF [59,68]. They are also cheap and easily
face area for particle attachment. The sizes of the bub- available, but both show high O2 evolution overpo-
bles generated by electroflotation were found to be tential and low durability. In addition, for the PbO2
log-normally distributed with over 90% of the bubbles anodes, there exists a possibility to generate highly
in the range of 15–45 ␮m for titanium-based DSA® toxic Pb2+ , leading to severe secondary pollution. A
anode [62]. In contrast, typical bubble sizes range few researchers reported use of Pt or Pt-plated meshes
from 50 to 70 ␮m for DAF [63]. Burns et al. [59] re- as anodes [58,60]. They are much more stable than
ported that values of gas bubble size vary from 46.4 graphite and lead oxide. However, the known high cost
to 57.5 ␮m with the pressure decrease from 635 to makes large-scale industrial applications impractic-
414 kPa for DAF. The electrostatic spraying of air [64] able.
gives gas bubbles range from 10 to 180 ␮m with mean The well-known TiO2 –RuO2 types of dimension-
diameter being 33–41 ␮m [59]. Impeller flotation (IF) ally stable anodes (DSA® ) discovered by Beer [25]
produces much smaller gas bubbles but its pollutant possess high quality for chlorine evolution but their
removal efficiency is not good probably due to the service lives are short for oxygen evolution [69]. In
quick coalesce of the tiny bubbles to form larger ones the last decade, IrOx -based DSA® have received much
soon after they are generated. Table 5 summaries the attention. IrOx presents a service life about 20 times
comparison of different flotation processes for treating longer than that of the equivalent RuO2 [70]. In gen-
oily wastewater [65]. IC, OC and F in the table denote eral, Ta2 O5 , TiO2 , and ZrO2 are used as stabilizing or
inorganic coagulants, organic coagulants and floccu- dispersing agents to save cost and/or to improve the
lants, respectively. Electroflotation clearly shows ad- coating property [71–75]. Occasionally, a third com-
vantages over either DAF, settling or IF. When the ponent such as CeO2 is also added [70,75]. It should
conductivity is low, direct application of EF consumes be noted that although incorporation of Ta2 O5 , TiO2
large amount of electricity. For this case, addition of and ZrO2 can save IrOx loading, the requirement of
table salt (NaCl) is helpful [66]. molar percentage of the precious Ir component is still
very high. The optimal IrOx contents are 80 mol% for
4.3. Oxygen evolution electrodes IrOx –ZrO2 , 70 mol% for IrOx –Ta2 O5 , and 40 mol%
for IrOx –TiO2 , below which electrode service lives de-
The electrode system is the most important part and crease sharply [73]. The IrOx –Ta2 O5 -coated titanium
thus considered as the heart of an EF unit. Although electrodes have been successfully used as anodes of
iron, aluminum and stainless steel are cheap, readily EF [42,76]. Nevertheless, due to the consumption of
Table 5
Economic parameters in treating oily effluents
Treatment type EF DAF IF Settling
Bubble size (␮m) 1–30 50–100 0.5–2

Specific electricity consumption (W/m3 ) 30–50 50–60 100–150 50–100
Air consumption (m3 /m3 ) water 0.02–0.06 1
Chemical conditioning IC OC + F OC IC + F
Treatment time (min) 10–20 30–40 30–40 100–120
Sludge volume as percent of treated water 0.05–0.1 0.3–0.4 3–5 7–10
Oil removal efficiency (%) 99–99.5 85–95 60–80 50–70
Suspended solids removal efficiency (%) 99–99.5 90–95 85–90 90–95
large amounts of the IrOx , Ti/IrOx –Ta2 O5 electrodes

are very expensive, limiting their wide application.
The recently discovered Ti/IrOx –Sb2 O5 –SnO2 an-
odes have extremely high electrochemical stability
and good electrocatalytic activity for oxygen evolu-
tion [77,78]. A Ti/IrOx –Sb2 O5 –SnO2 electrode con-
taining only 10 mol% of IrOx nominally in the oxide
coating could be used for 1600 h in an accelerated life
test and was predicted to have a service life over 9
years in strong acidic solution at a current density of Fig. 17. Combined electrocoagulation and electroflotation.
1000 A/m2 . Considering the much lower current den-
sity used and nearly neutral operating environments media have been used [81], Fig. 18. This design allows
in EF, the IrOx content in the coating layer can be an intensive contact of the solid phase in the mixing
reduced to 2.5 mol% with sufficient electrochemical chamber with coagulants to form suspension particle
stability and good activity retained [62]. agglomerates and at the same time not to break up the
The electrode service life is strongly dependent on flocculates formed. The two stages of electrofloation
the current density used. A simple model relating the ensures the removal of finely dispersed particles. The
service life (SL) to the current density (i) has been installation of an ion exchange membrane between the
obtained [35]: electrodes in the fine electroflotation unit serves the
purpose of controlling the pH of the treated water. The
1
SL ∝ , (20) addition of partitions in an electroflotation unit helps
iα to better utilize the gas generated and the flotation vol-
where α ranges from 1.4 to 2.0. ume if non-rectangular flotation unit is employed [82],
Fig. 19. Co-current and counter-current electroflota-
4.4. Typical designs tion systems, Fig. 20, were also investigated in in-
dustrial scale [83]. Frequently, it may be necessary to
The electroflotation system consists of two elec- separate the cathode and anode chambers in order to
trodes, a power supply and a sludge handling unit. The avoid the atomic hydrogen or oxygen to react with
electrodes are usually placed at the bottom or close the solid particles in mining system, the automatic pH
to the bottom of the cell. Depending on the geometry adjustment in each chamber has to be provided [84].
of the EF cell, the electrodes can be placed vertically Although there are equations available for the design
or horizontally. The horizontal placement is the most of electroflotation unit [85], the actual design of an
popular choice [60,79,80]. Electroflotation is usually industrial operation has to base on careful laboratory
combined with electrocoagulation or chemical floccu- study.
lation, Fig. 17. In order for the chemical reagents to The following example can provide some guide-
mix well with the pollutants before flotation, fluidized lines in the design of an electroflotation system. This
Mixing
Sludge chamber
Coagulants Cleaned
water
Suspension +
- Ion exchange
- -+- -+--+- -+- + membrane
Rough EF Fine EF
Fig. 18. Electroflotation with a fluidized media.

Cleaned
water
Sludge
- Coagulants
Effluent
+ Liquid feed -+-+-+-+-+-+-+-+-+-+-+-+
Electroflotation unit
(a) Side view
(b) Top view

+ +
Electrocoagulation unit
Influent
- -
Cleaned
Fig. 19. Electroflotation with built-in partitions. - - water
design was made and tested for highly concentrated + +

industrial sewage from porcelain and faience indus-
Fig. 21. A typical electroflotation unit design.
try [80]. The schematic diagram is shown in Fig. 21.
The system consists of a case, a sludge collector, and
an electrode pile. The body is made of polypropy- are placed vertically in each chamber. The body is
lene and is of rectangular shape. The unit is divided equipped with inlet and outlet pipes with flanges con-
by a partition to have two sections. Each section is nected with pipelines and sludge collectors consisting
further partitioned into two chambers. Electrode piles of a scrubbing devices and a geared motor.
The electrode pile consists of a set of rectangular
plates 1 mm think. The cathodes are made of a stain-
solids
less steel and the anodes are made of titanium-based
DSA® -type materials (Ti/Ru–TiO2 ). The spacing be-
tween the electrodes is 3 mm. To prevent the formation
Water flow
of sediment, crest shaped electrodes are used which are
Gas flow arranged within the same plane to avoid short-circuit.
+ + DC power supply was employed. The overall dimen-
- - sions are 2100 mm × 1115 mm × 1500 mm with the
optimum height of the work zone being 0.8 m. The
(a) counter-current output of the system is up to 10 m3 /h. The specific
power consumption is 0.2–0.4 kW h/m3 .
solids The equipment operates as follows. The liquid is
fed into the first two chambers and then spills over the
partitions into the second two chambers before flow-
ing into a water header via an opening in the bottom
Water
part. The scrubbing device shifts the sludge from the
Gas
surface in a direction opposite to the liquid flow and
into a collecting pocket with a conic bottom located at
+ the end of the floater on the side of the liquid inlet. The
-
sludge is removed from the system via a branch pipe.
(b) co-current
Chemical coagulants and flocculants may be injected
Fig. 20. Water-gas flow in an electroflotation unit. into the feeding line to intensify the purification. For
Table 6 decomposition of cyanide was investigated [105]. Ex-

Electroflotation of industrial sewage in comparison with sedimen- tensive investigation of this technology commenced
tation
since the late 1970s. During the last two decades, re-
Parameter Purification method search works have been focused on the efficiency in
Sedimentation Electroflotation oxidizing various pollutants on different electrodes,
Duration (h) 2.0–7.0 0.2–0.4
improvement of the electrocatalytic activity and elec-
Coagulant consumption (g/l) 0.20–0.40 0.02–0.04 trochemical stability of electrode materials, investiga-
Efficiency (%) 70–80 95–99 tion of factors affecting the process performance, and
Moisture of sediment (%) 98.5–99.8 92.0–95.0 exploration of the mechanisms and kinetics of pol-
Volume of sediment (%) 17.0–20.0 0.1–0.2 lutant degradation. Experimental investigations focus
Initial conditions: pH 7, BOD5 = 50–100 mg/l, SS = mostly on the behaviors of anodic materials, the effect
1700–28,900 mg/l, milky color. of cathodic materials was not investigated extensively
although Azzam et al. [106] have found a consider-
this type of wastewater, the established chemicals to able influence of the counter electrode material in the
use are aluminosilicon floculant-coagulant (AKFK). anodic destruction of 4-Cl phenol.
Introduction of 15 mg/l AKFK into water containing
300 mg/l suspended particles removes 92–95% impu- 5.1. Indirect electrooxidation processes
rities whereas the same amount of aluminum sulfate
removes only 15% impurities. AKFK is made of SiO2 , Electrooxidation of pollutants can be fulfilled
Al2 O3 and Fe2 O3 with their respective concentrations through different ways. Use of the chlorine and hypo-
being 25, 17 and 0.9 g/l. Table 6 lists the results of the chlorite generated anodically to destroy pollutants is
electroflotation process in comparison with sedimen- well known. This technique can effectively oxidize
tation method. many inorganic and organic pollutants at high chlo-
ride concentration, typically larger than 3 g/l [50,107–
4.5. Wastewaters treated by electroflotation 113]. The possible formation of chlorinated organic
compounds intermediates or final products hinders
Mineral recovery remains the major user of elec- the wide application of this technique [109]. More-
troflotation [86]. In water and wastewater treatment, over, if the chloride content in the raw wastewater is
flotation is the most effective process for the separa- low, a large amount of salt must be added to increase
tion of oil and low-density suspended solids [87–91]. the process efficiency [113–116].
Electroflotation is found effective in treating palm Pollutants can also be degraded by the electro-
oil mill effluent [68], oily wastewater or oil–water chemically generated hydrogen peroxide [117–122].
emulsion [61,65,66,92,93], spent cooling lubricant In this system, the cathode is made of porous carbon-
[94], wastewater from coke-production [95], mining polytetrefluorethylene (PTFE) with oxygen feeding
wastewater [67], groundwater [60], food processing and the anode is either Pb/PbO2 , Ti/Pt/PbO2 , or Pt.
wastewater [96], fat-containing solutions [97], restau- Fe2+ salts can be added into the wastewater or formed
rant wastewater [42] or food industry effluents [98], in-situ from a dissolving iron anode [120] to make an
dairy wastewater [99], urban sewage [80], pit waters electro-Fenton reaction. The degradation of aniline
[100], colloidal particles [54], heavy metal containing was found to be about 95% when UV irradiation is
effluents [84,101–103], gold and silver recover from employed also. Simply sparging oxygen into the solu-
cyanide solution [104], and many other water and tion also helps the removal of aniline when electricity
wastewaters [56,65,83]. is on [119]. The electrically generated ozone is also
reported for wastewater treatment [123,124].
Farmer et al. [125] proposed another kind of elec-
5. Electrooxidation (EO) trooxidation, mediated electrooxidation, in treating
mixed and hazardous wastes. In this process, metal
Study on electrooxidation for wastewater treatment ions, usually called mediators, are oxidized on an
goes back to the 19th century, when electrochemical anode from a stable, low valence state to a reactive,
high valence state, which in turn attack organic pol- Table 7

lutants directly, and may also produce hydroxyl free Potential of oxygen evolution of different anodes, V vs. NHE
radicals that promote destruction of the organic pol- Anode Value Conditions Reference
lutants. Subsequently, the mediators are regenerated (V)
on the anode, forming a closed cycle. The typical Pt 1.3 0.5 M H2 SO4 [142]
mediators include Ag2+ , Co3+ , Fe3+ , Ce4+ and Pt 1.6 0.5 M H2 SO4 [219]
IrO2 1.6 0.5 M H2 SO4 [76,142]
Ni2+ [125–130]. Mediated electrooxidation usually
Graphite 1.7 0.5 M H2 SO4 [219]
needs to operate in highly acidic media. In addi- PbO2 1.9 1 M HClO4 [155]
tion, there exists the secondary pollution from the SnO2 1.9 0.5 M H2 SO4 [167]
heavy metals added. These disadvantages limit its Pb–Sn (93:7) 2.5 0.5 M H2 SO4 [142]
application. Ebonex® (titanium 2.2 1 M H2 SO4 [178]
oxides)
Si/BDD 2.3 0.5 M H2 SO4 [200,197]
5.2. Direct anodic oxidation Ti/BDD 2.7 0.5 M H2 SO4 [203]
DiaChem 2.8 0.5 M H2 SO4 [142]
Electrooxidation of pollutants can also occur di-
rectly on anodes by generating physically adsorbed
“active oxygen” (adsorbed hydroxyl radicals, • OH) [50], and reticulated vitreous carbon [139,140]. How-
or chemisorbed “active oxygen” (oxygen in the ox- ever, none of them have sufficient activity and at the
ide lattice, MOx+1 ) [131]. This process is usually same time stability. The anodes that were studied
called anodic oxidation or direct oxidation. The extensively are graphite, Pt, PbO2 , IrO2 , TiO2 , SnO2 ,
physically adsorbed “active oxygen” causes the com- and diamond film. We will discuss them in more
plete combustion of organic compounds (R), and the details subsequently.
chemisorbed “active oxygen”(MOx+1 ) participates in
the formation of selective oxidation products: 5.2.1. Overpotential of oxygen evolution
As discussed previously the anodic activity depends
R + MOx (• OH)z = CO2 + z H+ + z e + MOx . on the value of overpotential of oxygen evolution.
Table 7 gives a comparison of most extensively inves-
(21)
tigated anode materials. For a better understanding of
R + MOx+1 = RO + MOx . (22) the performance of the anodes, the formation poten-
tials of typical oxidants are listed in Table 8. It is clear
In general, • OH is more effective for pollutant oxi- that IrO2 , Pt, and graphite show much smaller values
dation than O in MOx+1 . Because oxygen evolution, of overpotential of oxygen evolution. This indicates
reaction (9), can also take place at the anode, high that effective oxidation of pollutants on these anodes
overpotentials for O2 evolution is required in order for occurs only at very low current densities or in the
reactions (21) and (22) to proceed with high current
efficiency. Otherwise, most of the current supplied Table 8
will be wasted to split water. Formation potential of typical chemical reactants [142,220]
The anodic oxidation does not need to add a large Oxidants Formation
amount of chemicals to wastewater or to feed O2 to potential
cathodes, with no tendency of producing secondary H2 O/• OH (hydroxyl radical) 2.80
pollution and fewer accessories required. These ad- O2 /O3 (ozone) 2.07
SO4 2− /S2 O8 2− (peroxodisulfate) 2.01
vantages make anodic oxidation more attractive than
MnO2 /MnO4 2− (permanganate ion) 1.77
other electrooxidation processes. The important part H2 O/H2 O2 (hydrogen peroxide) 1.77
of an anodic oxidation process is obviously the an- Cl− /ClO2 − (chlorine dioxide) 1.57
ode material. Anode materials investigated include Ag+ /Ag2+ (silver(II) ion) 1.5
glassy carbon [132], Ti/RuO2 , Ti/Pt–Ir [109,133], Cl− /Cl2 (chlorine) 1.36
Cr3+ /Cr2 O7 2− (dichromate) 1.23
fiber carbon [107], MnO2 [134,135], Pt–carbon black
H2 O/O2 (oxygen) 1.23
[136,137], porous carbon felt [138], stainless steel
presence of high concentrations of chlorides or metal- oxygen evolution side reaction. This leads to an effec-
lic mediators. When the current density is high, sig- tive and efficient process. It is indeed the most active
nificant decrease of the current efficiency is expected anode for oxidation of various pollutants as discussed
from the production of oxygen. The boron-doped dia- in the following sections.
mond (BDD) film on titanium substrate [141] or other
valve metals as in DiaChem electrodes [142] gives the 5.2.2. Performance of anodic oxidation
highest value of oxygen evolution overpotential. Thus, Table 9 compares the performance of different an-
anodic oxidation can take place on its surface at signif- odes in the degradation of various pollutants under
icantly high current density with minimal amount of different conditions. Two parameters are of particular
Table 9
Comparison of the performance of different anodes
Anode Pollutant Current density CE (%) Removal Comment Reference
(A/m2 ) efficiency
Granular graphite Phenol 0.03–0.32 70 70, 50% 5-month stable operation [144]
mineralization
Planar graphite Phenol 10–100 24.6–63.5 6–17%, COD NaOH as electrolyte [145]
Pt or Ti/Pt Phenol 300 30%, TOC pH 12, initial concentration [165]
1000 mg/l, in 0.25 M Na2 SO4
Ammonia 8.5 53 95% pH 8.2 using phosphate [146]
buffer, poor performance for
organics
Glucose 100–900 15–20 30% 1 M H2 SO4 [221]
15 organics 5 [148]
PbO2 Aniline I = 2A 15–40 >90% in 1 h Initial concentration 2.7 mM, [153]
pH 2, packed bed of PbO2
Phenol I = 1, 2, 3 A 46–80% Anodic cell: initial [211]
concentration 14–56 mM, in
1.0 sulfuric acid, packed bed
of PbO2
Ti/PbO2 Phenol 300 40%, TOC pH 12, initial concentration [165]
1000 mg/l, in 0.25 M Na2 SO4
Landfill leachate 50–150 30% for COD 90% for COD [172]
10% for 100% for
NH4 + –N NH4 + –N
Glucose 100–900 30–40 100% 1 M H2 SO4 [221]
2-Chlorophenol 80–160 35–40 80–95%, COD Pb2+ formation, initial COD [157]
= 1000 mg/l, 25 ◦ C
IrO2 Organic Low 17 [149]
1,4-Benzoquinone Rupture of rings only [151]
Chlorinated phenols 0.6 54 Na2 SO4 [150]
50 1.8
Ti/SnO2 –Sb2 O5 2-Chlorophenol 80–160 35–40 80–95%, COD Oxalic acid as intermediates [157]
Glucose 100–900 <20 30% 1 M H2 SO4 [221]
Phenol 300 100% pH 12, initial concentration [165]
1000 mg/l, in 0.25 M Na2 SO4
500 58 70 ◦ C, 10 mM [149]
CV method, similar to PbO2 [171]
Landfill leachate Similar to PbO2 [172]
Ebonex® Trichloroethylene Fixed potential <32 10–70% Stable in aqueous media, [179]
2.5–4.3 V Ti4 O7 to TiO2
concern, one is the current density, and the other is to increase the activity, PbO2 is sometimes doped
the current efficiency. Comninellis and Plattner [143] by Bi, Fe, Ag [154–156]. For oxidation of organic
proposed to use electrochemical oxidability index pollutants like aniline, PbO2 anode is very efficient
(EOI) to differentiate the performances of different with reasonable value of current efficiency [153]. The
electrodes. EOI is the mean current efficiency from operating current density is also of reasonable value,
the initial concentration of pollutant to the time when 80–160 A/m2 [157]. PbO2 electrodes are relatively
the pollutant is nearly zero, τ [143]. To calculate cheap and effective in oxidizing pollutants. The only
EOI, one needs to know the instantaneous current concern for this electrode is the formation of Pb2+
efficiency, ICE, defined as the current efficiency at a ions from the electrochemical corrosion.
given time of electrooxidation. Thus, Pure SnO2 is an n-type semiconductor with a band
τ gap of about 3.5 eV. The valence band arises due
ICE dt
EOI = 0 . (22) to the overlap of filled oxygen 2p levels. The tin 5s
τ states are at the bottom of the conduction band [158].
Because EOI calculation so defined include signifi- This kind of oxide exhibits a very high resistivity
cantly the contribution of ICE at long reaction time at room temperature and thus cannot be used as an
when the pollutant concentration is very low and mass electrode material directly. However, its conductivity
transfer rather than electrochemical kinetics controls can be improved significantly by doping Ar, B, Bi,
the process. Hence, the EOI so calculated is very low, F, P and Sb [159–165]. In electrochemical applica-
ranging from less than 0.05 to 0.58 for electrochemi- tion, Sb is the most common dopant of SnO2 . Doped
cally degrading various benzene derivatives on Pt an- SnO2 films are usually used as transparent electrodes
ode [143]. If EOI is to be used, I believe the value of in high-efficiency solar cells, gas detectors, far IR
τ should be so selected that it equals to the time when detectors and transparent heating elements [158]. The
mass transfer control just starts. Since we do not have conductive SnO2 films can be prepared by vapor
the values of ICE where mass transfer control just be- deposition [160], sputtering [166], spray pyrolysis
gins, the average current efficiencies from initial to [165,167], sol–gel [168], and brush-dry-bake tech-
final values of a process are used for comparison in- nique [169]. The onset potential for O2 evolution on
stead. Sb-doped SnO2 is about 1.9 V versus NHE in 0.5 M
For graphite electrodes the maximum CE obtained H2 SO4 solution [170], similar to that on PbO2 .
was as high as 70% at very low current densities rang- Kotz et al. [165] first reported anodic oxidation
ing from 0.03 to 0.32 A/m2 [144]. When current den- of pollutants on Sb-doped SnO2 -coated titanium
sities increased to 10–100 A/m2 , the CE values were electrodes (Ti/SnO2 –Sb2 O5 ). The CE obtained on
only 6–17% [145]. Despite the satisfactory results ob- Ti/SnO2 –Sb2 O5 was about five times higher than
tained in oxidizing simple inorganic pollutants at very that on Pt [148]. Comninellis [149] measured the CE
low current densities [146], Pt electrodes show poor of SnO2 –Sb2 O5 to be 0.58 for 71% degradation of
efficiencies in anodic oxidation of organic compounds phenol while the values for PbO2 , IrO2 , RuO2 and
[147,148]. The carbon black addition was found to Pt are, respectively, 0.18, 0.17, 0.14 and 0.13 at i =
enhance the performance of Ti/Pt anodic oxidation of 500 A/m2 , pH 12.5, initial concentration of 10 mm,
aqueous phenol significantly [136]. As mentioned be- reaction temperature of 70 ◦ C. Grimm et al. [171]
fore, IrO2 has been widely investigated as an electro- investigated phenol oxidation on SnO2 –Sb2 O5 and
catalyst for O2 evolution. The low current efficiency PbO2 using a cyclic voltammetric method and also
is expected [149,150]. The low activity of this anode found that the former was more active. Nevertheless,
in oxidizing 1,4-benzoquinone may be related to the Cossu et al. [172] reported that there was no sub-
low current value has to be employed [151]. stantial difference in activity between SnO2 –Sb2 O5
PbO2 is the most widely investigated anode mate- and PbO2 in treating landfill leachate. This might be
rial for electrooxidation. Usually, PbO2 electrodes are associated with the presence of high concentrations
prepared either by anodically polarizing metal lead in of chlorides in this type of waste.
H2 SO4 solutions [152,153] or by electrochemically Despite the high efficiency for pollutant ox-
coating PbO2 films on Ti substrates [149]. In order idation, Sb2 O5 –SnO2 electrodes lack sufficient
electrochemical stability just like PbO2 . Lipp and [180]. It exhibits many unique technologically
Pletcher [169] conducted a long term test of important properties, including high thermal conduc-
SnO2 –Sb2 O5 in 0.1 M H2 SO4 solution at a con- tivity, wide band gap, high electron and hole mobil-
stant potential of 2.44 V versus NHE and found ities, high breakdown electric field, hardness, optical
that the current dropped from initial 0.2 to about transparency, and chemical inertness [181]. Struc-
0.1 A within a few hours and to 0.06 A after 700 h. turally, diamond has a cubic lattice constructed from
Correa-Lozano et al. [173] also investigated the sta- sp3 -hybridized tetrahedrally arranged carbon atoms
bility of Sb2 O5 –SnO2 electrodes and found that the with each carbon atom bonded to four neighbors [182].
service life of Ti/Sb2 O5 –SnO2 was only 12 h under an The stacking sequence is ABCABC with every third
accelerated life test performed at a current density of layer plane identical. This structure is fundamentally
1000 A/m2 in 1 M H2 SO4 solution. At 10,000 A/m2 different from that of graphite which consists of layers
and 3 M H2 SO4 , this electrode can only last a few of condensed polyaromatic sp2 -hybridized rings with
seconds [174]. Although addition of IrO2 into the each carbon atom bonded to three neighbors. Impuri-
SnO2 –Sb2 O5 mixture increased the service life sig- ties in diamond can make it an insulator with a resistiv-
nificantly [77,78], the resulting electrodes have an ity of >106 m and a band gap energy of 5.5 eV [181].
overpotential of O2 evolution of 1.5 V versus NHE in A recent finding from Sweden shows that pure dia-
0.5 M H2 SO4 electrolyte. mond can be a very good conductor of electrons [183].
Pure TiO2 has a band gap of 3.05 eV [175] and thus Diamond films are usually synthesized by chem-
shows poor conductivity at room temperature. TiO2 ical vapor deposition (CVD) [184]. Early CVD of
is usually used as a photocatalyst in wastewater treat- diamond was carried out by thermal decomposi-
ment. By doping with Nb and/or Ta, TiO2 conductiv- tion of carbon-containing gases such as CH4 and
ity was successfully improved [176,177] to be used as CO [185,186] at gas temperatures between 600 and
an electrocatalyst for pollutant oxidation. This type of 1200 ◦ C. The gas temperatures were about the same
electrodes is usually made by baking the Ti substrates as the surface temperature of the diamond seeds that
coated with Nb and/or Ta-doped TiO2 films at 450 ◦ C, were exclusively used as substrates. The diamond
followed by annealing the films at 650–800 ◦ C in the growth rates were only about 0.01 ␮m/h, too low
presence of H2 and a small amount of water vapor to be of commercial significance. In addition, the
to reduce the Nb(V) to Nb(IV). The preferred molar material was often contaminated with non-diamond
concentration of (Nb + Ta) in the oxide coating is carbon and required frequent interruptions to remove
2–6% [176]. TiO2 electrodes are stable at low cur- the accumulated graphite by hydrogen etching at a
rent densities (below 30 A/m2 ), but their lifetimes are temperature >1000 ◦ C and a pressure >50 atm, or by
significantly shortened when operated at high current oxidizing in air at the atmospheric pressure [187].
densities [177]. Another conductive titanium oxide In the mid-1970s, Derjaguin and Fedoseev [188]
is Ebonex® that is also able to serve as an anode recognized the crucial role of atomic hydrogen in
material. Ebonex® is a non-stoichiometric titanium etching graphite deposits preferentially and success-
oxide mixture comprised of Magneli phase titanium fully synthesized diamond on non-diamond substrates
oxides Ti4 O7 and Ti5 O9 , and made by heating TiO2 at a commercially practical deposition rate (>1 ␮m/h).
to 1000 ◦ C in the presence of H2 [178]. Although This was a historic milestone in the development of di-
Ebonex® is stable in aqueous media throughout the amond CVD techniques. However, intensive interests
practical pH range, anodic oxidation in 1 M sulfuric in diamond CVD did not arise until the early 1980s
acid results in partial oxidation of Ti4 O7 to TiO2 , and when Matsumoto et al. [189,190] revealed the details
surface passivation under extreme conditions may be of synthesizing high-quality diamond films on Si and
an issue [179]. Mo substrates using hot-filament CVD (HFCVD).
The typical deposition conditions were: methane
5.2.3. Boron-doped diamond electrode concentration 1% in hydrogen, substrate tempera-
Diamond is a fascinating material. Diamond is ture 700–1000 ◦ C, filament temperature ∼2000 ◦ C,
known for its high strength, extreme hardness, high re- total gas pressure 13–133 mbar, and reaction time
sistance to thermal shock, and infrared transmissivity 3 h. Since then, new techniques such as microwave
Table 10
Treatment of different wastewaters and solutions using Si/BDD electrodes [199]
Wastewater/solution Oxidation conditions COD reduction (%)
Kodak E6 first developer Initial COD 32,500 mg/l; solution volume 30 ml; current 0.31 A; 73
current density 1000 A/m2 ; electrolysis time 6.25 h
Kodak E6 color developer Initial COD 19,050 mg/l; solution volume 30 ml; current 0.31 A; 80
current density 1000 A/m2 ; electrolysis time 4.75 h
Phenol solution Initial COD 3,570 mg/l; solution volume 60 ml; current 0.31 A; 94
current density 1000 A/m2 ; electrolysis time 18 h
Hydroquinone solution Initial COD 23,530 mg/l; solution volume 60 ml; current 0.15 A; 97
current density 500 A/m2 ; electrolysis time 38 h
plasma-assisted CVD [191] and DC discharge CVD studies. Particularly, BDD film was found to be the
[192] were developed rapidly. The diamond growth most active anodic material for degradation of refrac-
rates are in the order of 0.1 to near 1000 ␮m/h [193], tory or priority pollutants such as ammonia, cyanide,
demonstrating the good prospect of diamond films for phenol, chlorophenols, aniline, TCE, various dyes,
industrial applications. surfactants, landfill leachate [141,201–204].
The conductivity of diamond can be improved sig- Unlike PbO2 , SnO2 and TiO2 , the BDD thin films
nificantly by doping boron. Boron doping is usually deposited on Si, Ta, Nb, and W by CVD have shown
achieved by adding B2 H6 [194,195], or B(OCH3 )3 excellent electrochemical stability [197]. The lifetime
[196,197] to the gas stream, or placing boron pow- of Nb/BDD, for example, is over 850 h in the accel-
der near the edges of the substrate prior to insertion erated life test performed at 100,000 A/m2 in 0.5 M
into the CVD chamber [198]. A general useful range H2 SO4 solution. Even after several weeks of oxida-
of the boron/carbon weight ratio in the boron-doped tion, the properties of these electrodes were not af-
diamond is from ca. 0.02 to ca. 10−6 [199]. The fected and poisoning of the surface was not detectable.
onset potential for O2 evolution on boron-doped dia- However, Si/BDD electrodes are not suitable for in-
mond film on silicone substrate (Si/BDD) electrodes dustrial applications because Si substrates are very
in 0.5 M H2 SO4 solution is about 2.3 V versus NHE brittle and their conductivity is poor. Yet, large-scale
[197,200], 0.4 V higher than that on PbO2 and SnO2 . usage of Nb/BDD, Ta/BDD, and W/BDD electrodes
This indicates that diamond electrodes have higher is impossible due to the unacceptably high costs of
CE for pollutant oxidation. Besides the increase in Nb, Ta and W substrates.
oxygen overpotential, the increase in hydrogen over- Basically, the function of a substrate is to provide a
potential was also found by doping nitrogen leading facile pathway for the flow of current through the elec-
to the widest window for water split reaction [142]. trode assembly and a mechanical support for the thin
This conductive BDD film opened new frontiers of the diamond film. The materials that can probably be used
diamond application in electrochemical synthesis and as substrates must simultaneously have three impor-
analysis, sensor development for in vitro or in vivo tant attributes: good electrical conductivity, sufficient
biomedical application, for long-term environmental mechanical strength, and electrochemical inertness or
Table 11
Oxidation of various organic compounds on Si/BDD electrodes [197,206,207]
Compound Oxidation conditions CE (%)
Phenol Initial concentration 0.002 M; current density 300 A/m2 ; pH 2; 33.4a

charge loading 4.5 Ah/l; final phenol concentration <3 mg/l
CN− Initial concentration 1 M; current density 360 A/m2 ; 95% CN− elimination; 1 M KOH 41
Isopropanol Initial concentration 0.17 M; current density 300 A/m2 ; <90% conversion >95
Acetic acid Initial concentration 0.17 M; current density 300 A/m2 ; 90% conversion; 1 M H2 SO 85
a Calculated value based on charge loading.
Table 12
Comparison of Ti/BDD with Ti/Sb2 O5 –SnO2 for pollutant oxidation [203]
Pollutant Current density Charge (Ah/l) Initial COD Ti/BDD Ti/Sb2 O5 –SnO2
(A/m2 ) (mg/l)
Final COD CE (%) Final COD CE (%)
(mg/l) (mg/l)
Acetic acid 200 5.53 1090 33 64.0 756 20.2
Maleic acid 200 6.43 1230 46 61.7 557 35.0
Phenol 100 4.85 1175 39 78.5 450 50.1
orange II 200 6.25 1120 95 54.9 814 16.4
Reactive red HE-3B 200 6.25 920 45 46.9 714 11.0
easy formation of a protective film on its surface by other electrodes. The performance of Ti/BDD anode
passivation [199]. In addition, the costs of the materi- is given in Table 12 [203].
als should be acceptable. Titanium possesses all these
features and is therefore considered to be a good sub- 5.3. Typical designs
strate material. Actually, this metal has been widely
used in DSA® for over 30 years. The deposition of The electrooxidation reactors are similar to those
stable BDD films on Ti substrates with CVD from the seen in Section 2.1 for metal recoveries. The concerns
standard gas mixture of H2 + CH4 is very difficult up are also the current efficiency and also the space–time
to date. Cracks may appear leading to the delamina-
tion of the diamond films under electrochemical attack
at high loads [197]. By adding CH2 (OCH3 )2 in the
precursor gas, Chen et al. [141,203] have managed to + - +
deposit a BDD film on Ti substrate with satisfactory
stability. Nowadays, diamond films can be deposited
on the substrates with various geometries up to 0.5 m2
using HFCVD method [205].
Carey et al. [199] patented the use of diamond
films as anodes for organic pollutant oxidation. The
Si/BDD electrodes they used were commercially
obtained from Advanced Technology Materials Inc.
The boron concentrations in the diamond films were
1000–10,000 ppm. Different wastewaters and solu-
tions were investigated. Some results are summa-
rized in Table 10. A Switzerland research group
[197,206,207] also investigated anodic oxidation of
various pollutants on Si/BDD electrodes. The results
are summarized in Table 11. The CE obtained is very
high, ranging from 33.4 to over 95%, depending on
pollutant properties and oxidation conditions.
Beck et al. [208] compared Si/BDD with Ti/SnO2 ,
Ta/PbO2 and Pt for oxidation of phenol. At a charge
loading of 20 Ah/l, the total organic carbon (TOC)
was reduced from initial 1500 to about 50 mg/l on
Si/BDD, and to about 300, 650, and 950 mg/l on
Ti/SnO2 , Ta/PbO2 and Pt, respectively. Obviously,
Si/BDD electrodes have much higher activity than Fig. 22. Reactor with cylindrical electrodes.
employed with insulating net separating adjacent lay-

ers of bi-polarized packing [213,214]. Filter press re-
actor is another design [215]. In order to improve mass
Treated water transfer to the surface of the electrode, sonoelectro-
Anode feeder
chemical process has been tested and proven enhance-
Glass
beads
ment was achieved [216,217]. A thin layer of biofilm
Bed of pellets
can be immobilized on the surface of electrodes to
SS screen have a bio-electro reactor. It was found to be capable
Cathode of oxidation and reduction simultaneous in nitrifica-
feeder Luggin
capillary
tion and denitrification when respective microorgan-
isms are immobilized on the anode [218].
6. Summary
Gasket IE membrane Wastewater inlet
Electrochemical technologies have been investi-
Fig. 23. Packed bed electrochemical reactor.
gated as the effluent treatment processes for over
a century. Fundamental as well as engineering re-
yield. The simplest electrooxidation reactor design is searches have established the electrochemical de-
the bi-polar cell. Besides plane electrodes, the cylin- position technology in metal recovery or heavy
drical electrodes can also be employed [137,209,210], metal-effluent treatment. Electrocoagulation has been
Fig. 22. Inside the cylindrical anode, there are spheri- used industrially and demonstrated its superior per-
cal particles with BDD coating serving as the bi-polar formances in treating effluents containing suspended
electrodes. Packed bed of about 1 mm pellets of proper solids, oil and grease, and even organic or inorganic
anode materials can also be used [211,212], Fig. 23. pollutants that can be flocculated. Electroflotation is
Fig. 24 shows the bi-polar trickle tower that can be widely used in the mining industries and is finding
increasing applications in wastewater treatment. The
uniform and tiny sized bubbles-generated electrically
give much better performance than either dissolved
air flotation, sedimentation or even impeller flotation.
This process is compact and easy to facilitate with
automatic control. With the invention of stable, ac-
tive and cheap materials for oxygen evolution, this
Raschig ring technology will gradually replace the conventional
flotation techniques. Indirect oxidation is still a viable
Insulator
technology for treating toxic or biorefractory pollu-
Feeder tants although there are concerns about the formation
electrodes of chlotinated intermediates in the case of using chlo-
rine ions or about the complicated facilities in the
case of using electrically formed hydrogen peroxide
or ozone. Direct anodic oxidation represents one of
the simplest technologies in the pollutant mineral-
Cooling
water ization provided the anode materials are stable and
have high overpotential of oxygen evolution. The
investigation of various materials so far shows that
titanium or other noble metal-based boron-doped dia-
mond film is the candidate for industrial application.
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Separation and Purification Technology 38 (2004) 11–41

Electrochemical technologies in wastewater treatment

Received 19 September 2003; accepted 13 October 2003

1. Introduction electricity supply, electrochemical water or wastewater

such as electrophotooxidation, electrodisinfection will

Fig. 1. Tank cell.

There are quite a few types of reactors found ap- +

Fig. 3. Filter press reactor.

trical contact is not always maintained thus the current

Fig. 5. Pump cell.

Fig. 6. Fluidized bed reactor.

Metal solution Carbon granules

(a) side view

(b) end view

Fig. 7. Tumbling bed electrodes. Fig. 8. Fixed bed reactor.

Fig. 9. Design of a RenoCell.

cathode materials can be the metal to be recovered 3. Electrocoagulation

(a) Horizontal flow

Fig. 10. Electrocoagulation units.

at acidic conditions high chance of wasting electrical energy in heating

Al3+ (mg) E (W h/m3 ) Al3+ (mg) E (W h/m3 )

Turbidity 1 mg 0.04–0.06 5–10 0.15–0.2 20–40

Fig. 11. Mode of water flow.

Because there are a definite amount of metal ions re-

Water inlet Chemicals Table 2

2 45–90 20–80 18–60 15–30

electrolysis [53]. Therefore, the electrochemical reac-

4.1.3. Arrangement of the electrodes

Fig. 15. Novel electrodes arrangement for electroflotation.

Fig. 16. Alternative electrode arrangement for electroflotation.

Bubble size (␮m) 1–30 50–100 0.5–2

large amounts of the IrOx , Ti/IrOx –Ta2 O5 electrodes

Fig. 18. Electroflotation with a fluidized media.

(b) Top view

design was made and tested for highly concentrated + +

Table 6 decomposition of cyanide was investigated [105]. Ex-

high valence state, which in turn attack organic pol- Table 7

Phenol Initial concentration 0.002 M; current density 300 A/m2 ; pH 2; 33.4a

employed with insulating net separating adjacent lay-

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