Catalytic Wet Air Oxidation of Phenol: Review of The Reaction Mechanism, Kinetics, and CFD Modeling

Critical Reviews in Environmental Science and
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ISSN: 1064-3389 (Print) 1547-6537 (Online) Journal homepage: https://www.tandfonline.com/loi/best20
Catalytic wet air oxidation of phenol: Review of the

reaction mechanism, kinetics, and CFD modeling
Tladi J. Makatsa, Jeffrey Baloyi, Thabang Ntho & Cornelius M. Masuku
To cite this article: Tladi J. Makatsa, Jeffrey Baloyi, Thabang Ntho & Cornelius M. Masuku
(2020): Catalytic wet air oxidation of phenol: Review of the reaction mechanism, kinetics,
and CFD modeling, Critical Reviews in Environmental Science and Technology, DOI:
10.1080/10643389.2020.1771886
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CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/10643389.2020.1771886
Catalytic wet air oxidation of phenol: Review of the

reaction mechanism, kinetics, and CFD modeling
Tladi J. Makatsaa,b, Jeffrey Baloyib, Thabang Ntho, and
Cornelius M. Masuku a
a
Department of Civil and Chemical Engineering, University of South Africa, Florida, South Africa;
b
Advanced Materials Division, Mintek, Randburg, South Africa
ABSTRACT
Advanced oxidation processes,
specifically catalytic wet air oxida-
tion (CWAO), are considered as
useful and robust methods for
the treatment of refractory
organic compounds such as phe-
nol in wastewater. This paper
reviews reaction mechanisms, kin-
etics and computational fluid
dynamics (CFD) modeling of
CWAO of phenol. Different reac-
tion mechanisms have been pro-
posed by various researchers to
account for possible intermedi-
ates during phenol oxidation.
These mechanisms can be either
direct or indirect; with the indir-
ect path resulting in the forma-
tion of intermediates, while with
the direct mechanism, no intermediates are formed, the reaction proceeds straight to
carbon dioxide and water. Acetic acid is considered as the most stable intermediate of
phenol oxidation. Power law and Langmuir–Hinshelwood models were used to account
for the adsorption/desorption of the reactants on the surface of the catalyst. The
reviewed studies show that phenol conversion increases with increased temperature,
pressure, gas velocity and decreases with increasing liquid space velocity. The formation
of hot spots next to the walls of the reactor leads to safety issues and may cause cata-
lyst deactivation and reactor thermal run away. This prompted a review of liquid mal-
distribution and the formation of hot spots inside the reactor using the CFD modeling
technique. In most cases, liquid channeling was observed, resulting in the formation of
hot spots and catalyst deactivation.
KEYWORDS Computational fluid dynamics; kinetics modeling; phenol oxidation; reaction mechanism;
wastewater treatment
CONTACT Cornelius M. Masuku [email protected] Department of Civil and Chemical Engineering,

University of South Africa, Florida, South Africa.
ß 2020 Taylor & Francis Group, LLC
2 T. J. MAKATSA ET AL.
1. Introduction
Industrial processes use a lot of water which must be treated in the effluent
plant before discharging it to the municipal wastewater treatment plant
(Adekola & Majozi, 2017). Industrial wastewater usually contains a high
concentration of toxic organic compounds including phenol and its deriva-
tives (Lal & Garg, 2015; Zuo et al., 2017; Baloyi et al., 2018b). Phenolic
wastewaters originate from a number of industrial processes making it a
model pollutant for bio-toxic and non-biodegradable organic pollutants.
Moreover, phenol is an intermediate product found in the oxidation of aro-
matic hydrocarbocns (Chicinaş, 2018). In addition, it is listed as a priority
pollutant by the United States Environmental Protection Agency (Lal &
Garg, 2015). The use of phenol in petroleum, petrochemical, pharmaceut-
ical, paint, pulp and paper, plastic and refinery industries is common (Sun
et al., 2015; Villegas et al., 2016; Baloyi et al., 2018a, 2018b; Seadira et al.,
2018, 2020; Masuku & Biegler, 2019).
There are different wastewater treatment methods available such as, bio-
logical (Krastanov et al., 2013; Pradeep et al., 2015; Alves et al., 2017; Zhou
et al., 2018), adsorption (Luo et al., 2015; Frascari et al., 2019; Sun et al.,
2019), electrochemical oxidation (Abbas & Abbas, 2019; Liu et al., 2019),
incineration (Ye et al., 2011; Wang et al., 2019), reverse osmosis (Al-Obaidi
et al., 2017; Al-Obaidi et al., 2019b, 2019a) and advanced oxidation proc-
esses (Cao et al., 2018; Dewidar et al., 2018; Radwan et al., 2018). Microbial
degradation is unsuitable for waste that is too concentrated and toxic,
moreover, it produces by-products that pose environmental problems such
as sludge (Krastanov et al., 2013; Yu et al., 2016; Guerra-Que et al., 2019).
Incineration is energy-intensive and is only applicable when waste has a
chemical oxygen demand (COD) of at least 300 g/L (Cybulski, 2007).
Reverse osmosis produces a concentrated and smaller waste making dis-
posal easy, however, the costs of membrane replacement and energy
requirement are high (Crini & Lichtfouse, 2019; Pervov & Nguyen, 2019;
Tałałaj et al., 2019). The incapability of traditional methods to effectively
remove refractory organic wastewater makes it clear that there is an urgent
need to develop more efficient and economic processes of treating refrac-
tory wastewater before discharging it to water bodies.
Advanced oxidation processes (AOPs) such as catalytic wet air oxidation
(CWAO) offer an alternative solution of treating refractory wastewater.
CWAO gained a lot of interest over the past two decades because of its
ability to oxidize toxic wastewater and complete mineralization (Fortuny et
al., 1995; Maugans & Akgerman, 2003; Suarez-Ojeda et al., 2007; Monteros
et al., 2015; Baloyi et al., 2018b). Moreover, CWAO is a heterogeneous pro-
cess, so an additional stage of separating the catalyst from the solution is
not required in most instances hence making the process more economic
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 3
(Serra-Perez et al., 2019). However, there is limited literature that reviews

reaction mechanisms, kinetics and CFD modeling of CWAO process
(Cybulski, 2007; Levec & Pintar, 2007; Kim & Ihm, 2011). A study by
Eftaxias et al. (2001) proposed a reaction network path for phenol oxida-
tion and also proposed a mechanism after performing HPLC analysis. It
was shown that phenol breaks down to form aromatics (hydroquinone, cat-
echol, and benzoquinone) and carboxylic acids (oxalic and formic acid).
Furthermore, traces of malonic, maleic and fumaric acid were also detected.
The obtained results were in agreement with what was reported by Devlin
and Harris (1984). These authors (Devlin & Harris, 1984) proposed a reac-
tion pathway for oxidation of phenol and suggested that at elevated tem-
peratures in the presence of water, the oxidation process takes place in
three different ways when oxygen is used as an oxidant. According to the
proposed path, oxidation occurs by substitution reaction whereby the oxy-
gen atom is substituted into an aromatic ring resulting in the formation of
dihydric phenol or quinone. Furthermore, oxygen can attack double
bonded carbon-carbon chain to form carbonyl compounds and these com-
pounds (carbonyl) together with alcohol can be oxidized to form carboxylic
acids. Low concentrations of maleic, fumaric, succinic, propionic, malonic
and acrylic acid were detected whereas significant amounts of catechol,
hydroquinone, p-benzoquinone, oxalic acid, glyoxylic acid, acetic acid, for-
mic acid, and glyoxal were also detected.
Eftaxias et al. (2001) used both simple power law and Langmuir-
Hinshelwood (L-H) models to determine the reaction rate and the power-
law model only succeeded in fitting phenol removal. When the L-H
model was used for phenol and intermediates, all experimental concentra-
tion profiles were accurately described with mean deviations less than 8%.
Similarly Guo and Al-Dahhan (2003) used both power-law and Langmuir-
Hinshelwood-Hougen-Watson (LHHW) and found that a simple power-
law model fails to predict phenol especially when concentrations are too
high. The average absolute relative error (AARE) found for phenol was
15.7% whereas when the LHHW model was used, good results were
obtained with AARE at less than 15%.
The use of trickle bed reactors (TBR) is common in CWAO of phenolic
compounds; however liquid mal-distribution may cause hot spot formation,
reactor thermal runaway and deactivation of the catalyst. Mousazadeh
(2013) used CFD to predict the formation of hot spots in a trickle bed
reactor. A hot spot was observed when there was a local blockage prevent-
ing the fluid from flowing. Furthermore, there was a temperature difference
of 153 C between the hot spot and the surrounding area. It was concluded
that the hot spots were formed when liquid could not convect in the radial
or axial direction.
This review is primarily focused on the recent advances and develop-

ments in computational fluid dynamics, reaction kinetics and reaction
mechanism of phenol oxidation. The use of L-H model in heterogeneous
catalysis is common because of its ability to accurately predict adsorption-
desorption kinetics on the surface of the catalyst.
2. Homogenous and heterogeneous systems

Numerous researchers have reported salts of Fe, Cu and Mn-based catalysts
as commonly used homogenous catalysts in CWAO process, due to
remarkable performance for degradation of phenol at lower temperature
(120–180 C) and lower pressure (5–80 bar) (Gao, 2018; Sanchez-Trinidad
et al., 2019; Guerra-Que et al., 2019). Moreover, the process control and
reactor design of homogenous catalysts is reported to be less complex as
compared to the heterogeneous CWAO process. Arena et al. (2010) found
that Fe-, Cu- and Mn-based catalysts were able to remove phenol at oxygen
partial pressure of 9 bar, temperature of 150 C and reaction time of
360 min. Parvas et al. (2014) reported that the CuO/CeO2–ZrO2 nanocata-
lysts synthesized via co-precipitation and ultrasound-assisted method was
able to achieve complete conversion of phenol with initial phenol concen-
tration of 1000 mg/L at 160 C and atmospheric oxygen partial pressure
after 180 min. Garg and Mishra (2013) reported the 90% degradation of
phenol over CuSO4 as homogenous catalyst by CWAO process at 120 C
and 5 bar pressure after 4 h reaction time. The homogenous catalysts have
proven to be highly active for the phenol degradation and TOC removal at
lower temperature and lower pressure. However, the homogenous catalyst
system is not economically viable due to additional separation steps of dis-
solved ions after CWAO process which would increase surplus equipment
and cost required. Therefore, finding an alternative catalytic system for
phenol oxidation which is effective, high energy efficient and cheap with
the potential to treat phenol and other highly toxic organic pollutants is
important. In this case, the heterogeneous CWAO process has been
reported by various researchers as the most promising process for phenol
oxidation on large scale applications due to its easiness in separation and
operation on a large scale.
Recently, numerous heterogeneous catalysts such as noble metals, non-
noble metals and metal oxides have been used. The catalytic activities of
the various catalysts in the CWAO reaction of phenol are summarized in
Table 1. Various researchers have synthesized different heterogeous cata-
lysts with an aim of discovering robust, cheap and efficient solid catalysts,
ensuring the total oxidation of highly toxic and recalcitrant in wastewater
at mild reaction conditions (Davies et al., 2018; Ukonu, 2018). For example,
Table 1. Performance comparison of the results of phenol oxidation with CWAO using
various catalysts.
Catalyst Reactor Conditions Effect Ref.
MWCNTs Batch 155 C, 25 bar, 100% phenol removal, (Yang, 2012)
1000 mg/L, 120 min 75% TOC removal
MnOx-CeO2 Autoclave 140 C, 20 bar, 100% phenol removal, (Arena et al., 2012)
Cu3-Al-500 Autoclave 120 C, 10 bar, 100% phenol removal, (Lai et al., 2019)
2000 mg/L, 120 min 99% COD removal
GO Batch 155 C, 25 bar, 100% phenol removal, (Yang et al., 2014)
rGO Batch 160 C, 7 bar, 100% phenol removal, (Yang et al., 2014)
(Ru,Pt)-TiO2–CeO2 Batch 160 C, 20 bar, 100% phenol removal, (Monteros
2098 mg/L, 180 min 88% TOC removal et al., 2015)
Al/Zr-PILCs Autoclave 100 C, 10 bar, 100% phenol removal, (Baloyi et al., 2018c)
Yang (2012) studied the CWAO of phenol at 155 C and 25 bar pressure
using Multi-walled carbon nanotubes (MWCNTs) functionalized by differ-
ent oxidants (HNO3/H2SO4,H2O2,O3 and air). All functionalized catalysts
show good catalytic activity, whereas the O3-treated MWCNTs have the
highest activity with 100% phenol and 80% TOC removals after 120 min
reaction. Furthermore, the O3-treated MWCNTs show high stability in the
cyclic reactions. It was suggested that the high amount of carboxylic acid
groups and weakly acidic nature of the surface on the functionalized
MWCNTs play a significant role for the superior catalytic activity of the
MWCNTs. Arena et al. (2012) studied phenol oxidation over MnOx-CeO2
catalyst and found that the catalyst was highly active at mild temperatures
such as 100 C and a total pressure of 10 bar. It was reported that complete
phenol removal was achieved within 40 min reaction time, while 80% of
TOC conversion was achieved after 60 min. The high catalytic performance
of the catalyst was attributed to the rapid adsorption of phenol and its
intermediates. The treatment of phenol oxidation was studied by Lai et al.
(2019) using Cu3-Al-500 at 120 C and 10 bar pressure. The catalyst was
found to be stable and complete conversion of phenol and 99% COD was
achieved within 120 min. Good catalytic performance was attributed to the
redox transitions of Cu2þ/Cuþ and/or the formation of H2O2 and the sur-
face acidity of the catalyst in reaction mixture. Yang et al. (2014) studied
the treatment of phenol by CWAO process at 155 C and 25 bar pressure
using graphene oxide (GO) and chemically reduced graphene oxides
(rGO). The phenol conversion of 100% and mineralization of 84% and
80% was observed with GO and rGO, respectively. High catalytic perform-
ance was due to high surface area and high pore volume of graphene which
provides higher adsorption capacity to the catalyst. Monteros et al. (2015)
studied CWAO of phenol over Ru and Pt supported on TiO2–x wt% CeO2
at 155 C and 20 bar pressure. The (Ru,Pt)-TiO2–CeO2 catalysts showed
high activity toward oxidation of phenol by achieving 100% phenol conver-

sion and 88% TOC removal. Baloyi et al. (2018c) reported the complete
removal of phenol and 88% TOC removal after 120 min at 100 C and
10 bar over low-cost Al/Zr-PILCs catalyst. The catalyst showed excellent
chemical and structural stability with insignificant leaching of Zr4þ after six
consecutive catalytic runs.
3. Reaction mechanism
The reaction mechanism of phenol oxidation is a complex process resulting
in the formation of aromatics, lightweight carboxylic acids and inorganic
compounds (CO2 and H2O). The reaction mechanism requires an under-
standing of the reactions that take place on the surface of the catalyst
together with intermediates and final oxidation products (Braga et al.,
2018). In most instances, phenol oxidation takes the following route; oxida-
tion, decarboxylation, dehydration or combination of all steps (Eftaxias,
2002). According to Eftaxias (2002), the relevant phenol oxidation reactions
at the catalyst surface causing the oxidation of phenol can be expressed as
follows:
RH OH þ cat ! R H ¼ O þ H cat (1)
R H ¼ O þ O2 ! RHO OO (2)
RHO OO þ RH OH ! ROH OOH þ R H ¼ O (3)
where RH OH represents phenol, R H ¼ O is phenoxy radical while
RHO OO corresponds to peroxy radical.
Several studies have been conducted by different researchers with the
aim of determining intermediate species formed on the surface of the cata-
lyst. The findings are still controversial because as depicted in Figures 1
and 2, some scholars reported that phenol can be directly oxidized to CO2
and H2O without the formation of intermediates while others, shown in
Figure 3, claim the formation of polymerization product and acetic acid via
an indirect mechanism. In some instances, acetic acid can be fully oxidized
to CO2 and H2O while in some cases it is resistant to the oxida-
tion process.
3.1. Indirect mechanism

Wang et al. (2014) proposed a different mechanism from the ones in litera-
ture, portrayed in Figure 4, they used functionalized carbon materials as
catalysts (multiwalled carbon nanotubes, nanofibers, and graphite) to inves-
tigate phenol oxidation. Phenol was oxidized in a 1 L autoclave reactor
equipped with a stirrer, heating device and cooling coil. The reactor tem-
perature and pressure were kept constant at 160 C and 25 bar. To identify
Figure 1. CWAO of phenol oxidation reaction mechanism (Zapico et al., 2015).
intermediates they used HPLC with 60% methanol in water plus 0.1%
acetic acid as mobile phase and ODS-3 column. The removal of phenol
over this catalyst reached almost 100% after 120 min, suggesting that these
catalysts are very active. The results obtained can be attributed to carbox-
ylic acids found on the surface of functionalized carbon material improving
their activity. In their study, catechol was not detected like in most papers
in open literature and they suggested that it might be because of different
catalysts used. Maleic, fumaric and very low concentrations of cis butene-
dioic anhydride were also detected. To further understand the reaction
path; pure standards of maleic, malonic, acetic, oxalic and formic acid were
also oxidized. In CWAO of maleic acid, the following intermediates were
found; malonic acid, oxalic acid, acetic acid, and formic acid. Acetic acid
was not detected in the first 30 min of the experiment meaning that it is
not directly produced from the oxidation of maleic acid instead it might be
produced from malonic and oxalic acid. In the oxidation of malonic acid, a
sharp decrease in concentration was observed while both acetic and formic
acids were shortly detected in the solution suggesting that these two are
Figure 2. Reaction mechanism of phenol oxidation proposed by (Castaldo et al., 2019).
direct products of malonic acid oxidation. Two peaks were detected by

HPLC when acetic acid was oxidized, one was assigned to acetic acid and
the other one was unknown. An assumption was made that this unknown
peak belongs to dioxirane but it was never confirmed since dioxirane of
high purity was not available. Oxidation of formic acid follows the same
route as the one reported by Santos et al. (2002). These authors (Santos et
al., 2002) proposed a mechanism for formic acid oxidation and suggested
that it follows a termination path in the free radical mechanism whereby
hydroxyl radical attacks it to remove hydrogen bonded to carbon and the
free radical COOH to form oxalic acid. Moreover, they found that when
conditions are suitable, formic acid and oxalic acid mutually interconvert.
Quintanilla et al. (2006) proposed a reaction pathway illustrated
in Figure 5 for phenol oxidation over Fe supported on activated carbon
(AC) catalyst. The proposed study was carried out in a trickle bed reactor
with an inside diameter of 8.5 and 305 mm length and the reactor was
operated between (100, 127 C and 8 bar), pressure and flow rates were
kept constant by mass flow controller and back pressure valve. Phenol and
Figure 3. Proposed reaction pathway for the CWAO of phenol in the presence of CuSO4
catalyst (Lal & Garg, 2015).
other intermediates were measured by HPLC using Nucleosil C18 column

(15 cm, 4.6 mm, 5 mm) with a mobile phase of 4 mM sulfuric acid mixed
with acetonitrile (9:1, v/v). During CWAO of phenol calculated values of
total organic carbon (TOC) were higher than the measured ones at low
reaction times, indicating that there are some unidentified intermediates.
These unidentified intermediates were assigned to condensation products
belonging to aromatics or quinone-like since a strong brownish color was
Figure 4. Reaction mechanism for CWAO of phenol in a batch reactor using functionalized
carbon material as catalyst proposed by (Wang et al., 2014).
observed. At high reaction times, these compounds were not present since
calculated TOC results were in agreement with measured results and this
was confirmed by a colorless solution.
The formation of p-hydroxybenzoic acid follows two routes: it can be
formed when phenol interacts with oxygen groups found on the surface of
activated carbon or from the oxidation of chemically adsorbed species on
the surface of AC previously formed by oxidative coupling reaction of phe-
nol and aromatics. During oxidation of intermediates, 90% of hydroquin-
one was converted to p-benzoquinone. When p-benzoquinone was oxidized
100% conversion was reached with maleic, malonic, acetic and formic acid
identified as intermediates. However, a small difference was observed
between TOC and p-benzoquinone conversion values in the reactor exit.
Thus, suggesting that most of p-benzoquinone was converted to CO2 and
H2O via oxalic acid. Oxidation of p-hydroxybenzoic acid produced maleic,
acetic and formic acid. Unidentified species were neglected due to close
values of measured and calculated TOC. Maleic acid was the main product
Figure 5. Schematic diagram of CWAO of phenol reaction mechanism in the presence of Fe/AC
catalyst (Quintanilla et al., 2006).
of oxidation. At high reaction time, 100% of oxalic acid was converted to

CO2 and H2O. In addition, oxidation of maleic acid produced fumaric,
acetic and formic acid whereas formic acid concentrations were higher
than acetic acid at TOC values ranging between 20 and 40%. The measured
and calculated TOC values were in agreement indicating complete oxida-
tion of maleic acid. Formic acid was completely mineralized when it was
oxidized at 127 C and 8 bar whereas no conversion was observed when
acetic acid was oxidized. Furthermore, malonic acid was oxidized to acetic
acid and CO2. However, traces of formic acid were detected but measured
and calculated TOC values indicated that all intermediates were identified.
Lal and Garg (2015) investigated phenol oxidation under mild operating
conditions (120 C and 5 bar) using a homogeneous copper catalyst in a
0.7 L high-pressure stainless steel batch reactor equipped with a stirring
rod. The reactor was equipped with a heating jacket and the temperature
was regulated using a proportional integral derivative (PID) controller.
Similarly, they used HPLC to measure intermediates and Synergi C18
column (25 cm, 4.6 mm, 4 mm). Phosphate buffer was mixed with aceto-
nitrile (9:1, v/v) and used as a mobile phase. Phenol was completely oxi-
dized within 30 min and parallel reaction pathway was confirmed by the
appearance of hydroquinone and catechol. Samples collected between 15
and 30 min showed the presence of p-benzoquinone due to breaking down
of hydroquinone. However, o-benzoquinone was not detected when cat-
echol was oxidized due to the unstable nature of this compound caused by
two adjacent C ¼ O groups. All organic acids (oxalic, formic, malonic,
maleic and fumaric) were detected within 15 minutes except acetic acid
which appeared after 30 min. Acetic acid is formed during decarboxylation
of malonic acid and oxalic acid might break down to formic acid during
this process. Moreover, traces of maleic and fumaric acids were also
detected and a significant concentration of oxalic acid was found after 3 h.
In addition, formic acid was decarboxylated by hydroxyl radicals to form
CO2 and H2O as represented in Figure 3. The reaction of hydroxyl radical
can happen in three ways: by hydroxyl addition, hydrogen abstraction or
electron transfer. In the presence of transition metals, CWAO follows auto-
oxidation mechanism in this manner:
C6 H5 OH !Cu2þ C6 H5 OH þ H (4)
C6 H5 OH þ O2 ! C6 H5 OOO (5)
C6 H5 OOO þ H2 O ! C6 H5 OOOH þ HO (6)
C6 H5 OOOH ! C6 H5 O þ HO2 (7)
C6 H5 O þ C6 H5 O ! C6 H5 OOC6 H5 (8)
Hydroxyl radicals are known to be neutral electrons and they attack at
the high electron density area of the molecule. Phenolic compounds have
high electron density available at ortho and para positions because of the
resonance effect. Due to this effect; hydroxyl radical attacks these positions
to remove hydrogen or add oxygen leading to the formation of catechol or
hydroquinone. The formation of p-benzoquinone is due to the formation
of stable free radical formed when hydroquinone is attacked by the free
radical. Benzoquinone has six carbon chains and two have low electron
density caused by oxygen electronegativity. The electron density of the
other four carbons can be increased by the presence of oxygen by reson-
ance, causing ring opening when HO attacks these carbons. Some poly-
mers were also identified by Fourier Transmission Infrared (FTIR)
microscopy showing the presence of aromatics, olefinic and alcohols.
Most of the studies that suggest the formation of polymers as intermedi-
ates were performed in a batch reactor at mild operating conditions in the
presence of Cu2þ catalyst. These polymers are formed due to a high ratio
of liquid volume to catalyst in the reactor. When the catalysts was charac-
terized, the results indicated that polymerization products were present on
the surface of the catalyst. These polymerization products reduce the activ-
ity and reusability of the catalyst by blocking access to active sites.
However, when functionalized carbon materials were used as catalysts at
high pressure, polymerization products were not detected and phenol was
completely removed. Therefore, the use of a batch reactor in phenol oxida-
tion is not practical due to the high pressure required to avoid the forma-
tion of polymers and high costs of catalyst regeneration. On the other
hand, when TBR was used, polymerization products were not formed and
phenol was completely oxidized. However, when Cu2þ catalyst was used,
analysis results indicated that Cu2þ ions were present in the solution sug-
gesting leaching of the catalyst. Several studies reported that pillared clay
(PILC) catalysts are stable and leaching of active sites is insignificant (Guo
& Al-Dahhan, 2003; Baloyi et al., 2018b; Moma et al., 2018). Therefore,
TBR should be used in the wastewater treatment of phenolic compounds.
In order to minimize leaching of active sites, it is advisable to use PILC
catalyst in CWAO of phenolic compounds.
3.2. Direct mechanism

Using homogeneous copper catalyst in a 1 L stainless steel batch reactor
equipped with three blades of 20 mm propeller, Zapico et al. (2015) oxi-
dized phenol using the following operating conditions, temperatures (100 –
140 C) and oxygen partial pressures of (5 – 12.5 bar). The reaction tem-
perature was regulated using a temperature-controlled oven. Their main
aim was to determine the influence of operating conditions (temperature,
pH, and concentration) on phenol oxidation in acidic conditions. When
phenol was oxidized it was reported that a black solid (polymer) was
formed when the reaction was prolonged and this solid was insoluble in
both polar and non-polar organic solvent. This type of intermediate was
also reported by Levec and Pintar (1995), and after further testing, they
concluded that this intermediate was a polymer. To confirm their results,
the authors used GC/MSD and proposed a mechanism that explained the
formation of this compound. The authors suggested that polymers are
formed by stepwise addition of glyoxal to phenol. In addition, at low pH
value of 2, phenol conversion with time was found to be very low due to
the formation of maleic acid and this was explained by the fact that reac-
tion rate is proportional to pH. At low pH, phenol is not oxidized because
phenoxyl radicals produced are immediately protonated, avoiding the for-
mation of intermediates. After analyzing the final product, the following
intermediates were identified by HPLC using 5% acetonitrile in water as a
mobile phase and Agilent Zorbax SB-Aq column (15 cm, 4.6 mm, 5 mm);
hydroquinone, p-benzoquinone, catechol, maleic and oxalic acid.
Hydroquinone, p-benzoquinone and catechol were completely removed at

pH 4 after 5 hours; at lower pH values, high reaction time was required.
When COD analysis was performed, it was discovered that oxidation takes
place via two paths, direct oxidation of phenol to CO2 and H2O, depicted
in Figure 1, and indirect mechanism which involves the formation of
intermediates.
Castaldo et al. (2019) investigated phenol oxidation in a glass semi-
batch reactor operated at 95 C and 0.3 MPa over a nanocomposite cata-
lyst of PtRu/MoS2 embedded in a hyper-crosslinked resin. The reactor
was equipped with a magnetic stirrer and the temperature was controlled
using a heating jacket. In contrast to (Lal & Garg, 2015, Quintanilla et al.,
2006), these authors used UV-vis spectra and gas chromatography coupled
with a mass spectrometer (GC-MS) to measure phenol conversion.
Moreover, carbon dioxide evolution was measured using Siemens
Utramar 22 analyzer. To test catalyst activity; two experiments were con-
ducted at 1000 and 4000 mg/L of phenol concentration while keeping
operating conditions the same in all experiments. When the experiment
was conducted at high concentrations (4000 mg/L) both acetic acid and
hydroquinone were detected by UV-vis at low and high wavelengths after
240 min and 99.9% of phenol was removed. Further tests were performed
using GC analyzer and after 300 min, phenol content was 30.1% and a
high concentration of acetic acid (96.61%) was detected whereas insignifi-
cant amounts of hydroquinone (2.98%) and p-benzoquinone (0.41%) were
detected. These authors proposed a reaction mechanism in Figure 2 and
suggested that hydroquinone was the primary intermediate and it oxidizes
fast to form p-benzoquinone. Moreover, this intermediate (p-benzoquin-
one) oxidizes to form CO2 and carboxylic acids. When low concentration
(1000 mg/L) was used, UV-vis spectra indicated the presence of low
molecular weight organic acid (acetic) after 30 min and these results were
confirmed by GC-MS. Furthermore, 99.9 and 97.1% of phenol and TOC
were removed.
It is interesting to note that Castaldo et al. (2019) managed to oxidize
phenol directly to CO2 and H2O at mild operating conditions in a batch
reactor and no polymers were formed. However, the catalyst used in their
study might be too expensive when the process is scaled up. Similar
results were also reported by Zapico et al. (2015) in their study. However,
the authors reported the formation of polymerization products. It is there-
fore, advisable to avoid the use of a batch reactor in a homogeneous pro-
cess because of the added costs of separating a catalyst at the end of the
process. The future research should focus on the development of inexpen-
sive catalysts that are highly selective to CO2 and H2O for heteroge-
neous processes.
4. Kinetics
4.1. Effect of temperature
It is generally accepted that an increase in temperature will result in high
phenol conversion due to the fact that the reaction rate constant is a function
of temperature and activation energy, according to the Arrhenius equation:

Ea
k ¼ Aexp (9)
RT
Where k is the reaction rate constant, A is a preexponential factor, Ea is
activation energy, R is the gas constant and T is the temperature.
The increase in temperature also results in the formation of oxygen free
radicals which can react with oxygen and water to form peroxide (H2O2)
and ozone (O3) radicals. These radicals can participate in phenol oxidation,
thus increasing the efficiency of the process (Mohammed et al., 2016). The
study by Eftaxias et al. (2005) proved that the performance of unsupported
commercial activated carbon as a catalyst is highly dependent on tempera-
ture. They investigated phenol oxidation using activated carbon as a catalyst
in a trickle bed reactor operated between 120 C - 160 C. Phenol and COD
conversion improved when temperature and space-time were increased
resulting in conversions higher than 99% for phenol, 85% COD at 160 C
and space-time greater than 0.4 h. Similarly Mohammed (2014) studied the
effect of temperature on phenol oxidation in a trickle bed reactor operated
between (120 C - 160 C) using activated carbon as a catalyst. After 1 h they
reached 100% conversion at 160 C while at low temperatures (120 and
140 C) low conversions were reported (88.6 and 92.7%). Yang et al. (2014)
also used carbon-based catalysts (graphene oxide and reduced graphene) in a
batch reactor. The reactor temperature was kept constant at 155 C and gra-
phene oxide (GO) was found to be the most active catalyst achieving 100%
phenol conversion in 40 min while 120 min was required to remove all phe-
nol when reduced graphene oxide (rGO) was used. Furthermore, over 80%
of TOC was converted after 120 min in both cases. Wu et al. (2005) used
copper supported on activated carbon as a catalyst in a batch reactor with a
temperature range of (140 C - 160 C) and a similar trend was also reported.
Ahmed (2012) investigated phenol oxidation using 0.5% Pt supported on
c-Al2O3. Phenol was oxidized in a trickle bed reactor operated between the
temperatures of 85 C and 140 C. They reported phenol conversions of
88.59%, 75.6%, 65%, and 43.86% at 140 C, 120 C, 100 C and 85 C,
respectively. The formation of intermediates also increased with an increase
in temperature. Mohammed et al. (2016) developed a kinetic model for
phenol oxidation in a trickle bed reactor using 0.48% Pt/c-Al2O3 spheres as
a catalyst and the reactor was operated between (120 C - 160 C). In their
model kinetics parameters were estimated based on experimental data and

from the data obtained they up-scaled the reactor to predict the behavior
of phenol oxidation in industrial reactors. At a temperature of 120 C phe-
nol conversion was 87.954% and when the temperature was increased to
140 C and 160 C phenol conversion increased significantly to 90.878%
and 93.13%. On the other hand, several authors used less expensive cata-
lysts like MnO2/CeO2, Al/Zr pillared clay (PILC), Al/Cr pillared clay, Al/Fe
pillared clay, and Al-Fe pillared clay (Hamoudi et al., 1998; Guo & Al-
Dahhan, 2003; Mohammed & Abdullah, 2008; Baloyi et al., 2018b, 2018a;
Moma et al., 2018). Baloyi et al. (2018b) studied phenol oxidation in a
batch reactor operated at 100 C, over single metal oxide pillared clay (Al-
PILC & Zr-PILC)) and mixed metal oxides (Al/Zr-PILC) pillared clay cata-
lyst. After a reaction time of 180 min, 100% conversion was attained when
both single and mixed metal oxide catalysts were used in separate experi-
ments. However, high TOC removal was achieved when the mixed metal
oxide catalyst was used (88%) compared to single metal oxide (61%) after
180 min. Similar results were also obtained by Baloyi et al. (2018a) in their
study. Phenol was oxidized in a batch reactor operated at 100 C using single
metal oxide pillared clay (Al-PILC & Cr-PILC)) and mixed metal oxides (Al/
Cr-PILC) pillared clay catalyst. After 120 min 100% phenol was removed
when Al/Cr-PILC (1:1 molar ratio) was used and ca.84% of TOC was con-
verted after 180 min whereas when single metal oxides were used TOC con-
version decreased from 84 to 36%. In their study Guo and Al-Dahhan
(2003) studied wet air oxidation of phenol over Al-Fe pillared clay catalyst
extrudes. Phenol oxidation was investigated between 90 C and 150 C in a
basket stirred tank reactor. According to their findings, phenol and its inter-
mediates are highly influenced by temperature increase. Furthermore, it was
concluded that a 20 C increase in temperature can result in double phenol
conversion in 1 h. In addition, they managed to remove 0.5 g/L of phenol
completely when the reactor was operated at 90 C for 300 min, whereas at
130 C phenol was completely removed within 100 min. Phenol conversion
was faster compared to intermediates degradation due to the fact that short-
chained carboxylic acids are more stable and oxidation rate increase with a
molecular weight of the acid (Klinghoffer et al., 1998). Hamoudi et al. (1998)
investigated phenol oxidation in a batch reactor under mild conditions
(80 C – 130 C) using MnO2/CeO2 catalyst. They reported 100% phenol
removal at 130 C after 30 min while TOC conversion was more than 98. An
increase in temperature was less pronounced for intermediates compared to
phenol removal indicating the formation of carboxylic acids.
In summary, the studies that were conducted using carbon-based cata-
lysts indicated that at high-temperature phenol was completely removed in
a short space of time. This is because phenol is reduced in two ways,
adsorption and catalytic activity. The same results are also evident when
PGMs and PILC catalysts are used. However, PGMs are expensive and the
reaction temperature required to completely remove the pollutant is high
irrespective of the catalyst used. Furthermore, many studies involving the
use of PILC catalysts are conducted in a batch reactor. Therefore, more
studies should be conducted to develop catalysts that are cheap and highly
reactive (PILC) to reduce reaction temperature and space-time using a dif-
ferent reactor configuration (TBR) instead of batch.
4.2. Effect of initial phenol concentration

The study of the effect of initial phenol concentration is significant both
from a mechanistic and application point of view to investigate the depend-
ence of phenol reaction rate kinetics on the substrate concentration.
Mohammed et al. (2016) investigated phenol oxidation in a trickle bed
reactor using 0.48% Pt/c-Al2O3 catalyst while varying initial phenol con-
centration from, 0.001, 0.003 and 0.005 g/L. When phenol concentration
was increased from (0.001–0.005 g/L), conversion increased from 80.35 to
94.75% due to increased phenol molecules on the active sites of the catalyst.
Similarly, Abid et al. (2014) investigated the effect of initial phenol concen-
tration in a trickle bed reactor over 0.5% Pt/c-Al2O3 catalyst while varying
phenol concentration between, 0.9, 2.5 and 5 g/L. The authors reported that
an increase in phenol concentration has a negative impact on phenol con-
version, contradicting the results of Mohammed et al. (2016) above.
Moreover, the conversion of phenol at 0.9 g/L was 67.47% and when the
concentration was increased to 5 g/L the conversion dropped to 59.44%
indicating 8% reduction. Resini et al. (2008) also investigated the effect of
phenol concentration between (0.035–0.118 g/L) over lanthanum strontium
manganite catalyst in a batch reactor. According to their observations, phe-
nol conversion decreased with an increase in concentration and they attrib-
uted this occurrence to transport limitations of phenol on the surface of a
catalyst. Similar results were also reported by Lal and Garg (2015), the
researchers investigated the effect of initial phenol concentration between
(1–10 g/L) over the homogeneous copper salt catalyst in a batch reactor. A
significant amount of phenol was removed after 3 h with an increase from
approximately 60 to 96%. Moreover, phenol conversion increased with a
decrease in concentration and similar trends were also observed for TOC.
It is generally reported that the phenol oxidation rate increases with an
increase in concentration. However, this concept is true to a certain point
because a further increase in concentration beyond a saturation point usually
results in a decrease in phenol conversion. This phenomenon is demon-
strated in several studies conducted by different scholars to determine the
effect of phenol concentration. Their findings are still controversial because

some researchers claim that an increase in phenol concentration increases
conversion while others report the opposite. These controversial findings
necessitate the need to investigate the claim further to close the gap.
4.3. Effect of pH
It is common knowledge that at low pH values the following reaction takes
place (Zapico et al., 2015):
PhO þ Hþ $ PhOHþ (10)
Zapico et al. (2015) investigated the effect of pH in a batch reactor oper-

ated between pH values of (2–4) using a homogeneous copper catalyst.
According to their findings, phenol conversion increased with an increase in
pH. The induction period was also observed at pH 4, 3 due to the initializa-
tion step of radical reactions and this phenomenon decreased with increase
in pH. This suggests that phenol is not oxidized at low pH values because
initialization reaction produces phenoxyl radicals that are immediately proto-
nated avoiding the formation of intermediates. The reaction rate is heavily
dependent on pH, thus an increase in pH affects the reaction rate positively.
Abid et al. (2016) investigated the effect of pH in a trickle bed reactor oper-
ated between pH values of (3–10) using activated carbon (AC) catalyst. The
highest phenol conversion was achieved at pH 5 whereas when pH was
increased to 10, lowest conversions were observed. Furthermore, maximum
adsorption was recorded at pH 5 and when pH was increased above this
point adsorption capacity decreased and point of zero charge was found to
be at pH 8. The catalyst surface was positively charged during the reaction,
therefore, experiencing high affinity for anions or ionized compounds.
Similarly, Guo and Al-Dahhan (2003) studied the effect of pH between
(3.9–5.1) in a basket stirred tank reactor over Al-Fe pillared clay catalyst.
They studied phenol oxidation using two solutions; in the first solution, pH
was adjusted using sulfuric acid whereas in the second solution pH was not
adjusted. It was reported that when pH was adjusted, phenol removal rate
was 2 times higher compared to when pH was not adjusted and 100% con-
version was achieved at pH 3.9. Yadav et al. (2016) studied the effect of pH
between (2.8 -8) in a batch reactor using Fe supported on carbon-containing
nanoparticle catalysts. During phenol oxidation, a decrease in pH from 6 to
2.8 was observed indicating the formation of carboxylic acids and 100% con-
version was achieved at pH 2.8 after 210 min. However, for safety reasons
they adjusted the pH to 8 using KOH so that the final pH of the solution
after oxidation will be ca.5 and the oxidation rate remained the same when
compared with the first experiment without pH adjustment and complete

removal of phenol was achieved at the same reaction time of 210 min.
In summary, the studies indicate that the system performs better when
the solution is acidic. However, acidic solutions are highly corrosive and
can damage the reactor, thus necessitating the use of corrosion-resistant
materials during reactor design (Resende et al., 2018). Moreover, at low pH
most catalysts are leached increasing the cost of the catalyst. It is therefore
advisable to invest in the development of a catalyst that will reduce phenol
directly to inorganic compounds without the formation of carboxylic acids
to avoid low pH values in the reactor.
4.4. Effect of liquid and gas hourly space velocity

Liquid hourly space velocity (LHSV) has a negative impact on phenol con-
version. This is due to the fact that an increase in LHSV reduces space-
time resulting in less contact time between the phases. An increase in
LHSV also increases film thickness and liquid holdup which decreases con-
tact time between gas and liquid on the catalyst active sites therefore result-
ing in high resistance to mass transfer. However, the effect of gas flow is
the opposite of LHSV with an increase in gas flow resulting in improved
phenol removal due to decreased film thickness, liquid holdup and
enhanced mass transfer. Abid et al. (2016) investigated the effect of both
liquid and gas flow rates on phenol oxidation using a trickle bed reactor
over activated carbon catalyst. They studied liquid flow rate of 1.662, 0.996
and 0.6 ml/min while gas flow rates were 10, 20, 30 and 60 ml/min.
According to their observation, an increase in LHSV has a negative influ-
ence on phenol conversion with 79% reached at 1.662 ml/min while 86.8%
and 95.6% were reached when LHSV was decreased to 0.996 and 0.6 ml/
min. Furthermore, phenol removal reached 79.7%, 82.5%, 86.8% and 83.5%
at gas flow rate of 10, 20, 30 and 60 ml/min, respectively. The maximum
conversion was reached at 30 ml/min of gas flow due to the decrease in
film thickness and liquid holdup, whereas the decrease in conversion at
60 ml/min was due to a decrease in wetting of the catalyst surface caused
by liquid mal-distribution. Similarly, Mohammed et al. (2016) investigated
the effect of liquid and gas flow on phenol oxidation in a trickle bed
reactor using 0.48% Pt/c-Al2O3 catalyst operated in the following gas flow,
20, 40, 80 and 100% and liquid hourly space velocity between 1, 2 and
3 h1. The maximum conversion was reached at a gas flow rate of 80% and
a further increase in gas flow resulted in a slight decrease in conversion
due to the decreased spreading of the liquid film. In their study
Mohammed (2014) studied the effect of gas and LHSV in a trickle bed
reactor that was operated between (60–100%) stoichiometric oxygen excess
(S.E) and LHSV ranging from 1, 2 and 3 h1 over activated carbon catalyst.
It was reported that maximum conversion was achieved when the gas flow
rate was 80% S.E and when the flow rate was increased beyond this point,
conversion was decreased due to the decreased. However, phenol conver-
sion increased with a decrease in LHSV and the following results were
reported when LHSV was 2 and 3 h1, 87.16 and 82.5%.
It can be concluded that an increase in gas flow has a positive influence
whereas, LHSV has a negative impact. A prior knowledge of the flow
regime is required to choose the correct design equation for TBR.
Moreover, hydrodynamics and transport properties of the system can
change dramatically between the flow regimes impacting final results sig-
nificantly. Currently, empirical flow map or relationships are used to pre-
dict the flow patterns and there is a limited theoretical foundation
developed to predict the transition between the flow regimes. On the other
hand, an increase in computing memory and technological advances saw
an increase in the use of CFD and Tomography to understand the flow
transition between the regimes. For developing countries with limited
resources, CFD is the cheapest technique that can be used to understand
the interaction between the phases.
5. Kinetic model
Kinetics models are crucial for the design and up-scaling of laboratory reac-
tors to industrial reactors (Zarca et al., 2015). A simple power-law model can
be used to determine the rate of reaction in a trickle bed reactor as reported
by (Eftaxias, 2002; Eftaxias et al., 2005; Abid et al., 2014; Abid et al., 2016,
Makatsa et al., 2019). The simple power law can be expressed as follow:
rph ¼ koi : Exp ½Eai =RT :Ci :xO2 a (11)
Where, rph is reaction rate, koi is a frequency factor, Eai is activation
energy, R is ideal gas constant, T is temperature, xO2 is dissolved molecular
oxygen mole fraction, a is reaction order with respect to oxygen concentra-
tion and Ci is phenol concentration.
Abid et al. (2016) used a different catalyst and slightly higher tempera-
ture compared to their previous study (Abid et al., 2014). In this study,
they used activated carbon as a catalyst and the reactor was operated
between temperatures of (120 C – 160 C) and pressure of 2 to 9 bar. The
activation energy was a bit higher (77.7 KJ/mol) and the reaction order
with respect to oxygen was 0.6. Abid et al. (2014) also used a power-law
model to determine reaction rate parameters using 0.5% Pt/c-Al2O3 catalyst
in a trickle bed reactor operated between 85 – 140 C and pressure of 1 to
6 bar. Oxygen reaction order was found to be 0.69 and activation energy
was 29.3 KJ/mol. Similarly, Eftaxias et al. (2005) used power law model to
determine reaction rate parameters over activated carbon (AC) catalyst in a
trickle bed reactor operated between temperatures of 120 – 160 C and
pressure of 1 and 2 bar. The kinetic model was able to adequately predict
phenol conversion only when the conversion was below 70% and for con-
versions above 70%, the model overestimated experimental conversion. The
deviation was attributed to liquid maldistribution reinforced by the smaller
reactor configuration. Furthermore, phenol oxidation activation energy
over the catalyst was found to be 69, 3 6 0.4 KJ/mol and the oxygen mole
fraction was 1,015 6 0.02. Eftaxias (2002) used both power-law and
Langmuir-Hinshelwood (L-H) model in a trickle bed reactor operated
between temperatures of (120 C – 160 C) and pressure of 6 to 12 bar over
two catalysts (CuO/c-Al2O3 and AC). It was reported that when power law
model was used in the presence of CuO catalyst; phenol and acetic acid
were estimated very well, however, the model failed to predict the remaining
carboxylic acids and quinone-like compounds. In addition, L-H model was
not used for phenol oxidation because preliminary experiments obtained from
adsorption experiments indicated that phenol was not adsorbed on the surface
of the catalyst. The reaction activation energy was found to be 74.9 KJ/mol
and the oxygen order was 0.311. In contrast, when the AC catalyst was used,
phenol destruction activation energy was slightly lower (70.3 6 0.4 KJ/mol) and
reaction order with respect to oxygen was 0.95 6 0.02.
Another model that is commonly used to correlate adsorption-desorption
of heterogeneous catalysts is Langmuir-Hinshelwood (L-H) or Langmuir-
Hinshelwood-Hougen-Watson (LHHW) reported by (Eftaxias et al., 2001,
2006; Guo & Al-Dahhan, 2003; Wu et al., 2005). Langmuir-Hinshelwood
(L-H) model can be expressed as follows:
Ki Ci
ri ¼ kap, i P (12)
1 þ j K j Cj
Where ri is reaction rate, kap, i is reaction kinetics constant, Ki and Kj are

adsorption constants, Ci and Cj are species concentrations.
Eftaxias et al. (2001) used the L-H model to determine kinetics parame-
ters using a copper-based catalyst (CuO/c-Al2O3) with the temperature of
the reactor between 120 C – 160 C. They reported activation energy of
74.9 KJ/mol and an oxygen reaction order of 0.31. Table 2 summarizes kin-
etic models used by Guo and Al-Dahhan (2003) in a basket stirred tank
reactor operated between 90 and 150 C over Al-Fe pillared clay catalyst.
The power-law model (M1) is used to correlate the simplest form of the
surface reaction rate. As can be seen from the reaction mechanism of
model M2, adsorption and desorption of phenol and oxygen take place on
the same site and a more complex model like LHHW is used to model the
Table 2. Kinetic models proposed for heterogeneous CWAO reaction (Guo & Al-Dahhan, 2003).
Kinetic Model Equation Mechanism
M1 rH ¼ k1[A]P[O2]q Empirical Approach
M2 k1 KA KO2 ½O2 ½A Single site
rH ¼
ð1 þ KA ½A þ KO2 ½O2 Þ2
O2 þ $ O2
M3 k1 KA KO0:5 ½A O0:5
2
Dual site
rH ¼ 2
ð1 þ KA ½A þ KO0:5
2
½O20:5 Þ2
O2 þ 2 $ 2O2
Dual Sites
M4 k1 KA KO0:5 ½A O0:5
2
O2 þ2$ 2O2
rH ¼ 2
ð1 þ KA ½A þ KO0:5
2
½O20:5 Þ2
Note: refers to single catalyst site, 2 refers to dual catalyst sites.
process. The mechanism of M3 is similar to M2 because of single-site

adsorption. In contrast to M2, oxygen molecules dissociate to allow surface
reaction of physically adsorbed phenol and oxygen to take place. The last
model M4 is completely different from previous models because dissociated
molecules are adsorbed on two active sites. To check the quality of the
models, they were compared with experimental data. Parity plot was used
to compare experimental results with calculated results and experimental
data was adequately fitted when kinetic model M2–M4 was used whereas
M1 under predicted phenol of high concentration. When model M4 was
used, the activation energy of 34.29 KJ/mol was reported.
Eftaxias et al. (2006) used L-H model to determine the kinetic parame-
ters using an active carbon catalyst with the temperature of the reactor
between 120 C – 160 C and pressure of and 1 to 2 bar. The oxidation of
phenol to 4–HBA and p-benzoquinone were found to be 82.4 and 72 KJ/
mol whereas oxygen reaction orders were, 1.02 6 0.02 and 0.92 6 0.01,
respectively. Similarly, Wu et al. (2005) used an L-H model to predict kin-
etics parameter using copper supported on activated carbon catalyst with
the reactor operated between 140 C – 160 C. The activation energy was
found to be 35.4 KJ/mol and first order reaction for phenol was assumed.
A complete reduction of phenol to CO2 and H2O is very complex and
its reaction mechanism is not yet fully understood. Some oxidation by-
products are as toxic as phenol and therefore, kinetic models accounting
for all intermediates are very important. Most studies show that the power
law model can be used to predict phenol. However, this model has limita-
tions because it can’t be used when phenol and its intermediates are
adsorbed on the surface of the catalyst. As shown in Table 2, mathematical
correlations (M2–M4) can be used to account for adsorption and desorp-
tion of the organic pollutant on the surface of the catalyst, whereas Table 3
give a summary of activation energies and reaction conditions. In conclu-
sion, L-H model is the most suitable kinetic model for the oxidation of
phenol and its intermediates.
Table 3. Activation energies and reaction orders found in literature using different reactors.
Temperature Activation Oxidant
Catalyst Reactor Model Equation ( C) Energy(KJ/mol) Reaction Oder Ref
CuO/ c-Al2O3 TBR Ki Ci 120–160 74.9 0.31 (Eftaxias et al., 2001)
ri ¼ kap, i P
1 þ j K j Cj
Al/Fe pillared clay BSTR 0:5 190–150 34.29 – (Guo & Al-Dahhan, 2003)
k1 KA KO2 ½ACO2 0:5
rH ¼
1 þ KA ½A
AC TBR koi exp DH i 120–160 82.4 and 72 1.02 ± 0.02 and 0.92 ± 0.01 (Eftaxias et al., 2006)
Eai a RT Ci
ri ¼ koi exp xO2 P
RT DH
1 þ koj exp RTj Cj
Cu/AC BSTR CA CB 140–160 35.4 – (Wu et al., 2005)
rH ¼ khet;app
ð1 þ KA CA Þ0:5
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
23
6. CFD modeling
The use of TBR in heterogeneous catalysis is common, especially when gas
and liquid react to form products. However, most studies are conducted in
a laboratory fixed bed reactors and the scaling up of these reactors to
industrial reactors is problematic due to complex interactions of fluid
dynamics with reaction kinetics. Moreover, the change in hydrodynamic
parameters is significant when laboratory reactors are scaled up to com-
mercial reactors and correlations developed in a laboratory reactor might
not work. Ranade and Gunjal suggested that the scale of the reactor affects
its performance. In addition, these authors listed several factors that are
directly affected during reactor scaling-up as follows; reactor to particle
diameter ratio, reactor volume, bed porosity, wetting, channeling, liquid
mal-distribution, dispersion and reactor operating mode (isothermal/adia-
batic). Moreover, these researchers concluded that wall effect is predomin-
ant in laboratory TBR whereas flow mal-distribution is common in
industrial TBR due to large bed diameter. On the other hand, when CFD
model is developed correctly, it should be independent of the scale of the
reactor because these models are based on conservation of mass, energy
and momentum. CFD simulations provide a time saving and cost-effective
approach in the reactor design. In a typical design, the software is used to
solve a system of complex mathematical equations (Haro et al., 2016). The
software can be used to solve multiple phase flows like gas-liquid, liquid-
solid and gas-solid flows (Kapfunde et al., 2018). Multi-phase flow systems
can be modeled in three different ways using volume of fluid (VOF),
Eulerian–Lagrangian and Eulerian–Eulerian approach. The first method
(VOF) is the easiest and all phases are considered as a non-interpenetrating
continuum. The method solves a single set of momentum equations and
tracks the volume of all phases in a computational domain. The method is
suitable for analysis of multiple phase systems of the small domain and
modeling the behavior of the interface. In addition, the method is used
mostly when modeling large scale systems. The Eulerian–Lagrangian
method considers a fluid phase as a continuum and solves a system of
Navier–Stokes equations for the continuous phase while solving the dis-
persed phase by tracking the particles through the calculated flow field.
This model is recommended for modeling of the multiphase flow with less
volume fraction of the dispersed phase and for modeling liquid fuel and
spray dryers. In contrast, the Eulerian-Eulerian method is based on the
assumption that every phase is an interpenetrating continuum. The method
uses the approach of single pressure for all phases. Governing equations
are solved separately for each phase (continuity, momentum, energy, and
species transfer equations). This approach is suitable for the modeling of
the multiphase flow with volume fraction ranging from 0 to 1 and for
multiple phase reactors with more than one dispersed phase (Mousazadeh,
2013). The following sets of mathematical equations are incorporated into
a CFD code solver.
Mass conservation equation:
oek qk
þ r:ek qk Uk ¼ 0 (13)
ot
Momentum conservation equation:
oðek qk Uk Þ
þ r:ðek qk Uk Uk Þ ¼ ek rPk þ r:ðek lrU Þ
ot (14)
þ ek qk g þ FK, R ðUk Ur Þ
Where, ek is volume fraction for each phase, qk is the density of the k-th
phase,Uk is the cell velocity of the k-th phase and FK, R is an interphase
momentum exchange. The interface coupling term FK, R can be expressed
as follow

E1 lG ð1 eG Þ2 eS
FGL ¼ eG 0:667
eG dP
2 2
ð1 eG Þ
0:333
E2 qG ðUG UL Þð1 eG Þ eS
þ (15)
eG dp ð1 eG Þ
0:667
E1 lG ð1 eG Þ2 eS
FGS ¼ eG
eG 2 dP 2 ð1 eG Þ
0:333
E2 qG UG ð1 eG Þ eS
þ (16)
eG dp ð1 eG Þ
!
E1 lG eS 2 E2 qL UG eS
FLS ¼ eL þ (17)
eG 2 dP 2 eL d p
Where, FGL, FGS, FLS are gas-liquid, gas-solid and liquid-solid momentum
exchange terms. Ranade et al. used a model developed by Attou and
Ferschneider (1999) to simulate the flow regime where the liquid flow was in
the form of droplets. Mousazadeh (2013) used CFD to predict the formation
of hot spots in a trickle bed reactor. A hot spot was observed when there was
a local blockage preventing the fluid from flowing. Furthermore, there was a
temperature difference of 153 C between the hot spot and the surrounding
area. It was concluded that the hot spots were formed when liquid cannot
convect in the radial or axial direction. Lopes and Quinta-Ferreira (2007)
developed a computational fluid dynamics model of a trickle bed reactor oper-
ated between the temperature of 170 C – 200 C and pressures of 10 –
30 bar. These authors used FLUENT 6.1 and Euler–Euler multiphase flow
approach to model the behavior of the fluid inside the reactor. Furthermore,
the researchers studied the influence of gas and liquid flow rate within the
trickle flow regime ranging between (gas: 0.10 – 0.70 and liquid: 0.5 – 5 kg/
m2s). In order to validate their findings for pressure drop and liquid holdup,
a spherical catalyst of a 2 mm diameter was used as a reactor packing. In add-
ition, they mapped both gas and liquid flow; and found maximum velocities
to be 0.5 and 0.005 cm/s respectively. Their results showed that the reactor
was operated within a trickle flow regime. According to their findings, an
increase in liquid mass flux resulted in an increase in liquid holdup whereas
an increase in pressure resulted in a significant decrease of the liquid holdup.
The increase in liquid mass flux improves interaction between gas and liquid
which causes turbulence and thickens the liquid film. These changes resulted
in an increase in liquid side shear stress due to high-pressure drop and resist-
ance became more pronounced in comparison to the driving force. Their
results were in agreement with (Kuzeljevic, 2010; Mousazadeh, 2013; Beni &
Khosravi-Nikou, 2015). The researchers concluded that a change in reactor
pressure is more pronounced on pressure drop than liquid holdup. Similarly,
Beni and Khosravi-Nikou (2015) modeled hydrodynamics of the trickle bed
reactor and used 300 spherical particles arranged in a hexagonal pattern with
maximum space between them, not exceeding 3% of particle diameter. They
simulated only 12 layers due to computational limitation and investigated the
effect of pressure on hydrodynamics parameters at lower pressures ranging
between (0.1, 0.5 & 1 MPa). They also varied gas and liquid superficial veloc-
ities between (0.086 & 0.25 m/sec) and (<0.005–0.03 m/s) respectively.
Regardless of mild pressure they also reached the same conclusion as (Lopes
& Quinta-Ferreira, 2007).
Accurate estimation of hydrodynamic parameters is an important step
for reactor design and performance evaluation of the catalyst. The complex
internal bed structure and phase interaction are the controlling factor in
TBR. Hydrodynamics are affected by; particle properties, packing character-
istics of the bed and operating conditions. There are methods and correla-
tions available for determining hydrodynamic parameters such as liquid
holdup, axial dispersion and CFD.
In summary, CFD can be used to model liquid mal-distribution and pre-
dict the formation of hot spots. Hot spots are undesired because they may
reduce production by deactivating the catalyst or decrease the mechanical
strength of the wall. It is recommended that a simulation of TBR fitted
with a mechanical liquid distributer at the top be simulated.
7. Conclusions and future prospects

CWAO is an advanced oxidation process capable of treating refractory
organic wastewater at mild operating conditions. The primary objective is
to oxidize phenol to inorganic products and short-chain carboxylic acids

that are biodegradable. However, the phenol oxidation reaction pathway is
still controversial because some scholars report that phenol can be directly
oxidized to CO2 and H2O without the formation of intermediates while
others claim the formation of polymerization products and acetic acid via an
indirect mechanism. In some instances, acetic acid can be fully oxidized to
CO2 and H2O while in some cases it is resistant to the oxidation process.
The effects of operating parameters (temperature, pressure, pH, concen-
tration, LHSV, and gas flow rate) on phenol oxidation were reviewed.
Phenol conversion increases with an increase in temperature and pressure
but the effect of temperature is more pronounced than pressure. Moreover,
the effect of LHSV has a negative impact on phenol conversion whereas
the gas flow rate has the opposite effect. An increase in pH has a positive
effect on phenol conversion but when activated, carbon is used as a catalyst
or to support a further increase above pH 8 results in a decrease in conver-
sion because activated carbon has a point of zero charges of 8. In contrast,
the effect of initial concentration is controversial because some researchers
report an increase in phenol conversion with an increase in concentration
whereas others report the opposite.
Kinetics models play an important role in the design and upscaling of
laboratory reactors to industrial reactors. In our study, simple power law
and L-H models were reviewed, a simple power-law model can be used to
predict kinetics parameters very well but in some cases especially when
phenol concentration is high, it can underpredict the parameters and when
phenol conversion is above 70% it can overestimate the results. On the
other hand, a complex model like L-H can be used to predict kinetics
parameters when adsorption/desorption takes place on the surface of the
catalyst with high precision. Computational fluid dynamics models were
reviewed and it was concluded that the formation of hot spots is due to
local blockage preventing the fluid from flowing. This blockage results in a
temperature difference between the hot spot and the surrounding area.
Funding
The authors are thankful to the National Research Foundation of South Africa (Thuthuka
Grant No. 113652 and Mineral Science Council of South Africa (Mintek) under CWO of
Wastewater Project No. ADR 31904 for financial support. The opinions, findings and con-
clusions or recommendations expressed in this publication are those of the authors. The
funding bodies accept no liability whatsoever in this regard.
ORCID
Cornelius M. Masuku http://orcid.org/0000-0003-0556-4588
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Catalytic Wet Air Oxidation of Phenol: Review of The Reaction Mechanism, Kinetics, and CFD Modeling

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Critical Reviews in Environmental Science and

ISSN: 1064-3389 (Print) 1547-6537 (Online) Journal homepage: https://www.tandfonline.com/loi/best20

Catalytic wet air oxidation of phenol: Review of the

Tladi J. Makatsa, Jeffrey Baloyi, Thabang Ntho & Cornelius M. Masuku

To link to this article: https://doi.org/10.1080/10643389.2020.1771886

Published online: 11 Jun 2020.

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Catalytic wet air oxidation of phenol: Review of the

CONTACT Cornelius M. Masuku [email protected] Department of Civil and Chemical Engineering,

(Serra-Perez et al., 2019). However, there is limited literature that reviews

This review is primarily focused on the recent advances and develop-

2. Homogenous and heterogeneous systems

high activity toward oxidation of phenol by achieving 100% phenol conver-

3.1. Indirect mechanism

Figure 1. CWAO of phenol oxidation reaction mechanism (Zapico et al., 2015).

Figure 2. Reaction mechanism of phenol oxidation proposed by (Castaldo et al., 2019).

direct products of malonic acid oxidation. Two peaks were detected by

other intermediates were measured by HPLC using Nucleosil C18 column

of oxidation. At high reaction time, 100% of oxalic acid was converted to

3.2. Direct mechanism

Hydroquinone, p-benzoquinone and catechol were completely removed at

model kinetics parameters were estimated based on experimental data and

4.2. Effect of initial phenol concentration

effect of phenol concentration. Their findings are still controversial because

PhO þ Hþ $ PhOHþ (10)

Zapico et al. (2015) investigated the effect of pH in a batch reactor oper-

compared with the first experiment without pH adjustment and complete

4.4. Effect of liquid and gas hourly space velocity

Where ri is reaction rate, kap, i is reaction kinetics constant, Ki and Kj are

process. The mechanism of M3 is similar to M2 because of single-site

7. Conclusions and future prospects

to oxidize phenol to inorganic products and short-chain carboxylic acids

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