Journal of Sedimentary Environments

Published by Universidade do Estado do Rio de Janeiro

4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

OIL PRODUCED WATER TREATMENT USING ADVANCED OXIDATIVE PROCESSES:

HETEROGENEOUS-PHOTOCATALYSIS AND PHOTO-FENTON

PRISCILA CHRISTOPOULOS SILVA1, NATHÁLIA PEREIRA FERRAZ1, ELEN AQUINO PERPETUO1 AND YVAN JESÚS OLORTIGA
ASENCIOS1*

1 Universidade Federal de São Paulo, Instituto do Mar, Campus Baixada Santista, São Paulo, Brazil

* CORRESPONDING AUTHOR, [email protected]

Citation:
Received on 30 August 2018
Received in revised form on 20 March 2019 Christopoulos Silva, P., Ferraz, N.P., Perpetuo, E.A., Asencios,
Accepted on 22 March2019 Y.J.O., 2019. Oil Produced Water treatment using Advanced
Oxidative Processes: Heterogeneous-Photocatalysis and Photo-
Editor: Wânia Duleba, Universidade de São Paulo, Brazil Fenton. Journal of Sedimentary Environments, 4 (1): 99- 107.

Abstract

The Oil Produced Water (OPW) is an effluent produced (254nm); aiming to find the suitable conditions for OPW
during the oil extraction process. Owing to its complex treatment. The results showed an efficiency of 99% for
composition and toxicity it must be treated by wastewater phenol removal, despite the high content of salts present in
treatment technologies. However, traditional facilities may seawater. In the treatment of the two effluents by the
be unable to remove all the anthropogenic or naturally AOPs, the reaction reached chemical equilibrium in 1 h
occurring compounds. This can result in their discharge to under UV irradiation (254 nm); the best pH to treat the
surface water and ultimately affecting the sedimentary effluents was pH 7, in the presence of H2O2 (0.3%v/v) and
environment. The present work shows the application of by increasing temperature to 75°C (in the case of the real
two Advanced Oxidative Processes (AOPs), Photocatalysis sample of OPW). The results of this work show that the
and Photo-Fenton to treat two kinds of effluents: phenolic two studied AOPs can be used in the oil industry, for OPW
solution made in seawater, and a real sample of OPW from treatment and to treat effluents (with high salinity)
Rio Grande do Norte, Brazil. Two commercial catalysts were contaminated with phenol, to remove organic compounds
used: TiO2 (for Heterogeneous-Photocatalysis process), and in order to reduce their toxicity, and consequently assist
FeSO4.7H2O (for Photo-Fenton process). The catalysts were towards a better quality of the sedimentary environment.
characterized by X-Ray Diffraction Analysis (XRD), and The best results were obtained by the Photo-Fenton
Diffusive Reflectance Spectroscopy (DRS). In the two AOPs process.
the following parameters were evaluated: initial pH of
effluent (acid, neutral and alkaline), presence of H2O2 Keywords: Contaminants. Treatment. Oil Produced Water.
(0.3%v/v) and time under ultra-violet (UV) irradiation Seawater. Phenol. Advanced Oxidative Processes (AOPs).

have a variable composition, but often, barium and iron are the
1. Introduction major elements (Ray and Engelhardt, 1992).
During the extraction of oil in offshore operations, the The oil contained in the OPW can be classified into three
water that reaches the surface is called: Oil Produced Water fractions: dispersed oil, oil-in-water or water-in-oil emulsions,
(OPW), defined as a mixture of water, salts, suspended solids, and dissolved organic compounds (Liu et al., 2016). The first
organic compounds, heavy metals, microorganisms and two can be removed by gravity or hydrocyclone (after
dispersed oil droplets (Judd et al., 2014; Cheriyan and demulsifier addition), but the residual oil droplets and
Rajagopalan, 1998). The organic compounds present in OPW dissolved organic compounds (including aromatic
include: benzene, toluene, ethylbenzene, xylene, naphthalene, compounds and polycyclic aromatic hydrocarbons) remain
phenanthrene, dibenzothiophene, polyaromatic hydrocarbons unchanged.
(HPA), phenols, gases and heavy metals (Judd et al., 2014; The occurrence of aromatics is of great concern because of
Neff, 2002). Present in the OPW are also ions, such as Na+, their high resistance to biodegradation, toxicity to marine biota,
K+, Mg 2+, Ca2+, Cl-, SO-2, HCO3-1 and some heavy metals, and possible carcinogenicity and mutagenicity (Jing et al., 2014).
such as Cd, Mn, Hg, Zn, Fe, Cr and Cu; furthermore, metals The treatment of OPW is necessary due to the large volumes
99
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

that are generated during the production of crude oil and, (OPW). Thus, it is possible to affirm that applications of
especially, due to the impacts that it causes to the environment photocatalysis to the degradation of organic compounds in
when it is improperly discarded. These impacts, include seawater and in OPW, are topics not well studied, yet.
biological effects on marine pelagic ecosystems, causing: In this context, considering that depollution of water leads
endocrine, non-endocrine and reproductive problems (Bakke to a better quality of the sedimentary environment; the aim of
et al., 2013). In Brazil, according to the Exploration and this study was to investigate the degradation of organic
Production Database (of the National Agency of Petroleum), compounds in OPW using two AOPs: Heterogeneous-
the average OPW production in 2017 was around 3.7 million Photocatalyst and Photo-Fenton. Two effluents were used
bbl/day and oil production was approximately 2.4 million for this study. The first effluent was a phenolic solution made
bbl/day, considering the Brazilian onshore and offshore in seawater, in order to simulate an OPW. Phenol was used
production. In Brazil, the Resolution, nº 393/2007 of the as a model molecule representing the aromatic fraction of
National Environmental Council (CONAMA) establishes that crude oil (aromatic alcohols are highly soluble in water). The
the monthly average limit of Total Oils and Greases (TOG) in use of seawater is justified by considering that the high
OPW (for discard) is 29 mg.L-1. content of salts is similar to that present in OPW, and,
Numerous OPW treatment technologies have been moreover at longer reservoir lifetimes, seawater may
developed (including hydrocyclone, filtration, adsorption and predominate the composition of OPW since it is used as fluid
osmosis) that allow for injection, discharge to the land surface of injection into the reservoir (Ray and Engelhardt, 1992; Jing
(if managed correctly), or beneficial reuse (Ahmadun et al., et al., 2014). The other effluent analyzed in this study was a
2009; Carvalho, 2016). However, traditional facilities may be real sample of OPW collected from an oil company located
unable to remove all the contaminants contained in OPW. in Rio Grande do Norte, Brazil. For the two AOPs two
This can result in their discharge to surface water and commercial catalysts were used: TiO2 and FeSO4.7H2O. The
ultimately affecting the sedimentary environment. initial pH of effluents and irradiation time under UV light
Advanced Oxidative Processes (AOPs) are used for the were varied in order to identify the best conditions for the
degradation of contaminants in water. In Heterogeneous- OPW treatment by AOPs.
Photocatalysis (an AOP), a semiconductor, for example: TiO2,
is activated by UV or visible radiation. The semiconductor is
characterized by conduction bands (CB) and valence bands 2. Materials and Methods
(VB), the energetic region between bands is known as band- 2.1 Catalysts
gap energy (Ebt). The absorption of photons with energy
(E= h.v, where h is the Planck’s constant and v is the Two commercial catalysts were used: TiO2 (Synth 99,99%
photon’s frequency) greater than Ebt, promotes an electron P.A.) for the Heterogeneous-Photocatalysis and
FeSO4.7H2O for the Photo-Fenton. Both were characterized
from the valence band to the conduction band (e-) generating by X-Ray Diffraction (XRD) in a Rigaku miniflex
an electron-hole in the valence band (h-; Ibhadon and diffractometer (30 Kv-10mA) with scanning from 5º to 80º.
Fitzpatrick, 2013) (Equation 1): The crystalline structures were identified considering the
− − International Center of Diffraction Database (ICDD). The
Semiconductor + h.v (>𝐸𝑏𝑔 ) → 𝑒𝐶𝐵 + ℎ𝑉𝐵 (1) average crystallite sizes were determined from XRD line-
However, if electrons (𝑒𝐶𝐵 −
) and electron-holes (ℎ𝑉𝐵 −
) broadening measurements using the Scherrer Equation
migrate to the surface of the semiconductor without (Jenkins and Snyder, 1996): d= k.λ/(βhkl.cosθ), where d is the
recombination, they can participate in several oxidation average crystallite size, k is the shape factor, taken as 0.89, λ
reactions. In the oxidation of organic compounds in water the is the wavelength of CuKα radiation, βhkl is the full width at
electron-holes (ℎ𝑉𝐵 −
) present on the surface of the half maximum (FWHM) of the particular peak and θ is the
semiconductor induce the oxidative decomposition of Bragg’s angle.
adsorbed organic molecules. These electron-holes can also The catalysts were also characterized by diffuse
react with water molecules (and also with the -OH ions present reflectance spectroscopy (DRS) in a Cary 5E Spectrometer
in the water) to produce the hydroxyl radical (•OH). This •OH, (200 to 800nm). The band-gap energy (eV) of the catalyst was
quickly attacks organic pollutants in the solution leading to provided by the steep linear extrapolation part from the
mineralization (CO2 and H2O) (Nogueira and Jardim, 1998). absorption profile obtained in DRS, as described in the
A simple search in the Scopus database, using the literature (Wood and Tauc, 1972).
keywords: “seawater”, “photocatalysis”, reported that
between 1997 and 2018, only 60 scientific papers on this
subject were produced worldwide. The number of papers is 2.2 Effluents
even smaller when the search is restricted to the keywords: The effluents were identified as the following:
seawater, photocatalysis and phenol. The same occurs with
the terms: photocatalysis, catalysis, Oil Produced Water − Phenol in seawater: a stock solution of phenol (46 mg.l-1) was
100
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

prepared using seawater as solvent; the fresh seawater FeSO4.7H2O photocatalyst (Fig. 1b) is present as a single
was collected from a clean and preserved region of the monoclinic phase (PDF 25-0409), with unit cell parameters:
beach in Guarujá city (São Paulo State, Brazil) and a= 7.624 Å, b= 7.648 Å and c= 7.123 Å. Additionally, the
passed through a filter membrane (cellulose) of 0.22 average crystallite size calculated by the Scherrer equation
µm. (Jenkins and Snyder, 1996) was 23 nm. According to the
− Oil Produced Water (OPW): a real sample of OPW Diffuse Reflectance Spectroscopy (DRS) analysis, the band-
obtained from an oil company located in Rio Grande gap energy of FeSO4.7H2O photocatalyst was 1.98 eV.
do Norte, Brazil. This effluent was degassed and passed The XRD pattern of the TiO2 photocatalyst (Fig. 1a)
through a filter membrane (cellulose) of 0.22 µm. shows the single anatase phase (tetrahedral) (PDF 21-1272)
with a Bragg angle and unit cell parameters of the tetrahedral
2.3 Photocatalytic tests phase of a = 3.73 Å, b = 0 and, c = 9.37 Å. The average
crystallite size of TiO2 calculated by the Scherrer equation
In the Heterogeneous-Photocatalysis process: TiO2 was (Jenkins and Snyder, 1996) was 38 nm; and according to
used in a ratio of 1gcatalysts .Leffluent-1 and H2O2 (0.3% v/v). In the
Diffuse Reflectance Spectroscopy (DRS) the Band-gap
case of the Photo-Fenton process, 4.2 mg of FeSO4.7H2O and Energy of TiO2 was 3.2 eV. It is known that the anatase phase
H2O2 in a molar ratio of 1:10 (catalyst: H2O2) were used. of TiO2 presents good photocatalytic activity under UV light,
In both processes, 25 mL of effluent was used, and the better than the rutile phase. This is due to the fact that TiO2
initial pH was varied as: 3, 7 and 10, with addition of H2SO4 has low recombination rate of “photogenerated-holes and
(0.1 M) or NaOH (0.1 M). A glass beaker (500 ml) was used as
electrons” (Carp et al., 2004); this property is very important
a batch reactor, which was open to ambient air, the reactor was for heterogeneous photocatalysis.
under magnetic stirring. The reactor was confined in a dark
chamber with internal ventilation and exhaust. The irradiation
3.2 Photocatalytic test: Phenol in seawater
for each process was provided by six UV lamps (253.7 nm, 15-
watt, 220 volt) and the illumination to the reactor was from the 3.2.1 Heterogeneous-Photocatalysis Test (TiO2)
top. The catalyst/effluent separation was done by
Firstly, the photocatalytic tests were carried out over TiO2
centrifugation (12,000 rpm). in the absence of H2O2. The initial pH was regulated to: 3, 7
The phenol concentration was monitored during each
and 10. The results are shown on the chromatogram profile
photocatalytic reaction by spectrophotometry through the
(by HPLC analysis), in Fig. 2a-d. According to the result
colorimetric method with 4-aminoantipyrine (APHA Method
shown in Fig. 2a, the profile of the initial phenol solution
D 5530 and EPA Method 604), and a calibration curve at
presents two peaks, the first was assigned to salts present in
λ=510 nm. The colorimetric method was used previously by
seawater, and the second to phenol (46 mg.L-1). The profile
other researchers (Xu et al., 2015; Sun et al., 2016; Zhu et al., obtained for the sample after the photocatalysis at pH 3 (Fig.
2016), for studies of photocatalytic degradation of phenol. 2b), reported a final concentration of 31 mg.L-1 meaning that the
Some tests were also monitored by High Performance Liquid 33% of phenol was removed from seawater.
Chromatography (HPLC, Shimadzu i-series Chromatograph) Nevertheless, the results at pH 7 (Fig. 2c) and 10 (Fig. 2d)
with furnace temperature of 35°C, the mobile phase consisted reached lower removal percentage values (11% and 7%,
of aqueous acetonitrile solution with a flow of 0.8 mL.minute- 1, respectively) demonstrating that the pH of the initial solution
and a C-18 column (5 μm, 4.6 x 250 mm) in a reverse mode. influenced the removal of phenol. Similar results were
In this process the phenol removal percent (X%) was reported by Seftel et al. (2014) and Moraes (2003) for the
calculated as: X% = (Mi - Mf)/Mi) x 100, where Mi and Mf are photocatalysis of phenol in distilled water. Our finding
the phenol concentrations at the beginning and at the end of means that even in the presence of high seawater salinity, the
each experiment, respectively. low pH promotes high phenol removal rates. According to
In the case of the photocatalytic tests using OPW, the the chromatograph profiles of Figs. 2b-d, there were no other
organic matter present in this sample was characterized by intermediates formed after phenol degradation (not detectable under
UV/Vis Spectrophotometer (Global Trade Technology, chromatograph detection limit).
model: UV-5100) in scan mode, as described by Albrektienė et The chromatographs for samples after 1 hour of
al. (2012) and Claro (2013). Heterogeneous-Photocatalysis using TiO2 with addition of H2O2
(0.3%v/v) under UV are shown in Fig. 3a-c. In Fig. 3a-b, the peaks
of phenol after the photocatalysis at pH 3 and 7 correspond to 5.9
3. Results and Discussion mg.L-1 and 2.9 mg.L-1, which result in the phenol removal of 87%
3.1 Characterization of catalysts by X-Ray Diffraction (XRD) and 94%, respectively.
The photocatalysis at pH 10 (Fig. 3c) resulted in 71% of phenol
The results of the photocatalysts obtained by XRD removal. The excess H2O2 appears in the chromatograph,
analysis are shown in Fig. 1a-b. From this analysis and from however, the peak of H2O2 is less intense at pH 10 which is
the JCPDS database, it was possible to identify that the reasonable, since H2O2 is less stable at basic pH.
101
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

A.

A.

B.

C.
B.
Fig. 1. XRD diffraction patterns of photocatalysts: A. TiO2 and; B.
FeSO4.7H2O.

The pH of the phenolic solutions after photocatalysis were

also measured (final pH). There was a slight increase after the
photocatalysis in pH 3 and 7 samples and a significant
reduction for the pH 10 sample, reaching pH 8.5. D
The increase in the final pH of the samples at 3 and 7 (to 4 Fig. 2. Chromatograms of Heterogeneous-Photocatalysis tests
and 8, respectively), can be explained by the formation of using UV light (254nm) for 1 hour, without H2O2. A. initial solution
organic compounds such as short-chain organic acids, as a of phenol in seawater (46 mg.L-1), before photocatalysis; B. sample
product of phenol degradation process. Probably these after photocatalysis at pH 3; C. sample after photocatalysis at pH
organics are in very low concentration since they were not seen 7; D. samples after photocatalysis at pH 10.
by chromatography, and are in ionic form (example: acetate
ions) and in equilibrium in water. 3.2.2 Photo-Fenton test (FeSO4.7H2O)
The formation of these ions leads to a pH increase (due to The phenol removal % reported in Photo-Fenton process
the H+ protons suppressed from water) to maintain the was as high as that of Heterogeneous-photocatalysis. The
equilibrium (established by the Le Chatelier Principle; Atkins chromatographs are shown in Fig.5, where the phenol removal
and Jones, 2010). The results indicated that the reached 99% (Figs. 5a and 5b).
Heterogeneous-Photocatalysis under UV with TiO2 An almost complete phenol removal was obtained at pH 3.
photocatalyst plus H2O2 reached the highest removal values of The high efficiency of the process at this solution pH can be
phenol at pH 3 and pH 7. explained by the fact that Fe3+ and Fe2+ are very stable acidic
The kinetic results for the heterogeneous-photocatalysts media, which favors the interaction of these ions with H2O2,
with TiO2 plus H2O2 under UV light (254nm) are shown in generating hydroxyl radicals (•OH) and oxidizing phenolic
Fig.4. According to these results, at pH 3 and 7 the process molecules in water (equations 2 and 3):
kinetics are very fast, and, the most favorable result was at pH
𝐹𝑒 2+ + 𝐻2 𝑂2 → 𝐹𝑒 3+ + −𝑂𝐻 + .𝑂𝐻 (2)
7 (94% degradation). The reaction reaches the equilibrium
after 1 hour of exposure to UV light. 𝐹𝑒 3+ + 𝐻2 𝑂2 + ℎ𝑣 → 𝐹𝑒 2+ + 𝐻 + + .𝑂𝐻 (3)

102
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

8.2 mg.L-1, which result in 57% phenol removal. This can be

related to the low stability of H2O2 in basic media, which
hinders the interaction with Fe2+ and Fe3+, and therefore leads
to a less effective oxidation process.

A.

A.

B.

B.
C.
Fig. 3. Chromatograms of Heterogeneous-Photocatalysis tests using
UV light (254nm) plus H2O2 oxidizer (0.3% v/v): A. Photocatalysis
at pH 3; B. Photocatalysis at pH 7 and; C. Photocatalysis at pH 10.

C.
Fig. 5. Chromatograms of Photo-Fenton test using UV light
(254nm). A. Photo-Fenton at pH 3; B. Photo-Fenton at pH 7; C.
Photo-Fenton at pH 10.

The kinetic results in Photo-Fenton reaction are shown in

Fig. 6. According to the profiles, as expected, the reaction was
very fast at low pH (3 and 7), and was less efficient and slower
at pH 10. The kinetic test showed that the reaction reached the
equilibrium after 1 hour of irradiation. The results were similar
to those found in Heterogeneous-Photocatalysis experiments,
and seem to indicate that the pH of the solution influences the
Fig. 4. Kinects of phenolic degradation by heterogeneous- reactivity of H2O2 and the stability of the phenolic species in
photocatalysis with H2O2 (0.3% v/v) under UV (254nm). aqueous media at different pH.
Figure 7 presents the comparison of different AOPs studied
Wang et al. (2014) reported phenol removal of 85% (in in this work, for the degradation of phenol in seawater. That
distilled water) for samples with pH 3 when submitted to the figure also presents the adsorption of phenol over the catalysts
Fenton process. In parallel, Kuo (1992) and Kiwi et al. (2000) in the dark, which clearly shows that there was no significant
found that at pH ≈3 the hydroxyl radicals are the most active contribution of the adsorption of the phenol by the TiO2
species in the degradation of organic compounds in Photo- surface. UV radiation (254 nm) and UV+H2O2 (0.3%) removed
Fenton process. Similar results were found when the Photo- significantly phenol. Nevertheless, in all case, the
Fenton was carried out at pH 7. Heterogeneous-Photocatalysis and Photo-Fenton process
Similarly, for the heterogeneous-photocatalysis, the Photo- reached the highest value, showing that even in the presence of
Fenton process was less effective at pH 10 and the peak of high seawater salinity, the photocatalytic process is effective.
phenol present in Fig. 5c corresponds to the concentration of The results observed before, indicated that the AOP is
103
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

effective even in the presence of water with high salinity. As is process caused a greater character alteration in the region from
known, the presence of salts is interfering factors in reducing 300 to 400 nm (indicated with a narrow black in the Fig. 8),
the efficiency of AOPs, especially due to higher NaCl indicating that the photocatalytic process was effective to
contribution, which releases chloride ions (Cl-) that compete remove the dissolved organic matter present in OPW at these
for hydroxyl radicals. pHs (Tambani, 2011).

Fig. 6. Kinects study of Photo-Fenton reactions at different initial

solution pH.

Fig. 8. UV-Vis scan profile of OPW after 3 hours of Heterogeneous-

Photocatalysis over TiO2 plus H2O2 (0.3% v/v), under UV irradiation
(254nm).

In the next experiment, the same experiments described

above were carried out (Heterogenous-Photocatalysis at pH 3
and 7 for three hours of UV irradiation), but, this time with
heating at 75ºC and the results are shown in Fig. 9. In this
Figure there was a greater alteration (of the peak related to
organic matter located in intervals of 300-400 nm) when
compared with the results obtained at room temperature (Fig.
8). This change of character is more notable for the
photocatalysis at pH 7. It is known that the temperature is not
a very relevant factor for the UV/H2O2 system and for
hydroxyl radical generation (Gonçalves, 2004), however, the
Fig. 7. Comparison of the different AOPs studied in this work, for improvement of the removal of dissolved organic matter is
degradation of phenol in seawater clear. In this sense, we can affirm that the temperature favored
the kinetics of the reaction (by increasing the kinetic energy of
3.3 Water Produced from Oil (OPW) molecules), resulting in a higher oxidation rate.
3.3.1 Heterogeneous-Photocatalysis 3.3.2 Photo-Fenton
The UV-Vis spectra scan of the effluent before The UV-Vis spectra scan of the effluent after Photo-
Heterogeneous-Photocatalysis is shown in Fig. 8. As is Fenton is shown in Figure 10. Similar to the analysis in
presented, the initial OPW profile has a principal band at 254 heterogeneous-photocatalysis, the alteration of the initial OPW
nm, which was attributed to the dissolved organic matter profile, which has a principal band at 254 nm attributed to the
(Albrektien et al., 2012); the decrease in the profile intensity of dissolved organic matter (Albrektien et al., 2012); served to
this UV-Vis spectral was utilized to monitor the efficiency of monitor the efficiency of AOP (Claro, 2013).
AOP (Claro, 2013). In the spectra scan of the effluent after Photo-Fenton, the
In the spectra scan of the effluent after heterogeneous- strong band below 275 nm, corresponds to the remaining
photocatalysis, the strong band below 300 nm, corresponds to H2O2, which has a high absorption in this region. Therefore,
the remaining H2O2, which has a high absorption in this this region was not considered for analysis. The Photo-Fenton
region. Therefore, this region was not considered for analysis. carried out at pH 3 and 7 led to alteration of the OPW profile
On the other hand, at pHs 3 and 7, the two photocatalytic above 275nm, indicating that the photocatalytic process was
104
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

effective, the profile that corresponds to pH 7 denoted a more of the removal of dissolved organic matter is clear. At this
demarked difference when compared to the initial profile of point, we can affirm that the temperature favored the kinetics
OPW above 275 nm (see the black arrows in Fig.10). of the reaction (by increasing the kinetic energy of organic
molecules), resulting in a higher oxidation rate.

Fig. 9. UV-Vis scan profile of OPW after 3 hours of

Heterogeneous-Photocatalysis over TiO2 plus H2O2 (0.3% v/v),
under UV irradiation (254nm), and heating at 75°C.
Fig. 11. UV-Vis scan profile of OPW after 3 hours under UV
The same experiments described above (Photo-Fenton at irradiation (254 nm), Photo-Fenton process with FeSO4.7H2O plus
0.375 mL H2O2 and heating at 75ºC.
pH 3 and 7 for three hours under UV irradiation), were carried
out but with heating at 75ºC (Fig. 11). There was a greater
change of character in the absorption band above 275 nm, 4. Conclusion
related to organic matter in OPW, when compared with the
similar at room temperature (see Figs. 10 , 11). The results of Photo-Fenton and Heterogeneous-
Photocatalysis (both in the presence of H2O2) for the
degradation of phenol in seawater, indicated that these
processes are favored at low pH (< pH7), the kinetics of the
processes were also favored. These processes were very
favorable despite the high salt content in the seawater. The
efficiency of the Photo-Fenton process reached ≈99% at pH 7.
The Photo-Fenton process was more effective than
Heterogeneous-Photocatalysis to treat the two types of
effluents studied in this work. In the case of the effluent made
of phenolic solution in seawater, the treatment did not generate
any intermediates (detected by liquid chromatography)
indicating the mineralization of phenol to CO2 and H2O.
The results of OPW treatment by Heterogeneous-
Photocatalysis and Photo-Fenton, demonstrated that the two
photocatalytic processes were effective for the removal of
dissolved organic matter in OPW, the best treatment was at pH
7. These processes were improved by heating at 75ºC.
In future trials, it is feasible to substitute the UV irradiation
Fig. 10. UV-Vis scan profile of OPW after 3 hours under UV of lamps by sunlight, constituting an alternative with lower
irradiation (254 nm), Photo-Fenton process with FeSO4.7H2O plus energy and sustainable consumption.
0.375 mL H2O2. This study demonstrates that the two AOPs can be used in
This change was more marked for the photocatalysis at pH the oil industry, for OPW treatment and effluents (with high
7. As it is known, the temperature is not a very relevant factor salinity) contaminated with phenol, to remove organic
for the UV/H2O2 system and for the hydroxyl radical molecules in order to reduce their toxicity, and consequently
generation (Gonçalves, 2004). Nevertheless, the improvement provide better quality to the sedimentary environment.
105
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

Acknowledgment produced water oil-removal technologies for reinjection.

The authors thank to São Paulo Research Foundation Separation and Purification Technology 134, 241- 246.
https://doi.org/10.1016/j.seppur.2014.07.037
(FAPESP) for the financial support (Grant Nº 2014/24940-5),
Jenkins, R., Snyder, R.L., 1996. Introduction to X-ray Diffractometry,
the Brazilian National Council for Scientific Development
Wiley, New York, NY.
(CNPq, Grant Nº 407097/20) and to the University of São
Kiwi, J., Lopez, A., Nadtochenko, V., 2000. Mechanism and Kinects
Paulo (USP, CEPEMA) for the analysis by High Performance
of the OH-Radical Intervention during Fenton Oxidation in the
Liquid Chromatography analysis (HPLC). Presence of a Significant Amount of Radical Scavenger (Cl-).
Environmental science & technology 34 (11), 2162-2168.
http://dx.doi.org/10.1021/es991406i
References
Kuo, W.G., 1992. Decolorizing dye wastewater with Fenton’s
Albrektienė, R., Rimeika, M., Zalieckiene, E., Saulys, V., Zagorkis, reagent. Water Research 26(7), 881-886.
A., 2012. Determination of Organic Matter by UV Absorption in https://doi.org/10.1016/0043-1354(92)90192-7
Ground Water. Journal of Environmental Engineering and Liu, B., Chen, B., Zhang, B.Y., Jing, L., Zhang, H., Lee, K. J., 2016.
Landscape Management 20 (2), 163-167. Photocatalytic Degradation of Polycyclic Aromatic Hydrocarbons
https://doi.org/10.3846/16486897.2012.674039 in Offshore Produced Water: Effects of Water Matrix. Journal of
Ahmadun, F-R., Pendastech, A., Abdullah, L.C., Biak, D.R.A., Madaeni, Environmental Engineering 142(11), 1-7.
S.S., Abidin, Z.Z., 2009. Review of technologies for oil and gas https://ascelibrary.org/doi/10.1061/%28ASCE%29EE.1943-
produced water treatment. Journal of Hazardous Materials 170, 530- 7870.0001135
551. https://doi.org/10.1016/j.jhazmat.2009.05.044 Moraes, J.E.F., 2003. Photo-Fenton process application in the
APHA Method D 5530, 1989. Standard Methods for the degradation of industrial effluents containing organic pollutants.
Examination of Water and Wastewater, American Public Health PhD Thesis in Chemical Engineering, University of São Paulo,
Association (APHA), Washington. Brazil.
Atkins, J., Jones, L., 2010. Chemical Principles. 5th edition. New Neff, J.M., 2002. Bioacumulation in marine organisms effect of
York: W.H. Freeman and Company. contaminants from oil well produced water, Elsevier Science,
Bakke, T., Klungsøyr, J., Sanni, S., 2013. Environmental impacts of Duxbury.
Produced Water and Drilling Waste Discharges from the Norwegian Nogueira, R.F.P., Jardim, W.F., 1998. A fotocatálise heterogênea e
Offshore Petroleum Industry. Marine Environmental Reasearch 92, sua aplicação ambiental. Química Nova 21(1).
154-169. https://doi.org/10.1016/j.marenvres.2013.09.012 http://dx.doi.org/10.1590/S0100-40421998000100011
Carp, O., Huisman, C.L., Reller, A., 2004. Photoinduced reactivity of titanium Ray, J.P., Engelhardt., 1992. Produced water: Technological /
dioxide. Progress in Solid State Chemistry, Bucareste 32(1-2), 33-177. Environmental issues and solutions, Springer Science + Business
http://dx.doi.org/10.1016/j.progsolidstchem.2004.08.001 Media, Pittsburgh.
Carvalho, P.C.A., 2016. Tratamento Combinado de água produzida Seftel, E.M., Puscasu, M.C., Mertens, M., Cool, P., Carja, G., 2014.
de petróleo: filtração, adsorção e foto-fenton. PhD. Thesis in Petroleum Assemblies of nanoparticles of CeO2–ZnTi-LDHs and their
Engineering, Universidade Federal do Rio Grande do Norte, Brazil. derived mixed oxides as novel photocatalytic systems for phenol
https://repositorio.ufrn.br/jspui/handle/123456789/21946 degradation. Applied Catalysis B: Environmental 150- 151, 157-
Cheriyan, M., Rajagopalan, N., 1998. Membrane processing of oily streams. 166. https://doi.org/10.1016/j.apcatb.2013.12.019
Wastewater treatment and waste reduction. Journal of Membrane Science Sun, X., Zhang, H., Yu, W.Q., Yang, P., Zhang, F., 2016. Preparation of point-
151 (1), 13-28. https://doi.org/10.1016/S0376-7388(98)00190-2 line Bi2WO6@TiO2 nanowires composite photocatalysts with enhanced
Claro, E.M.T., 2013. Potential of application of the Photocatalytic UV/visible-light- driven photocatalytic activity. Material Science in
Process in Piracicaba River water. Master Thesis. Campinas State Semicondutor Processing, Harbin 45, 51-56.
University. https://doi.org/10.1016/j.mssp.2016.01.015
EPA Method 604, 1984. Methods for organic chemical analysis of Tambani, P.C., 2011. Estudo da degradação do fenol e sais
municipal and industrial wastewater. Environmental Protection intermediários pelo processo UV/H2O2. Dissertação,
Agency EPA. Part VIII, 40 CFR Part 136, Appendix A. Universidade de São Paulo, Escola Politécnica, Brazil.
Gonçalves, A.C., 2004. Treatment of effluents containing free Wang, C., Zhang, S., Zhang, Z., Zeng, M., Yuji, S., 2014 Optimization
cyanide through the system H2O2. PhD Thesis, Pontifical and interpretation of Fenton and UV/Fenton processes for
Catholic University of Rio de Janeiro. degradation of syringyl lignin. Journal of Environmental
Ibhadon A.O., Fitzpatrick P., 2013. Heterogeneous Photocatalysis: Analytical Chemistry 1(2), 1-5.
Recent Advances and Applications. Catalysts 3 (1), 189-218. http://dx.doi.org/10.4172/JREAC.1000115
https://doi.org/10.3390/catal3010189 Wood, D.L., Tauc, J., 1972. Weak Absorption Tails in Amorphous
Jing, L., Chen, B., Zhang, B., Zheng, J., Liu, B., 2014. Naphthalene Semiconductors. Physical Review B 5(8), 3144- 3151.
degradation in seawater by UV irradiation: The effects of fluence https://doi.org/10.1103/PhysRevB.5.3144
rate, salinity, temperature and initial concentration. Marine Xu, D., Cheng, B., Cao, S., Yu, J., 2015. Enhanced photocatalytic
Pollution Bulletin 81(1), 149-156. activity and stability of Z-scheme Ag2CrO4-GO composite
https://doi.org/10.10.16/jmarpolbul.2014.02.003 photocatalysts for organic pollutant degradation. Applied
Judd, S., Qiblawey, H., Al-Marri, M., Clarkin, C., Watson, S., Ahmed, Catalysis B: Environmental 164, 380-388.
A., Bach, S., 2014. The size and performance of offshore https://doi.org/10.1016/j.apcatb.2014.09.051
106
Journal of Sedimentary Environments
Published by Universidade do Estado do Rio de Janeiro
4 (1): 99-107. January-March, 2019
doi: 10.12957/jse.2019.40991
RESEARCH PAPER

Zhu, C., Zhang, L., Jiang, B., Zheng, J., Hu, P., Li, S., Wu, M., Wu, pollutant degradation. Applied Surface Science 377, 99-108.
W., 2016. Fabrication of Z-scheme Ag3PO4/MoS2 composites https://doi.org/10.1016/j.apsusc.2016.03.143
with enhanced photocatalytic activity and stability for organic

107