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Abstract
The relation between electrolysis voltage and the other variables of an electrocoagulation process was analyzed. Theoretical models
describing such a relation were established. Experiments were conducted to con4rm the theoretical analysis and to determine the constants
in the models. Both the theoretical analysis and experiments demonstrated that water pH and 7ow rate had little e8ects on the electrolysis
voltage within a large range. The electrolysis voltage depends primarily on the inter-electrode distance, conductivity, current density and
the electrode surface state. The models obtained can be used to calculate the total required electrolysis voltage for an electrocoagulation
process. ? 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Model; Overpotential; Aluminum electrode; Water; Wastewater
1. Introduction
Electrocoagulation is an e8ective process to destabilize
4nely dispersed particles for water and wastewater treatment. It has been successfully used to treat potable water
(Vik, Carlson, Eikum, & Gjessing, 1984), urban wastewater (Pouet & Grasmick, 1995) and a variety of industrial
wastewaters (Dobolyi, 1978; Pazenko, Khalturina, Kolova,
& Rubailo, 1985; Balmer & Foulds, 1986; Demmin &
Uhrich, 1988; Renk, 1988; Do & Chen, 1994; McClung
& Lemley, 1994; Lin & Peng, 1996; Chen, Chen, & Yue,
2000a, b).
Usually, aluminum or iron plates are used as electrodes
in the electrocoagulation process. When a DC voltage is
applied, the anodes sacri4ce themselves to produce Al3+
or Fe2+ ions. These electrochemically generated metallic
ions are good coagulants. They can hydrolyze near the
anodes to produce a series of activated intermediates that
are able to destabilize the 4nely dispersed particles present
in the water=wastewater to treat. The destabilized particles
then aggregate to form 7ocs. At the meantime, the tiny
hydrogen bubbles produced at the cathode can 7oat most
7ocs formed, reaching e8ective separation of particles from
water=wastewater. Compared with conventional coagulation, electrocoagulation has many advantages. Firstly, it
is more e8ective in destabilizing small colloidal particles.
0009-2509/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 2 ) 0 0 1 4 7 - 1
2450
Anode surface
Al 3+
2. Theoretical analysis
When current passes through an electrochemical reactor,
it must overcome the equilibrium potential di8erence, anode overpotential, cathode overpotential and ohmic potential drop of the solution (Scott, 1995). The anode overpotential includes the activation overpotential and concentration overpotential, as well as the possible passive overpotential resulted from the passive 4lm at the anode surface,
while the cathode overpotential is principally composed of
the activation overpotential and concentration overpotential.
Therefore,
d
U0 = Eeq + a; a + a; c + a; p + |c; a | + |c; c | + j:
(1)
Al3+ =Al =
+
ln CAl
3+ :
3F
(ii) The reduction reaction at the cathode,
2H+ + 2e = H2 ;
_
x
Diffusion layer
Fig. 1. Concentration variation of Al3+ , H+ and OH near the anode.
or
Jj (x) = Dj
RT CH2+
:
ln
2F
PH 2
@Cj (x)
@(x)
+ uj Cj (x)
+ Cj (x)v(x):
@x
@x
j = Fzj Jj
OH
Jj (x) = Dj
oAl3+ =Al
H+
(2)
(4)
|c; a | = ac + bc ln j:
(5)
@Cj (x)
@(x)
+ uj Cj (x)
= Fzj Dj
+ Cj (x)v(x)
@x
@x
or
@Cj (x)
j = zj F Dj
+ Cj (x)v(x) + tj j :
@x
Near the electrode surface, the convective 7ux term is
eliminated (Scott, 1995). Moreover, within the di8usion
layer adjacent to the anode surface, except for electrochemically and chemically reactive ions including Al3+ , H+ and
OH , non-reactive ions such as Na+ , SO2+
4 , and so on, can
produce a gradient of concentration and thus cause a diffusion current which is equal but opposite to the migration current at steady state. Consequently, the net transport and the net current of ions except for Al3+ , H+ , OH
through the anode di8usion layer is zero. Fig. 1 illustrates
the concentration variation of Al3+ , H+ and OH near the
2451
Cathode surface
@CAl3+ |x=0
+ tAl3+ j:
@x
OH
H+
0
then
j = 3FDAl3+
+ tAl3+ j:
Usually, CAl
3+ CAl3+ |x=0 .
Thus,
CAl3+ |x=0 =
(1 tAl3+ )j
3FDAl3+
Diffusion layer
Fig. 2. Concentration variation of H+ and OH near the cathode.
then
j = FDOH
@COH |x=0
+ tOH j:
@x
An analogous approximation is to assume a linear variation of OH concentration across the whole di8usion layer,
which is valid when bulk pH is not far away from neutral.
Then
C COH |x=0
@COH |x=0
= OH
:
@x
c
Thus,
CAl3+ |x=0 =
k1 (1 tAl3+ )j
3FDAl3+
1p
(6)
CAl
3+ =
CH3+
:
Kh
(7)
COH
COH |x=0
c
+ tOH j:
COH |x=0 =
(1 tOH )j c
:
FDOH
Therefore,
RT CAl3+ |x=0
RT k1 Kh (1 tAl3+ )j 1p
=
:
ln
ln
3F
CAl
3F
3FDAl3+ CH3+
3+
j = FDOH
Usually, COH
COH |x=0 , thus
CAl
3+ can be calculated from Eq. (2) as
a; c =
(8)
Similarly, the net transport and thus the net current of ions
except for H+ , OH through the cathode di8usion layer is
zero. Fig. 2 illustrates the concentration variation of H+ and
OH near the cathode. Because H+ is reduced to produce
hydrogen gas, pH near the cathode is alkaline even if bulk
pH is acidic but not extremely strong. In other words, the
concentration of OH near the cathode is much higher than
that of H+ and hence the current there comes predominantly
COH |x=0 =
k2 (1 tOH )j 1q
:
FDOH
The corresponding concentration of H+ at the cathode surface can be calculated according to the ion product of water
CH+ |x=0 =
Kw
COH |x=0
or
CH+ |x=0 =
Kw FDOH
:
k2 (1 tOH )j 1q
(9)
2452
Thus,
CH +
RT
ln
|c; c | =
F
CH+ |x=0
=
RT k2 (1 tOH )j 1q CH +
ln
:
F
Kw FDOH
(10)
Combining Eqs. (3) (5), (8) and (10), Eq. (1) can be
rewritten as
RT (pH2 )3=2
ln
+ aa + ac
U0 = oAl3+ =Al oH+ =H2 +
3F
Kh
+
RT k1 Kh (1 tAl3+ )
ln
3F
3FDAl3+
RT k2 (1 tOH )
d
ln
+ a; p + j
F
Kw FDOH
RT (1 p) RT (1 q)
+ ba + bc +
+
ln j:
3F
F
(11)
Let
A = oAl3+ =Al oH+ =H2 +
+
RT (pH2 )3=2
ln
+ aa + ac
3F
Kh
RT k1 Kh (1 tAl3+ ) RT k2 (1 tOH )
ln
+
ln
3F
3FDAl3+
F
Kw FDOH
and
RT (1 p) RT (1 q)
+
;
3F
F
then Eq. (11) becomes
d
U0 = A + a; p + j + K1 ln j:
(12)
3. Experimental verication
To con4rm the theoretical analysis, a series of experiments was conducted at di8erent pH, 7ow rate, current density, conductivity and anode surface state. The experimental
setup is schematically shown in Fig. 3. It consists of an electrocoagulation system, a DC power supply (PD 110 5 AD,
Kenwood TMI Corporation, Japan), a feed tank and a microprocessor pump (Model 7518-12, Master7ex, Cole-Parmer
Instrument Co., USA). The electrocoagulation system has
an electrochemical reactor of 0:30 L and a separator of 1:2 l.
The electrochemical reactor contains 4ve aluminum electrodes connected in a bipolar mode. The original dimension
of each electrode is 140 mm 44 mm 3 mm. Water 7ows
through the electrochemical reactor upward, perpendicular
to the electric current. Deionized water was used in all the
experimental runs. The conductivity and pH were adjusted
by adding Na2 SO4 (100 g=L) solution and H2 SO4 (0:1 M)
or NaOH (0:1 M) solution. Water pH and conductivity were
measured using pH meter (Model 420A, Orion Research Inc,
USA) and conductivity meter (Checkmate 90, Corning Incorporated Scienti4c Products Division, USA), respectively.
Sludge
Effluent
5
3
4
Influent
20
= 908 s/cm
= 1210 s/cm
15
U0 /V
2453
= 2090 s/cm
10
4.1. E.ect of pH
30
40
50
60
70
80
90
30
= 445 s/cm
= 849 s/cm
25
= 1390 s/cm
= 2120 s/cm
U0 /V
20
= 3130 s/cm
15
10
In the theoretical analysis, the water 7ow rate was assumed not to a8ect the electrolysis voltage signi4cantly.
This needs to be veri4ed experimentally. Although a slight
decrease in U0 was found as 7ow rate increased from 3 L=h
to 15 L=h using new electrodes, the extent of such a decrease was always less than 10%. In contrast, when the current density varied from 20 to 100 A=m2 , almost 4vefold increase in electrolysis voltage was measured. For passivated
electrodes, it was found that the electrolysis voltage was almost the same within the investigated water 7ow rate range
of 1.821:6 L=h. This phenomenon is expected because the
rough surface of passivated electrodes makes the e8ect of
7ow rate on turbulence insigni4cant. Such results support
the assumption made earlier regarding the e8ect of 7ow rate.
4.3. Dependence of U0 on j and
Fig. 4 demonstrates the electrolysis voltage between electrodes as a function of the conductivity and current density
for non-passivated electrodes. Through nonlinear regression
of the data in Fig. 4, the constant and coeMcient in Eq. (13)
were obtained as A = 0:76, K1 = 0:20. Hence
d
j + 0:20 ln j:
20
Current density/A m2
The theoretical analysis has demonstrated that the electrolysis voltage between electrodes is independent of pH as
long as water is not far away from neutral. In order to con4rm it, electrolysis voltages were measured at di8erent pH
values. It was found that the e8ect of pH on U0 was really
insigni4cant for both new and passivated electrodes. For the
new electrodes, an increase in pH from 3.75 to 10.41 resulted in only an increase in U0 from 13.2 to 13:8 V even
at a current density as high as 137 A=m2 . For the passivated
electrodes, when pH varied from 3.38 to 10.79, the maximum di8erence of U0 measured at a constant current density was only 7.7%. Therefore, both results from new and
passivated electrodes support the theoretical analysis well.
U0 = 0:76 +
10
(15)
10
20
30
40
50
60
70
80
90
100
Current density/A m2
at 25 C.
Better prediction was obtained for passivated electrodes
as shown in Fig. 5. This may be because the power-law
term with regard to j accommodates partially the variation
of A with
. Again the constants in Eq. (14) were obtained
2454
(16)
(17)
For the bipolar mode, the total required electrolysis voltage is U0 times the number of total cell which is the number
of electrodes minus one. Thus
U = (N 1)U0 :
(18)
5. Conclusions
p H2
R
T
tj
U
uj
U0
v(x)
zj
Greek letters
a
c
a; a
a; c
a; p
c; a
c; c
(x)
Acknowledgements
Notation
References
aa
ac
ba
bc
Cj
Cj (x)
Cj |x=0
d
Dj
Eeq
F
j
Jj (x)
Kh
Kw
m
n
N
p
q
2455