Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120

Contents lists available at ScienceDirect

Chemical Engineering & Processing: Process Intensification

journal homepage: www.elsevier.com/locate/cep

Electrocoagulation using perforated electrodes: An increase in metalworking T

fluid removal from wastewater
Oriane Avancini Diasa, Eduardo Perini Muniza,b, , Paulo Sérgio da Silva Portoa,c
⁎

a
Universidade Federal do Espírito Santo, Programa de Pós-graduação em Energia, Rodovia Governador Mário Covas, km 60, Bairro Litorâneo, CEP 29932-540, São
Mateus, ES, Brazil
b
Universidade Federal do Espírito Santo, Departamento de Ciências Naturais, Rodovia Governador Mário Covas, Bairro Litorâneo, CEP 29932-540, São Mateus, ES, Brazil
c
Universidade Federal do Espírito Santo, Departamento de Engenharias e Tecnologia, Rodovia Governador Mário Covas, km 60, Bairro Litorâneo, CEP 29932-540, São
Mateus, ES, Brazil

ARTICLE INFO ABSTRACT

Keywords: A continuous electrocoagulation reactor with electrode polarity switch was used for removal of a metalworking
Effluent remediation fluid from synthetic oily water. The effects of perforating the aluminum electrodes, changing the number of
Electroflotation holes, flow rate and the distance between electrodes were studied. Higher values of flow rate reduced final pH.
Metalworking fluid Perforating the electrodes led to faster convergence of pH to its maximum value with no measurable increase in
Perforated electrodes
mass loss. If the distance between electrodes is also increased, there is an improvement in efficiency. With
Flow rate
10 holes, adjusting flow rate and inter-electrode distance, 90.2 ± 0.3% oil removal was achieved with a final pH
of 8.83, which is within limits allowed by legislation.

1. Introduction electrodes help in the separation process [6].

The heavy manufacturing industry uses metal cutting fluids (MCF)
to reduce heat during the processing of metals, to lubricate between
workpiece and tool [1] and to carry the shards that must be removed to
improve finishing. These metalworking fluids contain emulsified oil and
surfactants which allow for the formation of a stable emulsion when
mixed with water [2] and thus reduce corrosion and bacterial growth
[3].
MCF suffer thermal degradation and accumulate impurities with use
and thus need to be replaced periodically. The organic waste generated
must be taken away and treated. These effluents contain surface-active
agents and other organic matters; they also tend to penetrate in the soil
being a danger to the purity of groundwater [3].
Electrocoagulation (EC), is a technique often used to remediate oily
wastewater. It combines coagulation, flocculation, and flotation; the
electrical current that goes through sacrificial electrodes releases posi-
tive metal ions in the solution, also forming negative hydroxyl ions and
hydrogen gas [4]. The metal ions combine with hydroxyl forming
flocculants that may react with the contaminants in the suspension [5].
EC is also called electroflotation since the air bubbles generated in the
The reactors used in EC are usually small with a high throughput
[7]. Chen and coworkers [8] for instance built a 0.30 L reactor to re-
move oil and grease from restaurant wastewaters and achieved more
than 95% of removal efficiency with a flow rate of 9 Lh−1 (2.5 mLs−1).
The critical components in EC reactors are coagulants, contaminants
and generated bubbles [7]. Material and geometry of the electrode are
crucial in the EC reactor project since they alter the coagulants, size and
amount of bubbles produced [9]. There is a significant discussion on the
appropriate electrode material for each contaminant. For oily waste-
water aluminum (Al) electrodes tend to result in a better treatment
performance than iron electrodes [10].
Increasing electrical current leads to a high aluminum dissolution
rate [11,12], thus higher rate of coagulant production. Tito and cow-
orkers [13] state that current intensity is the critical performance-lim-
iting parameter in EC while current density is secondary. However, the
authors that obtained an increase in efficiency by punching holes in the
electrodes often justified their results with arguments based on current
density.
According to Khandengar and Saroha [14], electrodes with punched
holes are expected to result in higher removal efficiency compared to

Abbreviations: EC, electrocoagulation; DE, distance between electrodes; N, number of holes drilled in the electrodes; Sc, spearman correlation; Q, flux rate; ORf,
percent of metal cutting fluid removed from the water after 30 min of EC; OR%, percent of metal cutting fluid removed from the water
⁎
Corresponding author at: Universidade Federal do Espírito Santo, Programa de Pós-graduação em Energia, Rodovia Governador Mário Covas, km 60, Bairro
Litorâneo, CEP 29932-540, São Mateus, ES, Brazil.
E-mail address: eduardo.muniz@ufes.br (E. Perini Muniz).

https://doi.org/10.1016/j.cep.2019.03.021
Received 29 November 2018; Received in revised form 27 March 2019; Accepted 31 March 2019
Available online 01 April 2019
0255-2701/ © 2019 Elsevier B.V. All rights reserved.
O. Avancini Dias, et al.
plane electrodes. They studied the effect of the number of holes in
aluminum electrodes in the color removal efficiency to remove acid 131
dye from distilled water [15]. Efficiency increases with the number of
holes from one to four and is not altered from four to eight holes. There
is no apparent change in efficiency with hole distribution. Removal
efficiency increases with hole diameter from 2 to 4 mm but not from 4
to 5 mm. The results were attributed to the higher current discharge
from the punched electrode.
Hussin and co-workers [16] propose the use of perforated zinc
electrodes for lead (Pb) separation from water. Removal efficiency was
higher for perforated electrodes with a hole diameter of 0.5 cm than for
those with a hole diameter of 0.2 cm, and both were more efficient than
the plane, non-perforated electrodes. The presence and size of the holes
altered the electrical current between the electrodes and the authors
associated the higher efficiency with higher current density.
In the present work, electrical current was kept constant while the
distance between electrodes, the number of holes drilled on them and
flow rate were varied. The objective was to verify if other factors be-
sides current intensity or current density interfere in the change of ef-
ficacy in oil removal (efficacy is defined as the amount of contaminant
removed expressed in % [13]) and in the final pH when electrodes are
perforated.
2. Methodology
2.1. Preparation of synthetic cutting oil effluent
To prepare 1 L of synthetic effluent, 0.2000 g of Exxon Mobil
MOBILCUT 102 soluble cutting fluid (density = 0.89 at 15 °C and
viscosity =35 cSt at 40 °C) and 10.0 g of sodium chloride were dis-
solved in distilled water. Sodium chloride was added to guarantee a
higher and near-constant electrical conductivity, independent of the
amount of aluminum dissolved [17]. This higher current with lower
voltage drop tends to decrease power consumption [18].
The solution was stabilized using a rotor-stator mixing device where
three blades rotated at 3000 rpm for 15 min, shearing the larger oil
surfaces. Preliminary tests indicated that oil content was stable after
10 h from preparation. The solution was then kept at rest and watched
for 24 h to check for stability before EC was performed.
2.2. Electrocoagulation system
As described in a previous work [17], a monopolar arrangement of
three pairs of aluminum electrodes, polarity switch to preserve the
electrodes and increase efficiency was used. Polarity reversal turns the
cathode into anode and vice versa, which contributes to reducing the
passivation effect on the cathode and increases the lifespan of the
electrode [17].
While the modulus of the electrical current was kept constant at 4 A,
polarity was changed each 30 s forming an input sign step function
(polarity reversal). Voltage modulus oscillated around 12 ± 3 V due to
electrical resistance changes created by electrode passivation during the
process. The voltage switch time was adjusted for electrical stability,
resulting in a higher value than the 10 s found in the literature [17,19].
The continuous flow EC pilot unit consisted of a rectangular elec-
trolytic cell, a set of aluminum electrodes, and an electronic device
(plate) to switch the polarity of the current from a DC power source
(Fig. 1). The monopolar mode electrodes were connected to the polarity
switch and then to the DC power supply brand MINIPA model MPC-
3005.
The electrodes are aluminum plates with the following dimensions:
130 mm height, 65 mm width and 0.50 mm thick, located vertically in
the central part of the interior of the plexiglass reactor, whose electrical
wiring passes through holes located in the lid (Fig. 1). The dimensions
of the feed tank, reactor and receiver tank are shown in Table 1.
Tests were performed by measuring MCF removal efficacy with non-
114
Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120
perforated and perforated plates, of same material and dimensions, to
evaluate the effect of the presence of holes when the electrical current
modulus is kept constant. The position of the drilled holes in the per-
forated plates is represented in Fig. 2. Holes with 6 mm diameter were
drilled in symmetrical patterns around the center of the plates, to
guarantee a uniform flux of oily water, oxygen and hydrogen bubbles.
The central hole and the hole at the top of the upper corner were filled,
used to realign the connection between the plates with the help of a
threaded rod.
A schematic drawing detailing the shape, layout, and assembly of
the electrode plates is shown in Fig. 3. Two sets of three plates were
aligned in the form of a beehive, each set interspersed and arranged in
parallel (monopolar mode), the plates being separated by screws cov-
ered with a polymer for electrical insulation.
Distances between electrodes (DE) were set as demanded by ex-
perimental design (next section). From the literature, there is a ten-
dency of improvement in the process of separation of oil from water
when DE is increased from 5 to 10 mm in a reactor with polarity switch
[17], justifying the use of 10 mm as a minimum value in the initial
experimental plan.
2.3. EC procedure
The transport of emulsified water from the storage tank to the re-
actor occurs by pumping. The inlet and the exit of the effluent from the
rectangular reactor are 2.0 and 14.0 cm above the bottom, respectively.
When the effluent reached the exit height, a useful volume of 3 L inside
the reactor was obtained. At that time the flow rate was adjusted using
a test tube, i.e., the volume of effluent collected in one minute was
measured.
After an amount of water equal to the useful volume of the reactor
passed through it, the system was considered to be in a steady state. For
each experiment, an aliquot was collected before turning on the power
supply (zero time). Then the power was turned on, and the chronometer
started. Each 5, 10, 20, and 30 min of the process, a sample of 350 mL
was collected, stored in an amber bottle and maintained in a re-
frigerator at 4 °C for subsequent analysis.
The values used for flow rate (Q), the number of holes (N) and the
distance between electrodes (DE) were as shown in Table 2. To de-
termine the experimental variables, initially a 23 factorial experimental
design was used (experiments 1–8), then a central point was added in
triplicate (experiments 9, 10 and 11).
After the initial analysis, since it showed some improvement in ef-
ficacy with increasing N, it was decided to do a second set of experi-
ments with maximum N (fixed value), using a central composite design
with Q and DE as variables (experiments 12,13 and 14). By design one
of the values tried for Q should be 1.18 mL.min−1 but this value was
discarded since it is too low to be of practical use. The central point of
this new set of experiments was made in triplicate (experiments 15, 16
and 17). Once all was finished, the system with nonperforated elec-
trodes had to be evaluated as a reference (experiments 18 and 19).
The electrical current tends to pass only in the metallic parts of the
electrodes. If holes are drilled the area of the plates will be reduced and
current density increased. The current density is estimated to be 493.83
A. m−2 for a flat plate without the presence of holes. It grows to 508.01
and 515.42 A. m−2 for 6 and 10 holes, respectively.
2.4. Analytical methodology
The characterization of the samples collected was carried out ac-
cording to methodologies adapted from the Standard Methods for the
Examination of Water and Wastewater [20].
2.5. Determination of pH
The pH of all samples was measured at 0, 5, 10, 20 and 30 min of
O. Avancini Dias, et al. Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120

Fig. 1. Schematic design of continuous flow electrolytic system. Where: (a) current power supply; (b) Polarity inverter; (c) Feed tank for raw fluent storage; (d)
submersible pump; (e) flow regulating valve; (f) electrode; (g) reactor input; (h) reactor output and (i) receiver tank for storing effluent after treatment.

Table 1 procedure were based on Method 4500 from the Standard Methods for
Dimensions of the EC apparatus. the Examination of Water and Wastewater [20].
Components of the system Dimensions Effective Volume
(cm) (mL)
2.6. Determination of electrical conductivity
Feed tank 33.0 × 22.0 × 22.0 15000
EC reactor (retangular) 30.2 × 15.2 × 15.0 3000
Receiver tank 25.2 × 18.0 × 18.0 8000
Electrical conductivity was obtained with the aid of the conductivity
meter BEL Engineering W12D, resolution of 0.1 μS. cm−1 and accuracy
of ± 1%. For each test the conductivity was verified, using a standard
electrocoagulation using a pH meter, Mark MS TECNOPON mPA210 NaCl solution of 1000 μS. cm−1. The calibration of the conductometer
with automatic temperature compensation, resolution 0.01 and accu- and the measurement procedure were based on Method 2510 from the
racy ± 0.01%. The calibration of the pH meter and the measurement Standard Methods for the Examination of Water and Wastewater [20].

Fig. 2. Aluminum plates used to compose the electrode: (a) perforated plates with 6 holes (b) perforated plates with 8 holes (c) plates with 10 holes.

115
O. Avancini Dias, et al. Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120

Fig. 3. Representation of the electrode assembly showing the mechanical connections between plates.

Table 2 function. From an analysis of the UV–vis spectra, the wavelength of

Operational conditions used for the experiments. 263 nm was ideal; a calibration curve was plotted and fit by a linear
Experiment N Q DE
model (adjusted R-square of 0.9996), Eq. (1):
(mL.s−1) (mm)
OC (gL 1) = (336 ± 2)(gL 1)* Absorbance (1)
1 6 2 10
2 10 2 10 Where OC is oil concentration.
3 6 6 10
Oil removal efficacy of the process was evaluated by percent of oil
4 10 6 10
5 6 2 20 removal (OR%) as calculated using Eq. (2):
6 10 2 20
7 6 6 20 OC0 OCf
OR% = × 100
8 10 6 20 OCf (2)
9 8 4 15
10 8 4 15
11 8 4 15
where: OC0 is the initial oil concentration (time zero), OCf is the oil
12 10 6.8 15 concentration at the end of the process (30 min).
13 10 4 7.95
14 10 4 22.05
15 10 4 15 2.8. Determination of electrode consumption
16 10 4 15
17 10 4 15
18 0 2 10 The mass of the electrodes was measured before and after each
19 0 6 20 experiment to estimate the mass loss occurring during the process
(gravimetric measurement). Electrodes were washed and dried before
mass measurement to avoid the influence of eventual flakes or other
2.7. Determination of the content of oils and greases impurities attached during the EC process. The measurements were
carried out in an analytical balance Bioprecise brand FA-2104 N with a
A spectral method was used, based on method 5520 from the precision of 0.1 mg.
Standard Methods for the Examination of Water and Wastewater [20].
The oil was extracted from 50 mL samples using hexane as a solvent.
Then the UV–vis spectrum was measured, and the absorbance at a given 2.9. Microscopy
wavelength was used in a calibration curve to obtain oil concentration.
The spectrometer used was a QUIMIS 4802. Spectra were measured The surface of the electrodes was observed with an optical USB
from 190 to 700 nm with a precision of 1 nm. linked Microscope with magnification up to 1,000X, connected to a
The value of the wavelength was chosen as the one where the re- laptop. The microscope lens was placed about 10 mm above, perpen-
lation between concentration and absorbance was closer to a linear dicular to the plate and with the same illumination for all samples.

116
O. Avancini Dias, et al.
2.10. Statistical analysis
To look for monotonic relations between input and output variables
Spearman’s coefficient was calculated for the raw data using Origin™
software. Spearman’s is a non-parametric rank statistic that can be used
as a measure of the strength of an association between two variables
[21] even when one of these variables is noncontinuous as is the case
for the number of holes drilled in a plate. The p-value test (p-value <
0.05 was considered statistically significant) was used to verify if a
Spearman correlation was significant. Only correlations that passed this
test are discussed in this work.
Since Spearman`s method finds only monotonic correlations, Q2, N2,
DE2, N x Q, N x DE, Q x DE and Q x N x DE were used as variables to
search for more complex relationships between input and output data.
The parameters of the kinetic models for pH and OR% were esti-
mated by nonlinear regression using Origin™ software. To evaluate the
quality of fit, the adjusted R-square, the standard error, the p-value test
(p-value < 0.05 was considered statistically significant) and the F-test
were used. All R-square were higher than 0.93.
3. Results and discussion
3.1. Variation of pH with time
Typical results for pH variation with time are represented in Fig. 4.
The data can be fit by an exponential model (Eq. (3)) as described in a
previous work [17]:
pH = Y 0 Be kpH t
(3)
where: Y0 is the adjusted value for the final pH, B is a constant that
subtracted from Y0 gives the estimated initial value, kpH (min−1) is a
reaction rate constant, a measurement of the number of dissolved ions
responsible for the rise in the pH value [17], t (min) is the time since the
beginning of the EC.
The variation of pH with time for the other experiments also can be
adjusted by Eq. (3), with the fit parameters shown in Table 3. Measured
pH value at the end of the EC process (pHf) is also displayed in the table.
High kpH does not mean maximum pHf (Fig. 4), but a fast con-
vergence to a final value as happened in experiment 8 where pH sta-
bilized after 10 min of treatment. It is usual for pH to rise during the EC
process. One known reason for this behavior is the formation of an
excess of OH− on the cathode [22]. Excess meaning OH− that does not
combine with the Al+3 released by the anode to form the aluminum
Fig. 4. pH as a function of time. The lines represent the exponential fit as de-
scribed in the text. ■ = experiment 3, = experiment 6, experiment 8.
117
Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120
hydroxides that are responsible for oil removal.
The relation between kpH and the input variables will be discussed
ahead, using Spearman correlation. For all experiments, adjusted R-
square is higher than 0.94, with pHf in the range from 8.60 to 9.75. As
listed in the methodology, the p-value test was considered statistically
significant for p-value < 0.05.
3.2. Variation of oil concentration with time
Typical results for variation of OR% with time are represented in
Fig. 5. All results could be adjusted, by non-linear fit, to an exponential
model, with the form of Eq. (4):
OR% = A (1 e kOR t )
(4)
In this model, kOR (min−1) is the reaction rate of oil with aluminum
hydroxide [17] and gives a measurement of reaction speed. The other
fitting parameter, A (%) is related to the amount of oil that might be
removed in an infinite time.
The fit parameters A and kOR are given in Table 4 together with the
final (t =30 min) percentage of oil removal (ORf). For all experiments,
the adjusted R-square of the exponential fit was higher than 0.93.
The exponential fit (Eq. (4)) is a characteristic equation for change
of concentration due to a pseudo-first-order chemical reaction. This
model is also used in the literature to describe EC, for the treatment of
water contaminated with synthetic effluents of acid blue 113 dye [23]
arsenic [24], phenol [25] and basic dye rhodamine [26]. The pseudo-
first-order behavior can be explained if the amount of aluminum hy-
droxide is constant with time.
3.3. Electrical conductivity
The electrical conductivity decreased by 0.9 ± 0.3 mScm−1 in all
experiments independent of the process variables (including the pre-
sence of holes in electrodes). The average value of the conductivity
calculated for all experiments was 14.02 ± 0.07 mScm−1. Electrical
conductivity is related to the salinity of the medium, and the same
amount of NaCl was used in all experiments. The slight tendency of
conductivity decrease may indicate a small reduction in salt con-
centration with time.
3.4. Electrodes loss of mass
Percent loss of mass by the electrodes during the process was within
the range of 3.4 ± 0.8% for all experiments. These results agree with
Faraday`s equation, where the ratio of mass released to the fluid is
dependent on the electrical current modulus.
Loss of mass is a critical component of the cost associated with EC,
and it can be altered by other variables besides electrical current, in-
cluding DE [27] or possibly N. If it had increased with N, drilling holes
would not be an economically viable way of raising efficacy.
Despite the similar total loss of mass, the corrosion of the electrodes
took a different form for each experimental set. Optical micrography
with 1000x magnification shows that the diameter of the corrosion pits
(black areas in Fig. 6) and the apparent roughness of the plate increase
when 10 holes are used, with Q = 2 mLs−1 (Fig. 6A and B). The op-
posite happens when Q and DE are higher, and the electrode is perfo-
rated by 10 holes, there is a visible reduction in corrosion pit diameter
and in roughness (Fig. 6C and D).
The surface texture of the aluminum electrode is determinant in the
production of large bubbles in EC [28]. Rough surfaces may make it
more difficult for EC to generate small bubbles that tend to increase
separation efficiency. However, independent on the observed variations
in roughness or pit diameter, ORf increased when holes were drilled if
the other variables were kept constant.
O. Avancini Dias, et al. Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120

Table 3
Fit parameters that describe the variation of pH with time.
Y0 B kpH Adjusted R-Square pHf

Exp. Value Standard Error Value Standard Error Value Standard Error

1 9.5917 0.1708 1.7529 0.2180 0.1302 0.0414 0.9452 9.69

2 9.5908 0.1530 1.8942 0.2122 0.1503 0.0422 0.9537 9.71
3 9.0477 0.0672 1.1815 0.0743 0.1034 0.0172 0.9875 9.03
4 8.5516 0.0365 0.8186 0.0606 0.2304 0.0443 0.9790 8.60
5 9.5982 0.1472 1.8518 0.1980 0.1423 0.0384 0.9582 9.70
6 9.6142 0.1392 2.1959 0.2063 0.1711 0.0401 0.9667 9.75
7 8.8992 0.0590 1.1872 0.0754 0.1308 0.0212 0.9854 8.92
8 8.5598 0.0526 1.1360 0.0931 0.3000 0.0721 0.9743 8.63
9 9.3733 0.1010 2.4986 0.1517 0.1765 0.0267 0.9859 9.47
10 9.4109 0.1133 1.9637 0.1514 0.1406 0.0274 0.9781 9.48
11 9.2053 0.0412 2.2284 0.0665 0.2117 0.0161 0.9965 9.23
12 8.5723 0.0288 1.6969 0.0439 0.1827 0.0118 0.9974 8.57
13 8.7326 0.0761 1.3046 0.1283 0.2443 0.0637 0.9631 8.83
14 9.2761 0.1303 2.2802 0.2081 0.2055 0.0475 0.9682 9.43
15 9.1833 0.0456 2.1786 0.0750 0.2243 0.0199 0.9954 9.24
16 9.2851 0.0214 2.2637 0.0328 0.1847 0.0067 0.9992 9.30
17 9.3683 0.0648 2.0618 0.0885 0.1460 0.0158 0.9931 9.40
18 9.4540 0.0518 1.8135 0.0800 0.1876 0.0207 0.9925 9.50
19 9.0071 0.1226 1.1657 0.1389 0.1076 0.0337 0.9545 9.03

Table 4
Parameters that describe the variation of oil removal with time.
A kOR Adjusted R- ORf (%)
Square
Exp. Value Standard Value Standard
Error Error

1 109.1354 20.4490 0.0625 0.0257 0.9619 89.3

2 96.3177 13.9830 0.0925 0.0378 0.9352 89.5
3 83.2771 3.0336 0.2009 0.0292 0.9872 86.5
4 83.4168 2.5992 0.3012 0.0489 0.9883 87.3
5 103.7627 13.6654 0.0757 0.0246 0.9680 90.5
6 106.7409 16.5129 0.0697 0.0253 0.9646 91.4
7 89.5475 8.1523 0.1312 0.0385 0.9529 88.5
8 92.8345 7.7904 0.1284 0.0343 0.9614 89.6
9 92.6149 1.6914 0.1177 0.0067 0.9983 90.1
10 92.9350 3.0087 0.1130 0.0112 0.9951 90.1
11 91.5662 1.5952 0.1161 0.0063 0.9985 90.1
12 82.7170 2.7875 0.3077 0.0550 0.9862 87.0
13 92.2164 1.8067 0.1136 0.0068 0.9982 90.1
14 92.9200 7.5894 0.1282 0.0333 0.9635 89.7
15 96.2243 4.4661 0.0975 0.0129 0.9926 90.7
16 95.4284 5.0410 0.0996 0.0152 0.9899 90.2
Fig. 5. OR% as a function of time. The lines represent the exponential fit as 17 96.0944 4.9490 0.0972 0.0142 0.9909 90.2
described in the text. ■ = experiment 3, = experiment 6, experiment 8. 18 106.8671 19.8072 0.0645 0.0267 0.9593 88.6
19 88.5883 8.0054 0.1324 0.0388 0.9529 87.9

3.5. Statistical analysis

Spearman's correlation coefficients between the variables have been
given in Table 5.
N has a significant positive correlation with kpH (Table 5). Since kpH
may be associated with the excess of OH− [22,17], drilling holes may
be helping in the production of this ion. Possible reasons are the in-
crease in electrical current density and the flux of gas through the holes.
Q has a significant negative correlation with pHf and ORf, as ex-
pected. With higher Q, the molecules of the fluid have less time to in-
teract with the aluminum, resulting in smaller total variation in pH. The
positive correlation with kOR shows that the faster removal of ions of
the electrode surfaces with higher Q leads to an increase in corrosion, as
was observed by Krystynik and Tito [29].
DE does not have a significant correlation with any other variable,
and this is unusual in EC; thus quadratic correlations were searched.
Spearman`s correlations were calculated with Q2, N2, DE2, N x Q, N x
DE, Q x DE and Q x N x DE as variables. The only combination that
resulted in correlations not seen for the component variables was be-
tween N x DE and ORf. The change in ORf when N x DE increases for Q
equal to 2 mL.s−1 and 6 mL.s−1 can be understood from Fig. 7. For Q
equal to 4 mL.s−1 the value of ORf was practically constant at
90.2 ± 0.3%, independent of N x DE.
For Q of 2 mL.s−1, ORf has a linear relationship with N x DE (Fig. 7).
While for Q of 6 mL.s−1 a linear fit of ORf with N x DE is possible, with
an exception for the non-perforated electrode. Nonetheless, Fig. 7
shows a tendency of growth in ORf if holes are made in non-perforated
electrodes.
For any value of Q, if DE is kept constant and N is increased, there is
a tendency of growth in ORf, but if DE is reduced and N increased, ORf
will be reduced. The ideal behavior to improve process efficacy is to
compensate the turbulence created by drilling holes in the electrode by
increasing DE.
The question posed in this work is answered, if increasing current
density were enough to improve efficacy, N would interfere in ORf in-
dependent of DE. Since the improvement depends on a combination of
the two variables, it must be related to the passage of fluid through the
holes.
Power consumption (related to electrical current modulus) and

118
O. Avancini Dias, et al. Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120

Fig. 6. Optical micrographs of the electrode plates after EC. A – Experiment 18 (N = 0, DE = 10, Q = 2), B- Experiment 2 (N = 10, DE = 10, Q = 2), C- Experiment
19 (N = 0, DE = 20, Q = 6), D - Experiment 8 (N = 10, DE = 20, Q = 6).

electrode replacement (related to mass loss) are the main responsible

for costs in EC and were not altered by drilling holes in the electrodes.
On the other hand, when electrodes are perforated, pHf is reduced, and
ORf increased.
The data for the two linear fits shown in Fig. 7 are in Table 6.
If the linear behavior from Fig. 7 is kept for higher values of DE, the
two lines, due to Q = 2 and Q = 6 mL.s−1 will meet when DE is 40 mm,
and N is 10. By this theoretical model, ORf will then be close to 94%.
For a good design, the values for Q, N, and DE must correspond to
the higher values of ORf, the higher kOR and to pHf closer to neutral. By
Brazilian law, the maximum concentration of oily effluents based on
mineral oil that can be discharged in the environment is 20 mg.L−1, and
the pH range must be between 5 and 9 [30]. The higher value of ORf
obtained with pHf smaller than 9 was 90.1% in Experiment 13 (Q
=4 mL.s-1, DE =7.95 mm, N = 10). This experiment generates an ef-
fluent compatible with the limits imposed by the legislation.

4. Conclusions

Effluents containing metalworking fluid can be treated by electro-

coagulation in a continuous flow, with more than 90% of removal ef- Fig. 7. Evolution of ORf with N x DE for Q = 2 mL.s−1 ( ) and 6 mL.s−1 ( ).
The label 10 means DE = 10 mm and 20 means DE = 20 mm.
ficiency and a final pH within the range allowed by legislation. Drilling

Table 5
Spearman’s correlation data.
ORf kOR pHf kpH Loss of Mass

Sc p-value Sc p-value Sc p-value Sc p-value Sc p-value

N 0.3652 0.1242 0.0822 0.7379 −0.1855 0.4470 0.6213 0.0045 0.1921 0.4307
Q −0.5640 0.0119 0.9441 < 0.0001 −0.9082 < 0.0001 0.0660 0.7884 −0.2723 0.2595
DE 0.2530 0.2960 0.1485 0.5440 0.0550 0.8230 −0.0880 0.7202 −0.0715 0.7712
N x DE 0.5059 0.0271 0.0428 0.8621 −0.0116 0.9625 0.3776 0.1110 0.2414 0.3195

Where: Sc means Spearman coefficient, N is the number of holes, Q is flow rate, DE distance between electrodes. A two-tailed test of significance was used, bold
values indicate significant correlations (p-value < 0.05).

119
O. Avancini Dias, et al.
Table 6
Linear fit of ORf as a function of N x DE.
Q Intercept Slope Adjusted R-
(mL.s−1) square
Value Standard Value Standard
Error Error
2 85.3176 0.5591 0.0224 0.0043 0.9295
6 88.4667 0.2310 0.0145 0.0020 0.8978
holes in the electrodes led to an increase in the ratio of change of pH,
resulting in faster convergence to its final value. Removal efficiency
depends on a combination of the number of holes and distance between
electrodes. If new holes are added and distance increased, efficiency
improves. These facts indicate that current density is not the only factor
acting when holes are drilled.
There was no noticeable increase in mass loss of the electrodes due
to the presence of holes, and there is no visual evidence of alteration in
corrosion around the holes. No evidence of alterations in corrosion due
to the non-uniform current density. There is nonetheless a change in the
average size and distribution of the corrosion pits.
Acknowledgments
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) -
Finance Code 001. The authors are also grateful for brazilian financial
support: CNPq (Conselho Nacional de Desenvolvimento Científico e
Tecnológico) and FAPES (Fundação de Amparo à Pesquisa e Inovação
do Espírito Santo).
References
[1] M. Kobya, E. Demirbas, M. Bayramoglu, M.T. Sensoy, Optimization of electro-
coagulation process for the treatment of metal cutting wastewaters with response
surface methodology, Water Air Soil Pollut. 215 (2011) 399–410, https://doi.org/
10.1007/s11270-010-0486-x.
[2] E. Demirbas, M. Kobya, Operating cost and treatment of metalworking fluid was-
tewater by chemical coagulation and electrocoagulation processes, Process Saf.
Environ. Prot. (2016), https://doi.org/10.1016/j.psep.2016.10.013.
[3] K. Bensadok, S. Benammar, F. Lapicque, G. Nezzal, Electrocoagulation of cutting oil
emulsions using aluminum plate electrodes, J. Hazard. Mater. 152 (2008) 423–430,
https://doi.org/10.1016/j.jhazmat.2007.06.121.
[4] P. Asaithambi, M. Susree, R. Saravanathamizhan, M. Matheswaran, Ozone assisted
electrocoagulation for the treatment of distillery effluent, Desalination 297 (2012)
1–7, https://doi.org/10.1016/j.desal.2012.04.011.
[5] A. Fernandes, M.J. Pacheco, L. Ciríaco, A. Lopes, Review on the electrochemical
processes for the treatment of sanitary landfill leachates: present and future, Appl.
Catal. B Environ. 176 (2015) 183–200, https://doi.org/10.1016/j.apcatb.2015.03.
052.
[6] Y.O. Fouad, Separation of cottonseed oil from oil-water emulsions using electro-
coagulation technique, Alexandria Eng. J. 53 (2014) 199–204, https://doi.org/10.
1016/j.aej.2013.10.005.
[7] I.L. Mickova, Advanced electrochemical technologies in wastewater treatment. Part
II: electro-flocculation and electro-flotation, Am. Sci. Res. J. Eng. Technol. Sci. 14
(2015) 273–294 (accessed March 23, 2018), http://asrjetsjournal.org/index.php/
American_Scientific_Journal/article/view/1017.
[8] X. Chen, G. Chen, P.L. Yue, Separation of pollutants from restaurant wastewater by
electrocoagulation, Sep. Purif. Technol. 19 (2000) 65–76, https://doi.org/10.1016/
S1383-5866(99)00072-6.
120
Chemical Engineering & Processing: Process Intensification 139 (2019) 113–120
[9] N.K. Khosla, S. Venkatachalam, P. Somasundaran, Pulsed electrogeneration of
bubbles for electroflotation, J. Appl. Electrochem. 21 (1991) 986–990, https://doi.
org/10.1007/BF01077584.
[10] M.M. Emamjomeh, M. Sivakumar, Review of pollutants removed by electro-
coagulation and electrocoagulation/flotation processes, J. Environ. Manage. 90
(2009) 1663–1679, https://doi.org/10.1016/J.JENVMAN.2008.12.011.
[11] N. Boudjema, N. Drouiche, N. Abdi, H. Grib, H. Lounici, A. Pauss, N. Mameri,
Treatment of Oued El Harrach river water by electrocoagulation noting the effect of
the electric field on microorganisms, J. Taiwan Inst. Chem. Eng. 45 (2014)
1564–1570, https://doi.org/10.1016/J.JTICE.2013.10.006.
[12] T. Ouslimane, S. Aoudj, M. Amara, N. Drouiche, Removal of copper and fluoride
from mixed Cu-CMP and fluoride-bearing wastewaters by electrocoagulation, Int. J.
Environ. Res. 11 (2017) 677–684, https://doi.org/10.1007/s41742-017-0058-7.
[13] D.N. Tito, P. Krystynik, P. Kluson, Notes on process and data analysis in electro-
coagulation—the importance of standardization and clarity, Chem. Eng. Process.
Process Intensif. 104 (2016) 22–28, https://doi.org/10.1016/J.CEP.2016.02.011.
[14] V. Khandegar, A.K. Saroha, Electrocoagulation for the treatment of textile industry
effluent - a review, J. Environ. Manage. 128 (2013) 949–963, https://doi.org/10.
1016/j.jenvman.2013.06.043.
[15] V. Khandegar, A.K. Saroha, Effect of electrode geometry on the performance of
electrocoagulation, Int. J. Adv. Res. Sci. Eng. 5 (2016) 379–376.
[16] F. Hussin, F. Abnisa, G. Issabayeva, M.K. Aroua, Removal of lead by solar-photo-
voltaic electrocoagulation using novel perforated zinc electrode, J. Clean. Prod. 147
(2017) 206–216, https://doi.org/10.1016/J.JCLEPRO.2017.01.096.
[17] L.C.A. Gobbi, I.L. Nascimento, E.P. Muniz, S.M.S. Rocha, P.S.S. Porto,
Electrocoagulation with polarity switch for fast oil removal from oil in water
emulsions, J. Environ. Manage. 213 (2018) 119–125, https://doi.org/10.1016/J.
JENVMAN.2018.01.069.
[18] H.K. Hansen, P. Nuñez, D. Raboy, I. Schippacasse, R. Grandon, Electrocoagulation
in wastewater containing arsenic: Comparing different process designs,
Electrochim. Acta 52 (2007) 3464–3470, https://doi.org/10.1016/j.electacta.2006.
01.090.
[19] Z.B. Gönder, G. Balcıoğlu, I. Vergili, Y. Kaya, Electrochemical treatment of carwash
wastewater using Fe and Al electrode: techno-economic analysis and sludge char-
acterization, J. Environ. Manage. 200 (2017) 380–390, https://doi.org/10.1016/J.
JENVMAN.2017.06.005.
[20] APHA, Standard Methods For Examination of Water And Wastewater. American
Public Health and Association/American Water Works 1 Association/Water
Environmental Federation, Washington, DC, 2005.
[21] J. Hauke, T. Kossowski, Comparison of values of Pearson’s and Spearman’s corre-
lation coefficients on the same sets of data, Quaest. Geogr. 30 (2011) 87–93,
https://doi.org/10.2478/v10117-011-0021-1.
[22] T. Harif, M. Khai, A. Adin, Electrocoagulation versus chemical coagulation: coa-
gulation/flocculation mechanisms and resulting floc characteristics, Water Res. 46
(2012) 3177–3188, https://doi.org/10.1016/j.watres.2012.03.034.
[23] N. Mohan, N. Balasubramanian, V. Subramanian, Electrochemical treatment of si-
mulated textile effluent, Chem. Eng. Technol. Ind. Chem. Equip. Process Eng. 24
(2001) 749–753.
[24] N. Balasubramanian, T. Kojima, C. Srinivasakannan, Arsenic removal through
electrocoagulation: kinetic and statistical modeling, Chem. Eng. J. 155 (2009)
76–82, https://doi.org/10.1016/j.cej.2009.06.038.
[25] Y. Yavuz, A.S. Koparal, Ü.B. Öğütveren, Treatment of petroleum refinery waste-
water by electrochemical methods, Desalination 258 (2010) 201–205, https://doi.
org/10.1016/j.desal.2010.03.013.
[26] A.I. Adeogun, R.B. Balakrishnan, Kinetics, isothermal and thermodynamics studies
of electrocoagulation removal of basic dye rhodamine B from aqueous solution
using steel electrodes, Appl. Water Sci. 7 (2017) 1711–1723, https://doi.org/10.
1007/s13201-015-0337-4.
[27] M. Changmai, M. Pasawan, M.K. Purkait, Treatment of oily wastewater from dril-
ling site using electrocoagulation followed by microfiltration, Sep. Purif. Technol.
210 (2019) 463–472, https://doi.org/10.1016/J.SEPPUR.2018.08.007.
[28] G. Chen, X. Chen, P.L. Yue, Electrocoagulation and electroflotation of restaurant
wastewater, J. Environ. Eng. 126 (2000) 858–863, https://doi.org/10.1061/(ASCE)
0733-9372(2000)126:9(858).
[29] P. Krystynik, D.N. Tito, Key process parameters affecting performance of electro-
coagulation, Chem. Eng. Process. Process Intensif. 117 (2017) 106–112, https://doi.
org/10.1016/j.cep.2017.03.022.
[30] Brasil, Resolução CONAMA no 430, de 13 de maio de 2011, (2011) (Accessed 22
November 2017), www.mma.gov.br.