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Faculty of Natural and Exact Sciences, University of State of Rio Grande do Norte, CP 70, 59620-625 Mossor, RN, Brazil
Institute of Chemistry, Federal University of Rio Grande do Norte, Campus Universitrio s/n, CEP 59078-970 Natal, RN, Brazil
h i g h l i g h t s
and BDD removes efciently the dissolved organic matter from PW.
DSA
a r t i c l e
i n f o
Article history:
Received 26 February 2013
Received in revised form 6 August 2013
Accepted 9 August 2013
Available online 16 August 2013
Keywords:
Electrochemical treatment
Boron-doped diamond
Dimensionally stable anode
Produced waters
Direct oxidation and indirect oxidation
a b s t r a c t
This study compares the anodic oxidation of three classes of produced water (PW) (fresh, brine and saline) generated by petrochemical industry using Ti/IrO2Ta2O5 and BDD electrodes in a ow reactor. During electrochemical treatment, various operating parameters were investigated, such as temperature, pH,
conductivity, current density, total organic carbon (TOC), chemical oxygen demand (COD) as well as
energy consumption and cost. When both electrodes materials are compared under the same operating
conditions, higher TOC and COD removal efciencies were achieved for BDD anode, nevertheless, the
energy consumption and cost were higher when compared with the values estimated for Ti/IrO2
Ta2O5. Different Cl concentrations in the efuents promoted the electrogeneration of strong oxidant species, such as chlorine and hypochlorite, increasing the efciency of treatment. These results encourage
the applicability of this method as a pre-treatment process for the petrochemical industry, reducing depuration time.
2013 Elsevier B.V. All rights reserved.
1. Introduction
The petrochemical companies deal with problems of difcult
solution in relation to activities aimed at environmental protection, due to the generation of large amounts of waste during oil
prospecting and exploitation, such as produced water (PW). The
amount of this kind of waste varies depending on the oil reservoir:
a new basin produces 515 vol.%, while at the end of its lifetime it
reaches 7590 vol.% [1].
PW contains with different pollutants, such as heavy metals
(Cd, Cr, Cu, Pb, Hg, Ag, Ni, Zn), organic compounds, and dissolved/suspended solids. Benzene, toluene, xylene, phenol, halogenated aromatic compounds, chloroform and trichloroethylene are
Corresponding author. Tel.: +55 8433153011.
E-mail address: suelycastro@uern.br (S.S.L. Castro).
1385-8947/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.08.023
48
2. Experimental
2.1. Produced water samples and chemicals
The PW samples (fresh, brine and saline) were supplied by
Petrobras Plant in Rio Grande do Norte, northeastern region of
Brazil. The characteristics of the efuents samples were analyzed
Table 1
Results of physical and chemical analyzes of PW samples.
Analytical parameters
PW fresh
PW brine
PW saline
Temperature (C)
pH
Conductivity (mS cm1)
COD (mg dm3)
Salinity (mg dm3)
Chloride (mg dm3)
TOC (mg dm3)
Benzene (lg dm3)
Toluene (lg dm3)
Ethylbenzene (lg dm3)
o-Xylene (lg dm3)
40.2
6.87
0.61
250
78.8
47.8
458
6.45
5.48
28.2
5.81
42.0
7.83
5.16
700
2593
1573
1186
5.45
7.02
37.2
4.86
40.1
7.03
143.9
11,541
143170
86,875
15,015
4.35
6.89
7.20
5.86
Limits permitted by Brazilian legislation (mg dm3): benzene = 1.2; toluene = 1.2;
ethylbenzene = 0.84 and xylene = 1.6.
49
where TOCi and TOCf are the initial and nal TOC measurements,
respectively.
The energy consumption per volume of treated efuent was
estimated and expressed in kW h dm3. The average cell voltage
during the electrolysis was taken into consideration for estimation
of the energy consumption the following equation.
EC DEC It=1000V
where t is the time of electrolysis (h), DEC is the average cell voltage
(V), I is the electrolysis current (A) and V is the sample volume
(dm3).
Taking into consideration the electrical energy cost of about US$
0.15 (U.S. currency) per kW h, the monetary value required to
degrade a unit volume of efuent is given by the following
equation:
3
3
Table 2
Average concentration of inorganic species in the PW samples before and after electrochemical treatment.
a
b
c
Inorganic species
(mg dm3)
Fresh PW
Before
After (Ti/IrO2
Ta2O5)a
After
(BDD)a
Before
After (Ti/IrO2
Ta2O5)b
After
(BDD)b
Before
After (Ti/IrO2
Ta2O5)b
After
(BDD)b
Barium
Boron
Calcium
Strontium
Iron
Magnesium
Manganese
Potassium
Sodium
1.23
6.78
384.56
26.52
4.78
3.90
1.20
15.56
405.58
c
6.48
89.42
11.84
2.45
c
c
6.48
123.59
c
5.89
88.0
10.0
2.78
c
c
6.85
118.78
5.42
12.35
459.30
148.7
5.57
23.29
1.54
22.51
615.90
c
12.28
283.20
145.2
2.36
2.27
c
158.5
5199
1.08
8.88
449.30
157.8
1.57
2.78
c
43.87
1194
4.89
15.35
23,880
98.71
9.57
33.29
2.54
56.51
515.90
c
10.62
9256
45.8
5.56
32.72
c
45.31
1059.3
2.58
8.56
459
109.8
2.78
12.6
c
c
854.6
5 mA cm2.
20 mA cm2.
Below detection limit of technique.
Brine PW
Saline PW
50
BDD is a non-active anode at which the principal reactive species is hydroxyl radicals, whereas Ti/IrO2Ta2O5 is an active anode
that depends mostly on the higher oxide mechanism. At Ti/IrO2
Ta2O5 electrode, the oxidation process depends on direct and mediated oxidation [3,5,40] for removing organic matter. During direct
oxidation, adsorption of organic compounds and by-products on
the anode surface plays an important role in the electrochemical
oxidation process, and these chemical mechanisms can reduce
the anode efciency [3,10].
The surface of active anode, as Ti/IrO2Ta2O5, strongly interacts
with OH produced during water electrolysis (H2O ? OH + H+ + e).
Metal cations in the oxide lattice may reach higher oxidation
states, so-called superoxide (MOx), participating as a mediator in
the oxidation of organics, which competes with the side reaction
of oxygen evolution via chemical decomposition of the higher
oxide species. Consequently, both hydroxyl radicals and higher
oxide formed on anode surface (Ti/IrO2Ta2O5(OH/MOx)) promote
the electrochemical conversion of organic matter dissolved in fresh
PW to other oxidized compounds [41,42].
Another interesting feature of the electrochemical treatment of
fresh PW is that this petrochemical efuent contains with
47.8 mg dm3 of chloride, and it probably participates in the electrogeneration of active chlorine. In fact, analyzing the solution pH,
originally around 6.87, it moderately increases to values of 7.1.
Thus, ClO will prevail during the electrolysis, but HClO can be active at the electrode surface, as a consequence of the large acidity
(pH is slightly acidic) due to the concomitant oxygen evolution, as
indicated previously by other authors [3]. Based on results
reported in Fig. 1and 1S, we can assume that, using
51
52
trode after 3.5 and 7 Ah dm3, respectively (Fig. 4S(a)). Nevertheless, an important observation from inset in Fig. 4a is that the
mineralization rate (TOC removal) seems not to be signicantly
inuenced by the higher concentrations of chloride in the petrochemical efuent, suggesting that the production of Cl2 is the preferential reaction (based on literature [43], DSA-electrodes are good
electrocatalysts for Cl2 production) instead the electrochemical
oxidation (direct or/and indirect). At the same time, the Cl-mediated oxidation does not lead to the strong oxidation conditions
necessary to eliminate completely the organic matter, but forming
recalcitrant compounds giving a false COD abatement. This outcome is conrmed by TOC removal efciencies, below 37%.
Likewise, for BDD anode, the COD removal, under similar conditions, occurs with similar efciencies than those achieved for Ti/
IrO2Ta2O5. As can be observed from Fig. 4b, 44% of COD removal
was achieved for BDD independent on applied current density
due to two features: higher Cl concentrations (86,875 mg dm3)
and higher initial COD (11,541 mg dm3).
From the information discussed above, it can be inferred that
the degradation process when higher Cl concentrations are present in the efuent, it occurs with signicant formation of Cl2 gas
in concomitance with higher production of O2, complicating the
complete oxidation of organic matter (see inset in Fig. 4b, TOC removal) and increasing the Q (3.5 Ah dm3 (10 mA cm2) and
7 Ah dm3 (20 mA cm2), see Fig. 4S(b)). Also, higher initial COD
is traduced in the production of several by-products decreasing
the efciency process [5]. This assertion is in agreement with the
TOC efciencies obtained during electrochemical treatment of
saline PW by applying 10 and 20 mA cm2 of current density.
These statements are important observations, because these demonstrate that for some kind of petrochemical efuents, no efcient
53
elimination of organic matter can be achieved, independent on nature of electrode material and experimental conditions used. But, as
pointed by Sales et al. [10], the electrochemical oxidation of industrial efuents in presence of higher concentrations of chloride may
lead to more toxic pollutants (organochloride by-products). In this
frame, the treatment of saline PW can be performed by using combined advanced oxidation processes, such as ltration, adsorption,
electrochemical and UV-radiation [46].
and conrmed by the decrease of conductivity. These results indicated that electrochemical treatment technology could be also
used for removing inorganic species from petrochemical wastewaters (Table 2). However, an integrate treatment (anodic oxidation
and electrocoagulation) could be planned in order to increase the
efciency and decrease the energy consumption.
Due to the high toxicity of BTEX, which can cause irreparable injury to the central nervous system even in small concentrations,
Brazilian environmental laws have been strongly restrictive
regarding the releases of these contaminants in the aquatic environments [3,5,39]. From the data obtained by GCMS analyses,
electrochemical treatment proved to be very effective for removing
BTEX in operating conditions using Ti/IrO2Ta2O5 and BDD. For all
PW efuents (fresh, brine and saline), these pollutants were completely removed, obtaining results below the detection limit of
the method (0.5 ppb). On the other hand, the variation of inorganic
species concentration dissolved in the PW after electrochemical
process using Ti/IrO2Ta2O5 and BDD anodes, under specic experimental conditions, is present in Table 2. As can be observed, the
initial amount of inorganic species was removed from petrochemical wastewater after the electrochemical treatment. It appears
that the OH species produced during electrolysis of water, favor
the formation of hydroxides with some heavy metals. These inorganic compounds are deposited on the cathode forming a salt deposit, as observed at this electrode after electrolysis treatment;
Table 3
Cost required for electrochemical treatment of fresh, brine and saline PW, as a
function of temperature and applied current density, after 2, 4 and 8 h of treatment,
respectively; according to the energy requirements obtained in Figs. 57.
PW
Electrode
j (mA cm2)
T (C)
Fresh
Ti/IrO2Ta2O5
1
2.5
5
5
1
2.5
5
5
25
25
25
40
25
25
25
40
0.05
0.17
0.56
0.36
0.07
0.24
0.70
0.51
10
20
30
20
10
20
30
20
25
25
25
40
25
25
25
40
1.90
7.74
14.76
4.77
2.51
7.51
15.08
4.30
10
20
10
20
25
25
25
25
0.03
0.11
0.05
0.17
BDD
Brine
Ti/IrO2Ta2O5
BDD
Saline
Fig. 5. Evolution of the energy consumption against% of COD removal during
electrochemical treatment of fresh (a) and brine (b) PWs on Ti/IrO2Ta2O5 and BDD
anodes. Insets: evolution of the energy consumption, as a function of temperature
and anode material.
Ti/IrO2Ta2O5
BDD
54
4. Conclusions
The study showed that the anodic oxidation can be an alternative treatment for COD and BTEX removal from petrochemical
efuent. Both electrode materials showed satisfactory results in
the oxidation process and it could be carried out by both direct
and mediated oxidation by powerful oxidants agents produced
on anode surface, using specic operating conditions.
The treatment efciency of petrochemical efuents shown to be
strongly dependent on nature of efuent and anode materials as
well as operating conditions, such as current density, chloride concentration and temperature. Consequently, the energy requirements can be traduced on lower costs of electrochemical
treatment, depending strongly on experimental conditions. It is
important to remark that, each efuent is different, for that reason,
when different concentrations of Cl are present; other undesired
by-products could be produced, as already conrmed by other
authors in a recent study [10].
Perhaps the production of undesired by-products, such as
organochloride compounds, can vary and it depends on Cl concentration into the real efuent. Then, particular attention and experimental observations must be taken into consideration before or
during the treatment of brine and saline PWs.
Finally, in the present work have recently allowed to start the
design of a pilot industrialelectrochemical cell to be used in petrochemical industry. These experiments are in progress and their
results will be reported in detail in a separate paper in a near
future.
Acknowledgments
Fig. 7. Evolution of the energy consumption, as a function of% COD removal, during
electrochemical treatment of fresh, brine and saline PWs on Ti/IrO2Ta2O5 and BDD
anodes, at 25 C.
decrease on power energy will be traduced on a decrease on treatment costs of brine PW (Table 3). These gures are in agreement
with the data reported in the literature, where it was demonstrated
that the electrochemical treatment is performed at lower potentials in the presence of chlorides, compared with those required
for the direct anodic oxidation [47], diminishing the energy consumptions and costs.
For the treatment of saline PW efuent, the results obtained at
both electrode materials demonstrated that, higher energy consumptions were achieved (Fig. 6), independent on anode material
and applied current density, obtaining lower COD removal efciencies (about 50% at both electrode materials). However, Ti/IrO2
Ta2O5 electrode by applying 10 mA cm2 at 25 C showed lower
energy requirements than those obtained at BDD anode. This
behavior is due to lower cell potentials (3.5 V and 4.4 V for 10
and 20 mA cm2, respectively) using Ti/IrO2Ta2O5 anode [43],
favoring principally the production of Cl2 [47]. Conversely to BDD
electrode, where higher cell potentials were attained (7.9 V and
9.9 V for 10 and 20 mA cm2, respectively), producing Cl2 in concomitance with O2, limiting the oxidation of organic matter.
A general comparison between the trend of energy consumption, as a function of% of COD removal, for Ti/IrO2Ta2O5 and
BDD anodes is presented in Fig. 7. This graph clearly evidences that
the brine PW requires more energy consumptions that those used
for treating fresh and saline PWs. Also, in the case of BDD, it allows
to remove a signicant% of COD employing lower energy requirements that those required at Ti/IrO2Ta2O5, at different petrochemical efuents. However, when an increase on the
temperature is attained, Ti/IrO2Ta2O5 anode exhibits better performances (see insets in Fig. 5a and b).
A.J.C. da S. and E.V. dos S. gratefully acknowledge for CAPESMaster and PhD-PETROBRASPFRH22 fellowships, respectively.
The authors thank Industrie De Nora S.p.A. (Milan, Italy) for supply
the electrodes and PETROBRAS for providing the PW samples.
Financial support from National Council for Scientic and Technological Development (CNPq, Brazil) is also gratefully acknowledged. The authors thank to Prof. Djalma Ribeiro da Silva for his
assistance for performing the analyses of petrochemical efuents
at the Ncleo de Processamento Primrio e Reuso de gua Produzida e Residuos (NUPRAR-UFRN).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2013.08.023.
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