Atmospheric Environment 140 (2016) 117e134

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Reviewarticle

( VOCs) e A review
Catalytic oxidationof volatile organic compounds
*
MuhammadShahzadKamalb, ShaikhA. Razzaka, MohammadM. Hossaina,
a
& Minerals, Dhahran 31261, Saudi Arabia
Department of Chemical Engineering, King Fahd University of Petroleum
b
& Minerals, Dhahran 31261, Saudi Arabia
Center for Integrative Petroleum Research, King Fahd University of Petroleum

highlights

Common VOCs, their sources and impacts.

Alternative techniques for VOCs destruction/separation.
Catalytic oxidation of VOCs.
Mechanism of catalytic oxidation of VOCs.
Recent development of VOCs oxidation catalysts.
articleinf Oxidation
Oxidation process
o Catalysts
Multicomponent catalysts
Mechanism
Article history: Kinetics
Received 22 January abstract
2016
Received in revised Emission of volatile organic compounds (VOCs) is one of the major contributors
form
to air pollution. The main sources of VOCs are petroleum refneries, fuel
27 April 2016 combustions, chemical industries, decomposition in the biosphere and biomass,
Accepted 17 May pharmaceutical plants, automobile industries, textile manufacturers, solvents
2016 Available
online 18 May 2016 processes, cleaning products, printing presses, insulating materials, of fce
supplies, printers etc. The most common VOCs are halogenated compounds,
aldehydes, alcohols, ketones, aromatic compounds, and ethers. High
concentrations of these VOCs can cause irritations, nausea, dizziness, and
K headaches. Some VOCs are also carcinogenic for both humans and animals.
e Therefore, it is crucial to minimize the emission of VOCs. Among the available
y technologies, the catalytic oxidation of VOCs is the most popular because of its
w versatility of handling a range of organic emissions under mild operating
o conditions. Due to that fact, there are numerous research initiatives focused on
r developing advanced technologies for the catalytic destruction of VOCs. This
d review discusses recent developments in catalytic systems for the destruction of
s: VOCs. Review also describes various VOCs and their sources of emission,
V mechanisms of catalytic destruction, the causes of catalyst deactivation, and
O catalyst regeneration methods.
C
2016 Elsevier Ltd. All rights reserved.
s
1. Introduction
and Pitts, 1997; Lakshmanan et al., 2010; Molina
Volatile organic compounds (VOCs) are those and Rowland, 1974; Peng and Wang, 2007; Rodhe,
organic compounds with a Reid vapor pressure of 1990). Rapid urbanization and industrialization
over 10.3 Pa at normal temperature (293.15 K) and contribute to the growing emissions of VOCs into
pressure (101.325 kPa). The VOCs are a large group the environment. Emission of VOCs can be from a
of carbon-based chemicals that easily evaporate at wide range of outdoor and indoor sources. Outdoor
room temperature (Li et al., 2009; sources include but are not limited to chemical
Ojala et al., 2011; Olsen and Nielsen, 2001). Table 1 industries, paper production, food processing, paint
lists the physicochemical and thermodynamic drying, transportation, petroleum refneries,
properties of common VOCs (Ihsan, 1995). VOCs automobile manufacturers, metal degreasing, textile
are classifed as major contributors to air pollution. manufacturers, electronic component plants,
They contribute both indirectly as ozone/smog solvents, and cleaning products. Indoor sources
precursors and directly as substances toxic to the include household products, offce supplies, printers,
environment (Amann and Lutz, 2000; Finlayson- heatexchanger systems, insulating materials, pressed
Pitts woods, wood stoves, and leaks from piping (Drobek
et al., 2015; Liotta, 2010 ;
 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 118

Ozturk and Yilmaz, 2006; Scire and Liotta, 2012).

Type and nature of VOCs depend on the source of emission.
Examples of VOCs are halogenated hydrocarbons, alcohols,
* Corresponding author.
E-mail address: mhossain@kfupm.edu.sa (M.M. Hossain).

http://dx.doi.org/10.1016/j.atmosenv.2016.05.031 1352-2310/ 2016 Elsevier Ltd. All rights reserved.

Table 1

Compound Formula Cp (J/mol C) B.P. (C) DGf (kJ/mol) DHf (kJ/mol) DHc (kJ/mol) @ 25 C
Toluene C7H8 C3H8 166.0 110.6 42 114.09 12.0 103.8 3909.8
Propane C6H6 73.8 136.1 80.1 23.4 49.0 12.5 2220.0
Benzene C8H10 185.9 136 124.5 24.4 3267.6
Ethylbenzene o- 144 84 120.0 226.7 248.1 4564.7
C8H10 188.8
Xylene Acetylene 56 19 110.8 209.2 115.9 4552.8
C2H2 44.1
68 155.3 109.9 198.8 1299.6
Acetone Formaldehyde n- 125.0
C3H6O CH2O 95.5 101.3 1789.9
Hexane 35.4 39.6 4.0 68.9
C6H14 132.8 19.1 563.4
Dicholoromethane 61.2 68.5
195.0 14.2 166.4 4163.1 583.8
CH2Cl2 76.72 62.5
Tricholoromethane 50.8 435.2
CHCl3 6.7 20.6 52.5
Tetracholoromethane 65.8 87.2 260.7
133.2
Tricholoroethylene CCl4 121.1 20.2 910.8
133.9 68.4
Tetracholoroethylene C2HCl3 103.7 772.8 1192.3
80.02
Acetaldehyde C2Cl4 95.6 1411.1
Ethylene C2 H4 O 53.7
C2 H4 42.9
Physical, chemical, and thermodynamic properties of common VOCs (Ihsan, 1995).
aldehydes, aromatics, alkanes, ketones, olefns, limitations of the condensation processes is the
ethers, esters, paraffns, and sulfur containing disposal of the spent coolants. Due to the energy
compounds (Carpentier et al., 2002; Doggali et al., intensive nature of the process, condensation is
2012; Khan and Kr Ghoshal, 2000; Miranda- limited to only evaporative solvents (Shah et al.,
Trevino and Coles, 2003; Ozturk and Yilmaz, 2006; 2000). Membrane separation is another possible
Soylu et al., 2010;
alternative for the removal of VOCs. Silicon rubber
Yosef et al., 2015). membranes are the most commonly used membrane
The effect of VOCs on the atmosphere depends for the separation of VOCs. In the biofltration
on the nature of VOCs, their concentration, and process, VOCs in the air is removed biologically in
emission sources. However, they have been a solid phase reactor (Leson and Winer, 1991). In
identifed as been responsible for stratospheric this approach, the contaminated wet-gas is fed at the
ozone depletion, tropospheric ozone formation, bottom of the flter and the contaminants in air
ground level smog formation, climate change, sick diffuse into a wet, biologically active layer (i.e.,
building syndrome, decay of plants, toxicity of the bioflm) on the surface of the flter particles. The
atmosphere, and carcinogenic effects in humans bioflm with aerobic bacteria degrades the target
(Carabineiro and Thompson, 2007; Masui et al., pollutant(s) and produces CO2, water, and microbial
2010; Ozturk and Yilmaz, 2006). As most of the biomass. Both the membranes and biofltration
countries have imposed strict conditions to limit process are costly and their operation/maintenance is
VOCs in the environment, there are numerous expensive.
research initiatives around the world developing
In the methods based on destruction, the
effcient technologies to meet the stringent
VOCs are converted into carbon dioxide and
environment regulations.
water. The destruction processes can be thermal,
The emission of VOCs can be controlled using catalytic, or biological oxidation. Thermal
methods based on recovery and destruction. The oxidation or thermal incineration is suitable for
techniques based on recovery include absorption, removing VOCs from fue gas streams with a
adsorption, membrane separation, and condensation. high fow rate and a high concentration of VOCs.
High concentrations of VOCs, especially More than 99% of the VOCs can be burned by
watersoluble compounds can be removed from fue thermal oxidation, typically at high temperatures
gas streams by absorption using a suitable solvent. (>1000 C), which requires additional fuel and
The disposal of VOCs and the spent solvent from an temperature resistant materials. Incomplete
absorber are the common problems faced by the thermal combustion produces undesirable
absorption processes. Physical and/or chemical byproducts such as dioxins and carbon monoxide
adsorption is another technique in which a suitable in the incinerator fue gas. Moreover, noxious
adsorbent (activated carbon, zeolite, polymeric byproducts are formed as a result of thermal
adsorbents etc.) is employed to selectively adsorb incineration (Moretti, 2002). The maximum
the VOCs. Adsorption approach is economical only concentration of the VOCs must be less than the
in situations where VOCs are highly diluted in a fue lower explosive limit (LEL) of a particular
gas stream. The high cost of the adsorbents and the compound in order to avoid any explosions
necessity of frequent regeneration of the adsorbent (Moretti, 2002). In practice, a maximum
are the major limitations of adsorption processes concentration of 25% of the LEL is used, which
(Kujawa et al., 2015). The VOCs can be removed can be achieved by diluting with ambient air.
using condensation induced by increasing the
Catalytic oxidation is one of the most
system pressure at a given temperature or lowering
effective and economically feasible techniques
the temperature at a given pressure. One of the
 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 119

for the oxidation of VOCs into CO 2, water, and Main sources of PCMs are the waste materials
other relatively less harmful compounds. The originating from water purifcation and
catalytic oxidation targets the complete evaporation systems (Huang et al., 2014). The
destruction of VOCs rather than transferring it to commonly encountered PCMs are chloroform,
another phase as in other techniques, such as in dichloromethane, trichloromethane, and carbon
condensation and adsorption. In this approach, tetrachloride (Cappelletti et al., 2012; Huang et
the VOCs are oxidized in presence of a suitable al., 2014; Doherty, 2000; Malaguarnera et al.,
catalyst at much lower temperatures (250e500 2012; Alvarez-Montero et al., 2011). Other
C) than thermal oxidation processes (Carabineiro halogenated VOCs include chlorobenzene,
et al., 2015b; Chen et al., 2008b, 2013, 2014b, dichloroethane, trichloroethane,
2014c; Konsolakis et al., 2013; Larsson and tetrachloroethane, trichloroethylene, and
Andersson, 1998; Papaefthimiou et al., 1998a; tetrachloroethylene (Giraudon et al., 2008).
Santos et al., 2010). Catalytic combustion is a Generally, these compounds are used in
more thermally effcient process than the other formulations and processing of chemical
non-catalytic thermal oxidation processes and extractants, paints, and adhesives, drugs
can be used for dilute effuent streams of VOCs manufacturing, polymer syntheses, as solvents in
(<1% VOCs). Furthermore, it can be more chemical reactions, and as cleaning agents
energy effcient if used in the recuperative mode, (Aranzabal et al., 2014). These compounds are
coupling with a heat exchanger after the catalytic highly volatile and often have long atmospheric
combustion chamber. As catalytic combustion lifetimes (Aranzabal et al., 2014). Humans can
takes place at lower operating temperatures and be exposed to halogenated VOCs by drinking
its startup fuel requirement is lower. Therefore, water, inhalation, and adsorption during
moderate volumes of contaminated air can be swimming (Huang et al., 2014). Halogenated
treated at much lower fuel costs (Musialik- VOCs have a signifcant impact on the
Piotrowska, 2007; Peng and Wang, 2007; Pope et destruction of the ozone layer and as a source of
al., 1978; Van der Vaart et al., 1991). Although radicals in the atmosphere, which contribute to
catalytic oxidation can be applied effectively to the greenhouse gas effects. The 100-year global
treat waste gas streams with varying warming potential (GWP) of halogenated VOCs
concentrations of VOCs and fow rates, it is most range from 10 to 1800, which is much higher
suitable for moderate fow rates and a low than that of CO2 with a GWP of only one (Abedi
concentration of VOCs (Ojala et al., 2011; et al., 2015).
Spivey, 1987). The technique is relatively more
environmentally friendly due to its low 2.2. Aldehydes
temperature operation and the formation of less
dioxins and noxious products (Abbasi et al., Aldehydes are among one of the largest
2011; Jamalzadeh et al., 2013). By the proper components of the total reactive VOCs in the
design of the catalyst system, formation of other atmosphere. Formaldehyde and acetaldehyde are
toxic reaction intermediates can also be two of the most commonly encountered aldehyde
minimized. As catalytic oxidation is the most VOCs. These belong to one of the groups acting
suitable for effuent streams with low as a source of new radicals, which control the
concentrations of VOCs, it is highly suitable for formation of ozone. The most important source
end-of-pipe VOCs pollution control (Solsona et of formaldehyde is the degradation of VOCs
al., 2011). One of the main challenges of (alcohols and other hydrocarbons) in multiple
catalytic destruction of VOCs is the selection of steps oxidations (Ivanova et al., 2013).
the proper catalysts from the large number of Aldehydes are one of the major indoor
available catalysts. Due to their wide variety and pollutants, which are emitted from decorative
nature of the range of mixtures of VOCs, it is materials and trapped in airtight buildings (Klett
most often diffcult to identify the best possible et al., 2014; Mitsui et al., 2008). They are also
catalysts. This article presents a comprehensive released from many industrial products, such as
review of the recent developments of catalytic treated wood resins, cosmetics, plastic adhesives,
oxidation of VOCs. This manuscript is divided construction materials, cleaning agents,
into the following sections; (i) Major VOCs and disinfectants, particleboard, medium-density
their sources, (ii) Mechanisms and kinetics of fbreboard, plywood, carpeting, cigarette smoke,
catalytic oxidation of VOCs, (iii) Catalysts for and fabrics (Li et al., 2014b). Aldehydes can also
the oxidation of VOCs, (iv) Deactivation and be formed by the breakage of the C-C bond of
regeneration of catalysts, and (v) Conclusion. alkoxy radicals (Atkinson, 1997). Biogenic
aldehyde sources include live and decaying
2. Major VOCs and their sources plants, bio-waste decomposition, biomass
burning, and seawater (Luecken et al., 2012).
2.1. Halogenated VOCs Exposure to a low level of aldehyde may cause
throat irritation, shortness of breath, eye irritation,
and chest tightness (Zhu and Wu, 2015). Exposure
Halogenated VOCs are hazardous compounds
to a high level of aldehyde increases the risk of
due to their strong bioaccumulation potential,
acute poisoning, and long-term exposure can have
acute toxicity, and resistance to degradation
adverse effects on human health that may lead to
(Alonso et al., 2002). Among the halogenated
chronic toxicity (Andersen et al., 2008; Liotta, 2010;
VOCs, polychloromethanes (PCMs) are the most
Main and Hogan, 1983; Zhu and Wu, 2015). Long-
common and widely used in various applications.
term exposure can also cause nasal tumors and
120 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134
irritation of the respiratory tract, mucous membranes
of the eyes, and skin (Collins, 2001; Yu and Crump,
1998). Due to the increased use of ethanol-based
biofuels in transportation vehicles, aldehydes from
biofuels in the atmosphere have signifcantly
increased in recent years (Scire and Liotta, 2012).
Owing to these reasons, the reduction of aldehyde in
the atmosphere is of signifcant interest, particularly
through low-temperature processes.
2.3. Aromatic compounds
Aromatic compounds such as benzene, toluene,
and ethylbenzene occur naturally in petroleum
products, including gasoline and other fuels
produced from crude oil. Consequently, the
incomplete combustion of liquid fuels in
automobiles releases signifcant amounts of
aromatic compounds into the atmosphere. These
compounds are also used in various products and
formulations such as petrochemicals, paint,
medicine, and detergents (Ozelik et al., 2009).
Aromatic compounds are not only toxic and
carcinogenic, but also cause severe damage to the
ozone layer, produce photochemical smog, and pose
mutagenic hazards (Kim and Shim, 2010). The
aromatic solvents commonly used in paints,
thinners, gums, adhesives, lacquers, and printing
inks, are classifed as priority pollutants (Shahna et
al., 2010). At low-level exposure, aromatic VOCs
can cause weakness, confusion, nausea, loss of
appetite and memory, tiredness, and loss of sight.
Inhalation of a high level of aromatic compounds
can cause unconsciousness, dizziness, and even
death (Kim, 2002; Suib, 2013). The maximum safe
limit of aromatic compounds is 1 mg/L in drinking
water and 200 ppm in air (Alifanti et al., 2007;
Blanco et al., 2007; Chen et al., 2008a; de Rivas et
al., 2006; Delimaris and Ioannides, 2008 b; Huang
et al., 2008a; Luo et al., 2007; Musialik-Piotrowska
and Landmesser, 2008; Palacio et al., 2008; Scire et
al., 2001b; Scire et al., 2003; Tidahy et al., 2007,
2008; Wang et al., 2008; Wu et al., 2000; Zhang et
al., 2008; Li et al., 2015).
2.4. Polycyclic aromatic
hydrocarbons
Polycyclic aromatic hydrocarbons (PAH) are a
family of VOCs, and they are mainly released by
combustion processes (VarelaGanda et al., 2013).
These compounds contain several benzene rings in
their structure. Some typical examples of PAH are
naphthalene (two rings), phenanthrene (three rings),
and pyrene ( four rings). The main sources of PAH
are incomplete fuel combustion, asphalt
transformation plants, and coal power plants (Diehl
et al., 2010; Puertolas et al., 2010). PAH have been
identifed as carcinogenic and therefore, it is
extremely important to reduce their emission (Kim
et al., 2007b).
2.5. Alcohols and ketones
Alcohols and ketones are commonly used in
cosmetics and personal care products such as nail
polish, nail polish removers, colognes, perfumes,
rubbing alcohol, and hair spray. Ketones are used in
aerosols, varnishes, window cleaners, paint thinners,
and adhesives (Makshina et al., 2008; Santos et al.,
2011). Common alcohol based VOCs include ethyl
alcohol, isopropyl alcohol, benzyl alcohol, while
acetone, methacrylates (methyl or ethyl), ethyl
acetate, and methyl ethyl ketone are ketone based
VOCs.
Alcohols (mainly ethanol) increase the formation
of aldehydes by secondary reactions which cause
throat irritation, shortness of breath, eye irritation,
and chest tightness (Zhu and Wu, 2015). Long-term
exposure to short-chain alcohols (ethanol,
isopropanol, and n-butanol) may cause central
nervous system depression (U.S. Department of
Health and Human Services. Hazardous Substances
Data Bank (HSDB, online database). National
Toxicology Information Program, National Library
of Medicine, Bethesda, MD. 1993). High
concentrations of ketones can cause the irritation of
eyes, nose, and throat. Other effects reported from
acute inhalation exposure in humans include central
nervous system depression, headache, and nausea.
Some studies have reported nerve damage due to
exposure to ketones (U.S. Environmental Protection
Agency. Updated Health Effects Assessment for
Methyl Ethyl Ketone. EPA/600/8-89/093.
Environmental Criteria and Assessment Offce,
Offce of Health and Environmental Assessment,
Offce of Research and Development,
Cincinnati, OH. 1990.)
2.6. Miscellaneous VOCs
Some alkenes also belong in the category of
VOCs. Propylene is considered to be extremely
polluting due to its large photochemical ozone
creativity potential (POCP). Ethylene is of
considerable importance as it is being used as a raw
material in many petrochemical syntheses
(Patdhanagul et al., 2012). Ethylene released during
storage of agricultural products, can induce physical
and chemical changes of vegetables and fruits
(Patdhanagul et al., 2010; Sue-aok et al., 2010; Trinh
et al., 2015). Ethylene is extensively used as a
solvent in the production of varnishes, synthetic
resins, adhesives, printing ink, organic intermediates
of pharmaceutical products, and perfumes due to its
low toxicity, good solubility, and good volatility
(Yuan et al., 2011; Zhang et al., 2009). Methyl
tertbutyl ether (MTBE) belongs in the category of
semi-volatile VOCs, and is used as a fuel enhancer
to improve octane ratings (ZadakaAmir et al., 2012;
Zhou et al., 2013) and the oxidation ability of the
fuel (Kujawa et al., 2015). The presence of MTBE
in drinking water sources has become a major issue
in Europe and USA (Ji et al., 2009; Rossner and
Knappe, 2008). The main sources of MTBE are
leakage from underground storage tanks, air
deposition, and exhausts from watercrafts. MTBE is
potentially carcinogenic and adversely affects the
odor and taste of drinking water. The safe limit for
MTBE in drinking water issued by the US
Environmental Protection Agency is 20e30 ppb
(Zadaka-Amir et al., 2012).
 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 121

3. Mechanisms and kinetics of
catalytic oxidation of VOCs
As discussed above, there are a range of volatile
compounds, which play a direct role in atmospheric
chemistry. Although the catalytic oxidation of VOCs
has been extensively studied, it is still diffcult to
provide a generalized correlation and a single
reaction mechanism due to the different properties
of pollutants and reaction conditions. Hermia and
Vigneron have established a correlation between the
oxidizability of VOCs and their molecular weight
(Hermia and Vigneron, 1993). According to them,
the higher the molecular weight, the more diffcult it
is to oxidize VOCs. This correlation agrees well
with the order established by Palazzolo and
Tichenor regarding the ease of oxidation: alcohols <
aldehydes < aromatics < ketones < acetates <
alkanes (Tichenor and Palazzolo, 1987).
At suffciently high reaction temperatures, the
catalytic oxidation mainly gives CO 2 and H2O
according to the following reaction:
between the adsorbed VOCs and the adsorbed
oxygen. Therefore, it is essential for both the
VOCs and oxygen molecule (species) to be
adsorbed on the surface of the catalyst (Everaert
and Baeyens, 2004). The VOCs and oxygen may
adsorb on similar type of active sites (single site
L-H model) or two different types of active sites
(duel site L-H model). Accordingly, the rate
expressions for the single site L-H model and
duel site L-H model are different as expressed by
Equations (3) and (4), respectively.
VOC 1KvocPvoc KO2PO2 2
kK r
vocKO2PvocPO2 (4)
r kK vocKO2PvocPO2 (3)

1 y
VOC
CxHy x yO2/xCO2 H2O 2
(1) 1 KvocPvoc 1 KO PO2
4 2
The mechanisms proposed for the complete
where, K O2 is the equilibrium constant for the
catalytic oxidation of VOCs generally fall into
adsorption of oxygen and Kvoc is the equilibrium
three main categories: (i) Marsevan Krevelen
constant for the adsorption of VOCs. The
(MVK) model, (ii) Langmuir-Hinshelwood (L-
advantage of this model is that it not only
H) model, and (iii) Eley-Rideal (E-R) model.
includes the reaction rate but also takes into
Mars-van Krevelen model considers that the consideration of the adsorption of VOCs and
reaction occurs between the adsorbed VOCs and oxygen.
the lattice oxygen of the catalyst rather than the
According to the EleyeRideal (EeR)
oxygen in the gas phase. This model assumes
mechanism, the reaction occurs between the
that the oxidation of the VOCs takes place in two
adsorbed oxygen species and reactant
steps as shown in Fig.1. In the frst step, the
adsorbed VOCs react with oxygen in the catalyst,
resulting in the reduction of the metal oxide. In
the second step, the reduced metal oxide is
reoxidized by the gas phase oxygen present in
the feed (Song et al., 2001). As the catalyst is
frst reduced and then reoxidized, this
mechanism is also known as the redox
mechanism. In the steady state, rates of the
reduction and oxidation steps must be equal. This
model has been widely used for kinetics
modeling of oxidation reactions of hydrocarbons
over metal oxide catalysts (Ordonez~ et al.,
2002). According to the Mars-van Krevelen
mechanism, the rate of oxidation of the VOCs Fig. 1. Schematic of oxidation of VOCs (benzene) on MnO (Li
can be expressed by Equation (2). et al., 2011).
molecules in the gas phase. The controlling step
is the reaction between an adsorbed molecule and
rVOC k a molecule in the gas phase (Behar et al., 2015).
O2kv
oc
PvocP2O2 (2) gkvocPvoc kO The following equation represents the kinetic
P O2 expression based on the E-R mechanism.

where, rVOC: reaction rate (mol/m3/s); PVOC: partial

pressure of the VOCs; PO2: partial pressure of

oxygen; kVOC: rate constant of VOCs oxidation; rVOC kK
kO2: rate constant of catalyst re-oxidation; g is vocPvocPO2 (5)
the stoichiometry coeffcient of O2 in the 1 KvocPvoc
oxidation.
The validity of each mechanism strongly
The Langmuir-Hinshelwood (L-H) depends on the properties of the catalyst (active
mechanism assumes that the reaction takes place metal and the support) as well as on the nature of
122 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134

the VOCs. Generally, one of the above models
provides a good ft for the experimental data for
the oxidation of the VOCs over metal-oxide and
noble-metal catalysts.
Table 2 summarizes the kinetics models and
the estimated activation energies for the
oxidation of a range of VOCs reported in the
literature. The activation energy varies between
10 and 50 kcal/ mol. Choudhary and Deshmukh
conducted a kinetic study of the combustion of
propane and methyl ethyl ketone (MEK) over
Crdoped ZrO2 (Choudhary and Deshmukh,
2005). Although the experimental data ft both
the power law and MVK model reasonably well,
the MVK model gave the best ft. Activation
energy for the combustion of propane and MEK
was determined to be 16.5 kcal mol 1 and 13.2
kcal mol1, respectively. Ordonez et al. showed
that the kinetics of the oxidation of aromatic
compounds (benzene and toluene) over Pt/ g-
Al2O3 cab be expressed using the MVK model.
The estimated activation energy of benzene and
toluene are 24 and 25 kcal/mol, respectively
(Ordonez et al., 2010). Radic et al. studied the
kinetics of the oxidation of n-hexane and toluene
over 0.12% Pt/Al2O3 (Radic et al., 2004). MVK
type rate expression was used to calculate the
reaction rate constant. The activation energy for
the chemisorption decreases with increasing Pt
crystallite size. On the other hand, the activation
energy for the surface reaction is independent of
the Pt crystallite size. Gangwal et al. also applied
the MVK mechanism to study the kinetics of the
oxidation of n-hexane (Gangwal et al., 1988). Pei
et al. ftted the experimental data of the catalytic
oxidation of formaldehyde over copper
manganese oxide to three models including frst
order kinetics, LH, and the MVK models (Pei et
al., 2015). They proposed the following models
and ftted the experimental data to them: ( i )
single-variable (surface concentration) kinetic
model; (ii) twovariable kinetic model (surface
concentration and water vapor concentration);
and three variable model (surface concentration,
water vapor concentration, and temperature). The
best ft of the experimental data was obtained for
the LH model that considers two adsorbed
reactants with competitive adsorption. The
goodness
Miranda et al. tested several kinetic models for
the oxidation of trichloroethene over different metal
oxide catalysts (Miranda et al., 2007). They showed
that the experimental data based on the Mn catalyst
follows frst-order kinetics, while the results
obtained with the Cr catalyst follows zeroth order
kinetics. The kinetic behavior of Cr can be best
described by the LH mechanism, taking into
consideration the inhibition effect of Cl 2. Tseng et
al. determined that the power law model provided
the best ft for the catalytic oxidation of
dichloroethane on the Mn 2O3/g-Al2O3 catalyst
(Tseng et al., 2010). Xin et al. studied the catalytic
oxidation of ethylene over a palladium catalyst and
the experimental data were ft to several kinetic
models (Xin et al., 2015). The reaction is frst order
in the ethylene concentration with a total activation
energy of 48.2 kJ/ mol. Hu studied the combustion
kinetics of acetone over the Cu 0.13Ce0.87Oy catalyst
using several models (Hu, 2011). Results indicate
that the power model does not provide a good ft for
the acetone combustion. Experimental data ft the
kinetic equation based on Langmuir-Hinshelwood
model well.
The above discussion indicates that the
mechanism of VOCs oxidation mainly depends on
the type of VOCs compounds and the characteristics
of the catalysts. Therefore, the understanding of the
characteristics of the catalyst is essential to
determine the reaction mechanism and develop the
kinetics models representing the destruction
reactions for the treatment of a given type of VOCs.
4. Catalysts for the oxidation of VOCs

Table 2
of the ft was found to be better at higher reaction
temperatures. Bedia et al. performed a kinetic study
on a catalyst based on Pd supported on carbon for
toluene oxidation (Bedia et al., 2010). Oxidation
temperature was in the range of 250e400 C. Model
based on the LH mechanism provided the best ft,
with a minimum standard deviation and the lowest
error. The rate-limiting step was reported to be the
surface reaction between adsorbed toluene and
dissociatively adsorbed oxygen. Behar et al. studied
the kinetics of toluene oxidation over nano-sized
Cu-Mn spinels (Behar et al., 2015). Results showed
that the experimental data did not ft the power law
model or the Langmuir model well. MVK model
provided a good ft for the experimental data.
 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 123

Catalysts used for the oxidation of VOCs can be metal-based catalysts are expensive and can be
classifed into three major groups: (i) noble metals deactivated by sintering or poisoning (Liotta, 2010)
catalysts (Papaefthimiou et al., 1997, 1998c; Tsou et and alone they are not normally selective enough
al., 2005); (ii) non-metal oxide catalysts (Barbero et
(Ojala et al.,
al., 2006; Bastos et al., 2012; Burgos et al., 2002 b;
Summary of the activation energy of the oxidation of some VOCs, and the catalysts and kinetics models used.
VOCs Catalyst Model type Activation energy (kcal/mol) Reference

Methyl ethyl ketone Cr-doped ZrO2 Mars-van Krevelen 16.5 Choudhary and Deshmukh, 2005
Methyl ethyl ketone Cr-doped ZrO2 Power law 13.2 Choudhary and Deshmukh, 2005
Ethylene Pd Power law 48.2 Xin et al., 2015
n-hexane Pt/Al2O3 Mars-van Krevelen 22.4 Radic et al., 2004
toluene Pt/Al2O3 Mars-van Krevelen 17.4 Radic et al., 2004
Benzene Pt,Ni/g-Al203 Mars-van Krevelen 22.9 Gangwal et al., 1988
n-Hexane Pt,Ni/g-Al203 Mars-van Krevelen 19.6 Gangwal et al., 1988
Formaldehyde CuO/MnO2 Langmuir-Hinshelwood 13.2 Pei et al., 2015
Toluene Pd/activated- C Langmuir-Hinshelwood 19.8 Bedia et al., 2010
Toluene Cu1.5Mn1.5O4 Mars-van Krevelen 26.6 Behar et al., 2015
Trichloroethene MnO2 Power Law 9.3 Miranda et al., 2007
Trichloroethene Cr2O3 Power Law 10.5 Miranda et al., 2007
Dichloroethane Mn2O3/g-Al2O3 Power Law 10.4 Tseng et al., 2010
Acetone Cu0.13Ce0.87Oy Langmuir-Hinshelwood 26.1 Hu, 2011
Benzene Pt/g-Al2O3 Mars-van Krevelen 24.1 (Ordonez~ et al., 2002)
Toluene Pt/g-Al2O3 Mars-van Krevelen 25.3 (Ordonez~ et al., 2002)
n-Hexane Pt/g-Al2O3 Mars-van Krevelen 31.8 (Ordonez~ et al., 2002)
Centeno et al., 2005; Cordi et al., 1997b; Garcia et Table 3
al., 2010 ; Krishnamoorthy et al., 2000; Lahousse et
al., 1998b; Parida and
Samal, 1999); and (iii) mixed-metal catalysts
(Gangwal et al., 1988; Garcia et al., 2006). Metal
oxide based catalysts are cheaper and more resistant
to poisoning, but they are less durable and less
effcient compared to supported noble-metal
catalysts in the oxidation of VOCs (Bastos et al.,
2009). Typically, the active metal oxides are
deposited on a suitable support. Several types of
supports with good thermal stability and high
surface area have been used, which include the
following: alumina (Al2O3), zirconia (ZrO2), CeO2,
SiO2, titania (TiO2),SnO2, CuO, Fe2O3, La2O3, MgO,
montmorillonite, zeolites, and carbon based
materials (Delimaris and Ioannides, 2008a, 2009;
Garcia et al., 2004; Gutierrez-Ortiz et al., 2006;
Heynderickx et al., 2010; Li et al., 2009; Masui et
al.; Mitsui et al., 2008; Wyrwalski et al., 2006). The
importance and different functions of support
materials were reviewed recently by several groups
(Corma and Garcia, 2008; Jntgen, 1986; Roth et
al., 2014; Trimm and Stanislaus, 1986). The use of
nanotubular materials as catalyst supports, in which
the active centers are nanoparticles inside the tubes,
has also been investigated. Carbon nanotubes, boron
nitride nanotubes, and halloysite nanotubes are
some typical examples of nanotubular supports.
Halloysite is a hydrated phase of kaolinite which is
cheaper and abundantly available and can acquire
different morphologies (Carrillo and Carriazo,
2015).

4.1. Noble-metal-based catalysts

Supported noble metals (Pt, Pd, Rh etc.) are

attractive as catalysts due to their high effciency for
the removal of VOCs at low temperatures
(Avgouropoulos et al., 2006; Liotta, 2010;
Maldonado-Hodar et al., 2004; Papaefthimiou et al.,
1999; Tidahy et al., 2007). The most common
support materials for the noble metal catalysts are
ceramics or metallic material in monolithic or
honeycomb form. Table 3 summarizes some noble
metal catalyst systems reported recently. Noble-
124 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134

Catalyst Support VOCs Temp (oC) Conversion % References

Pd Nb2O5 Toluene 440 90 (Rooke et al., 2015)

Au CeO2-ZrO2-TiO2 Propane 360 50 (Ali et al., 2015)
Au CeO2/Fe2O3 Benzene 200 100 (Tabakova et al., 2015)
Pd Co3O4 Xylene 249 90 (Wang et al., 2015)
Pt Al2O3 Toluene 200 95 (Rui et al., 2014)
Pt CeO2 n-butanol 167 90 (Sedjame et al., 2014)
Pt CeO2 n-butanol 135 90 (Sedjame et al., 2014)
Pt Al2O3 n-butanol 165 90 (Sedjame et al., 2014)
Au CuO Ethyl acetate 311 100 (Carabineiro et al., 2015b)
Au Fe2O3 Ethyl acetate 354 100 (Carabineiro et al., 2015b)
Au La2O3 Ethyl acetate 325 100 (Carabineiro et al., 2015b)
Au MgO Ethyl acetate 290 100 (Carabineiro et al.,2015b)
Au NiO Ethyl acetate 345 100 (Carabineiro et al., 2015b)
Au CuO Toluene 315 100 (Carabineiro et al.,2015b)
Au Fe2O3 Toluene 345 100 (Carabineiro et al.,2015b)
Au La2O3 Toluene >400 100 (Carabineiro et al., 2015b)
Au MgO Toluene 387 100 (Carabineiro et al., 2015b)
Au NiO Toluene 320 100 (Carabineiro et al., 2015b)
Au Co3O4 Benzene 189 90 (Liu et al., 2015)
Au Co3O4 Toluene 138 90 (Liu et al., 2015)
Au Co3O4 Xylene 162 90 (Liu et al., 2015)
Pt Activated carbon Benzene 112 100 (Joung et al., 2014)
Pt Activated carbon Toluene 109 100 (Joung et al., 2014)
Pt Activated carbon Ethylbenzene 106 100 (Joung et al., 2014)
Pt Activated carbon Xylene 104 100 (Joung et al., 2014)
Au Fe2O3 Toluene 260 90 (Han et al., 2014)
Pd Co3O4 o-Xylene 254 90 (Wang et al., 2013b)
Pd Al2O3 o-Xylene 145 90 (Huang et al., 2008b)
Reported Noble-metal catalyst systems for the oxidation of prepared by deposition-precipitation, chemical
VOCs.
vapor deposition, and cation adsorption methods
2011). Also they are less stable in the presence of
(Liotta, 2014). When deposited on a metal oxide
chloride compounds (Everaert and Baeyens,
support, the gold complexes and gold
2004). Several investigations on noble-metal
nanoparticles show good reactivity towards
catalysts on different supports have been
oxidation reactions (de Almeida et al., 2013;
reported (Cant and Hall, 1970). Performance of
Hashmi et al., 2010). Performance of gold
these catalysts depends on the method of
catalysts depends on many factors, including the
preparation, precursor type, particle size, metal
type and properties of the support, loading of
loading, concentration of the VOCs, reactor type,
gold particles, methods of preparation, size and
and the overall gas fow rate (Cant et al., 1998;
shape of the gold nanoparticles, and
Carballo and Wolf, 1978; Radic et al., 2004).
concentration of VOCs (Scire and Liotta, 2012).
Larger the heat of formation of an oxide the
lesser the activity of the catalyst. Use of noble- Carabineiro et al. used Au catalysts supported
metal catalysts in propylene oxidation indicates on La2O3, MgO, NiO, and Fe2O3 for the oxidation
that the total reaction rate increases with the of toluene (Carabineiro et al., 2015b). They
oxygen pressure and decreases with the olefn showed that the reducibility and the crystal size
pressure. For Rh and Ir the oxidation rate are major factors affecting the catalytic activity,
increases with the olefn pressure and decreases while the oxidation state of Au has no effect on
with the oxygen concentration. On the contrary, the catalytic activity (Carabineiro et al., 2015b).
Ru catalysts show higher oxidation rate with Au/Co3O4 system has been reported as the
increased oxygen pressure while the rate is most active system for the combustion of light
independent of the olefn pressure (Cant and alkanes (Haruta, 1997a; Waters et al., 1994).
Hall, 1970; Carballo and Wolf, 1978). Paulis et Au/CeO2 and Au/MnOx have been used to
al. studied the effect of chlorine, which is oxidize different VOCs such as toluene and ethyl
normally added as a catalyst precursor, on the acetate (Bastos et al., 2012). At 250 C, both
oxidation of toluene on the Pt/Al2O3 catalyst Au/CeO2 and Au/MnOx oxidize ethyl acetate into
(Paulis et al., 2001). Chlorinated precursors CO2. Au/Mn5O10 catalyst system completely
increase the surface acidity and decrease the oxidizes ethanol at 230 C. Toluene oxidation is
adsorption of carbonates and bicarbonates on the the toughest and it has been achieved at 300 C
surface of the support during CO oxidation. with Au/Mn3O4. Gold catalysts supported on
Moreover, using chlorinated precursors will ceria have been used for the oxidation of
result in platinum oxychloride species, which benzene, toluene, propanol, propene, and
have a higher reduction temperature. formaldehyde (Lakshmanan et al., 2010; Pinna,
1998; Scire et al., 2003; Shen et al., 2008).
Solsona et al. investigated a catalyst based on
4.1.1. Gold-based catalysts
gold supported on nickel-cerium oxide for the
For a long time, gold was considered a poor oxidation of propane (Solsona et al., 2011).
catalyst owing to its inertness to reactive These catalysts showed good activity, which is
compounds. In 1987 Haruta et al. found that the due to the high surface area of the catalyst, low
reactivity of gold catalysts can be improved by bond strength (Ni-O), and the high reducibility of
forming defective structures (Haruta, 1997b; the nickel sites (Solsona et al., 2011). Shen et al.
Haruta et al., 1989). Gold catalysts can be studied several Au/CeO2 catalysts with a gold
 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 125
content of less than 0.85%, prepared by different
routes for formaldehyde oxidation (Shen et al.,
2008). The results indicate that gold catalysts
with a high dispersion are more active in the
oxidation of formaldehyde, while the formation
of larger crystals decreases the activity of the
catalyst.
4.1.2. Palladium catalysts
Palladium catalysts have a higher thermal and
hydrothermal resistance compared to other noble
metal catalysts (Huang et al., 2008b). There are
different views on the contribution of the
metallic state and oxidized state of Pd to the
oxidation reactions of VOCs. Some authors
believe that the oxidized state is more important
(Burch et al.,1996; Gelin and Primet, 2002),
while others consider that the metallic state is
more important in oxidation reactions (Deg e et
al., 2000; Huang et al., 2008b; Ihm et al., 2004).
Some results suggest that both states are equally
important (Yazawa et al., 1998). The support
plays an important role in the activity of Pd-
based catalysts. Normally the porous supports
increase the activity of Pd catalysts due to the
stabilization of active Pd species on porous
structures (Centi, 2001; Wang et al., 2013b).
Acid-base properties of the supports are known
to infuence the activity of Pd catalysts. Weakly
acidic supports provide high catalytic activity
(Okumura et al., 2003). Pd-based catalysts are
more effcient than noble-metal catalysts and
metal-oxide catalysts in removing benzene,
toluene, xylene, and methane (Centi, 2001;
Huang et al., 2008b; Kim and Shim, 2009).
Wang et al. showed that Pd/Co3O4 catalysts
possess high effciency for the oxidation of
xylene. Effciency depends on the particle size,
oxidized Pd species, and the oxygen vacancies
on the support (Wang et al., 2013b). The
comparison of two Pd/Co3O4 catalysts
synthesized by in situ nanocasting and post-
impregnation methods indicates that the catalyst
synthesized by in situ nanocasting has a high
catalytic activity. The high activity is due to the
more ordered structure of the catalyst and the
well dispersed PdO species. Huang et al. found
that the catalytic activity of the Pd/Al2O3
catalysts increased with the increasing Pd
loading (Huang et al., 2008b). Ihm et al. showed
that the pre-treatment methods strongly affect the
activity of the Pd/Al2O3 catalysts [140]. Catalysts
treated in hydrogen showed higher activity
compared to the catalyst treated in air.
4.1.3. Platinum catalysts
Platinum-based catalysts are widely used in the
oxidation of VOCs due to their high activity and
stability (Joung et al., 2014). Although conventional
platinum catalysts are supported on metal oxides,
activated carbon has also been used as the support
(Joung et al., 2014; Wu and Chang, 1998). Industrial
applications of platinum catalysts are limited due to
their high cost and the likelihood of poisoning,
especially when dealing with chlorinated products
(Jones and Ross, 1997; Krishnamoorthy et al., 2000;
Petrosius et al., 1993).
In humid environments, Pt-based catalysts suffer
deactivation owing to the adsorption of water on the
support. Sedjame et al. used a Pt catalyst supported
on CeO2-Al2O3 for the complete oxidation of n-
butanol and acetic acid (Sedjame et al., 2014). The
addition of ceria to alumina decreases the surface
area and changes the physicochemical properties of
the catalytic material and the activity. Addition of
ceria enhanced the performance of the catalyst for
the oxidation of acetic acid, while the oxidation of
n-butanol was not signifcantly affected, which
shows that the nature of the VOCs infuences the
performance of the catalyst.
4.1.4. Mixed noble-metal catalysts
Hosseini et al. studied toluene oxidation over a
series of bimetallic Pd/Au/TiO 2-ZrO2 catalysts
(Hosseini et al., 2009). They found that the Au/Pd
catalysts showed higher activity than the
monometallic Au or Pd catalysts. The highest
toluene oxidation performance was found to be at a
Pd/Au ratio of 4. The enhanced performance of the
bimetallic catalyst is related to the synergistic effects
between palladium and gold. Barakat et al.
demonstrated the synergistic effects by using the Pd-
Nb-V/TiO2 catalyst for toluene oxidation (Barakat et
al., 2012). They showed that doping by a
hierarchically structured titania support with Nb and
V enhances the catalytic activity of the support in
the oxidation of VOCs. Modifcation with vanadium
increases the effciency of titaniasupported
palladium catalysts for the oxidation of short chain
alkenes (Garcia et al., 2004).
4.2. Non-noble metal oxides
Non-noble metal based catalysts can be either
supported or unsupported metal oxides (Carabineiro
et al., 2015a). The supported catalysts show better
activity and performance in the oxidation of VOCs
due to greater dispersion of the active component.
The transition and rare earth metal oxides are used
as nonnoble-metal catalysts. The most commonly
used metal-oxide catalysts include copper oxide,
manganese dioxide, iron oxide, nickel oxide,
chromium oxide, and cobalt oxide (Galvita et al.,
2014; Garcia et al., 2010; Huang et al., 2010;
Morales et al., 2013; Solsona et al., 2011; Xia et al.,
2009). Table 4 shows some commonly used
nonnoble-metal catalysts. The non-noble-metal
catalysts have several advantages, including being
readily available and their low price that make them
a good alternative to expensive noble-metal
catalysts. Although non-noble metal oxides have
relatively lower activity than the noble-metal
catalysts, they are commonly used for the oxidation
of VOCs due to their low cost (Ciuparu et al., 2002 ;
Delimaris and Ioannides, 2008a; Gelin and Primet,
2002; Kim, 2002; Rotter et al., 2004; Scire et al.,
2001a). Other advantages include the following:
long lifetime, masking tolerance, capability of
regeneration, and the availability of a range of metal
oxides in different sizes and shapes (Zimowska et
al., 2007).
126 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134

Support materials and the preparation methods

are crucial in determining the performance of metal-

Table 4
Some reported metal-oxide catalysts for the oxidation of VOCs.
Catalyst Support VOCs Temp Conversion % References

Co3O4 Clay Acetylene 360 100 (Assebban et al., 2015)

Co3O4 Clay Propylene 460 100 (Assebban et al., 2015)
Co3O4 e 1,2-Dichloroethane 350 100 (de Rivas et al., 2012)
Co3O4 e Ethyl acetate 245 100 (Chen et al., 2013)
CuO e Ethyl acetate 280 e (Chen et al., 2013)
Co3O4 e Propane 250 99 (Solsona et al., 2008)
CeO2 Aluminosilicate Acetone 200 85 (Lin et al., 2015)
Nb2O5 e Toluene 400 90 (Rooke et al., 2015)
oxide catalysts. Support plays an important role in
determining the physicochemical properties of the
active phase (Lin et al., 2015). Porous materials
with a high surface area and large pores favor high
dispersion and good catalytic activity in the
oxidation of VOCs (Chen et al., 2014a; He et al.,
2012; He et al., 2010; Jeong et al., 2014; Soylu et
al., 2010; Yan et al., 2014). In the open literature
there are numerous research articles reporting
attempts to enhance the activity of metal-oxide
catalysts. The methods used include making a
porous structure (Tang et al., 2014a; Xia et al.,
2010), forming a solid solution (Hanfeng et al.,
2011; Liotta et al., 2008; Wang et al., 2013a) or
perovskites crystal structure (Huang et al., 2008a;
MusialikPiotrowska and Syczewska, 2000; Pena
and Fierro, 2001), and doping (Chang et al., 2012).
Cheaper metal oxides are also more tolerant to
deactivation by poisoning compared to catalysts
based on noble metals (Baldi et al.,1998;
Carabineiro et al., 2015a; Li et al., 2009; Morales et
al., 2008; Rezlescu et al., 2015; Wenxiang et al.,
2015).

4.2.1. Cobalt-based catalysts

Co3O4 is one of the most active low-cost metal
oxides, which has been used for a wide range of
reactions (Busca et al., 1997; Choudhary and
Deshmukh, 2005; Chen et al., 2013; de Rivas et al.,
2012; Garcia et al., 2010; Solsona et al., 2008). High
activity of Co3O4 is associated with the presence of
mobile oxygen inside their spinel type structure
(Koodziej et al., 2012; Milt et al., 2002; Solsona et
al., 2008; Wyrwalski et al., 2007; Yuranov et al.,
2002). The catalyst has excellent reduction ability
and oxygen vacancies as well as a high
concentration of electrophilic oxide species (Liu et
al., 2009). However, activity of Co3O4 depends on
the method of preparation, treatment conditions,
oxidation state, and surface area (Kovanda et al.,
2006). Co3O4 is the most effcient catalyst available
for the total oxidation of toluene and propane
(Wyrwalski et al., 2006).
Co3O4 supported on TiO2 and Al2O3 was
investigated for the total oxidation of 1,2-
dichlorobenzene (Krishnamoorthy et al., 2000). For
the supported Co3O4, the activity depends mainly on
the nature of the support and the metal oxide-
support interactions. de Rivas et al. synthesized a
series of Co3O4 catalysts for the oxidation of 1,2-
dichloroethane using different routes (de Rivas et
al., 2011). The catalyst prepared by the precipitation
method with a particle size of 10 nm gave the
highest activity. The highly dispersed nano-sized
 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 127
crystals helped improve the activity of these
catalysts. According to de Rivas et al., the activity of
the supported Co3O4 catalyst is higher than that of
the supported noble-metal catalysts for the oxidation
of 1,2-dichloroethane (de Rivas et al., 2011).
4.2.2. Nickel-based catalysts
NiO is another active metal oxide used for
various catalytic applications including the
oxidation of VOCs (Solsona et al., 2011). The
catalyst is highly active because of its p-type semi-
conductor properties with an electron defciency in
the lattice (Heracleous et al., 2005). This allows
electrons to be easily removed from the metal
cations, resulting in the formation of active species
such as O. The formation of Ni3 in NiO has been
identifed by many researchers (Heracleous and
Lemonidou, 2006; Salagre et al.,1996). The addition
of one heteroatom such as cerium, which forms NiO
with a high surface area and a smaller crystal size
(Solsona et al., 2012), enhances the activity of NiO.
4.2.3. Titanium-based catalysts
Titania is a low cost, readily available, and
chemically stable catalyst suitable for the
removal of a range of VOCs, especially in
photocatalytic oxidation of VOCs. Titania can
degrade VOCs into CO2, acids, and H2O under
near UV light (Fresno et al., 2008 ; Hussain et
al., 2010; Sleiman et al., 2009; Zou et al., 2006).
Photocatalytic oxidation with titania occurs at
low temperature, and therefore, is suitable for
removing indoor pollutants (Fujishima and
Zhang, 2006; Periyat et al., 2008).
4.2.4. Manganese-based catalysts
Manganese oxide is among low cost active
catalysts for the oxidation of VOCs (Castano~
et al., 2015a). They have been evaluated for the
destruction of many VOCs, including n-hexane
(Lahousse et al., 1998a), acetone (Parida and
Samal, 1999), benzene (Luo et al., 2000), ethanol
(Aguero et al., 2009; Bastos et al., 2009 ;
Lamaita et al., 2005; Peluso et al., 2008), toluene
(Aguero et al.,
2009), propane (Finocchio and Busca, 2001) and
NOx (Kang et al., 2007). The manganese-based
catalysts are attractive due to their high
effciency in the oxidation and low toxicity.
Performance of manganese oxide depends
mainly on the catalyst structure, methods of
preparation, surface area, nature of the support
material, and the oxidation state (Einaga et al.,
2015). The activity of the MnO2 catalyst for the
oxidation of ethyl acetate and n-hexane is even
higher than the activity of the Pt/TiO 2 catalyst
(Sun et al., 2015). The high effciency of the
catalyst is attributed to the coexistence of mixed
valence states Mn2/Mn3 or Mn3/Mn4 and
lattice oxygen (Gandhe et al., 2007; Kim and
Shim, 2010). The reactivity of Mn2O3 is highest
followed by MnO2 and MnO for CO oxidation
(Ramesh et al., 2008). Manganese-based
catalysts are deactivated due to the deposition of
Cl species formed by the combustion reactions.
Therefore, Mn-based catalysts are best suited in
Cl-free environments (Finocchio et al., 2000).
4.2.5. Copper-based catalysts
Cupric oxide is also a highly active catalyst
for the deep oxidation of CO, methane,
methanol, ethanol, and acetaldehyde (Cordi et
al., 1997a; Hutchings and Taylor, 1999). CuO is
also used to catalyze the oxidation of methanol to
methyl formate and propylene to acrolein (Cordi
et al., 1997b). Several factors affect the
performance of the CuO catalyst in the total
oxidation of VOCs. Catalysts prepared by
different methods can demonstrate varying
activity (Heynderickx et al., 2010). The oxidation
state of Cu, which determines the mechanism of
oxidation, plays an important role. The lattice
oxygen in CuO plays an active role in the
oxidation and with the depletion of lattice
oxygen; the rate of oxidation becomes limited by
the diffusion of lattice oxygen to the surface.
VOCs can extract nearly all the lattice oxygen
from CuO.
The presence of CuO in the CuO/Al 2O3
catalyst signifcantly enhances the decomposition
rate (Cordi et al., 1997b). Supported CuO can
dehydrogenate and oxidize various VOCs such as
methanol, acetaldehyde, and formic acid. The
dehydrogenation rate is faster on CuO than on
the supported Cu catalyst system (Cordi et al.,
1997b). The addition of other metals such as
ceria can enhance its catalytic properties
(Heynderickx et al., 2010). Among the various
alumina supported catalysts, the activity of Cu is
highest followed by Co, Fe, and Ni for the total
oxidation of toluene (Kim et al., 2014).
4.2.6. Chromium-based catalysts
Chromium oxide catalysts are a group of very
active catalysts, particularly for the removal of
halogenated VOCs (Krishnamoorthy et al., 2000;
Petrosius et al., 1993). Crystalline chromium
oxide is more suitable than amorphous chromium
oxide as it favors the formation of CO 2 (Sinha
and Suzuki, 2007). Sinha et al. synthesized
mesoporous chromium oxide with high activity
for the oxidation of VOCs. The catalyst was
prepared by the neutral templating route and the
presence of mixed oxidation states of 2 and 5
was confrmed by XPS analysis (Sinha and
Suzuki, 2007).
Several studies have shown that chromium
oxide catalyst is the most effective catalyst for
the removal of VOCs. For example, the activity
of TiO2-supported catalysts for the catalytic
oxidation of trichloroethylene was highest for
chromium oxide (98%) followed by manganese
oxide (79%), cobalt oxide (58%), and iron oxide
(54%) (Rotter et al., 2005). Chromium oxide
catalyst supported on various supports such as
silica, alumina, porous carbon, clay, titania, and
clay was effective in the removal of carbon
tetrachloride, chloromethane, trichloroethylene,
ethyl chloride, chlorobenzene, and
perchloroethylene (Rotter et al., 2005).
Commercial application of the catalyst is
limited due to the loss of active Cr during long-
128 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134
term reaction. The loss of activity of Cr may be
due to the formation of other volatiles such as
CrO2Cl2, by cocking, by water, or attrition in
fuidized beds (Padilla et al., 1999; Yim et al.,
2001). High Cl content in fue gas can result in
the loss of chromium by attack of nascent Cl 2
(Padilla et al., 1999). Chromium trioxide
supported on carbon is a very active catalyst for a
range of VOCs. However, high toxicity of
chromium causes serious catalyst disposal
problems (Li et al., 2009).
4.2.7. Vanadium-based catalysts
Vanadium-based catalysts originally designed
for the removal of nitrogen oxides have proven
to be active in the destruction of various
polychlorinated pollutants (Cho and Ihm, 2002).
Vanadium-based catalysts have a high resistance
to sulfur dioxide poisoning, in addition to high
activity and selectivity (Jones and Ross, 1997).
Furthermore, these catalysts have a reasonable
stability in Cl2-HCl environments. Consequently,
the vanadium-based catalysts are suitable for the
oxidation of gas streams containing chlorinated
VOCs and NOx.
Delaigle et al. investigated the VOx/TiO 2
catalytic system for the abatement of different
aromatic pollutants and arrived at important
conclusions (Delaigle et al., 2009). Best
performance was achieved using sulphated
titania as it exhibits a large number of strong
Lewis acid sites. The higher number of Lewis
acid sites improve the spreading of active VOx.
The higher number of Brnsted acid sites also
helps in promoting the limited adsorption of
aromatics.
Krishnamoorthy et al. studied the catalytic
oxidation of 1,2dichlorobenzene over a series of
vanadium/TiO2-based catalysts (Krishnamoorthy
et al., 1998). Although the catalyst on a TiO2
support was active for the oxidation of 1,2-
dichlorobenzene, the addition of V2O5
considerably increases its activity. The oxidation
of 1,2-dichlorobenzene produces CO and CO 2,
and other incomplete combustion products were
not detected (Krishnamoorthy et al., 1998).
Co-pollutants of chlorobenzene such as CO,
CO2, and NOx can affect the performance of
vanadium-based catalysts. Overall effect of water on
the VOx catalyst is a sum of three dynamic effects: (
i ) retrieval of chlorine species, (ii) reduction of
VOx active species, and (iii) reduction in the
number of adsorption sites. CO can affect the acidity
of the catalyst but it has no overall infuence.
Chlorobenzene conversion is enhanced when NO is
added in the presence of oxygen (Delaigle et al.,
2009).
In summary, due to the reasonable stability of
vanadium-based catalysts in Cl2-HCl environment,
they have been proposed for the catalytic oxidation
of chlorinated VOCs.
4.2.8. Cerium-based catalysts
Cerium is the most abundant among the rare
earth elements. Cerium-based catalysts have unique
properties due to their abundant oxygen vacancies
associated with strong interactions with other
metals, oxygen storage capacity, and ready shuttling
between the Ce3 and Ce4 states (Gorte, 2010;
Zimmer et al., 2002). Owing to their outstanding
oxygen storage capacity, cerium-based catalysts are
often used as structural and electronic promoters
(Huang et al., 2015). CeO2 and CeO2-based catalysts
are cheaper, environmental friendly, and are
effective for non-chlorinated VOCs such as
methane, CO, methanol, and propane (Dai et al.,
2007). CeO2 catalysts have shown good activity in
the catalytic oxidation of phenolic wastewater and
the catalytic incineration of aromatic hydrocarbons
(Lin et al., 2002, 2003; Wang and Lin, 2004).
Cerium based catalysts have been tested for the
catalytic oxidation of a range of chlorinated VOCs.
Dai et al. investigated the catalytic activity of CeO 2
for the oxidation of various chlorinated VOCs (Dai
et al., 2007). They concluded that the catalytic
oxidation of chlorinated alkanes is easier than
chlorinated alkylenes. Dai et al. also investigated the
catalytic combustion of trichloroethylene using the
CeO2 catalyst (Dai et al., 2008). The CeO2 catalyst
showed a high activity for the catalytic combustion
of trichloroethylene, which is attributed to the high
mobility of oxygen, basicity, and oxygen-supplying
ability of CeO2 (Dai et al., 2008).
In summary, cerium-based catalysts are more
suitable for nonchlorinated VOCs, as they can be
deactivated by the adsorption of HCl or Cl2 (Li et al.,
2010). However, research has now moved to
increase the effciency of cerium-based catalysts for
destruction of chlorinated VOCs.
4.2.9. Mixed-metal catalysts
Generally, the destruction effciency of single-
metal-oxide catalysts is lower than that of precious
metal catalysts for the removal of VOCs. The
performance of metal-oxide catalysts can be
improved by combining two or more oxides to
impart a synergistic effect. Table 5 presents some
mixed metal catalysts reported in the open literature.
Generally, a synergistic effect is observed in a range
of composite oxides, including Mn-Ce oxides
(Delimaris and Ioannides, 2008a; Yu et al., 2010),
Mn-Cu oxides (Morales et al., 2006), Co-Ce oxides
(Liotta et al., 2008), Sn-Ce oxides (Vasile et al.,
2013), Mn-Co oxides (Tang et al., 2014b), and Ce-
Cu oxides. A study has shown that the rate
determining step in the total oxidation of VOCs is
the rate of oxygen removal from the metal oxide,
indicating that the reducibility of the metal oxide is
the most critical aspect (Bastos et al., 2009).
Reducibility of a metal oxide can be improved by
adding a second cation, i.e., using mixed metal
oxides (Saqer et al., 2011). The activity of ceria
containing catalysts is greatly enhanced by other
metal oxides such as nickel, copper, and vanadium
(Asgari et al., 2013; Liu et al., 2015; Trovarelli,
1996). The high catalytic activity is associated with
the dual oxidation states of ceria (Ce 3 and Ce4),
which facilitate oxygen storage and
Table 5
Some reported mixed-oxide catalysts for the oxidation of VOCs.
Catalyst VOC Temp (C) Conversion (%) References

Ce-Co Toluene 250 100 (Carabineiro et al., 2015a)

M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 129
La-Co Toluene 300 100 (Carabineiro et al., 2015a)
Mn-Ce Benzene 260 90 (Wenxiang et al., 2015)
Mn-Ce Toluene 245 90 (Wenxiang et al., 2015)
Mn-Ce Ethyl acetate 180 90 (Wenxiang et al., 2015)
Mn0.5Ce0.5-O2 Formaldehyde 270 100 (Li et al., 2014b)
Cu-Ce Chlorobenzene 328 99 (He et al., 2015)
Cu0.3Ce0.7Ox Toluene 212 90 (He et al., 2014)
Cu0.3Ce0.7Ox Propanol 192 90 (He et al., 2014)
Mn-Co Toluene 250 98.7 (Zhou et al., 2015)
Mn-Co Ethylbenzene 250 90 (Zhou et al., 2015)
Mn-Co Ethyl acetate 194 90 (Tang et al., 2014b)
Mn-Co n-hexane 210 90 (Tang et al., 2014b)
Mn-Co Toluene 250 100 (Qu et al., 2014)
MnOx-TiO2 Chlorobenzene 177 90 (Li et al., 2014a)
MnOx-TiO2-SnOx Chlorobenzene 177 90 (Li et al., 2014a)
Ce-Zr 1-2 Dichloroethane 120 90 (de Rivas et al., 2013)
Cu-Co Benzene 290 90 (Li et al., 2015)
release from the catalyst matrix (Yosef et al.,
2015). For example, CeO2 catalysts achieved 90%
conversion of trichloroethylene, but is not thermally
stable and deactivates within a few hours due to
adsorption of HCl and Cl 2 (Dai et al., 2008).
However, modifying CeO2 with other metals can
improve the oxygen storage capacity, thermal
resistance, and enhance its activity (Gluhoi et al.,
2005; Trovarelli et al., 1999).
CuO-CeO2 mixed-metal catalysts have been
investigated in the combustion reactions of CO and
CH4, the reduction of NO, and the wet oxidation of
phenol (Avgouropoulos and Ioannides, 2003; Liu
and Flytzanistephanopoulos, 1995; Liu et al., 1994).
The high effciency is attributed to the promoting
effect of ceria due to the high oxygen storage
capacity. Cu-Ce oxides have been studied for the
oxidation of the following VOCs: ethyl acetate,
ethanol (Larsson and Andersson,1998), benzene (Hu
et al., 2008), and toluene (Delimaris and Ioannides,
2009). This catalyst system has been synthesized
using combustion (Rao et al., 2003), thermal
decomposition (Xiaoyuan et al., 2001),
impregnation, co-precipitation, and sol-gel method
(Zheng et al., 2005). He et al. synthesized Cu-Ce
mixedoxide catalysts using the self-precipitation
approach and investigated their effciency for
toluene and propanol oxidation (He et al., 2014). Cu
and Ce have a synergistic effect on the reducibility
of the mixed-oxide catalyst. Low temperature
reducibility is the highest for Cu 0.3Ce0.7Ox followed
by Cu0.15Ce0.85Ox, Cu0.4Ce0.6Ox, and CuCeOx.
In the oxidation of ethyl acetate, ethanol, and
toluene the mixed catalyst system has a lower
activity compared to the individual metal oxides due
to the suppression of the intrinsic activity by
combining the two metal oxides (Delimaris and
Ioannides, 2009). MnOx-CeO2 catalyst system has
been investigated for the abatement of different
types of VOCs, such as ethanol (Rao et al., 2007),
formaldehyde (Tang et al., 2006), hexane (Picasso et
al., 2007), phenol (Chen et al., 2001), ethyl acetate
(Delimaris and Ioannides, 2008a), and toluene
(Delimaris and Ioannides, 2008a). These catalysts
are mainly prepared by the sol-gel method (Rao et
al., 2007; Tang et al., 2006), co-precipitation (Chen
et al., 2001; Picasso et al., 2007; Qi et al., 2004;
Silva et al., 2004; Tang et al., 2006), and combustion
(Delimaris and Ioannides, 2008a).
CeO2-CrOx mixed catalysts show excellent
performance in the removal of various halogenated
VOCs (Yang et al., 2015b). Yang et al. (2015a)
showed that the formation of Cr 6 species with its
strong oxidizing ability and the oxygen defects are
enhanced due to the good synergism between CeO 2
130 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134
and CrOx. All the mixed catalysts prepared under
different conditions show better performance
compared to the individual metal oxide catalysts.
Mn-Co are effcient systems for the removal
of VOCs (Castano~ et al., 2015b; Liotta et al.,
2013). Mixed-oxide catalysts of these two metals
are more effcient compared to the individual
metal catalysts due to the synergistic effects.
Tang et al. showed that the Mn and Co mixed-
oxide catalyst performed better in the removal of
ethyl acetate and n-hexane as compared to the
individual MnOx and Co3O4 catalysts (Tang et
al., 2014b). This high effciency is due to the
higher surface area, better low temperature
reducibility, and the porous structure of the
mixed oxide.
Li et al. investigated the removal effciency
of MnOx-TiO2 and MnOx-TiO2-SnOx catalysts for
the oxidation of chlorobenzene (Li et al., 2014a).
Both catalysts showed excellent performance
with 90% conversion below 180 C. The stability
of MnOx-TiO2-SnOx is higher than that of MnOx-
TiO2, indicating that the addition of Sn increases
the stability of Mn-Ti oxides. The high stability
of MnOxTiO2-SnOx is due to the low energy
required to desorb Cl species and the absence of
MNOxCly species on active sites. Mn is the active
part of the mixed catalyst, while Sn has a
minimal effect on the activity. Sn acts as an
additive and increases the stability of the
catalyst. TiO2 acts as a support and has very low
activity and it helps to disperse active Mn (Li et
al., 2014a). Genty et al. developed a different
mixed-metal-oxide catalyst (Fe, Cu, Zn, Ni, Co,
Mn or Mg) for the catalytic oxidation of toluene
and CO (Genty et al., 2012). Among the
synthesized catalysts, Mn-Co is a very promising
candidate for CO and toluene oxidation. Li et al.
investigated the catalytic combustion of toluene
over Mn-containing mixed oxides (Li et al.,
2004). They found that the catalytic conversion
of toluene on the Mn-Zr mixed oxides prepared
by the reverse microemulsion method is much
higher than that on other mixed oxides of Mn.
They have also reported that the catalytic activity
gradually increases with increasing Mn loading.
Li et al. also reported the catalytic oxidation of
toluene using Fe-Mn, Co-Mn, and Cu-Mn mixed
oxides. Among these metal oxides, the Cu-Mn
catalyst provides the highest activity (Li et al.,
2004).
Gennequin et al. demonstrated the doping
effects of Co on MgCo-Al hydrotalcite catalysts
in the oxidation of toluene (Gennequin et al.,
2010). The addition of cobalt has a benefcial
effect on the activity. The reconstruction of the
layered structure enhances the interaction
between the cobalt species and the support,
which improves the performance of the catalyst.
De Rivas et al. studied the oxidation of 1,2-
dichloroethane over Ce-Zr mixed-oxide catalysts
after treating them with H2SO4 and HNO3 (de
Rivas et al., 2013). Although mixed catalysts
treated with HNO3 did not show any change in
activity, a signifcant increase in the activity was
observed with sulphated catalysts. This increase
in the activity is attributed to the increase in the
total acidity and the concentration of active sites
with a moderate/strong acid strength. In addition,
the treatment with H2SO4 does not change the
surface area of the catalyst or the redox
properties associated with Ce4/Ce3.
4.3. Catalytic oxidation of mixtures of VOCs
The composition of VOCs signifcantly
varies depending on their source. Generally, the
industrial fue gas streams contain a mixture of
VOCs rather than a pure compound. The
concentration of the different VOCs mainly
depends on the source of the emission. The
physical and chemical properties of these VOCs
may also be different. Therefore, it is very
important to develop technology/ catalysts,
which can decompose mixtures of VOCs
effectively.
Studies on the effects of mixtures on the
catalytic oxidations of VOCs are reported in the
open literature. Normally the presence of other
molecules inhibits the destruction of VOCs.
Reports of mixtures promoting the destruction of
VOCs are rare (Ivanova et al., 2013). The
inhibition effects are mainly due to the
competition among the different species of VOCs
and the reaction intermediates for adsorption
sites (Marecot et al.,1994; Papaefthimiou et
al.,1997; Tsou et al., 2005). Burgos et al.
demonstrated that the catalytic oxidation rate of
2-propanol over a platinum-based catalyst
signifcantly decreases in the presence toluene
and methyl ethyl ketone (Burgos et al., 2002a).
They proposed that both toluene and methyl
ethyl ketone compete for active Pt sites, leaving
much lower number of active sites for 2-
propanol. Santos et al. reported the inhibition
effects of toluene in the oxidation of ethyl
acetatetoluene and ethanol-toluene mixtures
(Santos et al., 2011). Inhibition by toluene is
more pronounced on ethyl acetate-toluene
oxidations. Piotrowska et al. also reported the
inhibition effects of toluene and n-hexane during
the oxidation of n-butyl-acetate on the perovskite
catalyst (Musialik-Piotrowska and Syczewska,
2000). Tsou et al. showed that the oxidation of
methylisobutyl ketone over a Pt/zeolite catalyst
can be severely affected due to the presence of o-
xylene (Tsou et al., 2005). The affnity of o-
xylene for the sites on the catalyst causes strong
adsorption of o-xylene on the catalyst, which
affects the adsorption/reaction of methylisobutyl
ketone (Ordonez~ et al., 2002). Ordonez et al.
showed that the presence of n-hexane does not
affect the conversion of benzene and toluene.
However, the presence of benzene or toluene
inhibits the combustion of hexane, and the
aromatic compounds inhibit each other when
present together (Ordonez~ et al., 2002).
Papaefthimiou et al. studied the oxidation of
ethyl acetate and benzene over Pt/Al 2O3 and
Pt/TiO2 (W6) catalysts (Papaefthimiou et
al.,1998b). The oxidation of benzene is strongly
inhibited by ethyl acetate in binary benzene-ethyl
acetate mixtures, while ethyl acetate oxidation is
not infuenced by the presence of benzene,
suggesting different interaction mechanisms of
benzene and ethyl acetate with the catalyst.
 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134 131
Barakat et al. reported the oxidation of a
mixture of methylethyl ketone-toluene over a
Pd5%V-TiO2 catalyst (Barakat et al., 2014). They
showed that the presence of toluene enhanced the
oxidation performance of the catalyst unlike in
other mixtures. As the oxidation of MEK is
easier than toluene, they proposed that the
toluene adsorption is decreased by MEK. They
also suggested that the variations in the surface
temperature of the catalyst caused by adsorption
enhances the oxidation of toluene molecules
present in the gaseous stream.
There are some studies reported in the
literature on the effects of other compounds on
the oxidation of VOCs. Such conditions are
commonly present in fue gas streams. As water
molecules generally compete for the adsorption
sites, water can also inhibit the catalytic
processes involving VOCs. In some cases water
can have poisoning effects by decreasing the
activity of the catalysts (Ivanova et al.,). For
example, the addition of water vapor
signifcantly decreases the oxidation of propane
over Pt- and Pd-based catalysts (Marecot et
al.,1994). Papaefthimiou et al. demonstrated the
effects of water vapor on the catalytic destruction
of ethyl acetate and benzene over Pt/Al 2O3 and
Pt/TiO2 catalysts (Papaefthimiou et al., 1998b).
They found that the oxidation of benzene is
drastically decreased when water was added to
the feed streams. Strong adsorption of water on
the metal sites is believed to be responsible for
the decreased oxidation. In fact, the adsorbed
water molecules react with ethyl acetate,
converting it into ethanol and acetic acid. 5.
Deactivation and regeneration of
catalysts
Several factors are responsible for the change in
the activity and selectivity of catalysts with the
passage of time, leading to their deactivation.
Catalyst deactivation is a signifcant additional
expense as the cost of the catalyst may be as high as
28% of the operating cost of an oxidizer unit
(Gallastegi-Villa et al., 2014). Bartholomew
reviewed the deactivation of catalysts and classifed
the deactivation process into the following six
groups: fouling or coking, poisoning, vapor-solid
and/or solid-solid reaction, thermal degradation,
crushing, and vapor compound formation
(Bartholomew, 2001). Poisoning is the loss of active
sites of the catalyst due to chemisorption of
impurities on the catalyst (Forzatti and Lietti, 1999;
Neyestanaki et al., 2004). A poison can block the
active sites or can alter the activity of the catalyst. In
addition, as the adsorption coeffcient of a poison is
higher than that of the reactants, the poison can limit
the access of the reactants to the active sites. A
catalyst can be deactivated by the loss of active sites
due to the structural modifcation of the catalyst
caused by sintering, which is a thermally induced
process (Neyestanaki et al., 2004). Coke formation
is the result of side reactions taking place on the
catalyst surface when carbonaceous byproducts
deactivate the catalyst either by covering the catalyst
surface or by pore blocking. Mechanisms of coke
formation have been described in several reviews
(Rostrup-Nielsen and Trimm, 1977; Trimm, 1983).
Catalysts used for the oxidation of VOCs are
also deactivated by additional factors that are
normally not commonly encountered in other
catalytic reactions. Phosphorus can penetrate
alumina catalysts and form a glassy phase (Libanati
et al., 1998). Various byproducts, which adsorb on
titania catalysts, such as alcohol, aldehyde, and
carboxylic acid can also deactivate them. Interaction
of chlorine with catalysts leading to their
deactivation is a major problem in the oxidation of
chlorinated compounds. Coke formation and
chlorine deposition are the main reasons of catalyst
deactivation in the oxidation of trichloroethylene
using zeolites. Chlorine atoms attack the Bronsted
acid sites which causes structural changes of the
catalyst (Aranzabal et al., 2012). Almost all types of
catalysts are affected by chlorine deposition (Abbas
et al., 2011). Following are some of the catalysts
which can be subjected to chlorine poisoning:
cerium oxide based catalysts (Dai et al., 2008),
supported noble-metal catalysts (Abdullah et al.,
2006 ; Guillemot et al., 2007), transition metal
oxides, vanadia based catalysts (Kuazy_ nski et al.,
2002), perovskites (Kieling et al.,1998) , and
mixed-metal catalysts. Catalyst deactivation can also
be due to water present in almost all exhaust gases
and formed in oxidation reactions. Catalyst
deactivation in the ozone-catalytic oxidation of
benzene using MnO2 nanoparticles supported on
zeolites is due to the occupation of active sites and
adsorption centers by water. Deactivation can be
suppressed by reducing the amount of water vapor
and increasing the reaction temperature (Teh et al.,
2015). However, water also helps remove the
chlorine which can be deposited on the surface of
the catalyst during the oxidation reaction of
chlorinated VOCs (Gonzalez-Velasco et al., 2000).
As wet air can remove both coke and chlorine, wet
air is more effective in regenerating catalysts
compared to dry air (Gallastegi-Villa et al., 2014).
Intermediates produced during the oxidation are also
another major source of deactivation. Hsieh at al.
investigated the deactivation of Pt catalysts during
the oxidation of streams containing wastewater
(Hsieh et al., 2002) due to the agglomeration of Pt
clusters. Thevenet et al. investigated the deactivation
of the catalyst in acetylene conversion using TiO2
nanoparticles (Thevenet et al., 2014). Deposited
organic acids are a major source of deactivation of
catalysts and they can be regenerated using synthetic
air (Aranzabal et al., 2012, 2014; Gallastegi-Villa et
al., 2014). Synthetic air removed more than 80% of
the adsorbed acid and converted it into CO2. Ihm et
al. found that the deactivation during oxidation of n-
hexane using Pd/Al2O3 catalyst is mainly due to the
formation of carbonaceous intermediates (Ihm et al.,
2004). Dissociative adsorption of the reactant causes
the deactivation of the catalyst at low temperature in
the oxidation of trichloroethylene over the Co and
Cr oxide catalyst. Oliveira et al. investigated the
oxidation of chlorobenzene and xylene over
chromium and Pd-impregnated Alpillored bentonite
(Oliveira et al., 2008). The catalyst was deactivated
mainly due to the loss of Cr owing to the formation
of the volatile compound CrO 2Cl2, decrease in the
surface area, and formation of coke. Apart from the
catalyst itself, the temperature and space velocity
can also cause catalyst deactivation.
132 M.S. Kamal et al. / Atmospheric Environment 140 (2016) 117e134
Regeneration of a catalyst depends on the
reversibility of the deactivation process. For
example, coke formation can easily be reversed
while sintering is typically irreversible. Some
catalyst poisons can be selectively removed by
chemical washing, mechanically or by oxidation
(Argyle and Bartholomew, 2015). The decision to
regenerate or discard a catalyst depends mainly on
the rate of deactivation and cost of the catalytic
systems. Most of the available catalysts for the
removal of VOCs are expensive and they are
frequently deactivated. Therefore, regeneration of
catalysts is of utmost importance in terms of
operation and economics. Several methods available
for the regeneration of catalysts, such as heat
treatment methods, pressure swing, chemical
regeneration, oxygen plasma, ozone injection, pin-
to-plate dielectric barrier discharge, and radio
frequency (RF) plasma (HafezKhiabani et al., 2015;
Kim et al., 2007a; Sultana et al., 2015; Zhu et al.,
2015). The surface carbonate species on the
deactivated catalyst can be removed using
conventional heat treatment methods. However, the
method has the negative effect of aggregating
nanoparticles. (Konova et al., 2004a, 2004b).
Oxygen plasma and ozone injection was found to be
effective in regenerating the Au/TiO 2 catalyst (Kim
et al., 2007a). Air is much cheaper and have easier
access compared to oxygen as a discharge gas for
plasma regeneration. However, the presence of
nitrogen can cause extra poisoning due to the
formation of nitrogen oxide. Cold plasma of humid
air can solve the problem of nitrogen oxide
formation due to the presence of water vapor (Zhu et
al., 2015). In general, modern catalyst regeneration
techniques are replacing conventional heat treatment
or mechanical techniques.
6. Conclusion
Oxidation using catalysts is one of the most
promising techniques for the removal of VOCs.
Toxic VOCs can be oxidized into CO2, water, and
other relatively less harmful compounds over a
catalyst at relatively low temperatures (250e500 C)
compared to thermal oxidation. Operations at low
temperatures result in lowering of the fuel cost and
the formation of less dioxins and noxious products.
Catalytic oxidation is most suitable for effuent
streams with a low concentration of VOCs and
therefore most suitable for pollution control due to
end-of-pipe VOCs. This article reviewed various
catalytic systems that have been used in the removal
of a range of VOCs. These catalytic systems are
based on noble metal catalysts, metal oxides, and
mixed-metal catalysts. Supported noble-metal
catalysts such as Pt, Pd, Au, and Ag are the most
promising due to their high effciency for the
removal of VOCs at low temperature. The activity
of the supported noble metals depends on several
factors such as the type and nature of the support,
metal loading, and metal type. Although supported
noblemetal catalysts have the highest effciency,
they are expensive and can be deactivated by
sintering or poisoning. In addition, noblemetal
catalysts alone are not selective enough. Metal-
oxide catalysts have several advantages that make
them a good alternative to expensive noble-metal
catalysts. Metals oxides are more tolerant to
deactivation by poisoning compared to noble metals.
Other advantages include long lifetime, masking
tolerance, capability of regeneration, and availability
of a range of metal oxides in different sizes and
shapes. However, the effciency of single-metal-
oxide catalysts in removing different types of VOCs
is lower than that of the noble-metal catalysts. The
synergistic effect of two or more metal oxides can
have a higher effciency compared to a singlemetal-
oxide catalyst. Even though, catalytic oxidation has
achieved considerable success in removing VOCs, it
still faces several challenges. Catalyst deactivation
is a major problem associated with catalytic
oxidation. Catalysts can be easily deactivated by
adsorption of water vapor and other intermediates.
Future work should focus on the development of
effcient catalytic systems that can oxidize a range
of VOCs at much lower temperatures.
Acknowledgements
This project was funded by the National Plan
for Science, Technology and Innovation
(MAARIFAH) of the King Abdulaziz City for
Science and Technology (KACST) through the
Science & Technology Unit at the King Fahd
University of Petroleum & Minerals (KFUPM),
Kingdom of Saudi Arabia (award number
13ENV1968-
04).
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