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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
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
from waste water (Donini et al., 1989). The research has chemically dissolving with time, the current efficiency of
also shown that electrocoagulation works well for a large aluminum dissolution was above 100% and was in the range
range of applications (Domini et al., 1989; Kharchenko and of 165%-215%. Higher than 100% current efficiency of
Nasonova, 1985; Zolotukhin, 1989; Sleptsov et al., 1987; aluminum dissolution was also reported by others (Bozin and
Zhul ’kov, 1978). Mikhailov, 1990; Przhegorlinskii et al., 1987).
During the electrocoagulation process, an anode, made of If electrocoagulation systems are to be practically
aluminum in this experiment, dissolves, producing in situ applicable to environmental problems, the costs of electro-
aluminum cations which coagulate the suspensions. Two coagulation systems are critical. Unfortunately, not much
different mechanisms can be expected during the anodic work has been published in this area even though industrial-
aluminum dissolution; one is electrochemical, a strictly scale electrocoagulation units have been available in the
Faradaic process, and the other is the purely chemical market (Zolotukhin, 1989; Przhegorlinskii et al., 1987a,b;
dissolution of aluminum. Therefore, the following electrode Ryan and Stanczyk, 1988). Therefore, studies on cost-
reactions occur: affecting factors in elecvocoagulation processes are necessary,
especially in view of the role these factors must play in future
Anode system design.
Thus, the purpose of this work was to study the operating
A l o = A13+ + 3e- ......................... (1) cost incurred during experiments. The cost of energy of the
electrocoagulation cell and the cost of aluminum electrode
Cathode consumed were obtained from the experimental results and
the sum was taken as the operating cost. Particular attention
2 H20 + 2e- = 2 OH- + H 2 . ............... (2) was given to the effect on the cost of sodium chloride
concentration, feed rate with and without recirculation, and
additionally, both the anode and the cathode will be dissolving
the formation of the passivation layers on the aluminum
chemically:
electrodes. This work also investigated how the concentration
of sodium chloride affects the current efficiency of aluminum
A1° + 3 H 2 0 = Al(OH), + 1.5 H2 . . . . . . . . . . . (3) dissolution and the aluminum electrode material consumption
Przhegorlinski et al. (1987) determined the contribution of due to the dissolution.
the individual reactions of Equations (1) - (3). Each of 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
*Author to whom correspondence should be addressed. 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, fixed at 0.03 mass%. Temperature and pH values of the feed
and the control and data acquisition system. The cell and product were measured for each experiment run. Feed
contained four parallel aluminum electrode plates forming temperature was around 20°C. Product temperature was
three parallel cells. The electric circuit of the cell is shown several degrees Celsius higher than that of the feed depending
in Figure 1 . Polarities of the electrodes could be switched on the electric current applied and the main flow rate of the
periodically. The opposite aluminum electrodes worked in electrocoagulation process. The process did not change sig-
turns. In the cathodic period, the electrode can clean off nificantly the pH of the feed, which was around 8. The effect
some of the sticking clay particles. Pulse duration could be of pH and thermokinetics will not be discussed in this paper.
controlled by the power unit. The gap between the two In this study, aluminum concentration in sample suspension
neighbouring electrode plates was 6 mm. Each of the four was measured using a colorimetric method. However, the
rectangular plates was 16.5 cm high and 58 crn wide. ICP (inductively coupled plasma) method was also applied
The experimental set-up is illustrated schematically in for the purpose of calibration. Comparison showed that the
Figure 2 . Aqueous suspensions of 0.16 mass% kaolinite and two methods gave very similar results. The consumption of
0.04 mass% bentonite were used as feed material. The the aluminum electrode material per unit volume of feed was
concentration of sodium chloride in the suspension was obtained from the difference between the aluminum contents
adjusted from 0 to 0.1 mass% and, in most cases, it was 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


cost. , percentage of power cost; o , percentage of aluminum
The applied electric voltage on the cell, VAp (volmeter cost; + , operating cost.
reading across the electrocoagulation cell) and current, I,
measured every two seconds were used to obtain the average Aluminum electrode material cost accounted for about 80%
power during one cycle, N = VApI. Let Q be the flow of of the operating cost in both experiments (Figure 4) where
the product in litres per minute; then the energy consumed the concentration of sodium chloride was changed up to 0.1
per unit volume of feed in kilowatt-hours per cubic meter, mass%. Using the Faraday law it is possible to further
E can be derived: E = N/60Q. analyze the effect of vAl on aluminum content.
Assuming an energy price of $O.OS/kWh and consumable
aluminum electrode material cost of $7/kg (Donini et al., Aluminum Content = vAl x I/O.l787Q.. . . . . . . . (5)
1989) and assuming the total costs are composed of the
energy cost and the aluminum material cost, the operating By substituting Equation (5) into Equation (4), we have the
cost can be calculated as: 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 The first term on the right hand side of Equation (6)
represents the energy cost and the second term is the
EFFECTOF CONCENTRATION OF SODIUM CHLORIDE aluminum cost. That is, aluminum cost is in most of the
cases the largest contribution to the operating cost based on
The concentration of sodium chloride in the suspension the assumption that the current efficiency of aluminium dis-
was varied from 0 to 0.1 mass% and the corresponding slurry solution is approximately 200% and the voltage is about 20
conductivity values were measured. Current efficiency of V. However, it should be noted that when the voltage
aluminum dissolution (Figure 3) increased with the concen- becomes higher, because of passivation and high cell
tration of sodium choloride if it was smaller than 0.05%. resistance, the energy cost could increase and become
If 190-200% is estimated to be the average aluminum comparable to the aluminum cost.
efficiency, the relative error for most of the data would fall Figures 5-6 display the effect of sodium chloride concen-
within 25 % . tration on the settling properties. The data show that the
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72. DECEMBER, 1994 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.

lo
EFFECTOF RECIRCULATION
0 100 200 300 400 500
Flow rate ( c d s )
It is believed that a high turbulence level in the flow
through the cell not only enhances mass transport, but also Figure 9 - Effect of flow rate on turbidity.
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 In most cases, the turbidity with recirculation was lower
increased, the residence time of feed and the energy con- than that without recirculation (Figure 9). The more interesting
sumed per unit volume of feed are decreased (Figure 7). In discovery was that recirculation caused a consistently higher
order to maintain the same residence time while increasing setting rate and much lower cake height (Figures 10 and 1 I).
the flow through the cell to induce turbulence, a recirculation This is contrary to the usual results, where better clarity
loop was installed (see Figure 2). Energy consumed per unit implies lower settling rate and higher cake height. This is
volume of feed was set lower on purpose in the cases with an important result since high clarity and low cake volume
recirculation than in the corresponding cases without recir- are desirable, but usually competing, processes. The authors
culation (Figure 7). Figure 8 shows that the operating cost reason that the high shear rate obtained due to the high
was consistently lower when recirculation was used for the flow rate made the flocs more compact and, therefore, they
whole flow rate range than when recirculation was not used. settled faster and contained less water.
1010 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994
4 25
0.02
o w n
@

E
h

'2i0.018 n
3.2

8E 2.4
ar
Y

2
M \
e
0.016 I rl
Y W
ar
r
A + 1.6
\
Iwithout circulation 0 with circulation CI
0.014
0.8
0 100 200 300 400 500
Flow rate (cm3/s)
0
Figure 10 - Effect of flow rate on settling rate.
Time (d)
Figure 12 - Increase in electric resistance of the cell due to the
formation of the passivation layers and time effect on percentage

rm ____

1
Iwithout circulation 0 with circulation
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 voltage, V,, was suggested to be composed of three main
I
components:

0 100 200 300 400 500 where VIRis IR drop and V, is the voltage drop on the
Flow Rate (cm%) passivation layers, Vov is the potential related to kinetic and
concetration overvoltage, including the thermodynamic
Figure 11 - Effect of flow rate on cake height. potential (Walsh, 1993). Vov is small (usually only a fraction
of a volt) compared to other voltage drops in this case; eg,
EFFECTOF THE FORMATION OF PASSIVATION LAYERS VApis about 20V. Therefore, we can focus below on the
other two voltage drops, V,R and V,. The IR drop is
The growth of the passivation layers on the electrode plates described by the following relation:
and their effect on cell performance was observed and
measured during the whole experimental process. When the VIR = (I X d)l(A X k ) = IR,,. . . . . . . . . . . . . . . . . (8)
controlled voltage waveform is square, the current wave
should follow. However, it was noticed that the current where d is the inter-electrode distance [ m] A is the active
waveforms were gradually changing and deviating from a anode surface area [m'] k is the solution conductivity
square form, although the voltage was fixed and other [ lo3 m . S/m] and R,, = d / A . k is the resistance of the
parameters were kept almost constant during the ongoing suspension of the cell assuming there is no passivation layer
experiments. The change of the waveforms can be seen in generated. IR drop is a function of the geometry of the cell,
the following: and the solution conductivity. With a constant electric current
a) During the two month experiment, the deviation from passing through the cell, the IR drop, V,R stays constant
rectangular waveform and the fluctuation of current increased according to Equation (8). However, as the passivation layer
with time. In the late stage of the experiment, the fluctuation becomes thicker and thicker, the total voltage applied, VAp,
reached more than 50% of the average current, while in must be increased to maintain the same current. This increase
the early stage of the experiment no fluctuation has been is caused solely by the increase in the resistance of the
noticeable and a rectangular current pattern was obtained. passivation layers R,, which would be added to the total
b) During the two month period experiment, the ratio resistance, RT, of the system. RT can be calculated by the
between current and voltage (Figure 12) decreased from 3 measured values of actual voltage and current: RT = VAp/I.
for the first test to only 0.4 for the last test. For virgin electrodes, the IR drop was found to be about 90%
c) After all the experiments were completed, the cell was of the total applied voltage. Vo, and V, are small compared
separated and the electrodes removed. A layer of non-metallic to the constant IR drop (when the current is fixed). To
substance was found sticking on each side of the electrodes. estimate the increase in voltage drop due to the formation
This layer could be scraped off. Its outer surface looked as of the passivation layers at the late stage of the experiment,
white as clay and the inside surface looked as dark as metal. one can assume that V, = V,, - if VL becomes
the scraped-off chips were hard, brittle and fragile. The comparable or larger than the IR drop. Let a be the ratio
substance was carefully weighed after it was dry. The mass of the energy wasted on the passivation layers to the total
of the scraped layers on each side of the electrode was 35 g energy consumption; we then have:
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994 101 1
a = V L / V A P . .. . . . . . . . . . . . . . . . . , . .. . . . . . . . . . .(9) lpy = equivalent current, A
k = specific conductivity, (m . /Sm)x lo3
During the two month experimental period the percentage N = average power during one cycle, W
of operating cost wasted on the passivation layers went Q = flow rate of the product, L/min
up sharply with time reaching 23% of the operating cost R, = d/(A.k), the resistance of the suspension of the cell
(Figure 12). assuming there is no passivation layer generated, Ohm
Neither current efficiency of aluminum dissolution nor RL = resistance of the passivation layers, Ohm
R, = total resistance of the cell, Ohm
aluminum material cost showed obvious correlation with = total applied voltage, V
VAp
time. Aluminum material cost accounted for most of the total VL = voltage drop on the passivation layers, V
cost although the percentage of the energy cost was increasing VIR = IR drop, V
as the passivation layers developed. V,, = potential drop related to kinetic and concentration
overvoltage, V
Conclusions
Greek letters
1. Current efficiency of aluminum dissolution increases
a = percent of energy wasted on the passivation layers to
linearly with the increase in concentration of sodium
the total energy supplied to the cell
chloride up to around 0.05 mass%. T o reduce the oper- = current efficiency of aluminium dissolution
qA,
ating cost, more attention should be focused on optimizing
the aluminium material cost which accounts for most of References
the operating cost.
2. Higher sodium chloride concentration results in better Donini, J. C., R. G. Frenette, K. L. Kasperski and S. Kelebek,
clarity, but lower settling rate and bigger cake volume. “Electrocoagulation - Final Report, “Division Report CRL
3. Based on controlled voltage, the higher the concentration 89-82(CF), CANMET, Energy, Mines and Resources Canada,
of NaCl, the greater the current and the amount of September (1989).
aluminium dissolved and the higher the operating cost. Kharchenko, L. F. and S. N. Nasonova, “Removal and Emulsified
Substances From Water by Electrolytic Methods”, Khimiya i
However, aluminium material cost stays constant at about Tekhnologiya Vody. 7(5), 84-85 (1985).
80% of the operating cost with changing concentration Przhegorlinskii, V. I., A. I. Ivanishvili and V. D. Gebenyuk,
of sodium chloride. ‘‘Dissolution of Aluminum Electrodes in the Electrocoagulation
4. Proper recirculation enhances the mass transport in the Treatment of Water”, Khymiya i Technologiya Vody 9(2),
cell and reduces the total cost while improving floc 81-182 (1987).
structure for faster settling and lower cake height. A better Przhegorlinskii, V . I., A. I. Ivanishvili and T. D. Kalinichenko,
electrocoagulation cell design should be able to optimize “A Comparative Evaluation of the Efficiency of a Electro-
the hydrodynamic conditions inside the cell and the whole coagulation and Reagent Methods of Clarifying Waste Waters”.
system. Khymiya i Technologiya Vody. 9(5), 468-69 (1987).
5. The formation of passivation layers represents only a Ryan, P. E. and T. F. Stanczyk, “Enhancing Liquid-Liquid and
Solid-Liquid Phase Separation by Integrating Alternating Current
small portion of the operating cost initially. The thickness ElectrocoagulatorsWith Processing and Wastewater Control”,
of the passivation layer develops fast, resulting in a rapid Symposium, November 16, Wilmington, DE (1988).
increase in the operating cost. The operating cost could Sleptsov, G. V., A. I. Gladkii, E Ya. Sokol and S. P. Novikova,
double due to the formation of the passivation layer after “Electrocoagulation Treatment of Oil Emulsion Wastewater of
a period of operation. Current efficiency of aluminium Industrial Enterprises”, Elektronnaya Obrabotka Materiallov 6,
dissolution does not show correlation with the formation 69-72 (1987).
of passivation layers. Szynkarczuk, J., J. Kan, T. A. Hassen and J. C. Donini, “Electro-
6. Further studies are necessary in two main areas: a) Better coagulation of Clay Suspensions”, submitted to Journal of Clays
cell design to improve mixing near the electrode surface and Clay Minerals.
and thus improve mass transport and shear of flocs. Walsh, F. C. “A First Course in Electrochemical Engineering”,
Alresford Press Ltd., Alfresford Hants, UK (1993), pp. 204-206.
b) Further studies on electrode passivation, taking into Zhul’kov, N.I., “The use of ElectrecoagulationMethod for Treating
account variables such as: type of aluminum plate, Effluents from Thermal Stations Containing Oil”. Teploener-
frequency of electrode polarity inversion and the role of getika 24(12), 53-55 (1978).
cell design. Zolotukhin, I. A. “A Pilot-scale System for Treatment of Mine
Water by Electrocoagulation-flotation”,Khimiya i Teknologiya
Acknowledgements Vody. 11(2), 147-151 (1989).

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 Manuscript received March 12, 1993; revised manuscript received
I = electric current measured during the process, A July 18,1994; accepted for publication July 26, 1994.

1012 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 72, DECEMBER, 1994