The Operating Cost of Electrocoagulation

J . C. DONINP, J . KAN,J . SZYNKARCZUK, T. A. HASSAN and K. L. KAR

CANMET, Western Research Center, P.O. Bag 1280, Devon, Alberta TOC 1EO
The electrocoagulation of kaolinite and bentonite suspensions was studied in a pilot electrocoagulation system at the
Western Research Center of CANMET to assess the operating cost and efficiency of the process. Factors affecting
the operating cost such as, the formation of passivation layers on electrode plates, flow velocity and concentration of
sodium chloride in the suspension were examined. The operating costs investigated in this paper were the power cost
of the electrocoagulation cell and the material cost due to the consumption of the aluminum electrode. Comparison
was based on the settling properties of the treated product: turbidity, settling rate, and cake height. Higher concentration
of sodium chloride resulted in greater amount of aluminum dissolved chemically and electrochemically into the suspen-
sion and thus a better clarity of the supernatant of the treated product. Increased flow velocity could reduce significantly
the operating cost while improving both clarity of the supernatant and the compactness of the sludge volume. The
passivation layers developed quickly with time during the electrocoagulationprocess and more energy became wasted
on the layers.

On a CtudiC 1’Clectrocoagulation de suspensions de kaolinite et de bentonite dans un systbme d’electrocoagulation

pilote au Centre de recherches de I’Ouest de CANMET afin d’kvaluer les coats de fonctionnement et I’efficacitC du
procCdC. On a analysC les facteurs influant sur le coat de fonctionnement, tels la formation de couches de passivation
sur des plateaux h Clectrodes, la vitesses d’kcoulement et la concentration en chlorure de sodium dans la suspension.
Les coats de fonctionnement CtudiCs dans cet article sont le coat en Cnergie de la cellule d’tlectrocoagulation et le coat
en rnatCrie1 dO 21 la consommation de I’Clectrode d’alurninium. La comparaison s’est basCe sur les propriCtes de decanta-
tion: turbiditC, vitesse de decantation et hauteur du glteau. Une plus forte concentration en chlorure de sodium entraine
une plus grande quantitk d’alurninium dissous chimiquement et tlectrochimiquedans la suspension et, donc, une meilleure
dart6 du supernatif du produit trait& Une vitesse d’tcoulement accrue pourrait reduire de facon significative le coat
de fonctionnement tout en amCliorant la clartk du supernatif et la compacitC du volume de boues. Les couches de passivation
se developpent rapidement dans le temps lors du processus d’klectrocoagulation,et davantage d’Cnergie est perdue sur
les couches.

Keywords: electrocoagulation, operating cost, current efficiency of aluminum dissolution, passivation layer.

D uring the recent decades, research on waste water

treatment using electrocoagulation has shown that it
could be an attractive and suitable method in separating solids
from waste water (Donini et al., 1989). The research has
also shown that electrocoagulation works well for a large
range of applications (Domini et al., 1989; Kharchenko and
Nasonova, 1985; Zolotukhin, 1989; Sleptsov et al., 1987;
Zhul ’kov, 1978).
During the electrocoagulation process, an anode, made of
aluminum in this experiment, dissolves, producing in situ
aluminum cations which coagulate the suspensions. Two
different mechanisms can be expected during the anodic
aluminum dissolution; one is electrochemical, a strictly
Faradaic process, and the other is the purely chemical
dissolution of aluminum. Therefore, the following electrode
reactions occur:
Anode
A l o = A13+ + 3e- .........................
Cathode
2 H20 + 2e- = 2 OH- + H 2 . ...............
additionally, both the anode and the cathode will be dissolving
chemically:
A1° + 3 H 2 0 = Al(OH), + 1.5 H2 . . . . . . . . . . . (3)
Przhegorlinski et al. (1987) determined the contribution of
the individual reactions of Equations (1) - (3). Each of
*Author to whom correspondence should be addressed.
these reactions was evaluated from the weight loss of the
corresponding electrode and from the volume and composi-
tion of the collected hydrogen. Since both electrodes were
chemically dissolving with time, the current efficiency of
aluminum dissolution was above 100% and was in the range
of 165%-215%. Higher than 100% current efficiency of
aluminum dissolution was also reported by others (Bozin and
Mikhailov, 1990; Przhegorlinskii et al., 1987).
If electrocoagulation systems are to be practically
applicable to environmental problems, the costs of electro-
coagulation systems are critical. Unfortunately, not much
work has been published in this area even though industrial-
scale electrocoagulation units have been available in the
market (Zolotukhin, 1989; Przhegorlinskii et al., 1987a,b;
Ryan and Stanczyk, 1988). Therefore, studies on cost-
affecting factors in elecvocoagulation processes are necessary,
especially in view of the role these factors must play in future
system design.
Thus, the purpose of this work was to study the operating
(1) cost incurred during experiments. The cost of energy of the
electrocoagulation cell and the cost of aluminum electrode
consumed were obtained from the experimental results and
the sum was taken as the operating cost. Particular attention
(2) was given to the effect on the cost of sodium chloride
concentration, feed rate with and without recirculation, and
the formation of the passivation layers on the aluminum
electrodes. This work also investigated how the concentration
of sodium chloride affects the current efficiency of aluminum
dissolution and the aluminum electrode material consumption
due to the dissolution.
Donini et al. (1989) pointed out that for both electro-
coagulation and aluminum salts treatment (aluminum sulphate
or aluminum chloride), the mechanisms of coagulation are
similar. The difference is mainly in the way aluminum

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994 1007
 Coagulated
Product

1 3 5

2 4 6
Recirculation
Pump
Ell :trocoagula
Cell

Figure 1 - Schematic diagram of the electric circuit of the cell.

ions are delivered. A recent experiment of using aluminum

sulphate treatment on the same clay suspension as used
for the electrocoagulation test showed about 20 mg/kg of
aluminum was needed to achieve a good supernatant clarity.
This could cost in an electrocoagulation process $0.14 for
each cubic meter of suspension to be treated because of the
consumption of the aluminum electrode alone (assuming
aluminum material costs $7/kg.) Since in electrocoagulation
both chemical and electrochemical dissolution of aluminum
take place, several questions still remain: how is aluminum
dissolution affected by the concentration of sodium chloride
in the suspension and the electric current applied to the
electrocoagulation cell, and what is the optimum aluminum
dosage in the electrocoagulation process and how may it be
achieved?

Experimental Figure 2 - Schematic diagram of the flow circuit of the cell.

The pilot electrocoagulation system consisted of the power

supply, the electrocoagulation cell, the auxiliary equipment,
and the control and data acquisition system. The cell
contained four parallel aluminum electrode plates forming
three parallel cells. The electric circuit of the cell is shown
in Figure 1 . Polarities of the electrodes could be switched
periodically. The opposite aluminum electrodes worked in
turns. In the cathodic period, the electrode can clean off
some of the sticking clay particles. Pulse duration could be
controlled by the power unit. The gap between the two
neighbouring electrode plates was 6 mm. Each of the four
rectangular plates was 16.5 cm high and 58 crn wide.
The experimental set-up is illustrated schematically in
Figure 2 . Aqueous suspensions of 0.16 mass% kaolinite and
0.04 mass% bentonite were used as feed material. The
concentration of sodium chloride in the suspension was
adjusted from 0 to 0.1 mass% and, in most cases, it was
fixed at 0.03 mass%. Temperature and pH values of the feed
and product were measured for each experiment run. Feed
temperature was around 20°C. Product temperature was
several degrees Celsius higher than that of the feed depending
on the electric current applied and the main flow rate of the
electrocoagulation process. The process did not change sig-
nificantly the pH of the feed, which was around 8. The effect
of pH and thermokinetics will not be discussed in this paper.
In this study, aluminum concentration in sample suspension
was measured using a colorimetric method. However, the
ICP (inductively coupled plasma) method was also applied
for the purpose of calibration. Comparison showed that the
two methods gave very similar results. The consumption of
the aluminum electrode material per unit volume of feed was
obtained from the difference between the aluminum contents
in the product and the feed.

1008 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994
 Assuming the efficiency of aluminum dissolved due to the
electric current is loo%, according to Przhegorlinskii et al.
(1987) a relation between current and aluminum content
generated electrically can be calculated using the Faraday
law. Since the total aluminum content is the sum of the h
aluminum dissolved electrically and chemically, the current
efficiency of aluminium dissolution, vA1, is defined as:
4 200 I

vA1 = Ie9/I. Ie9is the equivalent current calculated from the

total aluminum content measured and I is the actual current
3 100
measured during the process.
A Cole-Parmer Model 5800-00 solution analyzer (Cole-
Parmer, Chicago, IL) was used to measure pH and conduc-
2
U
50
0

IV=18 0 v=30
TI
tivity of the feed and the processed product. The power
supply for the pilot plant was designed by Zeton Inc. 0 0.02 0.04 0.06 0.08 0.1
(Burlington, ON) for operation under either current or Concentration of NaCl (mass%)
voltage control. In this experiment, most of the runs were
conducted under voltage control. Those run under current Figure 3 - Effect of sodium chloride concentration on current
control will be indicated. Square voltage waves were efficiency of aluminium dissolution.
generated and pulse duration was set at 300 seconds. Voltage,
current, and pulse duration were measured and recorded in
the computer every two seconds under the control of the
commercially available software. Specifix version 2.3-7.88 0.5 1 + 100
(Intellution Inc., Norwood, MA). The settling rate of the
sludge/supernatant interface was determined manually in a
1-L cylinder by recording the interface height with time. The
average settling rate for the first 30 minutes was used in this
report. A Hach Ratio/XR turbidimeter (Hach, Loveland,CO)
c)

U
I; 0.3 1 + 160 a

was used to measure the turbidity of the feed and product.

Turbidity of the supernatant was determined for samples
taken from the settling cylinder after 10, 45, and 120 minutes
of settling. Only turbidity values measured after 10 minutes
of settling are used in this report. The cake height was the
height of the sludge/supernatant interface measured after 0.02 0.04 0.06 0.08
15 hours of settling. Concentration of NaCl (mass%)

Calculation of cost Figure 4 - Effect of sodium chloride concentration on operating

The applied electric voltage on the cell, VAp (volmeter
reading across the electrocoagulation cell) and current, I,
measured every two seconds were used to obtain the average
power during one cycle, N = VApI. Let Q be the flow of
the product in litres per minute; then the energy consumed
per unit volume of feed in kilowatt-hours per cubic meter,
E can be derived: E = N/60Q.
Assuming an energy price of $O.OS/kWh and consumable
aluminum electrode material cost of $7/kg (Donini et al.,
1989) and assuming the total costs are composed of the
energy cost and the aluminum material cost, the operating
cost can be calculated as:
cost. , percentage of power cost; o , percentage of aluminum
cost; + , operating cost.
Aluminum electrode material cost accounted for about 80%
of the operating cost in both experiments (Figure 4) where
the concentration of sodium chloride was changed up to 0.1
mass%. Using the Faraday law it is possible to further
analyze the effect of vAl on aluminum content.
Aluminum Content = vAl x I/O.l787Q.. . . . . . . . (5)
By substituting Equation (5) into Equation (4), we have the
operating cost:

Operating cost = 1.05 E + 0.007 x Aluminium Operating Cost = 0.03917 (0.02127VAp+ v A I ) X

content (mg/kg) . . . . . . . . . . . . . . . . . . . . . . . . . . . (4) (I/Q) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (6)

Results and discussion
EFFECTOF CONCENTRATION OF SODIUM CHLORIDE
The concentration of sodium chloride in the suspension
was varied from 0 to 0.1 mass% and the corresponding slurry
conductivity values were measured. Current efficiency of
aluminum dissolution (Figure 3) increased with the concen-
tration of sodium choloride if it was smaller than 0.05%.
If 190-200% is estimated to be the average aluminum
efficiency, the relative error for most of the data would fall
within 25 % .
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72. DECEMBER, 1994
The first term on the right hand side of Equation (6)
represents the energy cost and the second term is the
aluminum cost. That is, aluminum cost is in most of the
cases the largest contribution to the operating cost based on
the assumption that the current efficiency of aluminium dis-
solution is approximately 200% and the voltage is about 20
V. However, it should be noted that when the voltage
becomes higher, because of passivation and high cell
resistance, the energy cost could increase and become
comparable to the aluminum cost.
Figures 5-6 display the effect of sodium chloride concen-
tration on the settling properties. The data show that the
1009
 -__ ---_
i circulation 0 with circulation

3
z,
CI I= v 1

10 4
0.01 0.03 0.05 0.07 0.09
I
w"aJ 0.1 L,
0 100 200
-
u mri
I

300
Flow Rate (cd/s)
BE,
400 500
Concentration of NaCI (mass%)
Figure 7 - Effect of flow rate on energy consumption.
Figure 5 - Effect of sodium chloride concentration on turbidity.

11
____ 3 Iwithout circulation 0 with circulation
0 Cake Height + Settling Rate
2 0.019
h
2.6 3
0 0

2.2
u
v

2M
*
I; 0.6
U
1 0

.d

1.8 8
2
$ 0.016 - 1.4 - I
0
' 0 --T--

0.015-- ' 1 0 100 200 300 400 500

0.01 0.03 0.05 0.07 0.09 Flow Rate (cd/s)
Concentrationof NaCl (mass%)
Figure 8 - Effect of flow rate on operating cost.
Figure 6 - Effect of sodium chloride concentration on settling
rate and cake height.
1000 ___
Iwithout circulation 0 with circulaton
higher the concentration of sodium chloride, i.e., the higher
the current and energy input, the lower the turbidity of I
supernatant obtained and the lower the settling rate and higher
cake height. During electrocoagulation, a stronger current
generally results in looser flocs which settle more slowly;
they contain more water, and at the same time make clearer
supernatant.

EFFECTOF RECIRCULATION
It is believed that a high turbulence level in the flow
through the cell not only enhances mass transport, but also
reduces the passivation layers near the electrode plates.
Turbulence can be increased by increasing the flow rate
inside the cell. However, when the feed flow rate is
increased, the residence time of feed and the energy con-
sumed per unit volume of feed are decreased (Figure 7). In
order to maintain the same residence time while increasing
the flow through the cell to induce turbulence, a recirculation
loop was installed (see Figure 2). Energy consumed per unit
volume of feed was set lower on purpose in the cases with
recirculation than in the corresponding cases without recir-
culation (Figure 7). Figure 8 shows that the operating cost
was consistently lower when recirculation was used for the
whole flow rate range than when recirculation was not used.
1010 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994
lo
0 100 200 300 400 500
Flow rate ( c d s )
Figure 9 - Effect of flow rate on turbidity.
In most cases, the turbidity with recirculation was lower
than that without recirculation (Figure 9). The more interesting
discovery was that recirculation caused a consistently higher
setting rate and much lower cake height (Figures 10 and 1 I).
This is contrary to the usual results, where better clarity
implies lower settling rate and higher cake height. This is
an important result since high clarity and low cake volume
are desirable, but usually competing, processes. The authors
reason that the high shear rate obtained due to the high
flow rate made the flocs more compact and, therefore, they
settled faster and contained less water.

0.02
h
'2i0.018
ar
Y
2
M \
e
0.016 I rl
Y W
ar
r
A + 1.6
Iwithout circulation 0 with circulation
0.014
0 100 200 300 400
Flow rate (cm3/s)
Figure 10 - Effect of flow rate on settling rate.
rm ____
1
Iwithout circulation 0 with circulation
I voltage, V,, was suggested to be composed of three main
0 100 200 300 400
Flow Rate (cm%)
Figure 11 - Effect of flow rate on cake height.
EFFECTOF THE FORMATION OF PASSIVATION LAYERS
The growth of the passivation layers on the electrode plates
and their effect on cell performance was observed and
measured during the whole experimental process. When the
controlled voltage waveform is square, the current wave
should follow. However, it was noticed that the current
waveforms were gradually changing and deviating from a
square form, although the voltage was fixed and other
parameters were kept almost constant during the ongoing
experiments. The change of the waveforms can be seen in
the following:
a) During the two month experiment, the deviation from
rectangular waveform and the fluctuation of current increased
with time. In the late stage of the experiment, the fluctuation
reached more than 50% of the average current, while in
the early stage of the experiment no fluctuation has been
noticeable and a rectangular current pattern was obtained.
b) During the two month period experiment, the ratio
between current and voltage (Figure 12) decreased from 3
for the first test to only 0.4 for the last test.
c) After all the experiments were completed, the cell was
separated and the electrodes removed. A layer of non-metallic
substance was found sticking on each side of the electrodes.
This layer could be scraped off. Its outer surface looked as
white as clay and the inside surface looked as dark as metal.
the scraped-off chips were hard, brittle and fragile. The
substance was carefully weighed after it was dry. The mass
of the scraped layers on each side of the electrode was 35 g
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994
4 25
o w n
@
E
n
3.2
8E 2.4
\
CI
0.8
500
0
Time (d)
Figure 12 - Increase in electric resistance of the cell due to the
formation of the passivation layers and time effect on percentage
of cost wasted on the passivation layers.
on average. As time passed, there was an increasing
resistance between the two electrodes and more energy
was wasted on heating the passivation layers. In order to
quantitatively estimate the energy wasted, the total applied
I
components:
500 where VIRis IR drop and V, is the voltage drop on the
passivation layers, Vov is the potential related to kinetic and
concetration overvoltage, including the thermodynamic
potential (Walsh, 1993). Vov is small (usually only a fraction
of a volt) compared to other voltage drops in this case; eg,
VApis about 20V. Therefore, we can focus below on the
other two voltage drops, V,R and V,. The IR drop is
described by the following relation:
VIR = (I X d)l(A X k ) = IR,,. . . . . . . . . . . . . . . . . (8)
where d is the inter-electrode distance [ m] A is the active
anode surface area [m'] k is the solution conductivity
[ lo3 m . S/m] and R,, = d / A . k is the resistance of the
suspension of the cell assuming there is no passivation layer
generated. IR drop is a function of the geometry of the cell,
and the solution conductivity. With a constant electric current
passing through the cell, the IR drop, V,R stays constant
according to Equation (8). However, as the passivation layer
becomes thicker and thicker, the total voltage applied, VAp,
must be increased to maintain the same current. This increase
is caused solely by the increase in the resistance of the
passivation layers R,, which would be added to the total
resistance, RT, of the system. RT can be calculated by the
measured values of actual voltage and current: RT = VAp/I.
For virgin electrodes, the IR drop was found to be about 90%
of the total applied voltage. Vo, and V, are small compared
to the constant IR drop (when the current is fixed). To
estimate the increase in voltage drop due to the formation
of the passivation layers at the late stage of the experiment,
one can assume that V, = V,, - if VL becomes
comparable or larger than the IR drop. Let a be the ratio
of the energy wasted on the passivation layers to the total
energy consumption; we then have:
101 1
 a = V L / V A P . .. . . . . . . . . . . . . . . . . , . .. . . . . . . . . . .(9)
During the two month experimental period the percentage
of operating cost wasted on the passivation layers went
up sharply with time reaching 23% of the operating cost
(Figure 12).
Neither current efficiency of aluminum dissolution nor
aluminum material cost showed obvious correlation with
time. Aluminum material cost accounted for most of the total
cost although the percentage of the energy cost was increasing
as the passivation layers developed.
Conclusions
1. Current efficiency of aluminum dissolution increases
linearly with the increase in concentration of sodium
chloride up to around 0.05 mass%. T o reduce the oper-
ating cost, more attention should be focused on optimizing
the aluminium material cost which accounts for most of
the operating cost.
2. Higher sodium chloride concentration results in better
clarity, but lower settling rate and bigger cake volume.
3. Based on controlled voltage, the higher the concentration
of NaCl, the greater the current and the amount of
aluminium dissolved and the higher the operating cost.
However, aluminium material cost stays constant at about
80% of the operating cost with changing concentration
of sodium chloride.
4. Proper recirculation enhances the mass transport in the
cell and reduces the total cost while improving floc
structure for faster settling and lower cake height. A better
electrocoagulation cell design should be able to optimize
the hydrodynamic conditions inside the cell and the whole
system.
5. The formation of passivation layers represents only a
small portion of the operating cost initially. The thickness
of the passivation layer develops fast, resulting in a rapid
increase in the operating cost. The operating cost could
double due to the formation of the passivation layer after
a period of operation. Current efficiency of aluminium
dissolution does not show correlation with the formation
of passivation layers.
6. Further studies are necessary in two main areas: a) Better
cell design to improve mixing near the electrode surface
and thus improve mass transport and shear of flocs.
b) Further studies on electrode passivation, taking into
account variables such as: type of aluminum plate,
frequency of electrode polarity inversion and the role of
cell design.
Acknowledgements
The authors thank Dexter Woo and Jack Zalischuk for helping
with the experiment and Zohra Ali for processing data.
Nomenclature
A = active anode surface area, m2
d = inter-electrode distance, m
E = energy consumed per unit volume of feed, kWh/m3
I = electric current measured during the process, A
1012 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994
lpy = equivalent current, A
k = specific conductivity, (m . /Sm)x lo3
N = average power during one cycle, W
Q = flow rate of the product, L/min
R, = d/(A.k), the resistance of the suspension of the cell
assuming there is no passivation layer generated, Ohm
RL = resistance of the passivation layers, Ohm
R, = total resistance of the cell, Ohm
= total applied voltage, V
VAp
VL = voltage drop on the passivation layers, V
VIR = IR drop, V
V,, = potential drop related to kinetic and concentration
overvoltage, V
Greek letters
a = percent of energy wasted on the passivation layers to
the total energy supplied to the cell
= current efficiency of aluminium dissolution
qA,
References
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Manuscript received March 12, 1993; revised manuscript received
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