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Chemical Engineering and Processing 36 (1997) 255 260

New electrochemical reactor for wastewater treatment:


electrochemical characterisation
A. Buso a, M. Giomo a, L. Boaretto a, G. Sandona b, A. Paratella a,*
a
Istituto di Impianti Chimici, Facolta di Ingegneria, Via Marzolo 9, 35131 Pado6a, Italy
b
Dipartimento di Chimica Fisica, Facolta di Scienze Matematiche, Fisiche e Naturali, Via Marzolo 1, 35131 Pado6a, Italy

Received 6 August 1996; accepted 17 February 1997

Abstract

This paper analyses the effects of agitation level on the mass transport coefficient in a new electrochemical reactor equipped
with reciprocating sieve-plate electrodes. It also presents the results of experimental investigations carried out on laboratory
apparatus and in a pilot plant using stainless steel electrodes and an aqueous solution of potassium iodide in the presence of an
excess of supporting electrolyte (sodium sulphate). The mass transport coefficient was evaluated from limiting current measure-
ments and current polarisation curves, and correlated with vibrational variables by a controlling dimensionless numbers
relationship. 1997 Elsevier Science S.A.

Keywords: Agitation level; Electrochemical reactor; Sieve-plate electrodes

1. Introduction tion on theoretical and experimental bases has already


been carried out by the same authors [13].
There is currently growing interest in electrochemical The aim of the present work was to determine the
processes for wastewater treatment, due to the wide effects of agitation level on mass transfer rates.
range of applications generated by the various phenom-
ena in question [1].
Direct and indirect electrolysis, electrocoagulation 2. Experimental procedure
and electroflotation are all electrochemical techniques
which may be used either separately in different reac- The experiments were carried out using platinised
tors or combined in the same reactor, for municipal and titanium or stainless steel electrodes immersed in an
industrial wastewater treatment and recovery of chemi- aqueous solution of potassium iodide, with an excess of
cals [24]. However, the high costs normally involved sodium sulphate as supporting electrolyte.
in the use of these processes limit their widespread The main reactions at the anode were:
application, especially in cases of low concentrations of
2I l I2 + 2e (1)
pollutants which easily lead to polarisation phenomena.
Most recent research efforts have been addressed and/or
towards reducing the above phenomena by improving
mass transport by means of stirrers [5], turbulence 3I l I
3 + 2e

(2)
promoters [6] and rotating [7] or porous electrodes I + 3H2O l IO3 + 6H + + e (3)
[8 12].
The present study was undertaken in order to design 2H2O l O2 + 4H + + 4e (4)
a new electrochemical reactor equipped with reciprocat- Experimental tests were carried out in the pilot plant
ing sieve-plate electrodes. Fluid-dynamic characterisa- shown in Fig. 1 and in the laboratory apparatus shown
in Fig. 2.
* Corresponding author. Tel: + 39 049 8275461; fax: + 39 049 The reciprocating plate column (RPC) electrochemi-
8275461. cal reactor was composed of a 1060-mm plexiglass

0255-2701/97/$17.00 1997 Elsevier Science S.A. All rights reserved.


PII S 0 2 5 5 - 2 7 1 0 ( 9 7 ) 0 0 0 0 9 - 9
256 A. Buso et al. / Chemical Engineering and Processing 36 (1997) 255260

Fig. 1. (a) Diagram of pilot plant; (b) detail of electrochemical reactor.

column equipped with 16 stainless steel AISI Reciprocation was provided by an electric motor
316L plate electrodes, mounted on a central shaft and coupled to a gear drive fitted with frequency control,
uniformly distributed, with a distance of 50 mm be- allowing the reciprocating frequency to range from 60
tween adjacent plates. Each 6-mm thick plate had a to 120 rpm. A continuously variable eccentric cam
diameter of 400 mm and 106 holes, each 12 mm regulated reciprocation amplitude up to maximum plate
across. spacing.
A. Buso et al. / Chemical Engineering and Processing 36 (1997) 255260 257

Fig. 2. Diagram of laboratory apparatus. CE, counter-electrode; RE,


reference electrode; WE, working electrode.

Fig. 1(b) shows the sampling equipment: samples Fig. 3. Polarisation curves for: (a) platinised titanium electrodes; (b)
were taken between neighbouring plates and stored stainless steel electrodes, in aqueous solution of Na2SO4 (1 gmol l 1)
before analysis. obtained with laboratory-scale equipment shown in Fig. 2 (sweep
The column feed was stored in tanks S1 and S2, and rate = 0.05 V s 1).
the outlet flow was sent to tank S3.
A batch reactor (right of the RPC reactor in Fig.
1(a)) regenerated the exhaust solution by an electro- contemporaneous with oxygen evolution, whereas the
chemical process. The regenerator was separated into formation of I 3 occurred at the same potential as
three parts, subdivided by two porous separators. The metal oxidation and prevailed over oxygen evolution.
exhaust solution was sent to the cathodic compartment, Fig. 5 shows polarisation curves for the systems
while an aqueous solution of KI was stored in the shown in Table 1 (black symbols) for various agitation
anodic compartment and in the junction zone. Pla- levels. Comparison with the polarisation curves for the
tinised titanium nets were used as electrodes. supporting electrolyte solution (white symbols) allowed
Electrochemical characterisation of the systems any noise phenomena as a result of undesirable oxida-
shown in Table 1 was carried out on laboratory ap- tion to be identified.
paratus equipped with either a platinised titanium net Comparison of curves 7 and 8 (stainless steel elec-
or stainless steel electrodes having the same thickness trodes) with curves 3 and 4 (platinised titanium net)
and distance as those used in the pilot plant. clearly shows that stainless steel electrodes:
Polarisation curves for the supporting electrolyte so- have a large overpotential for iodide oxidation
lution were preliminarily obtained (see Fig. 3(a) and (about 0.6 V);
(b)). have a smaller plateau;
Fig. 3(b) shows that, with the stainless steel elec- show the same dependency as the limiting current on
trodes, oxygen evolution was preceded by a peak in the agitation level.
steel transpassivation zone, due to oxidation of Fe and Although titanium platinised electrodes gave better
Cr, as shown by atomic absorption analysis. resolution of limiting current conditions, economic rea-
The polarisation curve of the potassium iodide solu- sons indicated the use of stainless steel electrodes,
tion (Fig. 4) shows that the formation of IO3 was which are more suitable for industrial applications.

Table 1
Electrochemical characterisation systems and variables investigated

Chemical Concentration (mol l1) Supporting electrolyte (mol l1) pH Electrodes

KI 0.02 0.20 Na2SO4 = 0.51.0 12 Platinised titanium net surface: 20 cm2


KI 0.02 0.20 Na2SO4 = 0.51.0 12 AISI 316L rods surface: 20 cm2
258 A. Buso et al. / Chemical Engineering and Processing 36 (1997) 255260

Fig. 4. Polarisation curves for stainless steel electrodes (AISI 316L) in


aqueous solution of KI (0.2 gmol l 1) obtained with laboratory-scale
equipment shown in Fig. 2 (sweep rate= 0.05 V s 1).
Fig. 6. Pilot plant runs involving two cells: polarisation curves for
Tests on the pilot plant were based on the results various agitation levels.
obtained with laboratory-scale equipment. The same
aqueous solution of potassium iodide with an excess of feed distribution devices become less significant in the
sodium sulphate as supporting electrolyte was again cell adjacent to the feed zone.
used, and batch runs were carried out first on a single Agitation level (A f ) has a marked effect on current
cell and then on an increasing number of cells until the in mass transfer controlled regions. Fig. 8 shows how
whole reactor became involved. For each run, polarisa- limiting current increased with agitation level and how
tion curves were obtained by varying the agitation level the plateau zone decreased until mass transport be-
within the range 60 150 rpm. Typical results for two came a non-controlling phenomenon.
and four cells are shown in Figs. 6 and 7.
Limiting current values increased when higher agita-
tion levels were used. The limiting current plateau is 3. Mass transport coefficient determination
evident, particularly at a low agitation level, at poten-
tials in the range 2.4 2.8 V. In limiting current conditions, the kinetics of the
These values are close to those of the laboratory process were determined by the fluid-dynamic be-
apparatus results, since the potential difference is now haviour of the solution rather than the characteristics
measured with respect to the counterelectrode. of the electrode, so that the mass transport coefficient
In the same operating conditions, if the number of became the controlling parameter.
cells is increased, the definition of the plateau region When reactant concentrations fell to zero close to the
improves, because problems due to electric power and electrode surface, the flux expression was reduced to
[14]:
60Jl
Nj = =Kmc (5)
nF

Fig. 5. Polarisation curves detected with various electrodes and


solutions at two agitation le6els: 200 rpm: curves 1;3;5;7
700 rpm: curves 2;4;6;8
platinised titanium net: 12 Na2SO4 sol. (1 gmol 1 1) 3 4 Na2SO4
(1 gmol 1 1)+ KI (0.2 gmol l 1) sol.
stainless steel electrodes: 56 Na2SO4 sol. (1 gmol 1 1) Fig. 7. Pilot plant runs involving four cells: polarisation curves for
7 8 Na2SO4 (1 gmol 1 1)+ KI (0.2 gmol 1 1) sol. various agitation levels.
A. Buso et al. / Chemical Engineering and Processing 36 (1997) 255260 259

pressed through limiting current Il and total active


surface S. It is therefore possible to estimate the values
of the (Km S) group simply by measuring limiting
current Il and solution composition c . The above
values of the (Km S) group are therefore available in
the same form used in the mathematical model devel-
oped to simulate the behaviour of the electrochemical
reactor.
Since both system geometry and solution properties
are constant, Eq. (7) may be rewritten as follows:
KmS= j(Re)a
 
(8)
rd a
j(Re)a = j (Af )a (9)

 
sm
Fig. 8. Pilot plant runs involving four cells: polarisation curves for DS
various agitation levels. Amplitude 0.10.5 cm; frequency 60 150 j= cScq (10)
L
rpm.
Experimental values for the whole reactor are sum-
where: c , bulk ion concentration, mol cm ; F, Fara- 3 marized in Fig. 9, as a logarithmic plot of (Km S) vs.
days constant, 96500 C equiv 1; Jl, limiting current
density, A cm 2; Km, mass transport coefficient, cm estimated values of a= 0.4 and j
  n
(Af ). Least-squares treatment of the data gave the
rd a
=130, with
min 1; n, number of electrons involved in the reaction; sm
Nj, flux of j-th species, mol cm 2 min 1; provided an average deviation of 9 5%.
that reactant migration as a consequence of the electri- Unlike the dispersion coefficient, which was shown to
cal field was negligible. depend separately on stroke and frequency [9], experi-
In these conditions, the mass transport coefficient mental results showed that the mass transport coeffi-
may be determined experimentally by measuring the cient depends only on their product, (A f ).
concentration of solution c and of limiting current Eq. (9) combined with the equations obtained in a
density Jl [6] by means of the following: previous work [13] to quantify the dispersion coefficient
as a function of agitation level, revealed optimal oper-
60Jl ating conditions, ensuring maximal process yield with
Km = (6)
nFc lower energy consumption.
The effects of geometric, fluid-dynamic, physical and
chemical variables on the rate of mass transfer may be
5. Nomenclature
evaluated through the following controlling dimension-
less numbers relationship:
A stroke, cm
Sh = c(Re)a(Sc)q (7) c bulk ion concentration, mole cm3
d hole diameter, cm
with: a, u, c, empirical constants; Sc (m/rD) dimension-
D solution diffusivity, cm2 min1
less Schmidt number; D, solution diffusivity, cm2
f frequency, min1
min 1; m, solution viscosity, g cm 1 min 1; r, solution
F Faradays constant, 96 500C equiv1
density, g cm 3; Sh (Km L/D), dimensionless Sherwood
Il limiting current, A
number; L, characteristic length, cm; Re (Af )(d/s)(r/
Jl limiting current density, A cm2
m), dimensionless Reynolds number; A, stroke, cm; d,
Km mass transport coefficient, cm min1
hole diameter, cm; f, frequency, min 1; s, fractional
free flow area, dimensionless.

4. Results and conclusions

In order to analyse the effect of agitation level on


mass transport coefficient Km, a series of experiments
was carried out separately, varying the stroke and
frequency of plate oscillation.
The mass transport coefficient may be evaluated
using Eq. (6), where limiting current density is ex- Fig. 9. Correlation plot for mass transfer data according to Eq. (9).
260 A. Buso et al. / Chemical Engineering and Processing 36 (1997) 255260

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