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Ind. Eng. Chem. Res., Vol. 44, No. 12, 2005 4179
Experimental Section
Experimental Devices. The electrochemical dissolution experiments have been carried out in a continuous bench-scale plant, with a single-compartment
electrochemical flow cell (Figure 2). Aluminum electrodes (HE 18) were used as the anode and cathode.
Both electrodes were square in shape (100 mm sides)
with a geometric area of 100 cm2 each and with an
electrode gap of 9 mm. The electrical current was
applied using a DC Power Supply, FA-376 Promax. The
current flowing through the cell was measured with a
Keithley 2000 Digital Multimeter. The electrolyte was
stored in a 5000 mL glass tank stirred by an overhead
stainless steel rod stirrer, Heidolph RZR 2041, and
thermostatized by means of a water bath to maintain
the temperature at the desired set point, and circulated
through the electrolytic cell by a peristaltic pump.
Chemical dissolution experiments were carried out in
stirred batch reactors. To do this, a multistirrer device,
Isco, was used.
Experimental Procedure. Electrochemical dissolution experiments were carried out in the continuousoperation bench-scale plant, under galvanostatic conditions. The electrolyte was pumped into the cell and
collected in a tank. Samples were taken at the outlet of
the cell, and pH was measured using an inoLab WTW
pH meter. To determine the total aluminum concentration, samples were diluted 50:50 v/v with 4 N HNO3,
and after that, they were measured using a sequential
inductively coupled plasma spectrometer, Varian Liberty, according to an standard method18 (plasma emission spectroscopy). Preparative experiments were carried out to determine the amount of passed solution
required to reach the steady state. In every experiment,
this final state was tested. To determine the influence
of the passed electric current charge (I/Q), the flow rate
(Q) was maintained constant at 19.8 dm3 h-1 and the
employed current density was changed. The range of
the passed electrical charge studied was 0.00070.0138 A h dm-3. To determine the influence of the pH,
the feeding solution pH was changed in the range 1-13.
To determine the influence of the current density, the
current density and the flow rate were changed simultaneously in order to obtain the same amount of passed
current charge. To test the influence of the supporting
4180
Electrodissolution of the Aluminum Sheets. Figure 6 shows the aluminum, pH, and voltage profiles
versus time (dynamic response) generated in typical
aluminum electrodissolution experiments (current density ) 0.5 mA cm-2, temperature ) 25 C, flow rate )
19.8 dm3 h-1, and pH ) 6.0) carried out in a continuous
flow cell.
It can be observed that the concentration of aluminum
increases with time up to a steady-state value. Likewise,
it can be observed that the bulk pH increases and the
cell voltage decreases and that both parameters also find
a steady-state value.
The steady-state value for the concentration of aluminum is greater than the expected value if the process
is purely electrochemical. Thus, for the conditions used
in the experiments shown in Figure 6, only 0.95 mg
dm-3 of electrodissolved aluminum was expected. The
pH increase can be justified by the hydroxyl ion generation on the cathode as a consequence of the hydrogen
evolution process. The cell voltage decrease can be
justified by the increase in the ionic conductivity of the
treated solution.
Figure 7 shows the variation of the steady-state
aluminum concentration electrogenerated in the electrochemical processes with the passed electrical charge,
Ind. Eng. Chem. Res., Vol. 44, No. 12, 2005 4181
2Al + 6H2O f 2Al3+ + 3H2 + 6OHFigure 9. (a) Influence of the salinity on the amount of aluminum
electrodissolved: T, 25 C; pH, 6.0; flowrate, 19.8 dm3 h-1; j,
0.5 mA cm-2. Supporting media: [ NaCl, 0 Na2SO4. (b) Influence
of the current density on the amount of aluminum electrodissolved
for the same passed electrical charge: T, 25 C; pH, 6; passed
electrical charge, 0.0028 A h dm-3. Supporting media: [ 2450 mg
dm-3 NaCl; 0 3000 mg dm-3 Na2SO4.
(1)
Al f Al3+ + 3e-
(2)
(3)
(4)
Al(OH)4- + H+ a Al(OH)3
(5)
Al(OH)3 + H+ a Al(OH)2+
(6)
4182
Al(OH)2+ + H+ a Al(OH)+2
(7)
Al(OH)+2 + H+ a Al3+
(8)
(9)
(10)
HCO3- a CO32- + H+
(11)
H2O a OH- + H+
(12)
segregated flow approach has been successfully demonstrated in the literature using marker-pulse techniques for channel flow cells24.
The volume of each zone can be easily calculated25,26
if it is assumed that the thickness of the electrochemical
zone is equivalent to the Nernst diffusion layer (). This
assumption is acceptable because direct oxidation and
most of the mediated oxidation processes (those with
high reaction rates) occur in this zone. The thickness
of this zone can be evaluated as a function of the masstransfer coefficient (k) and the diffusivity (D) using eq
13.
D
k
(13)
ri ) kA([Si]* - [Si])
(14)
Ind. Eng. Chem. Res., Vol. 44, No. 12, 2005 4183
Va
d[Si]a
) kA([Si]b - [Si]a) + relectrochemi,a + rchemi,aVa
dt
(15)
[Al(OH)3]z[H+]z
Vc
d[Si]c
) kA([Si]b - [Si]c) + relectrochemi,c + rchemi,cVc
dt
(16)
[Al(OH)2+]z[H+]z
d[Si]b
) q([Si]0 - [Si]b) + kA([Si]a - [Si]b) +
dt
kA([Si]c - [Si]b) + rchemi,bVb (17)
[Al(OH)2+]z[H+]z
Vb
[Al(OH)2+]z
[Al(OH)2+]z
3+
[Al ]z
[HCO3-]z[H+]z
I
r)
F
I i
F
j j
(19)
[Al(OH)4-]z[H+]z
[Al(OH)3]z
[CO32-]z[H+]z
-
(18)
relectrochemi )
[H2CO3]z
) 10-8.0
[Al3+]z[OH-]z3 ) 10-32.9
(20)
(24)
[HCO3 ]z
) 10-5.7
(21)
) 10-4.3
(22)
) 10-5.0
(23)
) 10-6.37
(25)
) 10-10.25
(26)
[H+]z[OH-]z ) 10-14.0
n[An-]z m[Bm+]z ) 0
anionic species
cationic species
(27)
(28)
(30)
Figure 12 shows the time variation of pH and aluminum concentration calculated from the model compared
to those obtained experimentally for three different
experimental assays. It can be observed that the model
fits well the experimental data, with average errors
<5% for the reproducibility of pH and <10% for the
reproducibility of the aluminum concentration.
Figures 13 and 14 show the experimental steady-state
values of aluminum and bulk pH as a function of both
the initial solution pH and the specific passed electric
charge (for a constant flowrate) compared to the values
obtained from the model. It can be observed that there
is great reproducibility of the experimental results in
both the pH and the aluminum concentration, with
average regression coefficients (r2) of 0.920 and 0.958
for aluminum and pH, respectively. This validates the
assumptions on which the model is based.
Conclusions
The following conclusions can be drawn from the work
described here:
1. The aluminum dissolved in an electrochemical cell
comes from both chemical and electrochemical processes. The chemical process contribution is often more
important than that of the electrochemical process
2. The chemical dissolution of aluminum is strongly
influenced by the pH. Alkaline pHs increase the dissolution rate by orders of magnitude. Within the experimental conditions used, the supporting media does
not seem to greatly influence the chemical dissolution
process.
3. The electrochemical dissolution process depends
mainly on the specific passed electrical charge. The
salinity and the nature of the ions do not seem to
significantly affect the electrodissolution rate.
4184
Acknowledgment
This work was supported by the MCT (Ministerio de
Ciencia y Tecnologa, Spain) and by the EU (European
Union) through project CTM2004-03817/TECNO. The
contribution of Junta de Comunidades de Castilla La
Mancha is also acknowledged for the grant of F.M.
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Ind. Eng. Chem. Res., Vol. 44, No. 12, 2005 4185
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