ISSN 0965-5441, Petroleum Chemistry, 2017, Vol. 57, No. 5, pp. 457–465. © Pleiades Publishing, Ltd., 2017.

Published in Russian in Neftekhimiya, 2017, Vol. 57, No. 3, pp. 346–354.

Electrochemical Degradation of Petroleum Hydrocarbons (PAHS)

from Synthetic Aqueous Solutions1
Asim Yaquba, *, Mohamed Hasnain Isab, **, Huma Ajabc, ***, and Muhammad Junaidd, ****
a
Department of Environmental Sciences, COMSATS Institute of Information Technology Abbottabad, Pakistan
bDepartment of Civil and Environmental Engineering, Universiti Teknologi PETRONAS,
Bandar Seri Iskandar 32610, Perak, Malaysia
cDepartment of Chemistry, COMSATS Institute of Information Technology Abbottabad, Pakistan
d
Computer Sciences Department, University of Haripur, KPK Pakistan
*e-mail: environment_green@yahoo.com
**e-mail: hasnain_isa@yahoo.co.uk
***e-mail: humaajab@hotmail.com
****e-mail: mjunaid@uoh.edu.pk
Received October 3, 2016

Abstract⎯Water separated from crude oil and wastewater discharge from petroleum oil refineries contains
significant quantity of dissolved hydrocarbons. Polycyclic aromatic hydrocarbons (PAHs) are major toxicants
in wastewater of refineries. It is difficult to treat wastewater containing PAHs due to their recalcitrant property
and low solubility. Conventional techniques for the treatment of wastewater are still a concern of toxicity.
Electrochemical oxidation process has been found to be a favorable for treating wastewater. Electrodes with
high stability and electrocatalytic activity are important factors for a successful electrochemical oxidation of
toxic organics in wastewater. In this study titanium anodes were coated with tin, antimony and iridium oxide
mixture from their respective salts by thermal decomposition method. FESEM and XRD used for surface
characterization of Ti/SnO2–Sb2O5–IrO2 anode. Quantification of PAHs was done using GC–MS. Results
confirm the presence of respective oxides on anode surface. Their electrocatalytic capability was tested for
degradation of 16 priority PAHs in aqueous solution. Results reveal the complete degradation of naphthalene,
acenaphthylene, acenaphthene and fluorene without using NaCl electrolyte. While in the presence of NaCl
naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene
were completely removed. About 98% of total PAHs removal was found at all initial pH values 3, 6, and 9 in
the presence of electrolyte. Current study will be helpful in improving quality of petroleum industry wastewa-
ter containing PAHs.

Keywords: PAHs, electrochemical, degradation, SnO2–Sb2O5–IrO2

DOI: 10.1134/S0965544117050140

INTRODUCTION sote) is further donors of anthropogenic PAHs to the

PAHs are hydrocarbons containing two or more
benzene rings in their structure. Oil refineries wastes
and spills are major sources of PAH in water and
marine environments. However, PAHs penetrate into
the environment due to incomplete combustion of
solid waste, forest fires, internal combustion engines,
wood stoves, and coal coking. Significant amount of
16 priority PAHs were reported in marine environ-
ment ranged from 0.80 to 18.34 μgL–1 in sea water,
113.50 to 3384.34 ngg−1 in sediments, 3.99 to
46.64 ngg−1 in fish liver and 3.11 to 17.76 ngg−1 in gill
tissues [1]. Domestic sewage, storm-water runoff,
landfills; the wood preservative industry (e.g., creo-
1 The article is published in the original.
environment [2]. Their biodegradability is very slow in
the aqueous environment under aerobic conditions.
Increasing the number of aromatic rings drastically
decreases biodegradation rates. In soil, the measured
half-lives for the particular compounds vary widely,
from about 100 days to a couple of years [3].
The PAHs removal from water is challenging
because of their low solubility and stubborn nature but
it can be accomplished by chemical advanced oxida-
tion, biological degradation and electrochemical oxi-
dation [4–6]. Among them electrochemical oxidation
process has attracted wide attention as one of the envi-
ronmentally-friendly technologies. The most com-
mon electrodes mentioned in literature for PAHs deg-
radation in aqueous media were titanium based
Ti/Pt90–Ir10 anode [7], Ti/RuO2 [8], and Ti/Pt [9].

457
458 YAQUB et al.
Application of dimensionally stable anodes (DSA) for
wastewater treatment has led to technological enlarge-
ments, thus decreasing operating and installation
costs. IrO2 coated on titanium plate has attracted a lot
of attention in commercial application of dimension-
ally stable anodes (DSAs) due to its stability and lon-
ger service life [5]. It had been reported that the pres-
ence of an IrO2 with SnO2–Sb2O5 oxides increases the
service life of working electrodes during oxygen evolu-
tion reaction [10]. Ti/SnO2–Sb2O5–IrO2 had been
successfully applied in electrochemical oxidation of p-
chlorophenol [11], salicylic acid and salicylaldehyde
[12] decolorization of methyl orange dye [13] and pro-
duced water treatment [14].
The objectives of the present study are to investi-
gate the surface morphology of SnO2–Sb2O5–IrO2
oxides coated titanium and their electrocatalytic capa-
bility towards PAHs degradation in synthetic aqueous
solution.
EXPERIMENTAL
Electrode Coating
Coating of metal oxides on Ti metal plates was
done by thermal decomposition method [15]. The size
titanium plate was 2 mm × 80 mm × 10 mm. Follow-
ing steps were involved for pre-treatment of titanium
plate.
(i) Wash with distilled water and dry.
(ii) In order to remove oxides from the surface Ti
plate was etched by immersing it in HCl (18%) for 10
min at 80°C.
(iii) Ti plate was again washed with distilled water
after etching process.
Coating materials (CM) SnCl4, SbCl3 and IrCl3 ⋅
xH2O were used for to prepare coating solution. Eth-
ylene-glycol (EG) was used as solvent of solution in 10
and 2 mL Acetic acid (AA) was added as chelating
agent. Three solutions were prepared using 2 mL
SnCl4, 2 g SbCl3 and 0.1 g IrCl3 ⋅ xH2O at 60°C for 1 h.
Precursor solution was finally prepared by mixing
three solutions in proportion of 80 : 15 : 10 (SnCl4 :
SbCl3 : IrCl3 ⋅ xH2O). Precursur solution was applied
20 times on a degreased and etched Ti plate. Plate was
dried at 200°C for 10 min after each application of the
solvent and dried at 500°C for 10 min after 10 applica-
tions. To remove organic contents from the surface,
plate was heated at 600°C for 1 h [15].
Electrochemical Cell
Electrochemical experiments were performed in an
electrochemical cell of 100 mL volume. Ti/SnO2–
Sb2O5–IrO2 was used as a working electrode (anode)
and Ti plate as a counter electrode (cathode). Both
were connected to a DC power supply. All experiments
were conducted in Galvanostatic conditions. The
electrodes inter-distance was 2.5 cm. Applied current
density was 3.33 mA/cm2 and electrochemical experi-
ment time was 4 h.
Sample Preparation
Synthetic samples of 16 priority PAHs were pre-
pared in the lab from Accu-Standard® (2 mg/ml in
dichloromethane/benzene). Stock solution of
100 μg/L PAHs was prepared in dichloromethane.
Synthetic samples were prepared from stock solution
of PAHs in distilled water by continuous stirring for
24 h. Effects of initial pH were studied at three pH val-
ues (3, 6, and 9). Initial pH of the solution was adjusted
using molar solutions (1M) of sulfuric acid and
sodium hydroxide. NaCl (1 g/L) was added to check
the effect of electrolyte. Separate experiments were
conducted for each initial pH (3, 6, and 9) without
using electrolyte and with electrolyte.
Extraction Procedure
PAHs were extracted by Liquid-Liquid Extraction
Gas Chromatography Mass Spectroscopy Method
[16]. Extraction of PAHs was done by using dichloro-
methane DCM (99.9% pure Merck) as extraction sol-
vent.
For serial extraction of PAH, 100 mL water sample
was extracted thrice with 12.5, 5, and 5 mL DCM,
12.5 mL DCM was added and vigorously shaking for
10 minutes on an orbital shaker. Mixture was then
transferred into a separatory funnel and allowed to set-
tle for 10 min, solvent layer was separated from aque-
ous layer and collected in a conical flask. In the
remaining aqueous sample, 5 mL DCM was added
again followed by shaking of the separatory funnel and
collection of the separated solvent in the conical flask.
This procedure was repeated with 5 mL DCM. After
separation, the collected solvent was filtered through
anhydrous Na2SO4 in order to eliminate all traces of
water. DCM was evaporated using a rotary evaporator
at set at pressure 660 mm of Hg, rotation 40 rpm and
temperature 60°C. In the rotary evaporator sample
was concentrated to 0.5 mL volume and finally topped
up with acetonitrile to a final volume to 1 mL in sam-
ple vial for GC/MS analysis [14]. All 16 PAHs were
distinctly measured using a five-point calibration of
mixed standard solutions.
Limit of detection (LODs) proposed method was
calculated on the basis of LOD = 3.3 (σ/S) [σ is the
standard deviation of PAHs concentrations in balnk
solution replitcates and S is the slope of the calibration
curve taken from PAHs standards]. The LODs and
percentage recoveries for each PAHs are presented in
Table 1.
PETROLEUM CHEMISTRY Vol. 57 No. 5 2017