Advanced Oxidation Processes and Their Application in PDF

BRAZILIAN JOURNAL OF PETROLEUM AND GAS ISSN 1982-0593
MOTA, A. L. N.; ALBUQUERQUE, L. F.; BELTRAME, L. T. C.; CHIAVONE-FILHO, O.; MACHULEK JR., A.; NASCIMENTO, C. A. O. ADVANCED OXIDATION PROCESSES AND
THEIR APPLICATION IN THE PETROLEUM INDUSTRY: A REVIEW. Brazilian Journal of Petroleum and Gas. v. 2, n. 3, p. 122-142, 2008.
ADVANCED OXIDATION PROCESSES AND THEIR APPLICATION IN

THE PETROLEUM INDUSTRY: A REVIEW
1
A. L. N. Mota*, 1L. F. Albuquerque, 1L. T. C. Beltrame,
1
O. Chiavone-Filho, 2A. Machulek Jr., 3C. A. O. Nascimento
1
Departamento de Engenharia Qumica - Universidade Federal do Rio Grande do Norte (UFRN),
Campus Universitrio, UFRN, Lagoa Nova, Natal/RN, Brazil, CEP 59072-970
2
Faculdade de Cincias Exatas e Tecnologia - Universidade Federal da Grande Dourados (UFGD),
Rodovia Dourados - Itahum, km 12, Dourados/MS, Brazil, CEP 79804-970
3
Departamento de Engenharia Qumica Escola Politcnica, Universidade de So Paulo (USP),
Cidade Universitria, So Paulo/SP, Brazil, CEP 05508-900
* To whom all correspondence should be addressed.

Address: Universidade Federal do Rio Grande do Norte, Departamento de Engenharia Qumica,
Av. Sen. Salgado Filho 3000, Campus Universitrio, UFRN, Lagoa Nova, CEP 59072-970,
Natal/RN Brazil.
Telephone / fax numbers: + 55 84 3215-3773
E-mail: andremota@eq.ufrn.br
Abstract. Advanced oxidation processes (AOP) are technologies based on the

generation of highly reactive species, the hydroxyl radicals, used in oxidative
degradation procedures for organic compounds dissolved or dispersed in aquatic media.
These processes are promising alternatives for decontamination of media containing
dissolved recalcitrant organic substances, which would not be efficiently removed by
conventional methods. The present paper describes a series of AOP, analyzing the
aspects related to each type of process, such as the interference of external agents and
the ideal operating conditions, based on the analysis and comparison of different studies
in the area. In addition, several applied AOP studies on treatment of oil wastewater and
on remediation of soil contaminated with oil or its derivatives are presented.
Keywords: advanced oxidation processes; petrochemical wastewater; oil wastewater;

hydrocarbons degradation; photocatalysis; Fentons reagent; photo-Fenton; ozonation;
wet air oxidation; electro-oxidation; wastewater treatment
1. INTRODUCTION sedimentary basins and as a result of storage

Despite the importance of oil in the world tank leaks, including gasoline stations and
economy, the environmental question that during marine transport (oil tankers) (Watts et
surrounds its production must always be well al., 2000). Moreover, during its processing a
assessed, owing to the composition of its large volume of hydrocarbon-rich wastewater is
residues and of the oil itself, which consists generated, which, if left untreated, causes
mainly of aromatic and aliphatic compounds serious environmental impacts (Durell et al.,
(Mariano, 2005). 2006). A large part of this wastewater is
The toxicity of the aromatic fraction is produced along with oil during gas and oil
higher than that of the aliphatic fraction. extraction processes in oil wells. The amount of
Aromatic compounds are known to be more wastewater produced can be 95% higher than
recalcitrant, among which are benzene, toluene, the oil extracted in certain production wells.
ethylbenzene, xylene isomers (the so-called The liquid wastes generated in refineries
BTEX), and phenols (Stepnowski, 2002). vary considerably in terms of amount and
Contaminations from oil components can quality, as a function of the type of oil
occur during the extraction process in processed, the processing units of the refinery,
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BRAZILIAN JOURNAL OF PETROLEUM AND GAS
Table 1. Physical-chemical characteristics of oil refinery wastewaters.

Limits
Parameter
Minimum Maximum
Temperature (C) 22 41
pH 6.2 10.6
BOD (mg/L) 17 280
COD (mg/L) 140 3340
Sulfides (mg/L) 0 38
Hardness as CaCO3 (mg/L) 139 510
Alkalinity as CaCO3 (mg/L) 77 356
Oil (mg/L) 23 200
Phosphorus (mg/L) 0 97
NH3 (mg/L, as N) 0 120
Chlorides (mg/L) 19 1080
Sulfates (mg/L) 0 182
and the operation mode of these units. Saien and Nejati, 2007).
Refineries generally produce an amount of One of the processes for treating water
liquid waste that is relatively proportional to containing toxic organic pollutants that has
the amount of oil refined. Table 1 shows the been increasingly used in recent years is the
general physical-chemical characteristics of advanced oxidation process (AOP), a powerful
refinery wastewaters (Mariano, 2005). tool applied to degrade these pollutants (Bolton
The conventional techniques applied in the et al., 2001; Safarzadeh-Amiri et al., 1997;
treatment of these wastewaters are physical- Ghaly et al., 2001; Pera-Titus et al., 2004;
chemical and mechanical, generally associated Prez-Moya et al., 2007; Durn et al., 2008).
with biological treatment. The conventional
treatments include gravitational separation,
centrifugation, application of coagulants, 2. ADVANCED OXIDATION PROCESSES
flotation, filtration, and adsorption with Advanced oxidation processes (AOP) are
activated coal, among others (Yavuz and technologies characterized by the generation of
Koparal, 2006; Saien and Nejati, 2007). These hydroxyl radicals, which are highly reactive
conventional techniques manage to remove free and non-selective substances used to degrade
and emulsioned oil and solids in suspension toxic organic compounds present in a medium
from the wastewater, in addition to reducing (such as wastewater and soil).
BOD when associated with biological The hydroxyl radical has a high oxidation
treatment. However, applying the biological potential (E0 = 2.8 V), as shown in Table 2
process is inadequate when the wastewater (Pera-Titus et al., 2004), and is able to react
contains highly toxic recalcitrant compounds, with practically all classes of organic
such as the aromatic fraction from the dissolved compounds, resulting in complete
organic compounds. In this case, more mineralization of these compounds, that is, the
advanced techniques must be used to degrade formation of carbon dioxide, water and
these compounds (Yavuz and Koparal, 2006; inorganic salts, or their conversion into less
Table 2. Standard reduction potentials of some oxidants in volts (V) compared with the normal hydrogen
0
electrode (NHE, E = 0 V). Adapted from Legrini and coworkers (1993).
Oxidant Standard reduction potential / V
Fluorine (F2) 3.03

Hydroxyl radical ( OH) 2.80
Ozone (O3) 2.07
Hydrogen peroxide (H2O2) 1.77
Potassium permanganate (KMnO4) 1.67
Chlorine dioxide (ClO2) 1.50
Chlorine (Cl2) 1.36
Bromine (Br2) 1.09

aggressive products (Andreozzi et al., 1999; et al., 1999). These ions can react with the
Bolton et al., 2001; Pignatello, 1992). Pollutant hydroxyl radicals (Equations 4 and 5), hence
destruction and consequent inhibition of competing with the organic substrates through
generation of toxic residues are some of the the hydroxyl radicals.
main advantages of AOP, given that
conventional water treatment methods such as HO + HCO3 CO3 + H2O (4)
flotation, filtration and adsorption with active HO + CO32 CO3 + HO (5)
coal are non-destructive physical separation
processes, that is, they only remove the Hydroxyl radicals can be generated from
pollutants, transferring them to other phases, several AOP, enabling the application of a
thereby generating concentrated deposits, as better process for each specific treatment
reported by Crittenden and coworkers (1997a). condition. According to Huang and coworkers
The possible reaction pathways involving (1993), the AOP can be classified as
the attack of hydroxyl radicals onto organic homogeneous and heterogeneous. Domnech
compounds are: the electrophylic addition of a and coworkers (2001) presented this
hydroxyl radical to organic compounds classification in terms of whether light is used
(unsaturated or aromatic) that contain a bond in the process. Table 3 shows a classification of
leading to the formation of organic radicals AOP according to these authors.
(Equation 1), the hydrogen abstraction by The AOP are expensive processes owing to
reacting the hydroxyl radical with a saturated the high cost of reagents such as H2O2 and O3
aliphatic compound (Equation 2) and electron and electric energy when UV radiation is
transfer with reduction of the hydroxyl radical applied. For this reason they are considered in
into a hydroxyl anion by an organic substrate alternative treatment of wastewater that cannot
(Equation 3) (Bossmann et al., 1998; Tang, be biologically treated.
2004). Another significant aspect is the load of
pollutants present in the wastewater, regularly
HO
HO + or
or
OH
(1) expressed in terms of chemical oxygen demand
(COD). The use of these processes is indicated
HO + RH R + H2O (2)
only for wastewaters with COD below 5 g L-1,
HO + RX [RX]+ + HO (3) given that a higher COD index would require
very high consumption of reagents, precluding
The hydroxyl radical attack on organic the treatment (Andreozzi et al., 1999).
substrates may be influenced by the presence of For wastewaters with high organic load,
a number of chemical species in water (or pretreatment operations, like dilution,
originating in the mineralization process), such coagulation and flocculation, are required in
as carbonate and bicarbonate ions (Andreozzi order to reduce the initial load (Rivas et al.,
Table 3. Types and classification of advanced oxidation processes.

Non-photochemical Photochemical
Homogeneous processes
Ozonation in alkaline media (O3/HO)
Ozonation with hydrogen peroxide
Photolysis of water in vacuum ultraviolet
(O3/H2O2)
2+ 3+ (VUV)
Fenton (Fe or Fe /H2O2)
UV/H2O2
Electro-oxidation
UV/O3
Electrohydraulic discharge - ultrassound
UV/O3/H2O2
Wet air oxidation (WAO) 2+ 3+
Photo-Fenton (Fe or Fe /H2O2/UV)
Supercritical water oxidation (SCWO)
Heterogeneous processes
Heterogeneous photocatalysis: ZnO/UV,
Catalytic wet air oxidation (CWAO)
SnO2/UV, TiO2/UV, TiO2/H2O2/ UV
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2004). In contrast, AOP can be applied in the (1.7 V) than that of hydroxyl radicals (2.8 V);
treatment of contaminated waters with very low therefore, their generation is not interesting to
organic loads (in ppb) and which contain the process. Several studies have shown that
dissolved organic compounds which are the rise in the initial concentration of H2O2
difficult to remove. increases the degradation rate of contaminants
One way of reducing the costs of AOP is to up to a maximum value, after which they begin
use them as preliminary treatment operations to to decline when they reach very high H2O2
reduce toxicity, followed by biological levels (Lpez et al., 2000; Cisneros et al.,
treatment. This option has proven to be quite 2002; Lunar et al., 2000; Tang and Chen, 1996;
interesting from an economic point of view and Zhao et al., 2004). Lpez and coworkers (2000)
has been studied by several authors (Martn et attribute this decrease in the H2O2/UV process
al., 2008; Chamarro et al., 2001; Garca- yield to hydroxyl radicals reacting with excess
Montao et al., 2008; Lucas et al., 2007; H2O2 (Equation 7), instead of reacting with the
Malato et al., 2007; Prez-Moya et al., 2007). organic substrates, leading to the formation of
the hydroperoxyl radical HO.
2.1. H2O2/UV The photolysis of H2O2 is normally obtained
Hydrogen peroxide (H2O2) is a strong with low or medium pressure mercury vapor
oxidant (see Table 2) applied, among other lamps, both with high intensity, in order to
purposes, to reduce the low levels of pollutants reduce the amount of H2O2 needed. Nearly
present in wastewaters, as reported by Neyens 50% of the energy consumed is lost in the form
and Baeyens (2003). However, the individual of heat or in emissions of wavelengths shorter
use of H2O2 is not efficient in oxidizing more than 185 nm, which are observed by the quartz
complex and recalcitrant materials with a low jacket (Litter, 2005). The germicide lamp is a
reaction rate. The use of H2O2 becomes more widely used cheaper alternative; however, the
effective when it acts in conjunction with other efficiency is lower because it emits in the 210
reagents or energy sources capable of to 240 nm range and H2O2 absorption reaches a
dissociating it to generate hydroxyl radicals, maximum of 220 nm.
which will act as oxidizing agents. With UV The advantages of using the H2O2/UV
irradiation in wavelengths shorter than 300 nm, process can be attributed to the fact that the
H2O2 can decompose and generate hydroxyl reagent (H2O2) is totally soluble in water, there
radicals, as shown in Equation 6. is no mass transfer limitation, it is an effective
source of HO, and there is no need for a
H2O2 2HO (6) separation process after treatment (Gogate and
Pandit, 2004b; Litter, 2005).
The operational pH must be low (pH < 4) to
Hydrogen peroxide can also react with nullify the effect of sequestering radical
hydroxyl radicals and the intermediary products species, specifically ionic species such as
formed thereby, according to the reaction carbonate and bicarbonate ions, leading to a
mechanism described in a simplified way by better degradation rate.
Equations 7 to 11 (Alfano et al., 2001).
2.1.1. Application
H2O2 + HO HO2 + H2O (7) Stepnowski and coworkers (2002) assessed
H2O2 + HO2 HO + H2O + O2 (8) the use of H2O2 in the presence and in the
2HO H2O2 (9) absence of UV radiation, in degrading an oil
2HO2 H2O2 + O2 (10) refinery wastewater pretreated with flotation
HO + HO2 H2O2 + O2 (11) and coagulation, analyzing total petroleum
hydrocarbons (TPH), dichloromethane (DCM),
The attack on organic compounds occur due 1,2-dichloroethane (DCE) and methyl tert-butyl
to the hydroxyl (HO) and hydroperoxyl (HO2) ether (MTBE). It was observed that UV
radicals formed. However, the hydroperoxyl radiation did not significantly influence
radicals have a lower reduction potential

compound degradation, with the exception of power (Machulek Jr., 2007; Fenton, H. J. H.,
DCM, which was the most stable of all. In total 1894). However, Huang and coworkers (1993),
83% was removed with 11.76 nM of H2O2 in cited by Neyens and Baeyens (2003),
the presence of UV radiation. The authors mentioned that the application of Fentons
observed slow degradation of the TPH, which reagent in oxidation processes to destroy toxic
removed 69% of the total initial concentration organic compounds was only attempted in the
in 8 days of the experiment. The MTBE 1960s. There is considerable controversy about
degradation was similar to that of DCE and the reaction mechanism involving Fentons
after 24 hours there was total degradation. reaction. The classic Fenton reaction
The application of the H2O2/UV process to interpreted by Haber and Weiss (1934), as cited
purify oily wastewater from a lubricant- by Bossmann and coworkers (1998), consists
producing unit belonging to an oil company of an aqueous combination of hydrogen
was studied by Philippopoulos and peroxide (H2O2) and ferrous ions (Fe2+), in acid
Poulopoulos (2003). Chromatographic analyses medium, leading to the decomposition of H2O2
show that most of the compounds identified in into a hydroxyl ion and a hydroxyl radical, and
the wastewater were removed by the end of the the oxidation of Fe2+ to Fe3+, as represented by
treatment, using a high concentration of H2O2. Equation 12.
Nevertheless, a reduction of only 40% of the
initial COD of the wastewater was obtained Fe2+ + H2O2 Fe3+ + HO + HO (12)
(around 9000 mg/L-1). The authors attribute this
to the formation of organic acids, resulting The Fe2+ and Fe3+ species, shown in a
from the decomposition of organic compounds simplified form, correspond to the
present in the wastewater, which are more [Fe(OH)(H2O)5]+ aqueous complexes, which,
resistant to photo-degradation with H2O2. The together with H2O2, form the
effect of pH on the process was also analyzed [Fe(OH)(H2O2)(H2O)4]+ and [Fe(OH)(H2O)5]2+
and it was found that in acid pH (3.5), there complexes, respectively, as reported by
was enhanced reduction in the COD of the Bossmann and coworkers (1998).
wastewater, when compared to neutral and As shown by Walling and Weill (1974), the
3+
basic pHs. Fe formed in Equation 12 can react with the
Hu and coworkers (2008) studied the H2O2 present in the medium and be reduced to
degradation of MTBE, a gasoline additive and Fe2+ again, forming the hydroperoxyl radical,
one of the most common contaminants in according to Equation 13. This reaction,
contaminated underground waters in the USA, referred to by Neyens and Baeyens (2003) as
owing to leakages in gasoline station storage Fenton-like, occurs more slowly than reaction
tanks. The H2O2/UV process was assessed, 12, as reported by Pignatello (1992). The Fe3+
which, under specific conditions, removed up ions also react with the HO2 and are reduced to
to 98% of the MTBE. An increase in the Fe+2, as shown by Equation 14.
removal percentage was found with a rise in
H2O2 concentration, but up to a maximum Fe3+ + H2O2 [FeOOH]2+ + H+ Fe2+ + HO2 (13)
value, after which this percentage started to 3+
Fe + HO2 Fe + O2 + H 2+ +
(14)
fall. The authors attribute this effect to the
competitive reactions of H2O2 and hydroxyl The initial degradation rate using Fe+3 is
radicals shown in Equations 7 to 11. much lower than that using Fe+2, as pointed out
by Safarzadeh-Amiri and coworkers (1997) and
2.2. Fenton and photo-Fenton shown by Wang (2008).
Fentons reagent is a solution of hydrogen The ideal pH in Fentons reaction found in a
peroxide and ferrous ions and was discovered number of studies is 3 (Benitez et al., 2001;
by the chemical engineer Henry John Horstman Gallard et al., 1998; Guedes et al., 2003; Lin
Fenton (1854-1929), reporting in 1894 that this and Lo, 1997; Pignatello, 1992), considered
solution in acid medium had high oxidizing therefore to be the operating pH. At very low

pH (< 2.5), the formation of complexes, such as Although it has been widely studied and
[Fe(H2O)6]2+, occurs. These react more slowly provided good wastewater treatment results, the
with H2O2 than does [Fe(OH)(H2O)5]+, Fentons reaction was recognized as a powerful
producing a lower amount of hydroxyl radicals, tool to degrade organic compounds when
thus decreasing the system efficiency (Gallard ultraviolet radiation is added to the system.
et al., 1998). At basic pH, iron reacts with the This was achieved when Pignatello (1992)
hydroxide ions (HO), precipitating the iron applied it in the treatment of wastewaters
hydroxide (Fe(OH)2 or Fe(OH)3), which does containing toxic organic pollutants in the early
not react with H2O2, consequently precluding 1990s. It has served as a starting point for a
the Fenton reaction. Therefore, an adjustment number of studies related to the application of
in pH is required in the wastewater to be treated the photo-Fenton process (Bolton et al., 2001;
before adding the Fenton reagents. Celin et al., 2003; Derbalah et al., 2004; Durn
It is important to previously establish the et al., 2008; Emilio et al., 2002; Fallmann et
optimal relationship between ferrous and al., 1999; Gernjak et al., 2003; Kavitha e
hydrogen peroxide ions. When higher Palanivelu, 2004; Maletzky and Bauer, 1998;
concentrations of ferrous ions than hydrogen Moraes et al., 2004; Oliveros et al., 1997;
peroxide ions are used, the hydroxyl radicals Prez-Moya et al., 2007; Rodrguez et al.,
generated by Equation 12 may react with 2005; Skora et al., 1997; Xu et al., 2007).
excess ferrous ions, according to Equation 15, According to Pignatello (1992), UV
decreasing the attack of hydroxyl radicals on irradiation strongly accelerates the degradation
organic substrates (Neyens and Baeyens, 2003). rate of organic pollutants from Fentons
reagent, which has the advantage of being
Fe2+ + HO Fe3+ + HO (15) sensitive to UV-Vis radiation for wavelengths
above 300 nm. Under these conditions, the
Guedes and coworkers (2003) observed that, photolysis of Fe3+ complexes enables
although a [Fe2+]/[H2O2] ratio of 1:2 has a regeneration of Fe2+ and the occurrence of
higher degradation rate, it is usually Fentons reaction, if H2O2 is available. Faust
recommended to use the 1:5 ratio, which yields and Hoign (1990) reported that the dominant
similar results and requires fewer reagents. species (between pH 2.5-5) in the photo-Fenton
In most cases, the Fentons reaction alone is process is the ferric complex Fe(OH)2+, a
not capable of degrading organic compounds simplified form of representing the aqueous
and mineralizing them efficiently. The Fentons complex Fe(OH)(H2O)52+, and the photolysis of
reaction is effective up to the moment at which this complex (wavelengths < 410 nm) is the
all the Fe2+ present in the medium is oxidized largest source of hydroxyl radicals (Equation
to Fe3+, thus interrupting the generation of 17). Other photoreactive species are also
hydroxyl radicals and, consequently, the present in the reaction medium, such as
degradation of organic compounds. According Fe2(OH)24+ and Fe(OH)2+, possibly leading to
to Balanosky and coworkers (2000), cited by the formation of hydroxyl radicals (Faust and
Maciel and corworkers (2004), one of the Hoign, 1990).
factors that contribute to the interruption of the
Fentons reaction is that Fe3+ ions can form Fe(OH)2+ Fe2+ + HO (17)
stable organic compounds (under normal
conditions) with the degradation products
Safarzadeh-Amiri and coworkers (1997)
(mainly the organic acids) present in the
reported that Fe2+ regeneration can also occur
medium, as shown by Equation 16, impairing
with the photolysis of the complexes formed
the regeneration of Fe2+.
(Equation 16) from Fe3+ and the organic
products generated in the degradation process,
Fe3+ + (RCO2)2+ Fe3+(RCO2)2+ (16)
as shown by Equation 18.

Fe3+(RCO2)2+ Fe2+ + CO2 + R (18) Machulek Jr and coworkers (2007) found

that the formation of Cl2 radical anions, due
to the presence of chloride ions in the reaction
Thus, the ferrous ions regenerated by
medium, can be avoided by controlling pH at 3
Equations 17 and 18 can react again with the
during the reaction period, given that the
H2O2 in solution (Equation 12) to generate
degradation process of an organic substrate by
more hydroxyl radicals, creating a
2+ 3+ the photo-Fenton process leads to the formation
photocatalytic cycle in the Fe /Fe system.
of acids and thus pH reduction. It occurs due to
The use of radiation reduces significantly the
pH decrease lower than 2.5 in the presence of
concentration of ferrous ions required,
chlorides ions, leading to more intense
compared with the dark Fenton reaction (in the
formation of ferric chloride complexes (FeCl2+
absence of light). The concentration of ferrous
and FeCl2+). These complexes also undergo
ions must not be very high, as in the Fentons
photolysis, thereby decreasing the amount of
reaction, in order to achieve good efficiency,
Fe(OH)+2, which is the main source of
since the addition of ferrous ions increases
hydroxyl radicals in the photo-Fenton process,
solution opacity, hindering radiation
in addition to the formation of the Cl2 radical
penetration and compromising Fe2+
anion, which can react with Fe2+ (oxidizing to
regeneration when oxidized to Fe3+, As a
Fe3+ without the formation of hydroxyl
consequence, the degradation rate is
radicals) and the organic substrate.
diminished, as reported by Bhatkhande and
One of the main advantages of using the
coworkers (2004).
photo-Fenton process compared with the other
Malato and coworkers (2002) also cite the
oxidation processes consists on using solar
high depth of light penetration and the intense
radiation in its reaction process. In this case,
contact between the pollutant and the oxidizing
according to Machulek Jr. (2007), in the
agent as advantages of the photo-Fenton
process, since it is a homogeneous process. presence of oxalate ions (C2O42), the Fe3+
The disadvantages of the photo-Fenton present in the aqueous medium may form the
process are associated with the low pH values [Fe(C2O4)]+ complex (Equation 19), which
required (normally below 4) and the need to absorbs light at wavelengths below 570 nm (the
remove iron after the reaction. However, as larger part of the visible UV solar spectrum).
reported by Mota (2005), iron removal may not
be needed if is used at concentrations below the 2[Fe(C2O4)]+ 2Fe2+ + C2O42 + 2CO2 (19)
discard limit established by law. It is important
to have prior knowledge of the physical- The possibility of using solar radiation
chemical characteristics of the wastewater to be represents an enormous saving from the
treated by this process because some energetic point of view, given that there will be
substances or inorganic ions, such as Cl, no need to use lamps. The development of pilot
SO42, H2PO4 /HPO42 present in the wastewater treatment plants that use solar
wastewater or added as reagents (FeSO4, FeCl3, reactors applied to the advanced oxidation
HCl, H2SO4) may interfere in the reaction processes has been one of the main focuses of
mechanism of the Fenton and photo-Fenton research in the area (Blanco et al., 1999; Dillert
system, inhibiting the degradation process, as et al., 1999; Gernjak et al., 2006; Kositzi et al.,
reported by De Laat and coworkers (2004) and 2004; Malato et al., 2002; Malato et al., 2003;
Nadtochenko and Kiwi (1998). De Laat and Momani et al., 2007; Xu et al., 2007).
coworkers (2004) suggest that the possible
causes of these effects are the complexation 2.2.1. Application
reactions of the inorganic ion with Fe2+ or Fe3+ Safarzadeh-Amiri and coworkers (1997)
ions and the reactions with hydroxyl radicals used ferrioxalate as a source of iron in
that lead to the formation of less reactive degrading different wastewaters containing
inorganic radicals (Cl , Cl2 and SO4 ). BTEX, 1,4-dioxane and methyl tert-butyl ether,

using the photo-Fenton process and compared confirmed when the dark Fenton and photo-
it with other photodegradation processes. Based Fenton processes to degrade phenol were
on the use of energy, the results showed that, in compared. Degradation was twice as high when
some cases, the process was up to 30 times the photo-Fenton process was applied. The
more efficient than the UV/H2O2 and UV- phenol degradation rate increased with the rise
Vis/Fe2+/H2O2 processes. Thus, the authors in intensity of the radiation emission source,
concluded that the process using ferrioxalate owing to increased Fe2+ ion regeneration
requires less electric energy than the UV/H2O2 (Equation 17), and consequent elevation in the
process, resulting in lower treatment costs. hydroxyl radicals generated. The authors report
Moraes and coworkers (2004) used the that the study of this variable is important
photo-Fenton process to degrade the because it enables the construction of reactors
hydrocarbons present in saline synthetic that use lamps as the UV emission source,
wastewater prepared with gasoline to simulate which are important in companies that require
the water produced in oil production fields that continuous treatment of their wastewater. This
contain high concentrations of dissolved salts. cannot be done with solar reactors alone, given
It was found that, in the presence of salt that they only operate in periods in which there
(NaCl), total pollutant degradation did not is sunlight.
occur. This was achieved in tests without The photo-Fenton process for treating water-
adding salt to the synthetic wastewater. The containing diesel oil was studied by Galvo and
authors attributed this effect to Fe3+ ions that coworkers (2006). They conducted a study to
reacted with Cl ions, forming FeCl2+ optimize the amount of reagents used, in order
complexes, which, in the presence of UV to achieve high levels of degradation with a
radiation, may give rise to Cl2 radicals (lower smaller amount of reagents. With Fe2+ ion
oxidation potential than the HO radicals), concentrations of 0.1 mM, an amount below the
hence reducing the efficiency of the process. maximum discard limit permitted by Brazilian
Tiburtius and coworkers (2005) investigated law (0.27 mM), there was 99% degradation of
the oxidation potential of the Fenton and photo- the organic compounds originally present in the
Fenton processes to degrade a solution wastewater, expressed as total organic carbon
containing benzene, toluene and xylenes (BTX) (TOC). It is important for the photo-Fenton
and water contaminated with gasoline process to be effective, from the economic
(containing 25% ethanol). Rapid degradation of point of view, under these operational
the BTX compounds was observed as well as conditions, since it does not require subsequent
the formation of intermediate phenolic treatment to remove residual iron.
compounds in the initial reaction periods that Coelho and coworkers (2006) assessed the
were completely degraded after 30 minutes of degradation of acid water effluents from oil
reaction. A level of 75% in degradation of total refineries, which contained emulsified oil and a
hydrocarbons present in gasoline-contaminated series of low-biodegradability micropollutants
water was achieved, and the BTX compounds (such as phenols, sulphides, mercaptanes,
were removed in the first minutes of the ammonias, cyanides), through the application
reaction (when phenolic compounds were of different AOP. Among the processes
formed), after which they degraded slowly. analyzed, the Fenton and photo-Fenton
Mota and coworkers (2005) studied the obtained the best results. The dark Fenton
photo-Fenton process in degrading phenol, a reaction was used until reaction stagnation
very common pollutant in the petrochemical (with the removal of only 27% of initial
industry, using black light fluorescent lamps as dissolved organic carbon DOC), followed by
an UV-A radiation source. These are much the photo-Fenton process, with the use of UV
cheaper and more economical (from the energy radiation. The combination of these two
consumption point of view) compared with processes, applied continuously, reduced the
medium pressure mercury vapor lamps. The initial DOC by 94%. The BTEX pollutants
efficiency of black light fluorescent lamps was present in the original wastewater were

removed to non-detectable levels. The authors The remediation of diesel-contaminated soil

report that the Fenton and photo-Fenton was also studied by Kong and coworkers
processes were efficient in removing pollutants (1998). They used iron species in their mineral
from the wastewater; however, high form (geotite and magnetite) and in their
concentrations of reagents were used. They soluble salt form (FeSO4) as catalyst and
assert that an optimization study is needed to reagent for the Fentons reaction. It was found
reduce the amount of reagents, making the that, although the use of mineral iron takes
process more effective. more time to reach the indices of diesel
Mater and coworkers (2007) investigated the degradation (around 50%) obtained with the
efficiency of Fentons reagent in the FeSO4 solution, it requires a lower
mineralization of organic compounds present in concentration of H2O2, which makes its
water contaminated with crude petroleum. The application more economically effective than
process was assessed by monitoring the H2O2 that using FeSO4.
(with spectrophotometric measurements) and Watts and coworkers (2000) studied the
by the titrimetric quantification of CO2, which decontamination of soil containing gasoline,
enabled the authors to calculate the rate of using Fentons reagent, individually analyzing
mineralized total organic carbon (TOC). These the degradation of aliphatic and aromatic
analyses showed a 75% reduction in the initial compounds present therein. It was observed
TOC of water contaminated with crude oil. that, despite being more recalcitrant and toxic,
the aromatics need fewer reagents (iron and
2.2.2. Soil treatment application hydrogen peroxide) for oxidation than do the
In addition to contaminating water, oil and aliphatic components. The authors emphasize
its derivatives can also contaminate the soil, the rapid action of the Fentons reagent, which
requiring an effective remediation process. can effectively treat oil-contaminated soils in
Soil remediation is one of the greatest hours or days, whereas the bioremediation or
challenges to technicians and researchers. natural attenuation of soil can take months or
Studies applying advanced oxidation processes years.
have proven to be effective in treating and Mater and coworkers (2007), in addition to
recovering soil, mainly because they are faster assessing the efficiency of Fentons reagent in
than the biological processes and are able to mineralizing the organic compounds in oil-
degrade toxic recalcitrant matter. contaminated water, investigated the
Fentons reaction has been the most widely mineralization of organic pollutants in soils
used process in the remediation of soils contaminated with crude oil, calculating the
contaminated with toxic organic pollutants. In rate of mineralized TOC by monitoring CO2
the reaction, the sources of iron are varied, and and H2O2. Under certain operational conditions,
include the minerals found naturally in the soil. a 70% reduction in the initial TOC was
Watts and Dilly (1996) analyzed different obtained in soil contaminated with crude oil.
species of iron used as catalyst in the Fenton-
like reaction to remediate diesel-contaminated 2.3. Ozone (O3)
soil. It was shown that the reaction of H2O2 One of the uses of ozonation that has grown
catalyzed by iron (III) ions (Fenton-like) was considerably in recent years is the treatment of
more effective than that catalyzed by iron (II) drinking water, given that its action mechanism
ions (Fenton). Among the iron salts analyzed, does not produce chlorinated compounds that
iron (III) perchlorate and iron (III) nitrate were may originate in the chlorine disinfection
those that yielded the best percentages of diesel process (Augugliaro et al., 2006). In addition,
oxidation. However, the authors underscore the ozone itself has the advantage of not being
that the large-scale use of iron (III) perchlorate harmful to most organisms. However, its use in
is limited, since this reagent is not wastewater treatment is limited, owing to the
commercially available. high demand of energy to generate ozone
(Pera-Titus et al., 2004). Furthermore, the

efficiency of ozone is extremely dependent on The O3/UV process consists in UV

gas-liquid mass transfer, which is impeded by irradiation (254 nm) on an aqueous system
the low solubility of ozone in aqueous solution, saturated with ozone producing H2O2 (Equation
as reported by Gogate and Pandit (2004a). 31), which will also be exposed to the action of
Ozone has a high reduction potential UV light, producing hydroxyl radicals
(2.07V), and can react slowly and directly with (Andreozzi et al., 1999), as shown by Equation
an organic substrate (Augugliaro et al., 2006). 6. In this process, with the formation of
However, the use of ozone is only hydrogen peroxide, there is a new reaction
characterized as an AOP when it decomposes pathway to generate other hydroxyl radicals
to generate hydroxyl radicals (Equation 20), (Equations 21-29), creating a synergistic effect
and can be catalyzed by hydroxyl ions (HO) in that comprises direct ozonation, direct
alkaline medium or by transition metal cations photolysis and the decomposition of hydroxyl
(Augugliaro et al., 2006; Pera-Titus et al., radicals (Agustina et al., 2005; Wang et al.,
2004; Straehelin and Hoign, 1985). 2002).
2O3 + 2H2O 2HO + O2 + 2HO2 (20) O3 + H2O H2O2 + O2 (31)

The efficiency of ozone in degrading
Combined with other techniques, the use of
organic compounds is improved when
ultrasound and ozone may also strengthen the
combined with H2O2, UV radiation or
generation of hydroxyl radicals, since the
ultrasound.
turbulence created by the acoustic current
According to Huang and coworkers (1993),
induced by ultrasound reduces the limitations
cited by Augugliaro and coworkers (2006),
of mass transfer (Gogate and Pandit, 2004a).
H2O2 induces the decomposition of O3 by
electron transfer through a reaction that can be
2.3.1. Application
understood as H2O2 activation by O3 (Equation
Garoma and coworkers (2008) studied the
21), by means of a mechanism shown in a
use of the ozone/UV process in removing
simplified form in the following equations (22
components from gasoline, such as BTX,
through 29).
MTBE, tert-butyl alcohol and total petroleum
hydrocarbons such as gasoline, present in
O3 + H2O2 HO + O2 + HO2 (21)
contaminated groundwater samples. After
H2O2 HO2 + H+ (22) treatment under previously established
HO2 + O3 O3 + HO2 (23) experimental conditions, removal indices
HO2 O2 + H+ (24) higher than 99% of pollutants initially present
O2 + O3 O3 + O2 (25) in all contaminated water samples were
O3 + H+ HO3 (26) obtained. In natural samples containing iron,
HO3 HO + O2 (27) lower degradation rates were obtained than in
O3 + HO O2 + HO2 (28) iron-free samples or in those with lower
O3 + HO2 2 O2 + HO (29) concentrations. The authors report that,
although iron can act by degrading organic
Wang and coworkers (2002) reported that pollutants from the ferrous ion reactions with
hydrogen peroxide can simultaneously react the ozone itself to generate hydroxyl radicals
with the superoxide radical anion (O2) to (reactions 17, 32-33), the presence of iron
produce another hydroxyl radical, as shown by renders all samples progressively more turbid,
Equation 30. reducing radiation absorption by the solution.
H2O2 + O2 HO + OH + O2 (30) Fe2+ + O3 FeO2+ + O2 (32)

FeO2+ + H2O Fe3+ + HO + OH (33)

2.4. Heterogeneous photocatalysis radicals in the hole (h+) of the catalyst (Minero
The first studies developed on the use of et al., 1996; Alfano et al., 1997), as shown by
photocatalysis in the presence of a Equations 35 and 36.
semiconductor to degrade an organic pollutant
were conducted in the early 1980s by Pruden h+ + H2O HO + H+ (35)
and Ollis (1983), among others, as cited by h+ + HO HO (36)
Alfano and coworkers (2000). Since then this The dissolved oxygen present or added to
process has been one of the main study focuses the medium, can act as an electron acceptor,
among the advanced oxidation processes generating the superoxide radical (Equation 37)
(Alfano et al., 1997; Bhatkhande et al., 2003; and triggering a series of reactions that may
Bockelmann et al., 1995; Crittenden et al., lead to the formation of hydroxyl radicals
1997b; Curc et al., 1996; Fujishima et al., (Quina et al., 2004; Valente et al., 2005).
2000; Fujishima et al., 2007; Goslich et al., According to Bockelmann and coworkers
1997; Kositzi et al., 2004; Ljubas, 2005; (1995), the addition of hydrogen peroxide may
McLoughlin et al., 2004; Malato et al., 2002; also favor the process, given that, like oxygen,
Rodrguez et al., 1996; Romero et al., 1999; it may act as the acceptor of electrons available
Salah et al., 2004; Serpone, 1997; Sichel et al., in the system, generating hydroxyl radicals,
2007). according to Equation 38.
The principle of heterogeneous
photocatalysis is based on the activation of a O2 + e O2 (37)
semiconductor particulate material (CdS, TiO2, H2O2 + e HO + HO (38)
ZnO, WO3 etc.) by the action of radiation with
an appropriate wavelength. This activation is Figure 1 shows the reaction mechanism
achieved with the absorption of photons by the involving the electrons and holes produced by
semiconductor particle possessing enough UV light that can migrate to the surface of the
energy to promote the conduction of an anatase particle, where they react with adsorbed
electron (e) from its valence band (VB) to the oxygen, water, hydroxide ions or organic
conduction band (CB) (a transition called species via electron transfer reactions (Quina et
bandgap energy), creating holes in the valence al., 2004).
band (h+) that will act as oxidizing sites
(Serpone, 1997). According to Alfano and 2.4.1. Application
coworkers (1997), titanium dioxide (TiO2) in Bessa and coworkers (2001) studied the
the anatase form is the most indicated material treatment of water produced from oil fields via
for use in photocatalytic water treatment a photocatalytic process using TiO2/UV, with
processes, considering toxicity, resistance to
photocorrosion, availability, catalytic efficiency
and cost. TiO2 absorbs radiation at wavelengths O2
below 400 nm (which enables the use of
sunlight), capable of forming eh+ pairs
e
(Equation 34) that can recombine (Goslich et
al., 1997). O2
h
TiO2 TiO2 (eBC + h+BV) (34) HO + H+
TiO2
After the formation of these eh+ pairs, a h+
recombination occurs in the catalyst, generating
heat and adsorbing water molecules and H2O
hydroxyl ions present in the medium. These Figure 1. Schematic representation of the basic
will act as electron donors, generating hydroxyl mechanism of TiO2 photocatalysis. Adapted from
Quina and coworkers (2004).

the addition of H2O2. Chromatographic study also verified the influence of temperature
analyses showed the complexity of the and found that its increase leads to increased
wastewater, and most of the compounds present pollutant degradation, relating this effect to
in the medium, remained unidentified. electron transfers in valence band to higher
However, a considerable reduction in energy levels and, therefore, facilitating the
chromatogram peaks can be observed, showing production of eh+ pairs.
pollutant degradation and the presence of a
number of alkanes (considered non-toxic) in 2.5. Electrochemical oxidation
the treated wastewater. The addition of H2O2 in According to Brillas and coworkers (1998),
the photocatalytic process was unnecessary and electrochemical processes can produce
even undesirable, owing to the corrosive and hydroxyl radicals by two means: anodic
damaging effects of this substance on the oxidation (direct form) and mediated electro-
catalysts (TiO2). oxidation (indirect form). In anodic oxidation,
As previously mentioned, Hu and coworkers the hydroxyl radical is generated in the anode
(2008) studied the degradation of a gasoline (Pt, PbO2, doped with SnO2 etc.) of an
additive (methyl tert-butyl ether MTBE). In electrochemical cell from water oxidation
addition to the use of the H2O2/UV process, the (Equation 39). In mediated electro-oxidation,
use of TiO2/UV was compared with a modified chemical species, such as H2O2, are
catalyst (Ag/TiO2/UV). The use of continuously generated in the cathode by the
Ag/TiO2/UV achieved a higher degradation rate reduction of two electrons of dissolved oxygen,
than that obtained with TiO2/UV, reaching as shown by Equation 40 (Brillas and Casado,
higher MTBE removal indices (around 80%) 2002).
more rapidly. The authors suggested that this
difference was due to the formation of micro- H2O HO + H+ + e (39)
batteries on the surface of TiO2, where Ag acts O2 + 2H+ + 2e H2O2 (40)
as an electrode in coupling with TiO2, receiving
the electron from the activation reaction of The hydrogen peroxide generated can act as
TiO2 (Equation 34) and reducing the compound a reagent for Fentons system, with the addition
to its oxidized state. of iron, leading to the formation of hydroxyl
Saien and Nejati (2007) used the TiO2/UV radicals (Equation 12). This process, whereby
process to degrade the organic pollutants of a the hydrogen peroxide from Fentons reaction
refinery wastewater pretreated by physical- is electrochemically generated, is called the
chemical processes. They studied the effect of electro-Fenton process (Brillas and Casado,
TiO2 concentration, finding an optimal 2002). Oturan and Brillas (2007) reported that
condition (of maximum degradation, reaching the Fe3+ obtained with Fentons reaction
90%), in which increased TiO2 concentration (Equation 12) or added to the solution can be
caused a decrease in the degradation rate, continuously reduced to Fe2+, creating an
probably due to the increase in solution electrochemical catalysis process, as shown by
turbidity and consequent reduced light Equation 41.
transmission in the medium. An assessment of
pH obtained an optimal pH of around 3. The Fe3+ + e Fe2+ (41)
authors reported that this was due to the fact
that the formation of eh+ pairs (Equation 34) The oxidation power of the system can also
is favored under conditions of lower pH than be increased with the introduction of ultraviolet
the point of zero charge of TiO2 (pH = 6.25), radiation to help reduce Fe3+ to Fe2+, as shown
and for pH values below 3, the absorption of by Wang and coworkers (2008), consisting of a
anions formed from the dissociation of added combination of techniques known as the
sulfuric acid reduces the possibility of organic photoelectron-Fenton process.
matter absorption on the surface of the catalyst, According to Saltmiras and Lemley (2002),
decreasing the degradation rate. The same the Fentons electrochemical treatment can also

be used by means of an electrochemical cell (H2) and in the anode (O2 and Cl2). The authors
with iron electrodes (cathode and anode), in also found that the increased temperature
which the anode has the function of transferring favors the removal of COD by the
iron to the solution and the cathode functions as electrochemical process.
an inert electrode for water reduction, as shown
in Equations 42 and 43. The Fe2+ transferred by 2.6. Wet air oxidation and supercritical
the cathode acts in the Fentons reaction water oxidation
(Equation 12), with the addition of hydrogen Wet air oxidation (WAO) is an ecologically
peroxide to the system. safe technology for treating water containing
organic pollutants (Zerva et al., 2003). This
technique enables the oxidation of pollutants
Fe Fe2+ + 2e (42) from oxygen dissolved in water, under high
2H2O + 2e H2(g) + 2OH (43) pressure conditions (10-220 bar) and high
temperatures (150-370C), leading to the
One of the disadvantages of this process is formation of hydroxyl radicals (Domnech et
that, owing to the formation of hydroxide ions al., 2001; Rivas et al., 1998). Supercritical
in the cathode, the medium in which this water oxidation (SCWO) consists of submitting
process is applied is close to neutral pH, which water to higher temperature and pressure
is not suitable for Fentons reaction. In conditions than their critical point (above
addition, solids are formed in the solution, 374C and 221 bar, respectively). This
owing to iron hydroxide precipitation technique obtains rapid results, but requires
(Saltmiras and Lemley, 2002). high energetic demand and, consequently, high
operational costs.
2.5.1. Application Wet air oxidation may have its efficiency
Yavuz and Koparal (2006) studied the improved with the presence of homogeneous
degradation of phenol present in a refinery catalysts (such as Cu2+ salts) and heterogeneous
wastewater via electrochemical oxidation, catalysts (MnO2, CuO, Fe2O3 etc.) in the
using a titanium electrode coated with titanium reaction, as cited by Domnech and coworkers
oxide and ruthenium oxide. The initial phenol (2001), and known as catalytic wet air
concentration was 192.2 mg/L and the chemical oxidation (CWAO).
oxygen demand (COD) was 590 mg/L. After
treatment, a 94.5% removal of phenol and 2.6.1. Application
70.1% of chemical oxygen demand (COD) was Sun and coworkers (2008) applied
obtained, the latter because the wastewater still microwave assisted catalytic wet air oxidation
contained other organic and inorganic in the treatment of petrochemical wastewater. It
contaminants. was observed that the use of microwaves helps
Santos and coworkers (2006) used in heating and heat conduction, accelerating the
dimensionally stable anodes (or DSA, a pollutant degradation rate. A positive effect on
metallic base of titanium coated with titanium the pollutant degradation rate was also found
and ruthenium oxides) in the electro- with an increase in temperature and dissolved
remediation of oily wastewater produced oxygen in the medium, as well as with a rise in
during petroleum extraction and refining. The microwave power levels. The authors
authors managed to remove up to 57% of initial concluded that microwave assisted catalytic
COD from the wastewater and attributed this wet air oxidation was efficient in removing
reduction to the consequence of the electro- non-biodegradable organic pollutants and
degradation of organic compounds, through the demonstrated that this method, as a
anodic oxidation of components in the DSA pretreatment process, made the wastewater
electrode and the electro-flotation of oil adequate (with the increased biochemical
droplets in suspension that aggregate on the demand of oxygen) for biological treatment.
surface owing to the gas formed in the cathode

3. CONCLUSIONS unfeasible. These conventional techniques

Advanced oxidation processes provide an consists of simply removing the contaminated
efficient alternative for treating wastewater area, a process that has an environmental and
contaminated with toxic organic compounds. physical impact on the affected site, followed
With high oxidation power, the hydroxyl by the storage or extraction of contaminants,
radicals are capable of totally or partially which is a costly method that does not resolve
degrading practically all classes of organic the pollutant problem, but rather transfers the
compounds present in aqueous medium or in polluting load from one location to another.
soils, resulting in the complete mineralization One of the requirements to ensure the good
of these compounds or in their conversion to use of AOP is to conduct large scale studies
more biodegradable products. and scale-enlargement projects that more
The studies conducted in the petrochemical faithfully represent industrial applications
area presented in this study showed promising (which have large flows), given that most
results, reducing the organic pollution load of studies in the area are still carried out at
wastewaters, in many of the investigations, to laboratory scale.
negligible levels. Even when not completely
degraded, there is a large reduction in
wastewater toxicity, which enables subsequent ACKNOWLEDGEMENTS
biological treatment. This capacity of AOP to The authors would like to acknowledge
completely degrade the organic load or to financial support from the following Brazilian
convert it into products that enable biological agencies: CNPq (Conselho Nacional de
treatment is extremely important in the oil Desenvolvimento Cientfico e Tecnolgico),
industry, since they allow the reuse of water for CAPES (Coordenao de Aperfeioamento de
more productive purposes, such as irrigation, or Pessoal de Nvel Superior) and ANP (Agncia
in the production process itself, reducing the Nacional do Petrleo, Gs Natural e
environmental impact caused by discarding or Biocombustveis).
lowering the water consumption costs present
in practically all oil production stages.
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BRAZILIAN JOURNAL OF PETROLEUM AND GAS ISSN 1982-0593

ADVANCED OXIDATION PROCESSES AND THEIR APPLICATION IN

* To whom all correspondence should be addressed.

Abstract. Advanced oxidation processes (AOP) are technologies based on the

Keywords: advanced oxidation processes; petrochemical wastewater; oil wastewater;

1. INTRODUCTION sedimentary basins and as a result of storage

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Table 1. Physical-chemical characteristics of oil refinery wastewaters.

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Table 3. Types and classification of advanced oxidation processes.

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Fe3+(RCO2)2+ Fe2+ + CO2 + R (18) Machulek Jr and coworkers (2007) found

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removed to non-detectable levels. The authors The remediation of diesel-contaminated soil

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efficiency of ozone is extremely dependent on The O3/UV process consists in UV

2O3 + 2H2O 2HO + O2 + 2HO2 (20) O3 + H2O H2O2 + O2 (31)

H2O2 + O2 HO + OH + O2 (30) Fe2+ + O3 FeO2+ + O2 (32)

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3. CONCLUSIONS unfeasible. These conventional techniques

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ANDREOZZI, R., CAPRIO, V., INSOLA, A., concentrator technology development to

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COELHO, A., CASTRO, A. V., DEZOTTI, Comparison of deployed mussels (Mytilus

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LUCAS, M. S., DIAS, A. A., SAMPAIO, A., containing organic compounds.

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Programa de Ps-graduao em Engenharia Journal of Hazardous Materials B, v. 98, p.

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photodegradation of organic pollutants in SKORA, J., PADO, M., TATARKO, M.,

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