Journal of Hazardous Materials 364 (2019) 78–81

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Journal of Hazardous Materials

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

Selenium removal from petroleum refinery wastewater using an T

electrocoagulation technique
Henrik K. Hansena, , Sebastián Franco Peñaa, Claudia Gutiérreza, Andrea Lazoa, Pamela Lazob,
⁎

Lisbeth M. Ottosenc
a
Departamento de Ingeniería Química y Ambiental, Universidad Técnica Federico Santa María, Valparaíso, Chile
b
Instituto de Química y Bioquímica, Facultad de Ciencias, Universidad de Valparaíso, Chile
c
Department of Civil Engineering, The Technical University of Denmark, Denmark

ARTICLE INFO ABSTRACT

Keywords: In the present work, an electrocoagulation technique was tested as a possible technological alternative for the
Selenium treatment of selenium in wastewater from a petroleum refinery. For this purpose, a batch airlift reactor with air
Electrocoagulation stirring was used. The sacrificial electrodes were made of iron to generate the necessary ferrous ions for the
Oxidizing medium process. The results indicated a selenium removal of 90% from the wastewater after 6 h of treatment, achieving a
Current density
decrease in concentration from 0.30 mg L−1 to 0.03 mg L−1. The current density was found to be an important
Iron hydroxides
variable for the process. In conclusion, the electrocoagulation process seems to be a feasible selenium removal
technique applied to petroleum refinery wastewater.

1. Introduction
Selenium is an essential micronutrient in the 60–135 ppb range [1];
however, in slightly higher amounts selenium is toxic for animals and
humans [2]. The main sources of emission are oil refineries, power
plants, mineral processing plants, agriculture and fossil fuel use [2,3].
Aqueous selenium is mainly present as selenate Se(VI) and selenite Se
(IV). Usually, selenate present as SeO4−2 is more difficult to remove
and treat than selenite in the form of SeO3−2 or HSeO3− [4].
During the petroleum refining process, selenium is concentrated in
wastewaters exceeding in many cases the allowed local limits for dis-
charge [5]. Therefore, the search for appropriate technologies to re-
move selenium is very relevant. Several technologies have been re-
ported as solution for selenium treatment [6,7], such as co-precipitation
with iron salts (FeCl3), which was effective at pH below 7 but in-
effective for the removal of selenate (Se(VI)). The precipitation with
zero-valent iron (Fe°) reduced selenium oxyanions to elemental sele-
nium with a maximum efficiency of 87% but the removal of selenate (Se
(VI)) was not achieved [8,9]. Moreover, an effective bacterial process
was suggested, which reduced all chemical species of selenium to ele-
mental selenium; however, large treatment times were required [10].
Electrocoagulation (EC) is a well-known technique for the treatment
of several metals and metalloids present in wastewaters, especially for
arsenic [11,12]. Hansen et al. [11] proposed a cylindrical airlift reactor
design for the removal of arsenic from the wastewater. Two cylindric
and concentric sacrificial electrodes produced Fe+2 in the EC process
with polarity reversal to avoid the passivation of the anode. The solu-
tion was stirred by injection of air, where the oxygen oxidized Fe+2 to
Fe+3 promoting the formation of iron hydroxide colloids, which ad-
sorbed arsenic. Since arsenic and selenium behave chemically in many
cases similar, this method could be an alternative for selenium removal.
Previous works have used electrocoagulation to treat wastewaters
from copper industry achieving a reduction in the selenium con-
centration of 90% [10]. The chemical species that adsorbed selenium
were iron hydroxides (HFOs) and their effectivity varied according to
the pH. HFOs are sparingly soluble in a pH range between 4 and 6
(Kps = 10−38) but at very acidic pH (less than 3), HFOs are soluble, and
therefore the reduction reaction of Fe+3 to Fe+2 could occur, de-
creasing the amount of available HFOs [13–15]. A preliminary research
reported optimum pH values for the reduction of selenocyanate, SeCN
and selenite, SeO3 2 , in a moderately acidic range (4.5–6.5) [16,17]. The
rate of Se(IV) and Se(VI) removal was increased using iron nano-
particles (nZVI) a an pH of 4 [17,18]. Nevertheless, some authors have
reported low removals (∼10%) for selenate (Se(VI)) treated with iron
salts, at slightly acidic pH [6,18]. For basic pH values (7.8–10), sele-
nium adsorption was not observed, when HFOs were produced by
anodic dissolution or iron nanoparticles [19]. At slightly acidic pH,
anion adsorption took place on positively charged surfaces, because the

⁎
Corresponding author at: Departamento de Ingeniería Química y Ambiental, Universidad Técnica Federico Santa María, Avenida España 1680, Valparaíso, Chile.
E-mail address: henrik.hansen@usm.cl (H.K. Hansen).

https://doi.org/10.1016/j.jhazmat.2018.09.090
Received 31 August 2017; Received in revised form 28 September 2018; Accepted 30 September 2018
Available online 06 October 2018
0304-3894/ © 2018 Published by Elsevier B.V.
H.K. Hansen et al. Journal of Hazardous Materials 364 (2019) 78–81

Table 1 Table 2
Reaction mechanisms involved in selenium removal using HFOs. Compositional analysis of wastewater from the phenol treatment plant.
Formation of ferrous ions Anodic Reaction: Fe0 2e + Fe+2 (1) Parameter Unit Chilean Standard Wastewater
[14] Cathodic reaction: 2H2 0 + 2e H2 + 2OH (2) N°90/00
Formation of ferric ions 4Fe+2 + O2 + 4H3O+ 4Fe+3 + 6H2 0 (3)
[20] Oil and greases mg/L 20 6.41
Formation of HFOs Fe+3 + 3H2 0 Fe(OH)3 + 3H+ (4) Aluminium mg/L 1 0.180
[14] (5) Arsenic mg/L 0.2 0.0098
Fe+2 + 2H2 0 Fe(OH) 2 + 2H+
Cadmium mg/L 0.02 < 0.01
Adsorption of selenium Fe(OH)3 +SeO-2
3 +H
+ Fe(OH)2 CSeO3 + H2 O (6)
Cyanide mg/L 0.5 0.112
[21]
Copper mg/L 1 < 0.02
Hexavalent chromium mg/L 0.2 < 0.02
Total chromium mg/L 2.5 < 0.02
active sites were strongly protonated [2]. When increasing pH to basic BOD5 mg/L 60 24.8
values (above 8.0), the zeta potential became negative, so active ad- Fluoride mg/L 1.5 0.839
sorption sites were repelled with selenium oxyanions, decreasing the Phosphorous mg/L 5 2.51
Total hydrocarbons mg/L 10 <5
removal efficiency [2,19]. Volatile hydrocarbons mg/L 1 < 0.021
To treat wastewater with the electrocoagulation process, HFOs have Dissolved iron mg/L 10 0.403
to be formed. The suggested reaction mechanisms involved in selenium Phenol Index mg/L 0.5 0.188
removal are detailed in Table 1. It is expected that mainly selenium as Manganese mg/L 2 0.078
Mercury mg/L 0.005 0.0035
Se(IV) will be removed from wastewater because selenite can be ad-
Molybdenum mg/L 0.1 < 0.01
sorbed onto metal oxyhydroxides and Se(VI) presents low adsorption Nickel mg/L 2 < 0.02
and poor precipitation characteristics [4,6] Total Kjeldahl nitrogen mg/L 50 1.05
Previous studies about arsenic removal by EC showed that the re- pH range 6.0-9.0 7.13
moval rate of selenium increases proportionally with the current den- Lead mg/L 0.2 < 0.02
SAAM – Methylene Blue Active mg/L 10 0.181
sity, reducing the treatment time [22,23]. However, for longer periods Substances
of treatment the removal of arsenic was not affected by current density Selenium mg/L 0.01 0.30
[15,24]. The current density depends on the initial concentration of Sedimentable solids mL/L/h 5 <1
contaminants. Arsenic removal treatments at concentrations from 1 to Total suspended solids mg/L 100 12.6
Sulfides mg/L 1 0.042
440 mg L−1 were carried out with current densities between 6.5 and
Zinc mg/L 5 0.037
50 A m−2 [10,24,25]. On the other hand, treatments with higher con-
centrations of arsenic (between 3000–5000 mg L−1) were carried out Selenium (given in bold letters) is the only parameter exceeding the Chilean
with a current density between 170 and 250 A m−2 [11,12,21]. Standard.
Several studies show the effect of sulfate and phosphate on Sb and
As removal by EC. Phosphate has higher adsorptive affinity for active
sites on iron hydroxides than As, [25,27,28]. In the specific case of Se
removal, detrimental effects due to the presence of phosphate and
sulfate have been observed; however, the effect of sulfate is lower than
phosphate, because, the latter can bind strongly with the surface sites of
metal hydroxides while the sulfate bond is weakly [29].
The presence of other pollutants, specifically oxyanions, con-
siderably affects the removal of selenium, since these elements compete
for the active sites of the HFOs [6,17,26]. The main pollutants that
compete with selenium are: PO4−3, CO3−2, SO4−2, SiO3−2, among
others. PO4−3 and SO4−2 have the greatest impact, reducing removal
efficiencies of selenium to lower than 5% in their presence [29].
In the present work, the electrocoagulation process (EC) is pre-
sented as a pioneering and alternative technique for the treatment of
selenium contained in wastewater from an oil refinery.

2. Experimental

The oil refinery wastewater was sampled from the phenol treatment
plant at Empresa Nacional del Petróleo, ENAP Refinería Aconcagua, V
Region of Chile. The composition of the wastewater and the Chilean Fig. 1. Airlift electrocoagulation reactor.
Standard D.S. N°90/00 threshold concentrations [5] are shown in
Table 2.
analysed by the Chilean standard method NCh 2313/30 of. 99. All
The initial concentration of selenium in the wastewater was
analysis were carried out in triplicate. The standard deviation was
0.30 mg L−1, which exceeds the level allowed by the Chilean Standard.
lower than 5% in all cases.
Other substances as phenols and oils/greases, which also are harmful to
The experimental setup is shown in Fig. 1. The reactor was a cy-
the environment, meet the D.S.N°90/00 levels. For this reason, the aim
lindrical acrylic cell with a thickness of 2.5 mm, an internal height and
of the study is focussed on selenium concentration reduction.
diameter of 27 cm and 9.6 cm, respectively. The reactor volume was
For pH adjustment, 6 M NaOH and/or 37% (v/v) HCl of analytical
1 L. Two steel cylinders were placed inside the cell; the outer cylinder
grade were used. The pH was measured by combination pH electrode
and inner cylinder with a diameter of 5.9 cm and 3.3 cm, respectively,
connected to an ORION model 370 pH meter. After each experiment,
both with a height of 8.5 cm. The iron electrodes were placed at 3 cm
the treated wastewater was filtered with glass fibre filters grade A, pore
from the bottom of the cell. Air was injected through a diffuser at the
size 1.5 μm. The selenium content in the filtered wastewater was

79
H.K. Hansen et al. Journal of Hazardous Materials 364 (2019) 78–81

Table 3
Electrical data, residual selenium concentration, energy consumption and pH in
the EC experiments with a current density of 153.4 A m−2 (1.68 A).
Time min 60 120 240 360
Residual Selenium mg L−1 0.20 0.10 0.05 0.03
Initial pH – 5.0 5.0 5.0 5.0
Final pH – 6.7 6.9 7.9 8.0
Voltage V 3.5 3.7 3.9 3.2
Power W 5.88 6.22 6.59 5.37
Energy Wh 5.88 12.43 26.34 32.21
Energy consumption Wh mgSe−1 58 79 105 119

Table 4
Electrical data, residual selenium concentration, energy consumption and pH in
the EC experiments with a treatment time of 240 min.
Current density A m−2 76.7 153.4
Current intensity A 0.84 1.68
Residual Selenium mg L−1 0.15 0.05
Fig. 2. Selenium removal efficiency vs time for a current density of 153.4 A
Initial pH – 5.0 5.0
Final pH – 6.7 7.9 m−2.
Voltage V 2.8 3.9
Power W 2.35 6.59
the liquid phase, to oxidize the ferrous ions (Fe+2) to ferric ions (Fe+3),
Energy Wh 9.41 26.34
Energy consumption Wh mgSe−1 135 105 being possibly the limiting step [12]. On the other hand, EC experi-
ments of arsenic using O2 showed an improvement of 73% with respect
to the use of air as oxidizing medium [11,12]. According to this, the
bottom of the cell, allowing the mixing of the sample. The ratio of oxidizing medium acts as an accelerator of the formation of iron hy-
surface area per volume unit in the cell (S/V) was estimated to be 11 droxides, reducing treatment times and improving removal efficiency.
m2 m−3. For the electrical circuit, a power supply (EXTECH, model Energy consumption as a function of EC treatment time is showed in
382285, 0–120 V DC), a Multimeter (UNI-TREND International Limited, Fig. 3 for a current density of 153.4 A m−2. The increase in the treat-
UT60 Series) and a homemade polarity reversal (PR) device were used. ment time also produces a rise in the used energy per mg of removed
The operational conditions together with the results of the EC ex- selenium. A removal of 90% of the total selenium generates a con-
periments are reported in Tables 3 and 4. Treatment times were 1, 2, 4 sumption of 119 Wh mgSe−1.
and 6 h, and current densities of 76.7 and 153.4 A m−2, were used. pH The efficiencies for selenium removal for different treatment times
was initially adjusted to 5, since selenium removal is reported efficient showed a clear trend and increased to over 90% for longer EC treatment
in a pH range from 4 to 6. The injected air flow was 1.5 L min-1 to times since a stationary value of efficiency has not yet been reached. On
facilitate turbulence and mixing in the reactor. Finally, 4 g L−1 of NaCl the other hand, longer times would probably mean an increase in the
was added to improve the conductivity of the wastewater and, in this energy consumption. It would be desirable to continue the study of
way, the conductivity was increased from 1.14 to 7.42 mS. Hereby, a selenium removal using HFOs, changing the oxidant either to pure
reduction of 85% in the required power for the treatment was obtained oxygen or to hydrogen peroxide, for example. For future research, a pH
by decreasing the ohmic resistance of the solution. All EC experiments control during the treatment recommended to avoid alkalizing of the
were carried out in duplicate. The standard deviations were in all cases solution, which affects the selenium removal in a negative way.
lower than 5%. The iron hydroxide formation reaction (see Eq. (4) in Table 1) is
favored in a pH range between 4 and 6. In addition iron hydroxides are
highly insoluble precipitates (Kps = 10−38) [13,15]; therefore the re-
3. Results and discussion moval of selenium is favored. However, after 4 h of treatment the
aqueous medium became slightly basic, reaching a pH of 8 after 6 h
The efficiencies of selenium removal from wastewater for different (See Table 3); this produces a negative surface charge of the HFOs and
periods of EC treatment are presented in Fig. 2. A selenium removal
efficiency of 90% was obtained for 360 min of treatment with a current
density close to 153 A m−2. The removal efficiencies using the same
current density, but 60 and 240 min of EC treatment were 33.3% and
83%, respectively.
Other authors have reported selenium removal efficiencies of about
90% the treatment of wastewater from copper industry by EC with an
initial concentration of selenium of 5 mg L−1 using a treatment time of
20 min and a current density 50% lower than that used in this work
[10]. The above indicates that other chemical species contained in the
wastewater have a significant effect on the process, due to the com-
petition for active binding sites of iron hydroxide formed in EC process
[6,17]. The wastewater from a petroleum refinery contains traces of
oxyanions, such as: PO4−3 and SO4−2, which are compounds that may
affect the selenium removal [29]. Thus, there are competitive reactions
in the presence of these oxyanions, in which adsorption of PO4−3 and
SO4−2, are favored over selenium [29], requiring higher treatment
times.
The used oxidizing medium could be a limitation of the process,
since the oxygen present in the air must diffuse from the gas phase to Fig. 3. Energy consumption vs time for a current density of 153.4 A m−2.

80
H.K. Hansen et al.
Fig. 4. Selenium removal efficiency vs current density for 240 min of treatment.
thereby the repulsion of the contaminants, resulting in a decrease in
selenium removal.
In order to study the effect of the current density on the process,
current densities of 76.7 and 153.4 A m−2 for 240 min of treatment
were used. Results are presented in Fig. 4. The results show a clear
impact of the current density on the selenium removal. There is a clear
trend, which indicates the necessity to reach a certain value for the
current density, over which an efficient selenium removal would occur.
In this way, for the lowest current density applied only small amounts
of precipitates were observed. In order for electrochemical reactions to
take place (formation of iron hydroxides) and selenium to be removed
from the wastewater, a minimum energy must be applied to the system
in the form of work to overcome “resistances” such as Nernst potential,
over potential, and concentration polarization [30,31]. In this work,
when a fixed current of 1.68 A was applied, the voltage in the cell was
3.46, 3.70, 3.90 and 3.18 V, for treatment times of 60, 120, 240, and
360 min, respectively (see Table 3). This is equivalent to an average
potential 25% higher than the theoretical minimum required (2.82 V),
meaning that the necessary treatment reactions could take place in the
reactor. In the case of a current of 0.84 A, the voltage drop across the
cell just reached the minimum required and therefore only low Se re-
moval was observed.
4. Conclusions
Electrocoagulation (EC) of wastewater from a petroleum refinery is
a promising tool to remove selenium by adsorption and/or co-pre-
cipitation with iron hydroxides. With the use of a batch airlift reactor a
selenium removal of 90% was achieved after 6 h of treatment, with a
residual concentration of 0.03 mg L−1. However, local limits, as well as
US-EPA, allow a maximum concentration of 0.01 mg L−1.
The general trend of removal efficiency versus time indicates that it
would be possible to obtain higher efficiencies with longer treatment
times; however, the increase in removal efficiency is higher for shorter
times. The energy consumption increases in a similar manner as the
removal efficiency.
For the studied wastewater, the increase in the current density has a
notorious effect on the removal efficiency, since for 240 min of treat-
ment, when the current density is increased from 76.7 A m−2 to 153.4 A
m−2, the removal efficiency is almost doubled. EC experiments with
additional treatment times have to be studied in the future.
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